ORGANIC SEMICONDUCTOR ELEMENT, MANUFACTURING METHOD THEREOF, COMPOSITION FOR FORMING ORGANIC SEMICONDUCTOR FILM, COMPOUND, AND ORGANIC SEMICONDUCTOR FILM
20170229662 · 2017-08-10
Inventors
Cpc classification
H01L29/786
ELECTRICITY
H10K85/111
ELECTRICITY
H10K85/6574
ELECTRICITY
H10K10/464
ELECTRICITY
H10K71/13
ELECTRICITY
H10K85/6576
ELECTRICITY
H10K10/466
ELECTRICITY
International classification
Abstract
An object to be achieved by the present invention is to provide an organic semiconductor element and an organic semiconductor film having high mobility and excellent heat resistance, and a manufacturing method thereof, to provide a novel compound that is suitable as an organic semiconductor, and to provide a composition for forming an organic semiconductor film in which coating film formability is excellent, with which an organic semiconductor element that has high mobility can be obtained, and in which heat resistance is excellent, an organic semiconductor element in which the composition for forming an organic semiconductor film is used, and a manufacturing method thereof.
The organic semiconductor element according to the present invention includes a compound represented by Formula 1 below included in an organic semiconductor layer.
##STR00001##
Claims
1. An organic semiconductor element comprising: a compound represented by Formula 1 below in an organic semiconductor layer, ##STR01431## in Formula 1, X.sup.11 and X.sup.12 each independently represent a chalcogen atom, Z.sup.1a to Z.sup.1j each independently represent a hydrogen atom or a halogen atom, A.sup.11 represents ═CR.sup.A11— or a nitrogen atom, R.sup.A11 represents a hydrogen atom or a group represented by R.sup.11, A.sup.12 represents ═CR.sup.A12— or a nitrogen atom, R.sup.A12 represents a hydrogen atom or a group represented by R.sup.12, n1 represents 0 or 1, p1 represents an integer of 0 to 2 in a case where A.sup.11 is —CR.sup.A11— and represents 0 or 1 in a case where A.sup.11 is a nitrogen atom, q1 represents an integer of 0 to 2 in a case where A.sup.12 is ═CR.sup.A12— and represents 0 or 1 in a case where A.sup.12 is a nitrogen atom, R.sup.11 and R.sup.12 each independently represent a halogen atom, an aryl group, a heteroaryl group, or a group represented by Formula W below,
-S.sup.W-L.sup.W-T.sup.W (W) in Formula W, S.sup.W represents a single bond or an alkylene group represented by —(CR.sup.S.sub.2).sub.k—, R.sup.S each independently represent a hydrogen atom or a halogen atom, k represents an integer of 1 to 17, L.sup.W represents a single bond, a divalent linking group represented by any one of Formulae L-1 to L-16 below, or a group obtained by bonding any two or more of divalent linking groups represented by Formulae L-1 to L-16 below, T.sup.W represents an alkyl group, a cyano group, a vinyl group, an ethynyl group, an aryl group, a heteroaryl group, an oxyethylene group, an oligooxyethylene group of which the repetition number of oxyethylene units is two or greater, an oligosiloxane group having two or more silicon atoms, or a trialkylsilyl group, and ##STR01432## ##STR01433## in Formulae L-1 to L-16, * and wavy line portions represent bonding positions to other structures, p13 represents an integer of 0 to 4, p14, p15, and p16 each independently represent an integer of 0 to 2, R.sup.L1, R.sup.L21, R.sup.L22, R.sup.L13, R.sup.L14, R.sup.L15, and R.sup.L16 each independently represent a hydrogen atom or a substituent.
2. The organic semiconductor element according to claim 1, wherein all of Z.sup.1a to Z.sup.1j are hydrogen atoms.
3. The organic semiconductor element according to claim 1, wherein n1 is not 0.
4. The organic semiconductor element according to claim 1, wherein at least one of p1 or q1 is not 0.
5. The organic semiconductor element according to claim 1, wherein at least one of p1 or q1 is not 0, and at least one of R.sup.11 or R.sup.12 is a group represented by Formula W.
6. The organic semiconductor element according to claim 1, wherein p1 and q1 are 1.
7. The organic semiconductor element according to claim 1, wherein both of X.sup.11 and X.sup.12 are S atoms, A.sup.11 is ═CR.sup.A11—, and A.sup.12 is ═CR.sup.A12—.
8. The organic semiconductor element according to claim 1, wherein a compound represented by Formula 1 is a compound represented by Formula 2 below, ##STR01434## in Formula 2, X.sup.21 and X.sup.22 each independently represent a chalcogen atom, W.sup.21 and W.sup.22 each independently represent a group represented by Formula W.
9. The organic semiconductor element according to claim 1, wherein the compound represented by Formula 1 is a line symmetric structure.
10. The organic semiconductor element according to claim 1, wherein the number of carbon atoms in the group represented by Formula W is 5 to 40.
11. The organic semiconductor element according to claim 1, wherein L.sup.W is a single bond, a divalent linking group represented by any one of Formulae L-1 to L-4 and Formulae L-13 to L-16, or a divalent linking group obtained by bonding two or more divalent linking groups represented by any one of Formulae L-1 to L-4 and Formulae L-13 to L-16.
12. The organic semiconductor element according to claim 1, wherein L.sup.W is a single bond or a divalent linking group represented by any one of Formulae L-1 to L-4 and Formulae L-13 to L-16.
13. The organic semiconductor element according to claim 1, wherein S.sup.W is a single bond.
14. The organic semiconductor element according to claim 1, wherein L.sup.W is a single bond or a divalent linking group represented by any one of Formula L-1 and Formulae L-13 to L-16.
15. The organic semiconductor element according to claim 1, wherein T.sup.W is an alkyl group.
16. The organic semiconductor element according to claim 1, wherein a group represented by Formula W is an alkyl group.
17. A composition for forming an organic semiconductor film, comprising: a solvent having a boiling point of 100° C. or higher, and a compound represented by Formula 1, wherein a content of the compound represented by Formula 1 is 20 mass % or less with respect to a total amount of the composition for forming an organic semiconductor film, ##STR01435## in Formula 1, X.sup.11 and X.sup.12 each independently represent a chalcogen atom, Z.sup.1a to Z.sup.1j each independently represent a hydrogen atom or a halogen atom, A.sup.11 represents ═CR.sup.A11— or a nitrogen atom, R.sup.A11 represents a hydrogen atom or a group represented by R.sup.11, A.sup.12 represents ═CR.sup.A12— or a nitrogen atom, R.sup.A12 represents a hydrogen atom or a group represented by R.sup.12, n1 represents 0 or 1, p1 represents an integer of 0 to 2 in a case where A.sup.11 is ═CR.sup.A11— and represents 0 or 1 in a case where A.sup.11 is a nitrogen atom, q1 represents an integer of 0 to 2 in a case where A.sup.12 is ═CR.sup.A12—, and represents 0 or 1 in a case where A.sup.12 is a nitrogen atom, R.sup.11 and R.sup.12 each independently represent a halogen atom, an aryl group, a heteroaryl group, or a group represented by Formula W below,
-S.sup.W-L.sup.W-T.sup.W (W) in Formula W, S.sup.W represents a single bond or an alkylene group represented by —(CR.sup.S.sub.2).sub.k—, R.sup.S each independently represent a hydrogen atom or a halogen atom, k represents an integer of 1 to 17, L.sup.W represents a single bond, a divalent linking group represented by any one of Formulae L-1 to L-16 below, or a group obtained by bonding any two or more of divalent linking groups represented by Formulae L-1 to L-16 below, T.sup.W represents an alkyl group, a cyano group, a vinyl group, an ethynyl group, an aryl group, a heteroaryl group, an oxyethylene group, an oligooxyethylene group of which the repetition number of oxyethylene units is two or greater, an oligosiloxane group having two or more silicon atoms, or a trialkylsilyl group, and ##STR01436## ##STR01437## in Formulae L-1 to L-16, * and wavy line portions represent bonding positions to other structures, p13 represents an integer of 0 to 4, p14, p15, and p16 each independently represent an integer of 0 to 2, R.sup.L1, R.sup.L21, R.sup.L22, R.sup.L13, R.sup.L14, R.sup.L15, and R.sup.L16 each independently represent a hydrogen atom or a substituent.
18. The composition for forming an organic semiconductor film according to claim 17, wherein all of Z.sup.1a to Z.sup.1j are hydrogen atoms.
19. The composition for forming an organic semiconductor film according to claim 17, wherein n1 is 0.
20. The composition for forming an organic semiconductor film according to claim 17, wherein at least one of p1 or q1 is not 0.
21. The composition for forming an organic semiconductor film according to claim 17, wherein at least one of p1 or q1 is not 0, and at least one of R or R.sup.12 is a group represented by Formula W.
22. The composition for forming an organic semiconductor film according to claim 17, wherein p1 and q1 is 1.
23. The composition for forming an organic semiconductor film according to claim 17, wherein both of X.sup.11 and X.sup.12 are S atoms, A.sup.11 is ═CR.sup.A11—, and A.sup.12 is —CR.sup.A12.
24. The composition for forming an organic semiconductor film according to claim 17, wherein the compound represented by Formula 1 is a compound represented by Formula 2 below, ##STR01438## in Formula 2, X.sup.21 and X.sup.22 each independently represent a chalcogen atom, W.sup.21 and W.sup.22 each independently represent a group represented by Formula W.
25. The composition for forming an organic semiconductor film according to claim 17, wherein the compound represented by Formula 1 is a line symmetric structure.
26. The composition for forming an organic semiconductor film according to claim 17, wherein the number of carbon atoms in the group represented by Formula W is 5 to 40.
27. The composition for forming an organic semiconductor film according to claim 17, wherein L.sup.W is a single bond, a divalent linking group represented by any one of Formulae L-1 to L-4 and Formulae L-13 to L-16, and a divalent linking group obtained by bonding two or more divalent linking groups represented by any one of Formulae L-1 to L-4 and Formulae L-13 to L-16.
28. The composition for forming an organic semiconductor film according to claim 17, wherein L.sup.W is a single bond or a divalent linking group represented by any one of Formulae L-1 to L-4 and Formulae L-13 to L-16.
29. The composition for forming an organic semiconductor film according to claim 17, wherein S.sup.W is a single bond.
30. The composition for forming an organic semiconductor film according to claim 17, wherein L.sup.W is a single bond or a divalent linking group represented by any one of Formula L-1 and Formulae L-13 to L-16.
31. The composition for forming an organic semiconductor film according to claim 17, wherein T.sup.W is an alkyl group.
32. The composition for forming an organic semiconductor film according to claim 17, wherein a group represented by Formula W is an alkyl group.
33. The composition for forming an organic semiconductor film according to claim 17, further comprising: a binder polymer, wherein a content of the binder polymer is 10 mass % or less with respect to a total amount of the composition for forming an organic semiconductor film.
34. A compound represented by Formula 1 below, ##STR01439## in Formula 1, X.sup.11 and X.sup.12 each independently represent a chalcogen atom, Z.sup.1a to Z.sup.1j each independently represent a hydrogen atom or a halogen atom, A.sup.11 represents ═CR.sup.A11— or a nitrogen atom, R.sup.A11 represents a hydrogen atom or a group represented by R.sup.11, A.sup.12 represents ═CR.sup.A12— or a nitrogen atom, R.sup.A12 represents a hydrogen atom or a group represented by R.sup.12, n1 represents 0 or 1, p1 represents an integer of 0 to 2 in a case where A.sup.11 is ═CR.sup.A11— and represents 0 or 1 in a case where A.sup.11 is a nitrogen atom, q1 represents an integer of 0 to 2 in a case where A.sup.12 is ═CR.sup.A12— and represents 0 or 1 in a case where A.sup.12 is a nitrogen atom, R.sup.11 and R.sup.12 each independently represent a halogen atom, an aryl group, a heteroaryl group, or a group represented by Formula W below,
-S.sup.W-L.sup.W-T.sup.W (W) in Formula W, S.sup.W represents a single bond or an alkylene group represented by —(CR.sup.S.sub.2).sub.k—, R.sup.S each independently represent a hydrogen atom or a halogen atom, k represents an integer of 1 to 17, L.sup.W represents a single bond, a divalent linking group represented by any one of Formulae L-1 to L-16 below, or a group obtained by bonding any two or more of divalent linking groups represented by Formulae L-1 to L-16 below, T.sup.W represents an alkyl group, a cyano group, a vinyl group, an ethynyl group, an aryl group, a heteroaryl group, an oxyethylene group, an oligooxyethylene group of which the repetition number of oxyethylene units is two or greater, an oligosiloxane group having two or more silicon atoms, or a trialkylsilyl group, and ##STR01440## ##STR01441## in Formulae L-1 to L-16, * and wavy line portions represent bonding positions to other structures, p13 represents an integer of 0 to 4, p14, p15, and p16 each independently represent an integer of 0 to 2, R.sup.L1, R.sup.L21, R.sup.L22, R.sup.L13, R.sup.L14, R.sup.L15, and R.sup.L16 each independently represent a hydrogen atom or a substituent.
35. A method of manufacturing an organic semiconductor film, comprising: an applying step of applying the composition for forming an organic semiconductor film according to claim 17 to a substrate, and a removing step of removing at least a portion of the solvent having a boiling point of 100° C. or higher included in the composition for forming an organic semiconductor film.
36. The method of manufacturing the organic semiconductor film according to claim 35, wherein the applying step is performed by an ink jet method or a flexographic printing method.
