JP6297709B2 - Composition for forming organic semiconductor film, and method for producing organic semiconductor film - Google Patents

Description

  The present invention relates to a composition for forming an organic semiconductor film, an organic semiconductor film and a method for producing the same, an organic semiconductor element, and an organic semiconductor compound precursor.

Because it is possible to reduce weight, cost, and flexibility, organic semiconductor films (organic semiconductors) can be used for field effect transistors (FETs), radio frequency identifiers (RF tags), and the like used in liquid crystal displays and organic EL displays. Organic transistors having a layer) are used.
As the organic semiconductor material precursor used for forming the organic semiconductor film, the compositions described in Patent Documents 1 and 2 are known.

JP 2012-20987 A JP 2012-23334 A

Conventionally, many organic semiconductor compounds used for forming an organic semiconductor film have low solubility in general-purpose solvents.
As described in Patent Documents 1 and 2, some organic semiconductor material precursors have been proposed, but the resulting organic semiconductor film has low carrier mobility.

Problems to be solved by the present invention include an organic semiconductor film forming composition excellent in mobility and driving stability of the obtained organic semiconductor film, an organic semiconductor film formed from the organic semiconductor film forming composition, and the organic semiconductor film A manufacturing method and an organic semiconductor element are provided.
Another problem to be solved by the present invention is to provide a novel compound that can be suitably used as an organic semiconductor compound precursor.

The above-mentioned problems of the present invention have been solved by means described in the following <1>, <13>, <16>, <17> or <19>. It is described below together with <2> to <12>, <14>, <15>, <18> and <20> to <28> which are preferred embodiments.
<1> An organic semiconductor film-forming composition comprising an organic semiconductor compound precursor represented by the following formula 1,

In Formula 1, Z represents NR ¹ , an oxygen atom, a sulfur atom or a selenium atom, R ¹ represents a hydrogen atom, an alkyl group or an aryl group, and X and Y each independently represent a hydrogen atom or a leaving group. And at least one of X and Y is a leaving group, Q ^{1 to} Q ⁴ each independently represents a hydrogen atom, a halogen atom or a monovalent organic group, and Q ^{1 to} Q ⁴ are adjacent to each other. Groups may be bonded to each other to form a ring. When at least one pair of adjacent Q ^{1 to} Q ⁴ is not bonded to form a ring, at least one of Q ^{1 to} Q ⁴ Is a group having a condensed polycyclic aromatic group.

<2> The organic semiconductor film formation according to <1>, wherein the leaving group is a leaving group directly bonded to a ring structure through a nitrogen atom, an oxygen atom, a sulfur atom, or a silicon atom. Composition,
<3> The composition for forming an organic semiconductor film according to <1> or <2>, wherein one of the X and Y is a leaving group and the other is a hydrogen atom.
<4> For forming an organic semiconductor film according to any one of <1> to <3>, wherein the leaving group is a group represented by any one of formulas X-1 to X-10. Composition,

  In formulas X-1 to X-10, R ″ each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, a trialkylsilyl group, an alkenyl group, or an alkynyl group.

<5> The composition for forming an organic semiconductor film according to any one of <1> to <4>, wherein Z is a sulfur atom.
<6> One or more of Q ¹ and Q ² , Q ² and Q ³ , or a combination of Q ³ and Q ⁴ are combined to form a ring, <1> to <5> The composition for forming an organic semiconductor film according to any one of the above,
<7> The organic semiconductor compound according to <4>, wherein the organic semiconductor compound precursor represented by the formula 1 is an organic semiconductor compound precursor represented by any one of the following formulas 1-1 to 1-6. A film-forming composition,

In Formula 1-1 to Formula 1-4, X ′ and Y ′ each independently represent a hydrogen atom or a group represented by Formula X-1 to Formula X-10, and Q ′ ^{1 to} Q ′ ⁴ represent Each independently represents a hydrogen atom, a halogen atom or a monovalent organic group, ring A, ring B and ring C each independently represent a benzene ring, an azole ring, a furan ring or a thiophene ring, and k1 each independently , Represents an integer of 0 to 4, and when k1 is an integer of 2 to 4, a plurality of rings B may be the same or different.