37. An organic semiconductor film obtained by the method according to claim 35.
38. A method of manufacturing an organic semiconductor element, comprising: an applying step of applying the composition for forming an organic semiconductor film according to claim 17 to a substrate, and a removing step of removing at least a portion of the solvent having a boiling point of 100° C. or higher included in the composition for forming an organic semiconductor film.
39. The method of manufacturing the organic semiconductor element according to claim 38, wherein the applying step is performed by an ink jet method or a flexographic printing method.
40. An organic semiconductor element manufactured by the method according to claim 38.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
[0058]
[0059]
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0060] Hereinafter, the contents of the present invention will be specifically described. The constituents in the following description will be explained based on typical embodiments of the present invention, but the present invention is not limited to the embodiments. In the specification of the present application, “to” is used to mean that the numerical values listed before and after “to” are a lower limit and an upper limit respectively. Furthermore, in the present invention, an organic EL element refers to an organic electroluminescence element.
[0061] In the present specification, in a case where there is no description regarding whether a group (atomic group) is substituted or unsubstituted, the group includes both of a group having a substituent and a group not having a substituent. For example, an “alkyl group” includes not only an alkyl group not having a substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
[0062] In the present specification, in some cases, a chemical structural formula is described as a simplified structural formula in which a hydrogen atom is omitted.
[0063] In the present invention, “mass %” and “weight %” have the same definition, and “part by mass” and “part by weight” have the same definition.
[0064] In the present invention, a combination of preferred aspects is more preferable.
[0065] (Organic Semiconductor Element and Compound)
[0066] The organic semiconductor element according to the present invention includes a compound (hereinafter, referred to as a “specific compound”) represented by Formula 1 above in an organic semiconductor layer.
[0067] The compound represented by Formula 1 above is preferably an organic semiconductor compound.
[0068] As a result of diligent research, the present inventors found that an organic semiconductor element or an organic semiconductor film containing the compound represented by Formula 1 has high mobility and excellent heat resistance, so as to complete the present invention.
[0069] A specific mechanism for exhibiting the effect is not clear, but it is assumed that if the compound represented by Formula 1 has line symmetry with a molecular center as an axis of symmetry in a certain degree or greater, mobility improves since crystallinity becomes excellent, and heat resistance of the organic semiconductor element is improved since a melting point increases.
[0070] It is assumed that crystallinity is excellent and mobility is improved, since the compound represented by Formula 1 has a molecular shape that the terminal thiophene ring protrudes from a rod-like structure such as a phenanthrene structure or a picene structure, and the appearance of a liquid crystal layer is suppressed. The mechanism of the suppression of the appearance of the liquid crystal layer as above contributes to the improvement of the heat resistance of the organic semiconductor element.
[0071] <Specific Compound>
[0072] The specific compound according to the present invention is represented by Formula 1 below.
##STR00006##
[0073] In Formula 1, X.sup.11 and X.sup.12 each independently represent a chalcogen atom, Z.sup.1a to Z.sup.1j each independently represent a hydrogen atom or a halogen atom, A.sup.11 represents ═CR.sup.A11— or a nitrogen atom, R.sup.A11 represents a hydrogen atom or a group represented by R.sup.11, A.sup.12 represents ═CR.sup.A12— or a nitrogen atom, R.sup.A12 represents a hydrogen atom or a group represented by R.sup.12, n1 represents 0 or 1, p1 represents an integer of 0 to 2 in a case where A.sup.11 is ═CR.sup.A11— and represents 0 or 1 in a case where A.sup.11 is a nitrogen atom, q1 represents an integer of 0 to 2 in a case where A.sup.12 is ═CR.sup.A12— and represents 0 or 1 in a case where A.sup.12 is a nitrogen atom, R.sup.11 and R.sup.12 each independently represent a halogen atom, an aryl group, a heteroaryl group, or a group represented by Formula W below.
-S.sup.W-L.sup.W-T.sup.W (W)
[0074] In Formula W, S.sup.W represents a single bond or an alkylene group represented by —(CR.sup.S.sub.2).sub.k—, R.sup.S each independently represent a hydrogen atom or a halogen atom, k represents an integer of 1 to 17, L.sup.W represents a single bond, a divalent linking group represented by any one of Formulae L-1 to L-16 below, or a group obtained by bonding any two or more of divalent linking groups represented by Formulae L-1 to L-16 below, T.sup.W represents an alkyl group, a cyano group, a vinyl group, an ethynyl group, an aryl group, a heteroaryl group, an oxycthylene group, an oligooxycthylene group of which the repetition number of oxyethylene units is two or greater, an oligosiloxane group having two or more silicon atoms, or a trialkylsilyl group.
##STR00007## ##STR00008##
[0075] In Formulae L-1 to L-16, * and wavy line portions represent bonding positions to other structures, p13 represents an integer of 0 to 4, p14, p15, and p16 each independently represent an integer of 0 to 2, R.sup.L1, R.sup.L21, R.sup.L22, R.sup.L13, R.sup.L14, R.sup.L15, and R.sup.L16 each independently represent a hydrogen atom or a substituent.
[0076] The specific compound according to the present invention is preferably an organic semiconductor compound.
[0077] The specific compound according to the present invention is a novel compound.
[0078] The specific compound according to the present invention can be suitably used for an organic semiconductor element, an organic semiconductor film, and a composition for forming an organic semiconductor film.
[0079] In Formula 1, X.sup.11 and X.sup.12 each independently represent a chalcogen atom, it is preferable that X.sup.11 and X.sup.12 each independently represent an O atom or an S atom, and it is more preferable that both of X.sup.11 and X.sup.12 are S atoms. The chalcogen atom refers to an atom in Group 16 including an O atom.
[0080] Z.sup.1a to Z.sup.1j each independently represent a hydrogen atom or a halogen atom, and it is preferable that all of Z.sup.1a to Z.sup.1j are hydrogen atoms.
[0081] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a fluorine atom is preferable.
[0082] A.sup.11 represents ═CR.sup.A11— or an nitrogen atom, and ═CR.sup.A11— is preferable.
[0083] R.sup.A11 represents a hydrogen atom or a group represented by R.sup.11, and a hydrogen atom is preferable. The expression “R.sup.A11 represents a group represented by R.sup.11” refers to a case where one of R.sup.11's of which the number is specified by p1 in Formula 1 is bonded to a carbon atom in A.sup.11.
[0084] A.sup.12 represents ═CR.sup.A12— or a nitrogen atom, and ═CR.sup.A12— is preferable.
[0085] R.sup.A12 represents a hydrogen atom or a group represented by R.sup.12, and a hydrogen atom is preferable. The expression “R.sup.A12 represents a group represented by R.sup.12” refers to a case where one of R.sup.12's of which the number is specified by q1 in Formula 1 is bonded to a carbon atom in A.sup.2.
[0086] n1 represents 0 or 1 and preferably 0.
[0087] In a case where A.sup.11 is ═CR.sup.A11—, p1 represents an integer of 0 to 2, preferably represents 1 or 2, more preferably 1. In a case where A.sup.11 is a nitrogen atom, p1 represents 0 or 1 and preferably represents 1. In a case where A.sup.11 is ═CR.sup.A11—, and p1 is 1, R.sup.11 is preferably bonded to a carbon atom positioned between A.sup.11 and X.sup.11, not a carbon atom included in A.sup.11.
[0088] In a case where A.sup.12 is ═CR.sup.A12—, q1 represents an integer of 0 to 2, preferably represents 1 or 2, and more preferably represents 1. In a case where A.sup.12 is a nitrogen atom, q1 represents 0 or 1 and preferably represents 1. In a case where A.sup.12 is ═CR.sup.A12— and q1 is 1, R.sup.12 is preferably bonded to a carbon atom positioned between A.sup.12 and X.sup.12, not a carbon atom included in A.sup.12.
[0089] R.sup.11 and R.sup.12 each independently represent a halogen atom, an aryl group, a heteroaryl group, or a group represented by Formula W below and preferably represents a group represented by Formula W.
-S.sup.W-L.sup.W-T.sup.W (W)
[0090] In Formula W, S.sup.W represents a single bond or an alkylene group represented by —(CR.sup.S.sub.2).sub.k— and preferably represents a single bond.
[0091] R.sup.S each independently represent a hydrogen atom or a halogen atom and preferably a hydrogen atom.
[0092] k represents an integer of 1 to 17, preferably represents an integer of 1 to 15, and more preferably an integer of 1 to 10.
[0093] L.sup.W represents a single bond, a divalent linking group represented by any one of Formulae L-1 to L-16, or a group obtained by bonding any two or more of divalent linking groups represented by Formulae L-1 to L-16, preferably represents a single bond, a divalent linking group represented by any one of Formulae L-1 to L-4 and Formulae L-13 to L-16, or a divalent linking group obtained by bonding two or more divalent linking groups represented by any one of Formulae L-1 to L-4 and Formulae L-13 to L-16, more preferably a single bond or a divalent linking group represented by any one of Formulae L-1 to L-4 and Formulae L-13 to L-16, and even more preferably a divalent linking group represented by any one of Formulae L-1, L-3, L-15, and L-16.
[0094] L.sup.W preferably represents a single bond or a divalent linking group represented by any one of Formula L-1 and Formulae L-13 to L-16.
[0095] T.sup.W represented by an alkyl group, a cyano group, a vinyl group, an ethynyl group, an aryl group, a heteroaryl group, an oxyethylene group, an oligooxyethylene group of which the repetition number of oxyethylene units is two or greater, an oligosiloxane group having two or more silicon atoms, or a trialkylsilyl group.
[0096] The alkyl group is preferably an alkyl group having 2 to 18 carbon atoms, more preferably an alkyl group having 3 to 15 carbon atoms, and even more preferably an alkyl group having 4 to 13 carbon atoms. The alkyl group may have any one of a linear shape, a branched shape, or a cyclic shape, or may have a structure obtained by combining these. However, a linear or branched alkyl group is preferable, and a linear alkyl group is more preferable.
[0097] The alkyl group may be substituted and preferable examples of the substituent include a halogen atom.
[0098] Examples of the aryl group (an aromatic hydrocarbon group) include a group obtained by removing one hydrogen atom from benzene, naphthalene, anthracene, or the like. A group obtained by removing one hydrogen atom from benzene is preferable.
[0099] The aryl group may be substituted but is preferably not substituted.
[0100] Examples of a heteroatom included in a heteroaryl group (an aromatic heterocyclic group) include an oxygen atom, a nitrogen atom, and a sulfur atom. An oxygen atom and a sulfur atom are preferable, and a sulfur atom is more preferable.
[0101] Examples of the heteroaryl group include a group obtained by removing one hydrogen atom from a thiophene ring, a furan ring, a pyran ring, a pyrrole ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a selenophene ring, an imidazole ring, and the like. A group obtained by removing one hydrogen atom from a thiophene ring or a furan ring is more preferable, and a group obtained by removing one hydrogen atom from a thiophene ring is even more preferable.
[0102] The heteroaryl group may be further substituted, but it is preferable that the heteroaryl group is not substituted.
[0103] The oligooxyethylene group of which the repetition number of oxyethylene units is two or greater is preferably an oligooxyethylene group of which the repetition number is one to five and more preferably an oligooxyethylene group of which the repetition number is one to three.
[0104] The oligosiloxane group having two or more silicon atoms is preferably an oligosiloxane group having one to five silicon atoms and more preferably an oligosiloxane group having one to three silicon atoms.
[0105] In Formulae L-1 to L-16, it is preferable that wavy line portions represent bonding positions to S.sup.W, * represents a bonding position to T.sup.W or a bonding position to a divalent linking group selected from the group consisting of other L-1 to L-16.
[0106] p13 represents an integer of 0 to 4, p14, p15, and p16 each independently represent an integer of 0 to 2, and R.sup.L1, R.sup.L21, R.sup.L22, R.sup.L13, R.sup.L14, R.sup.L15, and R.sup.L16 each independently represent a hydrogen atom or a substituent.
[0107] In a case where L.sup.W represents a linking group obtained by bonding a divalent linking group represented by any one of Formulae L-1 to L-16 above, the number of linkages of the divalent linking groups represented by any one of Formulae L-1 to L-16 is preferably 2 to 4 and more preferably 2 or 3.
[0108] R.sup.L1, R.sup.L21, R.sup.L22, R.sup.L13, R.sup.L14, R.sup.L15, and R.sup.L16 each independently represent a hydrogen atom or a substituent and preferably represent a hydrogen atom. Examples of the substituent include various substituents exemplified as T.sup.W in Formula 1 above.
[0109] A plurality of R.sup.L1's, R.sup.L13's, R.sup.L14's, R.sup.L15's, and R.sup.L16's may be identical to or different from each other. R.sup.L1's, R.sup.L21's, and R.sup.L22's may form ring structures by being bonded to T.sup.W adjacent to each other or may form a fused ring as the ring structure.
[0110] The group represented by Formula W is preferably an alkyl group, more preferably an alkyl group having 2 to 18 carbon atoms, even more preferably an alkyl group having 3 to 15 carbon atoms, and particularly preferably an alkyl group having 4 to 13 carbon atoms. In a case where the group represented by Formula W is an alkyl group, it is preferable that S.sup.W and L.sup.W are single bonds, and T.sup.W is an alkyl group.
[0111] In Formula 1, it is preferable that at least one of p1 or q1 is not 0, and it is more preferable that at least one of p1 or q1 is not 0, and at least one of R.sup.11 or R.sup.12 is a group represented by Formula W.
[0112] In Formula 1, it is preferable that p1 and q1 are 1, it is more preferable that p1 and q1 are 1, and at least one of R.sup.11 or R.sup.12 is a group represented by Formula W, and it is even more preferable that p1 and q1 are 1, and both of R.sup.11 and R.sup.12 are groups represented by Formula W.
[0113] In Formula 1, it is preferable that both of X.sup.11 and X.sup.12 are S atoms, A.sup.11 is ═CR.sup.A11—, and A.sup.12 is ═CR.sup.A12—, it is more preferable that both of X.sup.11 and X.sup.12 are S atoms, A.sup.11 is ═CR.sup.A11—, A.sup.12 is ═CR.sup.A12—, and both of R.sup.A11 and R.sup.A12 are hydrogen atoms.
[0114] The compound represented by Formula 1 is preferably a compound represented by Formula 2 below.
##STR00009##
[0115] In Formula 2, X.sup.21 and X.sup.22 each independently represent a chalcogen atom, preferably an O atom or a S atom. It is more preferable that both of X.sup.21 and X.sup.22 are S atoms. W.sup.21 and W.sup.22 each independently represent a group represented by Formula W above, and a preferable aspect thereof is the same as the preferable aspect described in the group represented by Formula W above.
[0116] The compound represented by Formula 1 above is preferably a line symmetric structure.
[0117] The expression “a compound has a line symmetric structure” means that a structural formula thereof is line symmetric with respect to the entire molecule. Specifically, the compound represented by Formula 1 is preferably a compound represented by Formulae 3 to 5 below.
[0118] It is considered that, if the compound represented by Formula 1 has a line symmetric structure, crystallinity and melting point become high, and mobility or heat resistance of an obtained organic semiconductor element or an obtained organic semiconductor film increase.
##STR00010##
[0119] In Formula 3 or 4, X.sup.11, X.sup.12, Z.sup.1a to Z.sup.1j, A.sup.11, A.sup.12, p1, q1, R.sup.11, and R.sup.12 have the same meaning as X.sup.11, X.sup.12, Z.sup.1a to Z.sup.1j, A.sup.11, A.sup.12, p1, q1, R.sup.11, and R.sup.12 in Formula 1, and preferable aspects thereof are also the same.
[0120] In Formula 5, X.sup.21, X.sup.22, W.sup.21, and W.sup.22 have the same meaning as X.sup.21, X.sup.22, W.sup.21, and W.sup.22 in Formula 2, and preferable aspects thereof are also the same.
[0121] All of the compounds represented by Formulae 3 to 5 have line symmetry having broken lines as symmetry axes.
[0122] As specific examples of the specific compound used in the present invention, Compounds 1 to 1475 represented by Formulae a to c below and presented in Tables 1 to 59 are preferably exemplified. However, the present invention is not limited thereto.
##STR00011##
[0123] In Compounds 1 to 1475, X.sup.a1, X.sup.a2, R.sup.a11, R.sup.a12, R.sup.a21, R.sup.a22, X.sup.b1, X.sup.b2, R.sup.b11, R.sup.b12, R.sup.b21, R.sup.b22, X.sup.c1, X.sup.c2, R.sup.c11, and R.sup.c21 in Formulae a to c represent structures presented in Tables 1 to 59. In Tables 1 to 59, Ph represents a phenyl group, -Ph- represents a phenylene group, and * represents a bonding portion to another structure.
TABLE-US-00001 TABLE 1 X.sup.a1 X.sup.a2 R.sup.a11 R.sup.a12 R.sup.a21 R.sup.a22 Compound 1 S S C.sub.4H.sub.9—* H C.sub.4H.sub.9—* H Compound 2 S S C.sub.5H.sub.11—* H C.sub.5H.sub.11—* H Compound 3 S S C.sub.6H.sub.13—* H C.sub.6H.sub.13—* H Compound 4 S S C.sub.7H.sub.15—* H C.sub.7H.sub.15—* H Compound 5 S S C.sub.8H.sub.17—* H C.sub.8H.sub.17—* H Compound 6 S S C.sub.9H.sub.19—* H C.sub.9H.sub.19—* H Compound 7 S S C.sub.10H.sub.21—* H C.sub.10H.sub.21—* H Compound 8 S S C.sub.11H.sub.23—* H C.sub.11H.sub.23—* H Compound 9 S S C.sub.12H.sub.25—* H C.sub.12H.sub.25—* H Compound 10 S S C.sub.13H.sub.27—* H C.sub.13H.sub.27—* H Compound 11 S S C.sub.14H.sub.29—* H C.sub.14H.sub.29—* H Compound 12 S S C.sub.15H.sub.31—* H C.sub.15H.sub.31—* H Compound 13 S S C.sub.16H.sub.33—* H C.sub.16H.sub.33—* H Compound 14 S S C.sub.17H.sub.35—* H C.sub.17H.sub.35—* H Compound 15 S S C.sub.18H.sub.37—* H C.sub.18H.sub.37—* H Compound 16 S S C.sub.5H.sub.11—* C.sub.5H.sub.11—* C.sub.5H.sub.11—* C.sub.5H.sub.11—* Compound 17 S S C.sub.6H.sub.13—* C.sub.6H.sub.13—* C.sub.6H.sub.13—* C.sub.6H.sub.13—* Compound 18 S S C.sub.7H.sub.15—* C.sub.7H.sub.15—* C.sub.7H.sub.15—* C.sub.7H.sub.15—* Compound 19 S S C.sub.8H.sub.17—* C.sub.8H.sub.17—* C.sub.8H.sub.17—* C.sub.8H.sub.17—* Compound 20 S S C.sub.9H.sub.19—* C.sub.9H.sub.19—* C.sub.9H.sub.19—* C.sub.9H.sub.19—* Compound 21 S S C.sub.10H.sub.21—* C.sub.10H.sub.21—* C.sub.10H.sub.21—* C.sub.10H.sub.21—* Compound 22 S S C.sub.11H.sub.23—* C.sub.11H.sub.23—* C.sub.11H.sub.23—* C.sub.11H.sub.23—* Compound 23 S S C.sub.12H.sub.25—* C.sub.12H.sub.25—* C.sub.12H.sub.25—* C.sub.12H.sub.25—* Compound 24 S S C.sub.13H.sub.27—* C.sub.13H.sub.27—* C.sub.13H.sub.27—* C.sub.13H.sub.27—* Compound 25 S S C.sub.14H.sub.29—* C.sub.14H.sub.29—* C.sub.14H.sub.29—* C.sub.14H.sub.29—* Compound 26 S S C.sub.15H.sub.31—* C.sub.15H.sub.31—* C.sub.15H.sub.31—* C.sub.15H.sub.31—* Compound 27 S S C.sub.16H.sub.33—* C.sub.16H.sub.33—* C.sub.16H.sub.33—* C.sub.16H.sub.33—* Compound 28 S S C.sub.17H.sub.35—* C.sub.17H.sub.35—* C.sub.17H.sub.35—* C.sub.17H.sub.35—* Compound 29 S S C.sub.18H.sub.37—* C.sub.18H.sub.37—* C.sub.18H.sub.37—* C.sub.18H.sub.37—* Compound 30 S S p-C.sub.5H.sub.11—Ph—* H p-C.sub.5H.sub.11—Ph—* H Compound 31 S S p-C.sub.6H.sub.13—Ph—* H p-C.sub.6H.sub.13—Ph—* H Compound 32 S S p-C.sub.7H.sub.15—Ph—* H p-C.sub.7H.sub.15—Ph—* H Compound 33 S S p-C.sub.8H.sub.17—Ph—* H p-C.sub.8H.sub.17—Ph—* H Compound 34 S S p-C.sub.9H.sub.19—Ph—* H p-C.sub.9H.sub.19—Ph—* H Compound 35 S S p-C.sub.10H.sub.21—Ph—* H p-C.sub.10H.sub.21—Ph—* H Compound 36 S S p-C.sub.11H.sub.23—Ph—* H p-C.sub.11H.sub.23—Ph—* H Compound 37 S S p-C.sub.12H.sub.25—Ph—* H p-C.sub.12H.sub.25—Ph—* H Compound 38 S S p-C.sub.13H.sub.27—Ph—* H p-C.sub.13H.sub.27—Ph—* H Compound 39 S S p-C.sub.14H.sub.29—Ph—* H p-C.sub.14H.sub.29—Ph—* H Compound 40 S S p-C.sub.15H.sub.31—Ph—* H p-C.sub.15H.sub.31—Ph—* H Compound 41 S S p-C.sub.16H.sub.33—Ph—* H p-C.sub.16H.sub.33—Ph—* H Compound 42 S S p-C.sub.17H.sub.35—Ph—* H p-C.sub.17H.sub.35—Ph—* H Compound 43 S S p-C.sub.18H.sub.37—Ph—* H p-C.sub.18H.sub.37—Ph—* H Compound 44 S S p-C.sub.5H.sub.11—Ph—* p-C.sub.5H.sub.11—Ph—* p-C.sub.5H.sub.11—Ph—* p-C.sub.5H.sub.11—Ph—* Compound 45 S S p-C.sub.6H.sub.13—Ph—* p-C.sub.6H.sub.13—Ph—* p-C.sub.6H.sub.13—Ph—* p-C.sub.6H.sub.13—Ph—* Compound 46 S S p-C.sub.7H.sub.15—Ph—* p-C.sub.7H.sub.15—Ph—* p-C.sub.7H.sub.15—Ph—* p-C.sub.7H.sub.15—Ph—* Compound 47 S S p-C.sub.8H.sub.17—Ph—* p-C.sub.8H.sub.17—Ph—* p-C.sub.8H.sub.17—Ph—* p-C.sub.8H.sub.17—Ph—* Compound 48 S S p-C.sub.9H.sub.19—Ph—* p-C.sub.9H.sub.19—Ph—* p-C.sub.9H.sub.19—Ph—* p-C.sub.9H.sub.19—Ph—* Compound 49 S S p-C.sub.10H.sub.21—Ph—* p-C.sub.10H.sub.21—Ph—* p-C.sub.10H.sub.21—Ph—* p-C.sub.10H.sub.21—Ph—* Compound 50 S S p-C.sub.11H.sub.23—Ph—* p-C.sub.11H.sub.23—Ph—* p-C.sub.11H.sub.23—Ph—* p-C.sub.11H.sub.23—Ph—* Compound 51 S S p-C.sub.12H.sub.25—Ph—* p-C.sub.12H.sub.25—Ph—* p-C.sub.12H.sub.25—Ph—* p-C.sub.12H.sub.25—Ph—*
TABLE-US-00002 TABLE 2 X.sup.a1 X.sup.a2 R.sup.a11 R.sup.a12 R.sup.a21 R.sup.a22 Compound 52 S S p-C.sub.13H.sub.27—Ph-* p-C.sub.13H.sub.27—Ph-* p-C.sub.13H.sub.27—Ph-* p-C.sub.13H.sub.27—Ph-* Compound 53 S S p-C.sub.14H.sub.29—Ph-* p-C.sub.14H.sub.29—Ph-* p-C.sub.14H.sub.29—Ph-* p-C.sub.14H.sub.29—Ph-* Compound 54 S S p-C.sub.15H.sub.31—Ph-* p-C.sub.15H.sub.31—Ph-* p-C.sub.15H.sub.31—Ph-* p-C.sub.15H.sub.31—Ph-* Compound 55 S S p-C.sub.16H.sub.33—Ph-* p-C.sub.16H.sub.33—Ph-* p-C.sub.16H.sub.33—Ph-* p-C.sub.16H.sub.33—Ph-* Compound 56 S S p-C.sub.17H.sub.35—Ph-* p-C.sub.17H.sub.35—Ph-* p-C.sub.17H.sub.35—Ph-* p-C.sub.17H.sub.35—Ph-* Compound 57 S S p-C.sub.18H.sub.37—Ph-* p-C.sub.18H.sub.37—Ph-* p-C.sub.18H.sub.37—Ph-* p-C.sub.18H.sub.37—Ph-* Compound 58 S S
TABLE-US-00003 TABLE 3 X.sup.a1 X.sup.a2 R.sup.a11 R.sup.a12 R.sup.a21 R.sup.a22 Compound 74 S S
TABLE-US-00004 TABLE 4 X.sup.a1 X.sup.a2 R.sup.a11 R.sup.a12 R.sup.a21 R.sup.a22 Compound 92 S S
TABLE-US-00005 TABLE 5 X.sup.a1 X.sup.a2 R.sup.a11 R.sup.a12 R.sup.a21 R.sup.a22 Compound 110 S S