In Formula 1-5 and Formula 1-6, X ″ and Y ″ each independently represent a hydrogen atom or a group represented by Formula X-1 to Formula X-10, and Q ″ ^{1 to} Q ″ ⁴ represent Each independently represents a hydrogen atom, a halogen atom or a monovalent organic group, ring D, ring E and ring F each independently represent a benzene ring, an azole ring, a furan ring or a thiophene ring, and k2 each independently , 1 to 6 and k2 is an integer of 2 to 6, the plurality of rings E may be the same or different.

<8> The Q ¹ and Q ³ are groups represented by the following formula Q-1, or the Q ² and Q ⁴ are groups represented by the following formula Q-1. <1 >-<6> The composition for organic-semiconductor film formation as described in any one of
-LR (Q-1)
In formula Q-1, L is represented by any of the divalent linking groups represented by any of the following formulas L-1 to L-25 or any of the following formulas L-1 to L-25. R represents a divalent linking group in which two or more divalent linking groups are bonded, and R is a hydrogen atom, an alkyl group, an oligooxyethylene group having a repeating number v of oxyethylene units of 2 or more, and a silicon atom number of 2 It represents the above oligosiloxane group or trialkylsilyl group.

In Formula L-1 to Formula L-25, * represents the R-side bond position, the wavy line represents the other bond position, and Formula L-1, Formula L-2, Formula L-6, and Formula L- each R 'independently in 13 formula L-24, represent a hydrogen atom or a substituent, R ^N represents a hydrogen atom or a substituent in the formula L-20 and formula L-24, R ^si in formula L-25 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group.

<9> said ^{Q 1} and ^{Q 3,} alkyl group, aryl group or thioaryl group, or, wherein ^{Q 2} and ^{Q 4} is an alkyl group, an aryl group or a thioaryl group, according to <8> Composition for forming an organic semiconductor film,
<10> The composition for forming an organic semiconductor film according to any one of <1> to <9>, further containing an organic solvent,
<11> The composition for forming an organic semiconductor film according to <10>, wherein the organic solvent is an aromatic hydrocarbon solvent, a halogenated hydrocarbon solvent, a ketone solvent and / or an ether solvent.
<12> The composition for forming an organic semiconductor film according to any one of <1> to <11>, further containing a binder polymer,
<13> A film forming step of forming the organic semiconductor film forming composition according to any one of <1> to <12>, and applying an external stimulus to the organic semiconductor film forming composition And a desorption step in which at least a part of the organic semiconductor compound precursor represented by the formula 1 is aromatized with desorption of a leaving group to form an organic semiconductor layer. Method,
<14> The method for producing an organic semiconductor film according to <13>, wherein the external stimulus is heating at 100 ° C. or higher,
<15> The method for producing an organic semiconductor film according to <13> or <14>, wherein the film formation step is a step of forming a film by a solution coating method.
<16> An organic semiconductor film produced by the method for producing an organic semiconductor film according to any one of <13> to <15>,
<17> An organic semiconductor element having an organic semiconductor film manufactured by the method for manufacturing an organic semiconductor film according to any one of <13> to <15>,
<18> The organic semiconductor element according to <17>, which is an organic thin film transistor,
<19> A compound represented by the following formula 1,

In Formula 1, Z represents NR ¹ , an oxygen atom, a sulfur atom or a selenium atom, R ¹ represents a hydrogen atom, an alkyl group or an aryl group, and X and Y each independently represent a hydrogen atom or a leaving group. And at least one of X and Y is a leaving group, Q ^{1 to} Q ⁴ each independently represents a hydrogen atom, a halogen atom or a monovalent organic group, and Q ^{1 to} Q ⁴ are adjacent to each other. The groups may be bonded to each other to form a ring. When at least one pair of adjacent Q ^{1 to} Q ⁴ is not bonded to form a ring, at least one of Q ^{1 to} Q ⁴ Is a group having a condensed polycyclic aromatic group.