TABLE-US-00006 TABLE 6 X.sup.a1 X.sup.a2 R.sup.a11 R.sup.a12 R.sup.a21 R.sup.a22 Compound 128 S S H C.sub.5H.sub.11-* H C.sub.5H.sub.11-* Compound 129 S S H C.sub.6H.sub.13-* H C.sub.6H.sub.13-* Compound 130 S S H C.sub.7H.sub.15-* H C.sub.7H.sub.15-* Compound 131 S S H C.sub.8H.sub.17-* H C.sub.8H.sub.17-* Compound 132 S S H C.sub.9H.sub.19-* H C.sub.9H.sub.19-* Compound 133 S S H C.sub.10H.sub.21-* H C.sub.10H.sub.21-* Compound 134 S S H C.sub.11H.sub.23-* H C.sub.11H.sub.23-* Compound 135 S S H C.sub.12H.sub.25-* H C.sub.12H.sub.25-* Compound 136 S S H C.sub.13H.sub.27-* H C.sub.13H.sub.27-* Compound 137 S S H C.sub.14H.sub.29-* H C.sub.14H.sub.29-* Compound 138 S S H C.sub.15H.sub.31-* H C.sub.15H.sub.31-* Compound 139 S S H C.sub.16H.sub.33-* H C.sub.16H.sub.33-* Compound 140 S S H C.sub.17H.sub.35-* H C.sub.17H.sub.35-* Compound 141 S S H C.sub.18H.sub.37-* H C.sub.18H.sub.37-* Compound 142 S S H p-C.sub.5H.sub.11—Ph-* H p-C.sub.5H.sub.11—Ph-* Compound 143 S S H p-C.sub.6H.sub.13—Ph-* H p-C.sub.6H.sub.13—Ph-* Compound 144 S S H p-C.sub.7H.sub.15—Ph-* H p-C.sub.7H.sub.15—Ph-* Compound 145 S S H p-C.sub.8H.sub.17—Ph-* H p-C.sub.8H.sub.17—Ph-* Compound 146 S S H p-C.sub.9H.sub.19—Ph-* H p-C.sub.9H.sub.19—Ph-* Compound 147 S S H p-C.sub.10H.sub.21—Ph-* H p-C.sub.10H.sub.21—Ph-* Compound 148 S S H p-C.sub.11H.sub.23—Ph-* H p-C.sub.11H.sub.23—Ph-* Compound 149 S S H p-C.sub.12H.sub.25—Ph-* H p-C.sub.12H.sub.25—Ph-* Compound 150 S S H p-C.sub.13H.sub.27—Ph-* H p-C.sub.13H.sub.27—Ph-* Compound 151 S S H p-C.sub.14H.sub.29—Ph-* H p-C.sub.14H.sub.29—Ph-* Compound 152 S S H p-C.sub.15H.sub.31—Ph-* H p-C.sub.15H.sub.31—Ph-* Compound 153 S S H p-C.sub.16H.sub.33—Ph-* H p-C.sub.16H.sub.33—Ph-* Compound 154 S S H p-C.sub.17H.sub.35—Ph-* H p-C.sub.17H.sub.35—Ph-* Compound 155 S S H p-C.sub.18H.sub.37—Ph-* H p-C.sub.18H.sub.37—Ph-* Compound 156 S S H
TABLE-US-00007 TABLE 7 X.sup.a1 X.sup.a2 R.sup.a11 R.sup.a12 R.sup.a21 R.sup.a22 Compound 164 S S H
TABLE-US-00008 TABLE 8 X.sup.a1 X.sup.a2 R.sup.a11 R.sup.a12 R.sup.a21 R.sup.a22 Compound 200 S S
TABLE-US-00009 TABLE 9 X.sup.a1 X.sup.a2 R.sup.a11 R.sup.a12 R.sup.a21 R.sup.a22 Compound 231 S S H H p-C.sub.10H.sub.21—Ph-* H Compound 232 S S H H p-C.sub.11H.sub.23—Ph-* H Compound 233 S S H H p-C.sub.12H.sub.25—Ph-* H Compound 234 S S H H p-C.sub.13H.sub.27—Ph-* H Compound 235 S S H H p-C.sub.14H.sub.29—Ph-* H Compound 236 S S H H p-C.sub.15H.sub.31—Ph-* H Compound 237 S S H H p-C.sub.16H.sub.33—Ph-* H Compound 238 S S H H p-C.sub.17H.sub.35—Ph-* H Compound 239 S S H H p-C.sub.18H.sub.37—Ph-* H Compound 240 S S Ph H p-C.sub.5H.sub.11—Ph-* H Compound 241 S S Ph H p-C.sub.6H.sub.13—Ph-* H Compound 242 S S Ph H p-C.sub.7H.sub.15—Ph-* H Compound 243 S S Ph H p-C.sub.8H.sub.17—Ph-* H Compound 244 S S Ph H p-C.sub.9H.sub.19—Ph-* H Compound 245 S S Ph H p-C.sub.10H.sub.21—Ph-* H Compound 246 S S Ph H p-C.sub.11H.sub.23—Ph-* H Compound 247 S S Ph H p-C.sub.12H.sub.25—Ph-* H Compound 248 S S Ph H p-C.sub.13H.sub.27—Ph-* H Compound 249 S S Ph H p-C.sub.14H.sub.29—Ph-* H Compound 250 S S Ph H p-C.sub.15H.sub.31—Ph-* H Compound 251 S S Ph H p-C.sub.16H.sub.33—Ph-* H Compound 252 S S Ph H p-C.sub.17H.sub.35—Ph-* H Compound 253 S S Ph H p-C.sub.18H.sub.37—Ph-* H Compound 254 S S
TABLE-US-00010 TABLE 10 X.sup.a1 X.sup.a2 R.sup.a11 R.sup.a12 R.sup.a21 R.sup.a22 Compound 264 S S
TABLE-US-00011 TABLE 11 X.sup.a1 X.sup.a2 R.sup.a11 R.sup.a12 R.sup.a21 R.sup.a22 Com- pound 291 S S H H
TABLE-US-00012 TABLE 12 X.sup.a1 X.sup.a2 R.sup.a11 R.sup.a12 R.sup.a21 R.sup.a22 Compound 309 S S
TABLE-US-00013 TABLE 13 X.sup.a1 X.sup.a2 R.sup.a11 R.sup.a12 R.sup.a21 R.sup.a22 Compound 327 S S H H H
TABLE-US-00014 TABLE 14 X.sup.a1 X.sup.a2 R.sup.a11 R.sup.a12 R.sup.a21 R.sup.a22 Compound 345 S S H H
TABLE-US-00015 TABLE 15 X.sup.a1 X.sup.a2 R.sup.a11 R.sup.a12 R.sup.a21 R.sup.a22 Compound 363 S S
TABLE-US-00016 TABLE 16 X.sup.a1 X.sup.a2 R.sup.a11 R.sup.a12 R.sup.a21 R.sup.a22 Compound 390 S S C.sub.12H.sub.25—* H
TABLE-US-00017 TABLE 17 X.sup.a1 X.sup.a2 R.sup.a11 R.sup.a12 R.sup.a21 R.sup.a22 Compound 418 S S C.sub.10H.sub.21—* H H p-C.sub.5H.sub.11—Ph—* Compound 419 S S C.sub.10H.sub.21—* H H p-C.sub.6H.sub.13—Ph—* Compound 420 S S C.sub.10H.sub.21—* H H p-C.sub.7H.sub.15—Ph—* Compound 421 S S C.sub.10H.sub.21—* H H p-C.sub.8H.sub.17—Ph—* Compound 422 S S C.sub.10H.sub.21—* H H p-C.sub.9H.sub.19—Ph—* Compound 423 S S C.sub.10H.sub.21—* H H p-C.sub.10H.sub.21—Ph—* Compound 424 S S C.sub.10H.sub.21—* H H p-C.sub.11H.sub.23—Ph—* Compound 425 S S C.sub.10H.sub.21—* H H p-C.sub.12H.sub.25—Ph—* Compound 426 S S C.sub.10H.sub.21—* H H p-C.sub.13H.sub.27—Ph—* Compound 427 S S C.sub.10H.sub.21—* H H p-C.sub.14H.sub.29—Ph—* Compound 428 S S C.sub.10H.sub.21—* H H p-C.sub.15H.sub.31—Ph—* Compound 429 S S C.sub.10H.sub.21—* H H p-C.sub.16H.sub.33—Ph—* Compound 430 S S C.sub.10H.sub.21—* H H p-C.sub.17H.sub.35—Ph—* Compound 431 S S C.sub.10H.sub.21—* H H p-C.sub.18H.sub.37—Ph—* Compound 432 S S H C.sub.10H.sub.21—* H p-C.sub.5H.sub.11—Ph—* Compound 433 S S H C.sub.10H.sub.21—* H p-C.sub.6H.sub.13—Ph—* Compound 434 S S H C.sub.10H.sub.21—* H p-C.sub.7H.sub.15—Ph—* Compound 435 S S H C.sub.10H.sub.21—* H p-C.sub.8H.sub.17—Ph—* Compound 436 S S H C.sub.10H.sub.21—* H p-C.sub.9H.sub.19—Ph—* Compound 437 S S H C.sub.10H.sub.21—* H p-C.sub.10H.sub.21—Ph—* Compound 438 S S H C.sub.10H.sub.21—* H p-C.sub.11H.sub.23—Ph—* Compound 439 S S H C.sub.10H.sub.21—* H p-C.sub.12H.sub.25—Ph—* Compound 440 S S H C.sub.10H.sub.21—* H p-C.sub.13H.sub.27—Ph—* Compound 441 S S H C.sub.10H.sub.21—* H p-C.sub.14H.sub.29—Ph—* Compound 442 S S H C.sub.10H.sub.21—* H p-C.sub.15H.sub.31—Ph—* Compound 443 S S H C.sub.10H.sub.21—* H p-C.sub.16H.sub.33—Ph—* Compound 444 S S H C.sub.10H.sub.21—* H p-C.sub.17H.sub.35—Ph—* Compound 445 S S H C.sub.10H.sub.21—* H p-C.sub.18H.sub.37—Ph—* Compound 446 S S
TABLE-US-00018 TABLE 18 X.sup.a1 X.sup.a2 R.sup.a11 R.sup.a12 R.sup.a21 R.sup.a22 Compound 454 S S
TABLE-US-00019 TABLE 19 X.sup.a1 X.sup.a2 R.sup.a11 R.sup.a12 R.sup.a21 R.sup.a22 Compound 472 S S
TABLE-US-00020 TABLE 20 X.sup.a1 X.sup.a2 R.sup.a11 R.sup.a12 R.sup.a21 R.sup.a22 Compound 498 O O C.sub.16H.sub.33—* H C.sub.16H.sub.33—* H Compound 499 O O C.sub.17H.sub.35—* H C.sub.17H.sub.35—* H Compound 500 O O C.sub.18H.sub.37—* H C.sub.18H.sub.37—* H Compound 501 O O p-C.sub.5H.sub.11—Ph—* H p-C.sub.5H.sub.11—Ph—* H Compound 502 O O p-C.sub.6H.sub.13—Ph—* H p-C.sub.6H.sub.13—Ph—* H Compound 503 O O p-C.sub.7H.sub.15—Ph—* H p-C.sub.7H.sub.15—Ph—* H Compound 504 O O p-C.sub.8H.sub.17—Ph—* H p-C.sub.8H.sub.17—Ph—* H Compound 505 O O p-C.sub.9H.sub.19—Ph—* H p-C.sub.9H.sub.19—Ph—* H Compound 506 O O p-C.sub.10H.sub.21—Ph—* H p-C.sub.10H.sub.21—Ph—* H Compound 507 O O p-C.sub.11H.sub.23—Ph—* H p-C.sub.11H.sub.23—Ph—* H Compound 508 O O p-C.sub.12H.sub.25—Ph—* H p-C.sub.12H.sub.25—Ph—* H Compound 509 O O p-C.sub.13H.sub.27—Ph—* H p-C.sub.13H.sub.27—Ph—* H Compound 510 O O p-C.sub.14H.sub.29—Ph—* H p-C.sub.14H.sub.29—Ph—* H Compound 511 O O p-C.sub.15H.sub.31—Ph—* H p-C.sub.15H.sub.31—Ph—* H Compound 512 O O p-C.sub.16H.sub.33—Ph—* H p-C.sub.16H.sub.33—Ph—* H Compound 513 O O p-C.sub.17H.sub.35—Ph—* H p-C.sub.17H.sub.35—Ph—* H Compound 514 O O p-C.sub.18H.sub.37—Ph—* H p-C.sub.18H.sub.37—Ph—* H Compound 515 O O
TABLE-US-00021 TABLE 21 X.sup.a1 X.sup.a2 R.sup.a11 R.sup.a12 R.sup.a21 R.sup.a22 Compound 527 O O OC.sub.4H.sub.5—* H C.sub.4H
OC.sub.4H.sub.5—* H Compound 530 S S C.sub.2H.sub.5OC.sub.2H
—* H C.sub.2H.sub.5OC.sub.2H
—* H Compound 531 S S C
H.sub.12OC.sub.4H
—* H C
H.sub.12OC.sub.4H
—* H Compound 532 S S C.sub.2H.sub.3OC.sub.4H
—* H C.sub.2H.sub.3OC.sub.4H
—* H Compound 533 S S CH
OC.sub.3H.sub.6—* H CH
OC.sub.3H.sub.6—* H Compound 534 S S
indicates data missing or illegible when filed
TABLE-US-00022 TABLE 22 X.sup.a1 X.sup.a2 R.sup.a11 R.sup.a12 R.sup.a21 R.sup.a22 Compound S S 3,7-Dimethyloctyl H H H 545 Compound S S 2-Ethylhexyl H 2-Ethylhexyl H 546 Compound 547 S S
TABLE-US-00023 TABLE 23 X.sup.b1 X.sup.b2 R.sup.b11 R.sup.b12 R.sup.b21 R.sup.b22 Compound 563 S S C.sub.5H.sub.11—* H C.sub.5H.sub.11—* H Compound 564 S S C.sub.6H.sub.13—* H C.sub.6H.sub.13—* H Compound 565 S S C.sub.7H.sub.15—* H C.sub.7H.sub.15—* H Compound 566 S S C.sub.8H.sub.17—* H C.sub.8H.sub.17—* H Compound 567 S S C.sub.9H.sub.19—* H C.sub.9H.sub.19—* H Compound 568 S S C.sub.10H.sub.21—* H C.sub.10H.sub.21—* H Compound 569 S S C.sub.11H.sub.23—* H C.sub.11H.sub.23—* H Compound 570 S S C.sub.12H.sub.25—* H C.sub.12H.sub.25—* H Compound 571 S S C.sub.13H.sub.27—* H C.sub.13H.sub.27—* H Compound 572 S S C.sub.14H.sub.29—* H C.sub.14H.sub.29—* H Compound 573 S S C.sub.15H.sub.31—* H C.sub.15H.sub.31—* H Compound 574 S S C.sub.16H.sub.33—* H C.sub.16H.sub.33—* H Compound 575 S S C.sub.17H.sub.35—* H C.sub.17H.sub.35—* H Compound 576 S S C.sub.18H.sub.37—* H C.sub.18H.sub.37—* H Compound 577 S S C.sub.5H.sub.11—* C.sub.5H.sub.11—* C.sub.5H.sub.11—* C.sub.5H.sub.11—* Compound 578 S S C.sub.6H.sub.13—* C.sub.6H.sub.13—* C.sub.6H.sub.13—* C.sub.6H.sub.13—* Compound 579 S S C.sub.7H.sub.15—* C.sub.7H.sub.15—* C.sub.7H.sub.15—* C.sub.7H.sub.15—* Compound 580 S S C.sub.8H.sub.17—* C.sub.8H.sub.17—* C.sub.8H.sub.17—* C.sub.8H.sub.17—* Compound 581 S S C.sub.9H.sub.19—* C.sub.9H.sub.19—* C.sub.9H.sub.19—* C.sub.9H.sub.19—* Compound 582 S S C.sub.10H.sub.21—* C.sub.10H.sub.21—* C.sub.10H.sub.21—* C.sub.10H.sub.21—* Compound 583 S S C.sub.11H.sub.23—* C.sub.11H.sub.23—* C.sub.11H.sub.23—* C.sub.11H.sub.23—* Compound 584 S S C.sub.12H.sub.25—* C.sub.12H.sub.25—* C.sub.12H.sub.25—* C.sub.12H.sub.25—* Compound 585 S S C.sub.13H.sub.27—* C.sub.13H.sub.27—* C.sub.13H.sub.27—* C.sub.13H.sub.27—* Compound 586 S S C.sub.14H.sub.29—* C.sub.14H.sub.29—* C.sub.14H.sub.29—* C.sub.14H.sub.29—* Compound 587 S S C.sub.15H.sub.31—* C.sub.15H.sub.31—* C.sub.15H.sub.31—* C.sub.15H.sub.31—* Compound 588 S S C.sub.16H.sub.33—* C.sub.16H.sub.33—* C.sub.16H.sub.33—* C.sub.16H.sub.33—* Compound 589 S S C.sub.17H.sub.35—* C.sub.17H.sub.35—* C.sub.17H.sub.35—* C.sub.17H.sub.35—* Compound 590 S S C.sub.18H.sub.37—* C.sub.18H.sub.37—* C.sub.18H.sub.37—* C.sub.18H.sub.37—* Compound 591 S S p-C.sub.5H.sub.11—Ph—* H p-C.sub.5H.sub.11—Ph—* H Compound 592 S S p-C.sub.6H.sub.13—Ph—* H p-C.sub.6H.sub.13—Ph—* H Compound 593 S S p-C.sub.7H.sub.15—Ph—* H p-C.sub.7H.sub.15—Ph—* H Compound 594 S S p-C.sub.8H.sub.17—Ph—* H p-C.sub.8H.sub.17—Ph—* H Compound 595 S S p-C.sub.9H.sub.19—Ph—* H p-C.sub.9H.sub.19—Ph—* H Compound 596 S S p-C.sub.10H.sub.21—Ph—* H p-C.sub.10H.sub.21—Ph—* H Compound 597 S S p-C.sub.11H.sub.23—Ph—* H p-C.sub.11H.sub.23—Ph—* H Compound 598 S S p-C.sub.12H.sub.25—Ph—* H p-C.sub.12H.sub.25—Ph—* H Compound 599 S S p-C.sub.13H.sub.27—Ph—* H p-C.sub.13H.sub.27—Ph—* H Compound 600 S S p-C.sub.14H.sub.29—Ph—* H p-C.sub.14H.sub.29—Ph—* H Compound 601 S S p-C.sub.15H.sub.31—Ph—* H p-C.sub.15H.sub.31—Ph—* H Compound 602 S S p-C.sub.16H.sub.33—Ph—* H p-C.sub.16H.sub.33—Ph—* H Compound 603 S S p-C.sub.17H.sub.35—Ph—* H p-C.sub.17H.sub.35—Ph—* H Compound 604 S S p-C.sub.18H.sub.37—Ph—* H p-C.sub.18H.sub.37—Ph—* H Compound 605 S S p-C.sub.5H.sub.11—Ph—* p-C.sub.5H.sub.11—Ph—* p-C.sub.5H.sub.11—Ph—* p-C.sub.5H.sub.11—Ph—* Compound 606 S S p-C.sub.6H.sub.13—Ph—* p-C.sub.6H.sub.13—Ph—* p-C.sub.6H.sub.13—Ph—* p-C.sub.6H.sub.13—Ph—* Compound 607 S S p-C.sub.7H.sub.15—Ph—* p-C.sub.7H.sub.15—Ph—* p-C.sub.7H.sub.15—Ph—* p-C.sub.7H.sub.15—Ph—* Compound 608 S S p-C.sub.8H.sub.17—Ph—* p-C.sub.8H.sub.17—Ph—* p-C.sub.8H.sub.17—Ph—* p-C.sub.8H.sub.17—Ph—* Compound 609 S S p-C.sub.9H.sub.19—Ph—* p-C.sub.9H.sub.19—Ph—* p-C.sub.9H.sub.19—Ph—* p-C.sub.9H.sub.19—Ph—* Compound 610 S S p-C.sub.10H.sub.21—Ph—* p-C.sub.10H.sub.21—Ph—* p-C.sub.10H.sub.21—Ph—* p-C.sub.10H.sub.21—Ph—* Compound 611 S S p-C.sub.11H.sub.23—Ph—* p-C.sub.11H.sub.23—Ph—* p-C.sub.11H.sub.23—Ph—* p-C.sub.11H.sub.23—Ph—* Compound 612 S S p-C.sub.12H.sub.25—Ph—* p-C.sub.12H.sub.25—Ph—* p-C.sub.12H.sub.25—Ph—* p-C.sub.12H.sub.25—Ph—* Compound 613 S S p-C.sub.13H.sub.27—Ph—* p-C.sub.13H.sub.27—Ph—* p-C.sub.13H.sub.27—Ph—* p-C.sub.13H.sub.27—Ph—*
TABLE-US-00024 TABLE 24 X.sup.a1 X.sup.a2 R.sup.a11 R.sup.a12 R.sup.a21 R.sup.a22 Compound 614 S S p-C.sub.14H.sub.29—Ph—* p-C.sub.14H.sub.29—Ph—* p-C.sub.14H.sub.29—Ph—* p-C.sub.14H.sub.29—Ph—* Compound 615 S S p-C.sub.15H.sub.31—Ph—* p-C.sub.15H.sub.31—Ph—* p-C.sub.15H.sub.31—Ph—* p-C.sub.15H.sub.31—Ph—* Compound 616 S S p-C.sub.16H.sub.33—Ph—* p-C.sub.16H.sub.33—Ph—* p-C.sub.16H.sub.33—Ph—* p-C.sub.16H.sub.33—Ph—* Compound 617 S S p-C.sub.17H.sub.35—Ph—* p-C.sub.17H.sub.35—Ph—* p-C.sub.17H.sub.35—Ph—* p-C.sub.17H.sub.35—Ph—* Compound 618 S S p-C.sub.18H.sub.37—Ph—* p-C.sub.18H.sub.37—Ph—* p-C.sub.18H.sub.37—Ph—* p-C.sub.18H.sub.37—Ph—* Compound 619 S S
TABLE-US-00025 TABLE 25 X.sup.a1 X.sup.a2 R.sup.a11 R.sup.a12 R.sup.a21 R.sup.a22 Compound 636 S S
TABLE-US-00026 TABLE 26 X.sup.a1 X.sup.a2 R.sup.a11 R.sup.a12 R.sup.a21 R.sup.a22 Compound 654 S S
TABLE-US-00027 TABLE 27 X.sup.a1 X.sup.a2 R.sup.a11 R.sup.a12 R.sup.a21 R.sup.a22 Compound 672 S S
TABLE-US-00028 TABLE 28 X.sup.a1 X.sup.a2 R.sup.a11 R.sup.a12 R.sup.a21 R.sup.a22 Compound 708 S S H
TABLE-US-00029 TABLE 29 X.sup.a1 X.sup.a2 R.sup.a11 R.sup.a12 R.sup.a21 R.sup.a22 Compound 744 S S Ph H C.sub.18H.sub.37—* H Compound 745 S S
TABLE-US-00030 TABLE 30 X.sup.b1 X.sup.b2 R.sup.b11 R.sup.b12 R.sup.b21 R.sup.b22 Compound 772 S S H H H C.sub.18H.sub.37-* Compound 773 S S H H p-C.sub.5H.sub.11—Ph-* H Compound 774 S S H H p-C.sub.6H.sub.13—Ph-* H Compound 775 S S H H p-C.sub.7H.sub.15—Ph-* H Compound 776 S S H H p-C.sub.8H.sub.17—Ph-* H Compound 777 S S H H p-C.sub.9H.sub.19—Ph-* H Compound 778 S S H H p-C.sub.10H.sub.21—Ph-* H Compound 779 S S H H p-C.sub.11H.sub.23—Ph-* H Compound 780 S S H H p-C.sub.12H.sub.25—Ph-* H Compound 781 S S H H p-C.sub.13H.sub.27—Ph-* H Compound 782 S S H H p-C.sub.14H.sub.29—Ph-* H Compound 783 S S H H p-C.sub.15H.sub.31—Ph-* H Compound 784 S S H H p-C.sub.16H.sub.33—Ph-* H Compound 785 S S H H p-C.sub.17H.sub.35—Ph-* H Compound 786 S S H H p-C.sub.18H.sub.37—Ph-* H Compound 787 S S Ph H p-C.sub.5H.sub.11—Ph-* H Compound 788 S S Ph H p-C.sub.6H.sub.13—Ph-* H Compound 789 S S Ph H p-C.sub.7H.sub.15—Ph-* H Compound 790 S S Ph H p-C.sub.8H.sub.17—Ph-* H Compound 791 S S Ph H p-C.sub.9H.sub.19—Ph-* H Compound 792 S S Ph H p-C.sub.10H.sub.21—Ph-* H Compound 793 S S Ph H p-C.sub.11H.sub.23—Ph-* H Compound 794 S S Ph H p-C.sub.12H.sub.25—Ph-* H Compound 795 S S Ph H p-C.sub.13H.sub.27—Ph-* H Compound 796 S S Ph H p-C.sub.14H.sub.29—Ph-* H Compound 797 S S Ph H p-C.sub.15H.sub.31—Ph-* H Compound 798 S S Ph H p-C.sub.16H.sub.33—Ph-* H Compound 799 S S Ph H p-C.sub.17H.sub.35—Ph-* H Compound 800 S S Ph H p-C.sub.18H.sub.37—Ph-* H Compound 801 S S
TABLE-US-00031 TABLE 31 X.sup.b1 X.sup.b2 R.sup.b11 R.sup.b12 R.sup.b21 R.sup.b22 Compound 808 S S
TABLE-US-00032 TABLE 32 X.sup.b1 X.sup.b2 R.sup.b11 R.sup.b12 R.sup.b21 R.sup.b22 Compound 835 S S H H
TABLE-US-00033 TABLE 33 X.sup.b1 X.sup.b2 R.sup.b11 R.sup.b12 R.sup.b21 R.sup.b22 Compound 853 S S Ph H
TABLE-US-00034 TABLE 34 X.sup.b1 X.sup.b2 R.sup.b11 R.sup.b12 R.sup.b21 R.sup.b22 Compound 871 S S H H H
TABLE-US-00035 TABLE 35 X.sup.b1 X.sup.b2 R.sup.b11 R.sup.b12 R.sup.b21 R.sup.b22 Compound 889 S S H H
TABLE-US-00036 TABLE 36 X.sup.b1 X.sup.b2 R.sup.b11 R.sup.b12 R.sup.b21 R.sup.b22 Compound 907 S S Ph H
TABLE-US-00037 TABLE 37 X.sup.b1 X.sup.b2 R.sup.b11 R.sup.b12 R.sup.b21 R.sup.b22 Compound S S C.sub.10H.sub.21-* H p-C.sub.13H.sub.27—Ph-* H 931 Compound S S C.sub.10H.sub.21-* H p-C.sub.14H.sub.29—Ph-* H 932 Compound S S C.sub.10H.sub.21-* H p-C.sub.15H.sub.31—Ph-* H 933 Compound S S C.sub.10H.sub.21-* H p-C.sub.16H.sub.33—Ph-* H 934 Compound S S C.sub.10H.sub.21-* H p-C.sub.17H.sub.35—Ph-* H 935 Compound S S C.sub.10H.sub.21-* H p-C.sub.18H.sub.37—Ph-* H 936 Compound 937 S S C.sub.12H.sub.25-* H
TABLE-US-00038 TABLE 38 X.sup.b1 X.sup.b2 R.sup.b11 R.sup.b12 R.sup.b21 R.sup.b22 Compound 959 S S C H
-* H H C
H
-* Compound 960 S S C
H
-* H H C
H
-* Compound 961 S S C
H
-* H H C
H
-* Compound 962 S S C
H
-* H H C
H
-* Compound 963 S S C
H
-* H H C
H
-* Compound 964 S S C
H
-* H H C
H
-* Compound 965 S S C
H
-* H H p-C.sub.5H.sub.11—Ph-* Compound 966 S S C
H
-* H H p-C.sub.6H.sub.13—Ph-* Compound 967 S S C
H
-* H H p-C.sub.7H.sub.15—Ph-* Compound 968 S S C
H
-* H H p-C.sub.8H.sub.17—Ph-* Compound 969 S S C