<20> The compound according to <19>, wherein the leaving group is a leaving group that is directly bonded to the ring structure via a nitrogen atom, an oxygen atom, a sulfur atom, or a silicon atom,
<21> The compound according to <19> or <20>, wherein one of the X and Y is a leaving group and the other is a hydrogen atom.
<22> The compound according to any one of <19> to <21>, wherein the leaving group is a group represented by any one of formulas X-1 to X-10,

  In formulas X-1 to X-10, R ″ each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, a trialkylsilyl group, an alkenyl group, or an alkynyl group.

<23> The compound according to any one of <19> to <22>, wherein Z is a sulfur atom.
<24> One or more of Q ¹ and Q ² , Q ² and Q ³ , or a combination of Q ³ and Q ⁴ are combined to form a ring, <19> to <23> A compound according to any one of the following:
<25> The compound according to <22>, represented by any one of the following formulas 1-1 to 1-6,

In Formula 1-1 to Formula 1-4, X ′ and Y ′ each independently represent a hydrogen atom or a group represented by Formula X-1 to Formula X-10, and Q ′ ^{1 to} Q ′ ⁴ represent Each independently represents a hydrogen atom, a halogen atom or a monovalent organic group, ring A, ring B and ring C each independently represent a benzene ring, an azole ring, a furan ring or a thiophene ring, and k1 each independently , Represents an integer of 0 to 4, and when k1 is an integer of 2 to 4, a plurality of rings B may be the same or different.

In Formula 1-5 and Formula 1-6, X ″ and Y ″ each independently represent a hydrogen atom or a group represented by Formula X-1 to Formula X-10, and Q ″ ^{1 to} Q ″ ⁴ represent Each independently represents a hydrogen atom, a halogen atom or a monovalent organic group, ring D, ring E and ring F each independently represent a benzene ring, an azole ring, a furan ring or a thiophene ring, and k2 each independently , 1 to 6 and k2 is an integer of 2 to 6, the plurality of rings E may be the same or different.

<26> The Q ¹ and Q ³ are groups represented by the following formula Q-1, or the Q ² and Q ⁴ are groups represented by the following formula Q-1. <19 >-<24> The compound according to any one of
-LR (Q-1)
In formula Q-1, L is represented by any of the divalent linking groups represented by any of the following formulas L-1 to L-25 or any of the following formulas L-1 to L-25. R represents a divalent linking group in which two or more divalent linking groups are bonded, and R is a hydrogen atom, an alkyl group, an oligooxyethylene group having a repeating number v of oxyethylene units of 2 or more, and a silicon atom number of 2 It represents the above oligosiloxane group or trialkylsilyl group.

In Formula L-1 to Formula L-25, * represents the R-side bond position, the wavy line represents the other bond position, and Formula L-1, Formula L-2, Formula L-6, and Formula L- each R 'independently in 13 formula L-24, represent a hydrogen atom or a substituent, R ^N represents a hydrogen atom or a substituent in the formula L-20 and formula L-24, R ^si in formula L-25 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group.

<27> The Q ¹ and Q ³ are an alkyl group, an aryl group, or a thioaryl group, or the Q ² and Q ⁴ are an alkyl group, an aryl group, or a thioaryl group, Compound,
<28> The compound according to any one of <19> to <27>, which is an organic semiconductor compound precursor.

According to the present invention, an organic semiconductor film forming composition excellent in mobility and driving stability of the obtained organic semiconductor film, an organic semiconductor film formed from the organic semiconductor film forming composition, a manufacturing method thereof, and An organic semiconductor device could be provided.
Moreover, according to this invention, the novel compound which can be used suitably as an organic-semiconductor compound precursor was able to be provided.

It is a cross-sectional schematic diagram of one aspect | mode of the organic-semiconductor element of this invention. It is a cross-sectional schematic diagram of another one aspect | mode of the organic-semiconductor element of this invention.