H
-* H H p-C.sub.9H.sub.19—Ph-* Compound 970 S S C
H
-* H H p-C.sub.10H.sub.21—Ph-* Compound 971 S S C
H
-* H H p-C.sub.11H.sub.23—Ph-* Compound 972 S S C
H
-* H H p-C.sub.12H.sub.25—Ph-* Compound 973 S S C
H
-* H H p-C.sub.13H.sub.27—Ph-* Compound 974 S S C
H
-* H H p-C.sub.14H.sub.29—Ph-* Compound 975 S S C
H
-* H H p-C.sub.15H.sub.31—Ph-* Compound 976 S S C
H
-* H H p-C.sub.16H.sub.33—Ph-* Compound 977 S S C
H
-* H H p-C.sub.17H.sub.35—Ph-* Compound 978 S S C
H
-* H H p-C.sub.18H.sub.37—Ph-* Compound 979 S S H C
H
-* H p-C.sub.5H.sub.11—Ph-* Compound 980 S S H C
H
-* H p-C.sub.6H.sub.13—Ph-* Compound 981 S S H C
H
-* H p-C.sub.7H.sub.15—Ph-* Compound 982 S S H C
H
-* H p-C.sub.8H.sub.17—Ph-* Compound 983 S S H C
H
-* H p-C.sub.9H.sub.19—Ph-* Compound 984 S S H C
H
-* H p-C.sub.10H.sub.21—Ph-* Compound 985 S S H C
H
-* H p-C.sub.11H.sub.23—Ph-* Compound 986 S S H C
H
-* H p-C.sub.12H.sub.25—Ph-* Compound 987 S S H C
H
-* H p-C.sub.13H.sub.27—Ph-* Compound 988 S S H C
H
-* H p-C.sub.14H.sub.29—Ph-* Compound 989 S S H C
H
-* H p-C.sub.15H.sub.31—Ph-* Compound 990 S S H C
H
-* H p-C.sub.16H.sub.33—Ph-* Compound 991 S S H C
H
-* H p-C.sub.17H.sub.35—Ph-* Compound 992 S S H C
H
-* H p-C.sub.18H.sub.37—Ph-* Compound 993 S S
indicates data missing or illegible when filed
TABLE-US-00039 TABLE 39 X.sup.b1 X.sup.b2 R.sup.b11 R.sup.b12 R.sup.b21 R.sup.b22 Compound 999 S S
TABLE-US-00040 TABLE 40 X.sup.b1 X.sup.b2 R.sup.b11 R.sup.b12 R.sup.b21 R.sup.b22 Compound 1017 S S
TABLE-US-00041 TABLE 41 X.sup.b1 X.sup.b2 R.sup.b11 R.sup.b12 R.sup.b21 R.sup.b22 Compound 1039 O O C.sub.10H.sub.21-* H C.sub.10H.sub.21-* H Compound 1040 O O C.sub.11H.sub.23-* H C.sub.11H.sub.23-* H Compound 1041 O O C.sub.12H.sub.25-* H C.sub.12H.sub.25-* H Compound 1042 O O C.sub.13H.sub.27-* H C.sub.13H.sub.27-* H Compound 1043 O O C.sub.14H.sub.29-* H C.sub.14H.sub.29-* H Compound 1044 O O C.sub.15H.sub.31-* H C.sub.15H.sub.31-* H Compound 1045 O O C.sub.16H.sub.33-* H C.sub.16H.sub.33-* H Compound 1046 O O C.sub.17H.sub.35-* H C.sub.17H.sub.35-* H Compound 1047 O O C.sub.18H.sub.37-* H C.sub.18H.sub.37-* H Compound 1048 O O p-C.sub.5H.sub.11—Ph-* H p-C.sub.5H.sub.11—Ph-* H Compound 1049 O O p-C.sub.6H.sub.13—Ph-* H p-C.sub.6H.sub.13—Ph-* H Compound 1050 O O p-C.sub.7H.sub.15—Ph-* H p-C.sub.7H.sub.15—Ph-* H Compound 1051 O O p-C.sub.8H.sub.17—Ph-* H p-C.sub.8H.sub.17—Ph-* H Compound 1052 O O p-C.sub.9H.sub.19—Ph-* H p-C.sub.9H.sub.19—Ph-* H Compound 1053 O O p-C.sub.10H.sub.21—Ph-* H p-C.sub.10H.sub.21—Ph-* H Compound 1054 O O p-C.sub.11H.sub.23—Ph-* H p-C.sub.11H.sub.23—Ph-* H Compound 1055 O O p-C.sub.12H.sub.25—Ph-* H p-C.sub.12H.sub.25—Ph-* H Compound 1056 O O p-C.sub.13H.sub.27—Ph-* H p-C.sub.13H.sub.27—Ph-* H Compound 1057 O O p-C.sub.14H.sub.29—Ph-* H p-C.sub.14H.sub.29—Ph-* H Compound 1058 O O p-C.sub.15H.sub.31—Ph-* H p-C.sub.15H.sub.31—Ph-* H Compound 1059 O O p-C.sub.16H.sub.33—Ph-* H p-C.sub.16H.sub.33—Ph-* H Compound 1060 O O p-C.sub.17H.sub.35—Ph-* H p-C.sub.17H.sub.35—Ph-* H Compound 1061 O O p-C.sub.18H.sub.37—Ph-* H p-C.sub.18H.sub.37—Ph-* H Compound 1062 O O
TABLE-US-00042 TABLE 42 X.sup.b1 X.sup.b2 R.sup.b11 R.sup.b12 R.sup.b21 R.sup.b22 Compound 1072 O O H
OC
H
-* H C
H
OC
H
-* H Compound 1077 S S C
H
OC
H
-* H C
H
OC
H
-* H Compound 1078 S S C
H
OC
H
-* H C
H
OC
H
-* H Compound 1079 S S C
H
OC
H
-* H C
H
OC
H
-* H Compound 1080 S S CH
OC
H
-* H CH
OC
H
-* H Compound 1081 S S
H
-* H PhO
H
-* H Compound 1085 S S PhOC
H
-* H PhOC
H
-* H Compound 1086 S S
indicates data missing or illegible when filed
TABLE-US-00043 TABLE 43 X.sup.b1 X.sup.b2 R.sup.b11 R.sup.b12 R.sup.b21 R.sup.b22 Compound 1096 S S
TABLE-US-00044 TABLE 44 X.sup.c1 X.sup.c2 R.sup.c11 R.sup.c21 Compound S S C.sub.5H.sub.11-* C.sub.5H.sub.11-* 1110 Compound S S C.sub.6H.sub.13-* C.sub.6H.sub.13-* 1111 Compound S S C.sub.7H.sub.15-* C.sub.7H.sub.15-* 1112 Compound S S C.sub.8H.sub.17-* C.sub.8H.sub.17-* 1113 Compound S S C.sub.9H.sub.19-* C.sub.9H.sub.19-* 1114 Compound S S C.sub.10H.sub.21-* C.sub.10H.sub.21-* 1115 Compound S S C.sub.11H.sub.23-* C.sub.11H.sub.23-* 1116 Compound S S C.sub.12H.sub.25-* C.sub.12H.sub.25-* 1117 Compound S S C.sub.13H.sub.27-* C.sub.13H.sub.27-* 1118 Compound S S C.sub.14H.sub.29-* C.sub.14H.sub.29-* 1119 Compound S S C.sub.15H.sub.31-* C.sub.15H.sub.31-* 1120 Compound S S C.sub.16H.sub.33-* C.sub.16H.sub.33-* 1121 Compound S S C.sub.17H.sub.35-* C.sub.17H.sub.35-* 1122 Compound S S C.sub.18H.sub.37-* C.sub.18H.sub.37-* 1123 Compound S S p-C.sub.5H.sub.11—Ph-* p-C.sub.5H.sub.11—Ph-* 1124 Compound S S p-C.sub.6H.sub.13—Ph-* p-C.sub.6H.sub.13—Ph-* 1125 Compound S S p-C.sub.7H.sub.15—Ph-* p-C.sub.7H.sub.15—Ph-* 1126 Compound S S p-C.sub.8H.sub.17—Ph-* p-C.sub.8H.sub.17—Ph-* 1127 Compound S S p-C.sub.9H.sub.19—Ph-* p-C.sub.9H.sub.19—Ph-* 1128 Compound S S p-C.sub.10H.sub.21—Ph-* p-C.sub.10H.sub.21—Ph-* 1129 Compound S S p-C.sub.11H.sub.23—Ph-* p-C.sub.11H.sub.23—Ph-* 1130 Compound S S p-C.sub.12H.sub.25—Ph-* p-C.sub.12H.sub.25—Ph-* 1131 Compound S S p-C.sub.13H.sub.27—Ph-* p-C.sub.13H.sub.27—Ph-* 1132 Compound S S p-C.sub.14H.sub.29—Ph-* p-C.sub.14H.sub.29—Ph-* 1133 Compound S S p-C.sub.15H.sub.31—Ph-* p-C.sub.15H.sub.31—Ph-* 1134 Compound S S p-C.sub.16H.sub.33—Ph-* p-C.sub.16H.sub.33—Ph-* 1135 Compound S S p-C.sub.17H.sub.35—Ph-* p-C.sub.17H.sub.35—Ph-* 1136 Compound S S p-C.sub.18H.sub.37—Ph-* p-C.sub.18H.sub.37—Ph-* 1137 Compound 1138 S S
TABLE-US-00045 TABLE 45 x.sup.c1 X.sup.c2 R.sup.c11 R.sup.c21 Com- pound 1146 S S
TABLE-US-00046 TABLE 46 X.sup.c1 X.sup.c2 R.sup.c11 R.sup.c21 Com- pound 1164 S S
TABLE-US-00047 TABLE 47 X.sup.c1 X.sup.c2 R.sup.c11 R.sup.c21 Compound 1200 S S
TABLE-US-00048 TABLE 48 X.sup.c1 X.sup.c2 R.sup.c11 R.sup.c21 Compound 1236 S S
TABLE-US-00049 TABLE 49 X.sup.c1 X.sup.c2 R.sup.c11 R.sup.c21 Compound 1254 S S H
TABLE-US-00050 TABLE 50 X.sup.c1 X.sup.c2 R.sup.c11 R.sup.c21 Com- pound 1272 S S Ph
TABLE-US-00051 TABLE 51 X.sup.c1 X.sup.c2 R.sup.c11 R.sup.c21 Compound 1290 S S H
TABLE-US-00052 TABLE 52 X.sup.c1 X.sup.c2 R.sup.c11 R.sup.c21 Compound 1308 S S Ph
TABLE-US-00053 TABLE 53 X.sup.c1 X.sup.c2 R.sup.c11 R.sup.c21 Com- pound 1326 S S
TABLE-US-00054 TABLE 54 X.sup.c1 X.sup.c2 R.sup.c11 R.sup.c21 Compound 1353 S S C.sub.12H.sub.25—*
TABLE-US-00055 TABLE 55 X.sup.c1 X.sup.c2 R.sup.c11 R.sup.c21 Compound 1371 S S
TABLE-US-00056 TABLE 56 X.sup.c1 X.sup.c2 X.sup.c11 X.sup.c21 Compound 1389 S S
TABLE-US-00057 TABLE 57 X.sup.c1 X.sup.c2 R.sup.c11 R.sup.c21 Com- O O p-C.sub.13H.sub.27—Ph—* p-C.sub.13H.sub.27—Ph—* pound 1422 Com- O O p-C.sub.14H.sub.29—Ph—* p-C.sub.14H.sub.29—Ph—* pound 1423 Com- O O p-C.sub.15H.sub.31—Ph—* p-C.sub.15H.sub.31—Ph—* pound 1424 Com- O O p-C.sub.16H.sub.33—Ph—* p-C.sub.16H.sub.33—Ph—* pound 1425 Com- O O p-C.sub.17H.sub.35—Ph—* p-C.sub.17H.sub.35—Ph—* pound 1426 Com- O O p-C.sub.18H.sub.37—Ph—* p-C.sub.18H.sub.37—Ph—* pound 1427 Com- pound 1428 O O —* C.sub.4H.sub.5OC
H
—* pound 1442 Com- S S C.sub.2H.sub.3OC
H
—* C.sub.2H.sub.3OC
H.sub.4—* pound 1443
indicates data missing or illegible when filed
TABLE-US-00058 TABLE 58 X.sup.c1 X.sup.c2 R.sup.c11 R.sup.c12 Compound 1444 S S C H
OC.sub.4H
—* C
H
OC
H
—* Compound 1445 S S C.sub.2H.sub.3OC.sub.4H
—* C.sub.2H
OC.sub.4H
—* Compound 1446 S S CH
OC
H.sub.3—* CH
OC
H
Compound 1447 S S
indicates data missing or illegible when filed
TABLE-US-00059 TABLE 59 X.sup.c1 X.sup.c2 R.sup.c11 R.sup.c21 Compound 1462 S S
[0124] In the organic semiconductor layer of the organic semiconductor element according to the present invention or the organic semiconductor film according to the present invention described below, the content of the specific compound is preferably 30 to 100 mass %, more preferably 50 to 100 mass %, and even more preferably 70 to 100 mass %. In a case where a binder polymer described below is not contained, the content is preferably 90 to 100 mass % and more preferably 95 to 100 mass %.
[0125] <Binder Polymer>
[0126] The organic semiconductor layer of the organic semiconductor element according to the present invention preferably contains the binder polymer.
[0127] The organic semiconductor element according to the present invention may be an organic semiconductor element having a layer including the organic semiconductor layer and the binder polymer.
[0128] The types of the binder polymer are not particularly limited, and well-known binder polymers can be used.
[0129] Examples of the binder polymer include a polystyrene resin, an acrylic resin, rubber, and a thermoplastic elastomer.
[0130] Among these, as the binder polymer, a polymer compound (a polymer having a monomer unit having a benzene ring group) having a benzene ring is preferable. The content of the monomer unit having a benzene ring group is not particularly limited. However, the content is preferably 50 mol % or greater, more preferably 70 mol % or greater, and even more preferably 90 mol % or greater with respect to the entire monomer unit. The upper limit is not particularly limited, but examples of the upper limit include 100 mol %.
[0131] Examples of the binder polymer include polystyrene, poly(α-methylstyrene), polyvinyl cinnamate, poly(4-vinylphenyl), and poly(4-methylstyrene).
[0132] A weight-average molecular weight of the binder polymer is not particularly limited, but is preferably 1,000 to 2,000,000, more preferably 3,000 to 1,000,000, and even more preferably 5,000 to 600,000.
[0133] In a case where a solvent described below is used, it is preferable that the binder polymer exhibits solubility higher than the solubility of the specific compound in a used solvent. If the above aspect is adopted, mobility and heat stability of the obtained organic semiconductor are further improved.
[0134] A content of the binder polymer in the organic semiconductor layer of the organic semiconductor element of the present invention is preferably 1 to 200 parts by mass, more preferably 10 to 150 parts by mass, and even more preferably 20 to 120 parts by mass with respect to 100 parts by mass of the content of the specific compound. If the content is within the above range, mobility and heat stability of the obtained organic semiconductor are further improved.
[0135] <Other Components>
[0136] Other components may be included other than the specific compound and the binder polymer may be included in the organic semiconductor layer according to the organic semiconductor element of the present invention.
[0137] As other components, known additives and the like can be used.
[0138] In the organic semiconductor layer, a content of the components other than the specific compound and the binder polymer is preferably 10 mass % or less, more preferably 5 mass % or less, even more preferably 1 mass % or less, and particularly preferably 0.1 mass % or less. If the content of other components is within the above range, film formability is improved, and mobility and heat stability of the obtained organic semiconductor are further improved.
[0139] (Method of Forming Organic Semiconductor Layer)
[0140] The method of forming the organic semiconductor layer according to the organic semiconductor element of the present invention is not particularly limited. However, a desired organic semiconductor layer can be formed by applying the composition for forming the organic semiconductor film according to the present invention described below to a source electrode, a drain electrode, and a gate insulating film and performing a drying treatment, if necessary.
[0141] (Method of Manufacturing Organic Semiconductor Element and Organic Semiconductor Film)
[0142] The organic semiconductor element and an organic semiconductor film of the present invention is preferably manufactured using the composition for forming an organic semiconductor film of the present invention described below.
[0143] A method of manufacturing an organic semiconductor film or an organic semiconductor element by using the composition for forming an organic semiconductor film of the present invention is not particularly limited, and known methods can be adopted. Examples thereof include a method of manufacturing an organic semiconductor film by applying the composition onto a predetermined base material and if necessary, performing a drying treatment.
[0144] The method of applying the composition onto a base material is not particularly limited, and known methods can be adopted. Examples thereof include an ink jet printing method, a flexographic printing method, a bar coating method, a spin coating method, a knife coating method, a doctor blade method, and the like. Among these, an ink jet printing method and a flexographic printing method are preferable.
[0145] Preferred examples of the flexographic printing method include an aspect in which a photosensitive resin plate is used as a flexographic printing plate. By printing the composition onto a substrate according to the aspect, a pattern can be easily formed.
[0146] Among these, the method of manufacturing an organic semiconductor element and an organic semiconductor film according to the present invention preferably include an applying step of applying an composition for forming an organic semiconductor film according to the present invention to a substrate and a removing step of removing at least a portion of a solvent having a boiling point of 100° C. or higher included in the composition for forming the organic semiconductor film.
[0147] <Solvent Having Boiling Point of 100° C. or Higher>
[0148] The composition for forming the organic semiconductor film according to the present invention contains a solvent having a boiling point of 100° C. or higher (hereinafter, referred to a “specific solvent”).
[0149] Examples of the specific solvent include a hydrocarbon-based solvent such as octane, decane, toluene, xylene, mesitylene, ethylbenzene, decalin, 1-methylnaphthalene, tetralin, and dimethyltetralin, a ketone-based solvent such as methyl isobutyl ketone and cyclohexanone, a halogenated hydrocarbon-based solvent such as tetrachloroethane, chlorobenzene, dichlorobenzene, chlorotoluene, 1-fluoronaphthalene, and 1-chloronaphthalene, an ester-based solvent such as butyl acetate and amyl acetate, an alcohol-based solvent such as butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, and ethylene glycol, an ether-based solvent such as dibutyl ether, dioxane, anisole, 4-tertiary butyl anisole, and m-dimethoxybenzene, an amide-based solvent such as N,N-dimethylformamide and N,N-dimethylacetamide, an imide-based solvent such as 1-methyl-2-pyrrolidone and 1-methyl-2-imidazolidinone, a sulfoxide-based solvent such as dimethyl sulfoxide, and a nitrile-based solvent such as butyronitrile and benzonitrile.
[0150] The specific solvent may be used singly or two or more types thereof may be used in combination.
[0151] Among these, a hydrocarbon-based solvent, a halogenated hydrocarbon-based solvent and/or an ether-based solvent are preferable, toluene, xylene, mesitylene, tetralin, dichlorobenzene, or anisole is more preferable, and toluene is even more preferable.
[0152] If the specific solvent is the aforementioned solvent, coating properties are excellent, and thus an organic semiconductor film can be easily formed.
[0153] In view of stability of the composition for forming the organic semiconductor film, forming an even film, and drying, the boiling point of the specific solvent in normal pressure is 100° C. or higher, preferably 100° C. to 300° C., more preferably 100° C. to 200° C., and even more preferably 100° C. to 150° C.
[0154] The drying treatment in the removing step is a treatment performed if necessary, and the optimal treatment conditions are suitably selected according to the type of the specific compound used and the solvent. In view of further improving mobility and heat stability of the obtained organic semiconductor and improving productivity, a heating temperature is preferably 30° C. to 100° C. and more preferably 40° C. to 80° C., and a heating time is preferably 10 to 300 minutes and more preferably 30 to 180 minutes.
[0155] A thickness of the formed organic semiconductor layer is not particularly limited. From the viewpoint of mobility and heat stability of the obtained organic semiconductor, the film thickness is preferably 10 to 500 nm and more preferably 30 to 200 nm.
[0156] <Organic Semiconductor Element>
[0157] The organic semiconductor element is not particularly limited, but is preferably an organic semiconductor element having 2 to 5 terminals, and more preferably an organic semiconductor element having 2 or 3 terminals.
[0158] It is preferable that the organic semiconductor element is not a photoelectric conversion element.
[0159] The organic semiconductor element according to the present invention is preferably a non-luminous organic semiconductor element.
[0160] Examples of a 2-terminal element include a rectifier diode, a constant voltage diode, a PIN diode, a Schottky barrier diode, a surge protection diode, a diac, a varistor, a tunnel diode, and the like.
[0161] Examples of a 3-terminal element include a bipolar transistor, a Darlington transistor, a field effect transistor, insulated gate bipolar transistor, a uni-junction transistor, a static induction transistor, a gate turn-off thyristor, a triac, a static induction thyristor, and the like.
[0162] Among these, a rectifier diode and transistors are preferable, and a field effect transistor is more preferable.
[0163] An aspect of the organic thin film transistor of the present invention will be described with reference to drawings.
[0164]
[0165] In
[0166] In
[0167] Hereinafter, the substrate, the gate electrode, the gate insulating film, the source electrode, the drain electrode, the organic semiconductor film, the sealing layer, and methods for forming each of these will be specifically described.
[0168] <Substrate>
[0169] The substrate plays a role of supporting the gate electrode, the source electrode, the drain electrode, and the like which will be described later.
[0170] The type of the substrate is not particularly limited, and examples thereof include a plastic substrate, a glass substrate, a ceramic substrate, and the like. Among these, from the viewpoint of applicability to each device and costs, a glass substrate or a plastic substrate is preferable.
[0171] Examples of materials of the plastic substrate include a thermosetting resin (for example, an epoxy resin, a phenol resin, a polyimide resin, or a polyester resin (for example, polyethylene terephthalate (PET) or polyethylene naphthalate (PEN)) and a thermoplastic resin (for example, a phenoxy resin, a polyethersulfone, polysulfone, or polyphenylene sulfone).
[0172] Examples of materials of the ceramic substrate include alumina, aluminum nitride, zirconia, silicon, silicon nitride, silicon carbide, and the like.
[0173] Examples of materials of the glass substrate include soda lime glass, potash glass, borosilicate glass, quartz glass, aluminosilicate glass, lead glass, and the like.
[0174] <Gate Electrode, Source Electrode, and Drain Electrode>
[0175] Examples of materials of the gate electrode, the source electrode, and the drain electrode include a metal such as gold (Au), silver, aluminum (Al), copper, chromium, nickel, cobalt, titanium, platinum, tantalum, magnesium, calcium, barium, or sodium; a conductive oxide such as InO.sub.2, SnO.sub.2, or indium tin oxide (ITO); a conductive polymer such as polyaniline, polypyrrole, polythiophene, polyacetylene, or polydiacetylene; a semiconductor such as silicon, germanium, or gallium arsenide; a carbon material such as fullerene, carbon nanotubes, or graphite; and the like. Among these, a metal is preferable, and silver and aluminum are more preferable.
[0176] A thickness of each of the gate electrode, the source electrode, and the drain electrode is not particularly limited, but is preferably 20 to 200 nm.
[0177] A method of forming the gate electrode, the source electrode, and the drain electrode is not particularly limited, but examples thereof include a method of vacuum vapor-depositing or sputtering an electrode material onto a substrate, a method of coating a substrate with a composition for forming an electrode, a method of printing a composition for forming an electrode onto a substrate, and the like. Furthermore, in a case where the electrode is patterned, examples of the patterning method include a photolithography method; a printing method such as ink jet printing, screen printing, offset printing, or relief printing; a mask vapor deposition method; and the like.
[0178] <Gate Insulating Film>
[0179] Examples of materials of the gate insulating film include a polymer such as polymethyl methacrylate, polystyrene, polyvinylphenol, polyimide, polycarbonate, polyester, polyvinylalcohol, polyvinyl acetate, polyurethane, polysulfone, polybenzoxazole, polysilsesquioxane, an epoxy resin, or a phenol resin; an oxide such as silicon dioxide, aluminum oxide, or titanium oxide; a nitride such as silicon nitride; and the like. Among these materials, in view of the compatibility with the organic semiconductor film, a polymer is preferable.
[0180] In a case where a polymer is used as the material of the gate insulating film, it is preferable to use a cross-linking agent (for example, melamine) in combination. If the cross-linking agent is used in combination, the polymer is cross-linked, and durability of the formed gate insulating film is improved.
[0181] A film thickness of the gate insulating film is not particularly limited, but is preferably 100 to 1,000 nm.
[0182] A method of forming the gate insulating film is not particularly limited, but examples thereof include a method of coating a substrate, on which the gate electrode is formed, with a composition for forming a gate insulating film, a method of vapor-depositing or sputtering the material of the gate insulating film onto a substrate on which the gate electrode is formed, and the like. A method of coating the aforementioned substrate with the composition for forming a gate insulating film is not particularly limited, and it is possible to use a known method (a bar coating method, a spin coating method, a knife coating method, or a doctor blade method).
[0183] In a case where the gate insulating film is formed by coating the substrate with the composition for forming a gate insulating film, for the purpose of removing the solvent, causing cross-linking, or the like, the composition may be heated (baked) after coating.
[0184] <Organic Semiconductor Film>
[0185] The organic semiconductor film according to the present invention is a film formed of the composition for forming the organic semiconductor film according to the present invention.
[0186] The method of forming the organic semiconductor film is not particularly limited. A desired organic semiconductor film can be formed by applying the aforementioned composition to a source electrode, a drain electrode, and a gate insulating film and performing a drying treatment, if desired.
[0187] <Binder Polymer Layer>
[0188] The organic semiconductor element of the present invention preferably has a layer of the aforementioned binder polymer between the aforementioned organic semiconductor layer and an insulating film, and more preferably has a layer of the aforementioned binder polymer between the aforementioned organic semiconductor layer and the gate insulating film. A film thickness of the binder polymer layer is not particularly limited, but is preferably 20 to 500 nm. The binder polymer layer should be a layer containing the aforementioned polymer, and is preferably a layer composed of the aforementioned binder polymer.
[0189] A method of forming the binder polymer layer is not particularly limited, and a known method (a bar coating method, a spin coating method, a knife coating method, a doctor blade method, or an ink jet method) can be used.
[0190] In a case where the binder polymer layer is formed by performing coating by using a composition for forming a binder polymer layer, for the purpose of removing a solvent, causing cross-linking, or the like, the composition may be heated (baked) after coating.
[0191] <Sealing Layer>
[0192] From the viewpoint of durability, the organic semiconductor element of the present invention preferably includes a sealing layer as an outermost layer. In the sealing layer, a known sealant can be used.
[0193] A thickness of the sealing layer is not particularly limited, but is preferably 0.2 to 10 μm.