Hereinafter, the contents of the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the specification of the present application, “to” is used to mean that the numerical values described before and after it are included as a lower limit value and an upper limit value. The organic EL element in the present invention refers to an organic electroluminescence element.
In the notation of a group (atomic group) in this specification, the notation which does not describe substitution and unsubstituted includes what has a substituent with what does not have a substituent. For example, the “alkyl group” includes not only an alkyl group having no substituent (unsubstituted alkyl group) but also an alkyl group having a substituent (substituted alkyl group).
In addition, the chemical structural formula in this specification may be expressed as a simplified structural formula in which a hydrogen atom is omitted.
In the present invention, the term “mobility” means carrier mobility, and means either or both of electron mobility and hole mobility.
In the present invention, “mass%” and “wt%” are synonymous, and “part by mass” and “part by weight” are synonymous.
In the present invention, a combination of preferred embodiments is more preferred.

(New compound)
The compound of the present invention is represented by the following formula 1.

In Formula 1, Z represents NR ¹ , an oxygen atom, a sulfur atom or a selenium atom, R ¹ represents a hydrogen atom, an alkyl group or an aryl group, and X and Y each independently represent a hydrogen atom or a leaving group. And at least one of X and Y is a leaving group, Q ^{1 to} Q ⁴ each independently represents a hydrogen atom, a halogen atom or a monovalent organic group, and Q ^{1 to} Q ⁴ are adjacent to each other. Groups may be bonded to each other to form a ring. When at least one pair of adjacent Q ^{1 to} Q ⁴ is not bonded to form a ring, at least one of Q ^{1 to} Q ⁴ Is a group having a condensed polycyclic aromatic group.

The compound of the present invention is a novel compound and can be suitably used as an organic semiconductor compound precursor.
As a result of intensive studies, the inventors of the present invention have a mobility and driving stability of an organic semiconductor film obtained by having a 5-membered dihydroheteroaromatic ring structure having a leaving group represented by the above formula 1. The present invention has been found to be excellent in properties, and the present invention has been completed.
Although the detailed mechanism of the effect is unclear, the compound of the present invention has the highest occupied orbital (HOMO) orbital overlap due to the interaction of the terminal heterocycle represented by Formula 1, and the crystallinity is improved. It is estimated that the mobility becomes high by going up. In addition, since it can be converted into an organic semiconductor compound at low temperatures (100 ° C. to 200 ° C.) and almost no impurities are generated, there is little influence of carrier traps, crystallinity and orientation deterioration due to impurities, and threshold voltage changes after repeated driving Is estimated to be small (excellent driving stability).

Z in Formula 1 represents NR ¹ , an oxygen atom, a sulfur atom or a selenium atom, preferably an oxygen atom, a sulfur atom or a selenium atom, more preferably a sulfur atom or a selenium atom, and a sulfur atom. Is more preferable. It is more excellent in the mobility of the organic-semiconductor film obtained as it is the said aspect.
R ¹ in Formula 1 is hydrogen atom, an alkyl group or an aryl group, preferably an alkyl group or an aryl group, more preferably an alkyl group or a phenyl group having 1 to 8 carbon atoms, 1 to carbon atoms 8 is more preferable, and a methyl group is particularly preferable.

X and Y in Formula 1 each independently represent a hydrogen atom or a leaving group, and at least one of X and Y is a leaving group.
In Formula 1, it is preferable that one of X and Y is a leaving group and the other is a hydrogen atom. In the above embodiment, the stability and detachability of the compound are excellent, and the mobility of the obtained organic semiconductor film is excellent.
The leaving group is preferably a leaving group which is directly bonded to the ring structure via a nitrogen atom, oxygen atom, sulfur atom or silicon atom, and is directly bonded to the ring structure via an oxygen atom. It is more preferable that the leaving group is. In the above embodiment, the stability and detachability of the compound are excellent, and the mobility of the obtained organic semiconductor film is excellent.
The leaving group is preferably a group represented by any one of formulas X-1 to X-10, and is a group represented by any one of formulas X-1 to X-4. Are more preferable, and a group represented by Formula X-1 or Formula X-4 is even more preferable. In the above embodiment, the stability and detachability of the compound are excellent, and the mobility of the obtained organic semiconductor film is excellent.

  In formulas X-1 to X-10, R ″ each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, a trialkylsilyl group, an alkenyl group, or an alkynyl group.

R ″ in Formula X-1 to Formula X-7 is preferably an alkyl group or an aryl group, more preferably an alkyl group having 1 to 10 carbon atoms or a phenyl group, and further preferably a methyl group. preferable.
R ″ in Formula X-8 is preferably an alkyl group or an aryl group, more preferably a methyl group, a phenyl group, or a toluyl group, and even more preferably a methyl group.
R ″ in Formula X-9 is preferably each independently an alkyl group or an aryl group, more preferably an alkyl group having 1 to 4 carbon atoms or a phenyl group, and even more preferably a methyl group.
R ″ in formula X-10 is preferably independently an alkyl group, more preferably an alkyl group having 1 to 4 carbon atoms, and still more preferably a methyl group.

The alkyl group, aryl group, heteroaryl group, trialkylsilyl group, alkenyl group and alkynyl group in R ″ may have a substituent.
The type of the substituent is not particularly limited, and examples thereof include the substituent X described below.
As the substituent X, a halogen atom, an alkyl group, an alkynyl group, an alkenyl group, an alkoxy group, an alkylthio group, or an aryl group is preferable, and a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, or a carbon number A substituted or unsubstituted alkynyl group having 2 to 3 carbon atoms, a substituted or unsubstituted alkenyl group having 2 to 3 carbon atoms, a substituted or unsubstituted alkoxy group having 1 to 2 carbon atoms, a substituted or unsubstituted methylthio group, or More preferred is a phenyl group, a fluorine atom, a substituted or unsubstituted alkyl group having 1 to 3 carbon atoms, a substituted or unsubstituted alkynyl group having 2 to 3 carbon atoms, or a substituted or unsubstituted alkenyl group having 2 to 3 carbon atoms. A substituted or unsubstituted alkoxy group having 1 to 2 carbon atoms or a substituted or unsubstituted methylthio group is particularly preferable.

Q ^{1 to} Q ⁴ in Formula 1 each independently represent a hydrogen atom, a halogen atom or a monovalent organic group, and Q ^{1 to} Q ⁴ may form a ring by bonding adjacent groups to each other. If you do not form at least one set of neighboring was Q ¹ to Q ⁴ are bonded to the ring, at least one of Q ¹ to Q ⁴ is a group having a condensed polycyclic aromatic group.
Q ^{1 to} Q ⁴ are preferably 2 to 9, more preferably 3 to 7, in terms of mobility as an organic semiconductor when adjacent groups are bonded to each other to form a ring. 4-6 are more preferable.
The condensed polycyclic aromatic group is a group obtained by condensing a plurality of aromatic rings.
Examples of the aromatic ring include an aromatic hydrocarbon ring (for example, a benzene ring) and an aromatic heterocyclic ring (for example, a thiophene ring, a furan ring, a pyrrole ring, a selenophene ring, and an imidazole ring).
From the viewpoint of mobility as an organic semiconductor, the number of rings in the condensed polycyclic aromatic group is preferably 2 to 9, more preferably 3 to 7, and still more preferably 4 to 6.
From the viewpoint of mobility as an organic semiconductor, at least two rings in the condensed polycyclic aromatic group are selected from the group consisting of a sulfur atom, a nitrogen atom, a selenium atom, and an oxygen atom. It is preferable that 2-6 rings contain the said atom, and it is more preferable that 2-4 rings contain the said atom.
Further, from the viewpoint of mobility as an organic semiconductor, it is preferable that at least two heterocycles are contained in the condensed polycyclic aromatic group, and each heterocycle has one heteroatom. The kind of the hetero atom is not particularly limited, and examples thereof include an O atom (oxygen atom), an S atom (sulfur atom), an N atom (nitrogen atom), and an Se atom (selenium atom).
Further, from the viewpoint of mobility as an organic semiconductor in the condensed polycyclic aromatic group, it preferably has at least a thiophene ring structure and / or a selenophene ring structure, more preferably has at least a thiophene ring structure, Component A It is more preferable that all the heterocyclic structures possessed by are thiophene ring structures.