[0194] A method of forming the sealing layer is not particularly limited, but examples thereof include a method of coating a substrate, on which the gate electrode, the gate insulating film, the source electrode, the drain electrode, and the organic semiconductor film are formed, with a composition for forming a sealing layer, and the like. Specific examples of the method of coating the substrate with the composition for forming a sealing layer are the same as the examples of the method of coating the substrate with the composition for forming a gate insulating film. In a case where the organic semiconductor film is formed by coating the substrate with the composition for forming a sealing layer, for the purpose of removing the solvent, causing cross-linking, or the like, the composition may be heated (baked) after coating.
[0195]
[0196] In
[0197] The substrate, the gate electrode, the gate insulating film, the source electrode, the drain electrode, the organic semiconductor film, and the sealing layer are as described above.
[0198] In
[0199] The organic thin film transistor described above can be suitably used for electronic paper and a display device.
[0200] (Composition for Forming Organic Semiconductor Film)
[0201] The composition for forming the organic semiconductor film according to the present invention contains a solvent having a boiling point of 100° C. or higher and a compound represented by Formula 1, and a content of the compound represented by Formula 1 is 20 mass % or less with respect to a total amount of the composition for forming the organic semiconductor film.
[0202] The composition for forming the organic semiconductor film according to the present invention preferably contains a binder polymer.
[0203] The specific compound, the binder polymer, and the solvent in the composition for forming the organic semiconductor film according to the present invention are the same as the aforementioned specific compound, the aforementioned binder polymer, and the aforementioned solvent, and preferable aspects are also the same.
[0204] The content of the specific compound of the composition for forming the organic semiconductor film according to the present invention is 20 mass % or less, preferably 0.001 to 15 mass %, and more preferably 0.01 to 10 mass % with respect to the total amount of the composition for forming the organic semiconductor film. In a case where two or more types of specific compounds are used in combination, the total content of the specific compounds is preferably in the range described above. If the content of the specific compound is in the range described above, the organic semiconductor element having high mobility and high driving stability can be obtained, storage stability of the composition for forming the organic semiconductor film is also satisfactory.
[0205] The content of the specific compound is preferably 30 to 100 mass %, more preferably 50 to 100 mass %, and even more preferably 70 to 100 mass % with respect to the total solid content of the composition for forming the organic semiconductor film. In a case where a binder polymer described below is not contained, the total content is preferably 90 to 100 mass % and more preferably 95 to 100 mass %. The solid content is an amount of the component except for the volatile component such as the solvent.
[0206] The content of the binder polymer in the composition for forming the organic semiconductor film according to the present invention is preferably greater than 0 mass % and 20 mass % or less, more preferably 0.01 to 15 mass %, and even more preferably 0.25 to 10 mass % with respect to the total amount of the composition for forming the organic semiconductor film. If the content is in the range described above, mobility and heat resistance of the obtained organic semiconductor become more excellent.
[0207] The composition for forming the organic semiconductor film according to the present invention may include other component in addition to the specific compound and the binder polymer.
[0208] As the component, well-known additives may be used.
[0209] The content of the component in addition to the specific compound and the binder polymer in the composition for forming the organic semiconductor film according to the present invention is preferably 10 mass % or less, more preferably 5 mass % or less, even more preferably 1 mass % or less, and particularly preferably 0.1 mass % or less with respect to the total solid content. If the content is in the range described above, film formability is improved, and mobility and heat stability of the obtained organic semiconductor are further improved.
[0210] The viscosity of the composition for forming the organic semiconductor film according to the present invention is not particularly limited. However, in view of excellent coating properties, the viscosity is preferably 3 to 100 mPa.Math.s, more preferably 5 to 50 mPa.Math.s, and even more preferably 9 to 40 mPa.Math.s. The viscosity according to the present invention refers to viscosity at 25° C.
[0211] As a method of measuring the viscosity, a measuring method in conformity of JIS Z8803 is preferable.
[0212] The method of manufacturing the composition for forming the organic semiconductor film according to the present invention is not particularly limited, and well-known methods can be applied. For example, a desired composition can be obtained by adding a specific amount of a specific compound in the solvent and applying an suitable stirring treatment. In a case where the binder polymer is used, the specific compound and the binder polymer are simultaneously or sequentially added, so as to suitably manufacture the composition.
EXAMPLES
[0213] Hereinafter, the present invention will be more specifically described based on examples. The materials and the amount thereof used, the proportion of the materials, the content and procedure of treatments, and the like described in the following examples can be suitably changed within a scope that does not depart from the gist of the present invention. Accordingly, the scope of the present invention is not limited to the following specific examples. Herein, unless otherwise specified, “part” and “%” are based on mass.
[0214] (Specific Compounds and Synthesis Examples)
[0215] Structures of E-1 to E-10 used in the examples and C-1 to C-2 used in the comparative examples are provided below.
##STR01428##
[0216] <Synthesis of E-1>
[0217] An intermediate M1 was synthesized according to a scheme X1 below.
##STR01429##
[0218] The intermediate M1 and octyl zinc chloride were fused by negishi coupling reaction, so as to synthesize a compound E-1.
##STR01430##
[0219] <Synthesis of E-2 to E-10>
[0220] E-2 to E-10 were also synthesized in the same manner as in E-1, except for changing an organic zinc compound fused with the intermediate M1 to suitable compounds.
[0221] <Synthesis of C-1>
[0222] A compound C-1 was synthesized according to the method described in JP2010-177637A.
[0223] <Synthesis of C-2>
[0224] A compound C-2 was synthesized according to the method disclosed in WO2013/168048A.
Examples 1 to 10 and Comparative Examples 1 to 2
Manufacturing of TFT Element
[0225] The specific compound presented in Table 60 or a comparative compound (1 mg) and toluene (1 mL) were mixed with each other and heated to 100° C., and the composition for forming the organic semiconductor film was obtained.
[0226] An organic semiconductor film was formed by casting this composition to a substrate for measuring FET characteristics which was heated to 90° C. under the nitrogen atmosphere, and an organic thin film transistor element for measuring FET characteristics was obtained. As the substrate for measuring FET characteristics, a silicon substrate in a bottom gate-bottom contact structure including chromium/gold (gate width W=100 mm, gate length L=100 μm) arranged in a comb-shape as source and drain electrodes and SiO.sub.2 (film thickness: 200 nm) as an insulating film was used.
[0227] The obtained composition was applied to a substrate for measuring FET characteristics by flexographic printing. Specifically, a flexographic printability test machine F1 (manufactured by IGT Testing Systems) was used as a printing machine, and AFP DSH 1.70% (manufactured by Asahi Kasei Corporation)/a solid image was used as a flexographic resin version. After printing was performed in a pressure between a plate and a substrate of 60 N and a transportation speed of 0.4 m/second, drying was performed at 40° C. for two hours, so as to form an organic semiconductor film, and an organic thin film transistor element (organic TFT element) for measuring FET characteristics was obtained.
[0228] As the substrate for measuring FET characteristics, a silicon substrate in a bottom gate-bottom contact structure including chromium/gold (gate width W=100 mm, gate length L=100 μm) arranged in a comb-shape as source and drain electrodes and SiO.sub.2 (film thickness: 200 nm) as an insulating film was used.
[0229] The ink was applied to the substrate for measuring FET characteristics by ink jet printing. Specifically, DPP2831 (manufactured by FUJIFILM Global Graphic Systems Co., Ltd.) was used as an inkjet device and 10 pL heads were used, so as to form a solid film with a jetting frequency of 2 Hz and a pitch between dots of 20 μm. Thereafter, drying was performed for one hour at 70° C., so as to form an organic semiconductor film, and the organic TFT element for measuring FET characteristics was obtained.
[0230] In the examples and the comparative examples, evaluations of mobility, coating film formability, and heat resistance described below with respect to the organic TFT element obtained by ink jet printing were the same as those of the organic TFT element obtained by casting the composition.
[0231] <Carrier Mobility (Mobility)>
[0232] With respect to the FET characteristics of the organic thin film transistor elements of the respective examples and the respective comparative examples, carrier mobility was evaluated under normal pressure and the nitrogen atmosphere by employing a semiconductor parameter analyzer (manufactured by Agilent, 4156C) to which a semi automatic prober (manufactured by Vector Semiconductor Co., Ltd., AX-2000) was connected.
[0233] A voltage of −80 V was applied between source electrodes and drain electrodes of the respective organic thin film transistor elements (FET elements), a gate voltage was changed in the range of 20 V to −100 V, an equation below presenting a drain current Id was used, so as to calculate carrier mobility μ.
Id=(w/2L)μCi(Vg−Vth).sup.2
[0234] In the equation, L represents a gate length, W represents a gate width, Ci represents capacitance of the insulating layer per unit area, Vg represents a gate voltage, and Vth represents a threshold voltage. The numerical value of the carrier mobility is required to be practically 0.01 or greater, preferably 0.1 or greater, and more preferably 0.3 or greater.
[0235] The expression “no characteristics” in the tables presents the created element did not have TFT characteristics.
[0236] <Coating Film Formability>
[0237] The compound according to the present invention or the comparative compound (5 mg) and toluene (1 mL) were mixed and heated to 100° C., so as to obtain a non-luminescent organic semiconductor solution. This coating liquid was casted under nitrogen atmosphere to the entire surface of the substrate which was heated to 90° C. and on which channels for 50 elements were formed, so as to form an organic semiconductor thin film, and 50 organic thin film transistor elements for measuring FET characteristics were obtained. Evaluation standards of the coating film formability were set as below, and the evaluation results were presented in Table 60.
[Evaluation standard] A: 45 or more elements out of the obtained 50 elements were driven as organic thin film transistor element
[0238] B: Less than 45 elements out of the obtained 50 elements were driven as organic thin film transistor element
[0239] <Heat Resistance>
[0240] After the manufactured respective organic thin film transistor elements were heated for one hour at 130° C. in a nitrogen glove box, carrier mobility μ was measured, so as to calculate a carrier mobility maintenance rate after heating by the equation below.
Carrier mobility maintenance rate after heating (%)=Carrier mobility (after heating)/carrier mobility (initial value)×100
[0241] Obtained results were evaluated according to evaluation standards below. The evaluation results are presented in Table 60. The expression “N/A” in the table means that a heat resistance was not performed since a created element did not have TFT characteristics.
[Evaluation Standard]
[0242] A: Carrier mobility maintenance rate after heating was 95% or greater
[0243] B: Carrier mobility maintenance rate after heating was 70% or greater and less than 95%
[0244] C: Carrier mobility maintenance rate after heating was 40% or greater and less than 70%
[0245] D: Carrier mobility maintenance rate after heating was 20% or greater and less than 40%
[0246] E: Carrier mobility maintenance rate after heating was less than 20%
TABLE-US-00060 TABLE 60 Specific Solu- Coating film Heat compound Mobility bility formability resistance Example 1 E-1 1.1 A A A Example 2 E-2 1 B A A Example 3 E-3 0.5 A A A Example 4 E-4 0.7 B A A Example 5 E-5 0.6 A A B Example 6 E-6 0.3 A A A Example 7 E-7 0.05 B A A Example 8 E-8 0.03 B A B Example 9 E-9 0.03 C A A Example 10 E-10 0.01 B A A Comparative C-1 No C B N/A Example 1 Charac- teristics Comparative C-2 5 × 10.sup.−3 C B D Example 2
Examples 11 to 16, Comparative Examples 3 to 4
Manufacturing of TFT Elements
[0247] Respective evaluations were performed in the same manner as in Examples 1 to 10 and Comparative Examples 1 to 2 except for mixing the specific compound of the present invention or the comparative compound presented in Table 61, the binder polymer presented in Table 61, and the solvent presented in Table 61 in the concentrations presented in Table 61, performing heating to 100° C., and using the resultant as the composition for forming the organic semiconductor film. The respective evaluation results are presented in Table 61.
[0248] Abbreviations used in Table 61 are as below. [0249] PαMS: Poly(α-methylstyrene), Mw=300,000, manufactured by Sigma-Aldrich Co. LLC.) [0250] THF: Tetrahydrofuran
TABLE-US-00061 TABLE 61 Concentration Concentration of of binder semiconductor in polymer in Coating Specific Binder composition composition Heat film compound polymer Solvent (mass %) (mass %) Mobility resistance formability Example 11 E-1 PαMS Toluene 0.5 0.5 1.2 A A Example 12 E-2 PαMS Toluene 0.5 0.5 1.2 A A Example 13 E-5 PαMS Toluene 0.5 0.5 0.8 A A Example 14 E-6 PαMS Toluene 0.5 0.5 0.5 A A Example 15 E-1 PαMS THF 0.5 0.5 0.1 B A Example 16 E-1 PαMS Toluene 0.5 12.0 0.02 B A Comparative C-1 PαMS Toluene 0.5 0.5 2 × 10.sup.−3 D B Example 3 Comparative C-2 PαMS Toluene 0.5 0.5 No N/A B Example 4 characteristics
Comparative Examples 5 to 21
[0251] The organic semiconductor films were formed in the same manner as in Example 1 to 16 except for weighing the specific compounds and toluene (1 mL) presented in Tables 60 and 61 and further the binder polymer (5 mg) in the examples presented in Table 61 such that the content of the respective specific compounds become 21 mass %, performing mixture, performing heating to 100° C., and using the resultant as the composition for forming the organic semiconductor film. However, in all of Comparative Examples 5 to 21, due to insoluble matters, various defects were generated, and thus TFT characteristics were not exhibited.
EXPLANATION OF REFERENCES
[0252] 10: substrate [0253] 20: gate electrode [0254] 30: gate insulating film [0255] 40: source electrode [0256] 42: drain electrode [0257] 50: organic semiconductor film [0258] 60: sealing layer [0259] 100,200: organic thin film transistor