Moreover, it is preferable that one or more of Q ¹ and Q ² , Q ² and Q ³ , or a combination of Q ³ and Q ⁴ are bonded to form a ring.
Further, at least one of Q ^{1 to} Q ⁴ has one or more structures similar to the structure represented by Formula 1 as a monovalent organic group or a group in which one or more are bonded to form a ring. It is preferable to have one, and it is more preferable to have one.
Also, Q ¹ to dihydro heteroaromatic ring 5-membered ring in to Q ⁴ are the fused polycyclic aromatic group may be a condensed structure.

It is preferable that the Q ¹ and Q ³ are groups represented by the following formula Q-1 or the Q ² and Q ⁴ are groups represented by the following formula Q-1.
-LR (Q-1)
In formula Q-1, L is represented by any of the divalent linking groups represented by any of the following formulas L-1 to L-25 or any of the following formulas L-1 to L-25. R represents a divalent linking group in which two or more divalent linking groups are bonded, and R is a hydrogen atom, an alkyl group, an oligooxyethylene group having a repeating number v of oxyethylene units of 2 or more, and a silicon atom number of 2 It represents the above oligosiloxane group or trialkylsilyl group.

In Formula L-1 to Formula L-25, * represents the R-side bond position, the wavy line represents the other bond position, and Formula L-1, Formula L-2, Formula L-6, and Formula L- each R 'independently in 13 formula L-24, represent a hydrogen atom or a substituent, R ^N represents a hydrogen atom or a substituent in the formula L-20 and formula L-24, R ^si in formula L-25 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group.
In addition, when L represents a divalent linking group in which two or more divalent linking groups represented by any of the formulas L-1 to L-25 are bonded, * of one linking group is the other Combines with the wavy portion of the linking group.
The bonding position of R ′ and the bonding position * on the R side in Formula L-13 to Formula L-24 can take any position on the aromatic ring or heteroaromatic ring.
R ′ in Formula L-1, Formula L-2, Formula L-6, and Formula L-13 to Formula L-24 each independently represents a hydrogen atom or a substituent. ^RN represents a hydrogen atom or a substituent. R ^si each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group.
R ′ in Formula L-1 and Formula L-2 may be bonded to R adjacent to L to form a condensed ring.

  Among these, the divalent linking group represented by any one of the formulas L-17 to L-21, L-23 and L-24 is represented by the following formulas L-17A to L-21A and L It is more preferably a divalent linking group represented by -23A and Formula L-24A.

R ′ in Formula L-1, Formula L-2, Formula L-6, and Formula L-13 to Formula L-24 is a halogen atom, an alkyl group, an alkynyl group, an alkenyl group, an alkoxy group, an alkylthio group, or aryl. It is preferably a group.
Among them, R ′ in formula L-6 is preferably an alkyl group, and when R ′ in formula L-6 is an alkyl group, the alkyl group preferably has 1 to 9 carbon atoms, It is more preferable that it is 1-5 from a chemical stability and a viewpoint of carrier transport property, and it is still more preferable that it is 1-3. When R ′ in Formula L-6 is an alkyl group, the alkyl group is preferably a linear alkyl group from the viewpoint of increasing carrier mobility.
It represents ^{R N} represents a hydrogen atom or a substituent of the formula L-20 and wherein L-24, as the ^{R N,} there may be mentioned those exemplified as the ^{substituents R} 1a ^{to R 1f} of Formula 1 above can take it can. Among them, as the R ^N, a hydrogen atom or a methyl group is preferable.
R ^si in formula L-25 each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group, and is preferably an alkyl group. The alkyl group that R ^si can take is not particularly limited, but the preferred range of the alkyl group that R ^si can take is the preferred range of the alkyl group that the trialkylsilyl group can take when R is a trialkylsilyl group. It is the same. Although there is no restriction | limiting in particular as an alkenyl group which ^Rsi can take, A substituted or unsubstituted alkenyl group is preferable, It is more preferable that it is a linear alkenyl group, It is C1-C3 of an alkenyl group. preferable. The alkynyl group that R ^si can take is not particularly limited, but is preferably a substituted or unsubstituted alkynyl group, more preferably a linear alkynyl group, and the alkynyl group has 1 to 3 carbon atoms. preferable.

  L is a divalent linking group represented by any one of Formula L-1 to Formula L-5, Formula L-13, Formula L-17, and Formula L-18, or Formula L-1 to Formula L- 5, preferably a divalent linking group in which two or more divalent linking groups represented by any one of formula L-13, formula L-17, and formula L-18 are bonded. L-3, a divalent linking group represented by any of formula L-13 and formula L-18, or any of formula L-1, formula L-3, formula L-13 and formula L-18 Is more preferably a divalent linking group in which two or more divalent linking groups are bonded, represented by any one of formula L-1, formula L-3, formula L-13 and formula L-18. Or a divalent linking group represented by any one of formula L-3, formula L-13 and formula L-18 and one or more formula L-1. A divalent linking group with a divalent linking group It is particularly preferred is Yuimoto.

Among them, it is more preferable that at least one of Q ^{1 to} Q ⁴ is an alkyl group, an aryl group, or a thioaryl group, or Q ² and Q ⁴ are an alkyl group, an aryl group, or a thioaryl group.
^Further, at least one of Q 1 to Q ^4, preferably an alkyl group having 2 to 10 carbon atoms, more preferably an alkyl group having 4-8 carbon atoms. In the above embodiment, the solubility is excellent, and the mobility and driving stability of the obtained organic semiconductor film are excellent.

  The compound of the present invention is preferably a compound represented by any one of the following formulas 1-1 to 1-6, and represented by any one of the following formulas 1-1, 1-2, and 1-5. More preferably, it is a compound represented by either the following formula 1-1 or formula 1-2, and it is particularly preferable that it is a compound represented by the following formula 1-1. preferable. In the above embodiment, the mobility and driving stability of the obtained organic semiconductor film are excellent.

In Formula 1-1 to Formula 1-4, X ′ and Y ′ each independently represent a hydrogen atom or a group represented by Formula X-1 to Formula X-10, and Q ′ ^{1 to} Q ′ ⁴ represent Each independently represents a hydrogen atom, a halogen atom or a monovalent organic group, ring A, ring B and ring C each independently represent a benzene ring, an azole ring, a furan ring or a thiophene ring, and k1 each independently , Represents an integer of 0 to 4, and when k1 is an integer of 2 to 4, a plurality of rings B may be the same or different.

In Formula 1-5 and Formula 1-6, X ″ and Y ″ each independently represent a hydrogen atom or a group represented by Formula X-1 to Formula X-10, and Q ″ ^{1 to} Q ″ ⁴ are Each independently represents a hydrogen atom, a halogen atom or a monovalent organic group, ring D, ring E and ring F each independently represent a benzene ring, an azole ring, a furan ring or a thiophene ring, and k2 each independently , 1 to 6 and k2 is an integer of 2 to 6, the plurality of rings E may be the same or different.

In Formula 1-1 to Formula 1-4, it is preferable that one of X ′ and Y ′ bonded to the same ring is a leaving group and the other is a hydrogen atom. In the above embodiment, the stability and detachability of the compound are excellent, and the mobility of the obtained organic semiconductor film is excellent.
In Formula 1-5 and Formula 1-6, it is preferable that one of X ″ and Y ″ bonded to the same ring is a leaving group and the other is a hydrogen atom. In the above embodiment, the stability and detachability of the compound are excellent, and the mobility of the obtained organic semiconductor film is excellent.
In addition, the groups represented by the formulas X-1 to X-10 in the formulas 1-1 to 1-6 are synonymous with the groups represented by the formulas X-1 to X-10 described above, and are preferable. The aspect is also the same.

Q ′ ^{1 to} Q ′ ⁴ and Q ″ ^{1 to} Q ″ ⁴ in Formula 1-1 to Formula 1-6 each independently represent a hydrogen atom, a halogen atom, or a monovalent organic group.
The monovalent organic group in Q ′ ^{1 to} Q ′ ⁴ and Q ″ ^{1 to} Q ″ ⁴ is preferably a group represented by the formula Q-1.
The group represented by Formula Q-1 in Q ′ ^{1 to} Q ′ ⁴ and Q ″ ^{1 to} Q ″ ⁴ has the same meaning as the group represented by Formula Q-1 described above, and the preferred embodiments are also the same.
Among them, Q ^'1 and Q' ³ is an alkyl group, an aryl group or a thioaryl group, or, Q ^'2 and Q' ⁴ is an alkyl group, more preferably an aryl group or a thioaryl group.
In addition, at least one of Q ′ ^{1 to} Q ′ ⁴ is preferably an alkyl group having 2 to 10 carbon atoms, and more preferably an alkyl group having 4 to 8 carbon atoms. In the above embodiment, the solubility is excellent, and the mobility and driving stability of the obtained organic semiconductor film are excellent.
Furthermore, Q ′ ¹ and Q ′ ³ , or Q ′ ² and Q ′ ⁴ are preferably an alkyl group having 2 to 10 carbon atoms, and more preferably an alkyl group having 4 to 8 carbon atoms. In the above embodiment, the solubility is excellent, and the mobility and driving stability of the obtained organic semiconductor film are excellent.
Moreover, among them, it is more preferable that at least one of Q ^{1 to} Q ⁴ is an alkyl group, an aryl group, or a thioaryl group, or Q ″ ² and Q ″ ⁴ are an alkyl group, an aryl group, or a thioaryl group. preferable.
Further, at least one of Q ″ ^{1 to} Q ″ ⁴ is preferably an alkyl group having 2 to 10 carbon atoms, and more preferably an alkyl group having 4 to 8 carbon atoms. In the above embodiment, the solubility is excellent, and the mobility and driving stability of the obtained organic semiconductor film are excellent.

Ring A, Ring B, and Ring C in Formula 1-1 to Formula 1-4 each independently represent a benzene ring, an azole ring, a furan ring, or a thiophene ring, k1 represents an integer of 0 to 4, and k1 is 2 In the case of -4, the plurality of rings B may be the same or different.
Ring A, ring B and ring C are preferably each independently a benzene ring or a thiophene ring.
Each k1 is preferably independently an integer of 2 to 4, more preferably 2 or 3, and still more preferably 3.

Ring D, ring E, and ring F in Formula 1-5 and Formula 1-6 each independently represent a benzene ring, an azole ring, a furan ring, or a thiophene ring, k2 represents an integer of 1 to 6, and k2 is 2 When it is an integer of ˜6, the plurality of rings E may be the same or different.
Ring D, ring E and ring F are preferably each independently a benzene ring or a thiophene ring.
k2 is each independently preferably an integer of 1 to 4, more preferably 2 or 3, and still more preferably 2.

  Although the preferable specific example of the compound of this invention is shown below, it cannot be overemphasized that it is not limited to these.

(Composition for forming an organic semiconductor film)
The composition for forming an organic semiconductor film of the present invention (hereinafter, also simply referred to as “composition”) contains an organic semiconductor compound precursor represented by the following formula 1.

In Formula 1, Z represents NR ¹ , an oxygen atom, a sulfur atom or a selenium atom, R ¹ represents a hydrogen atom, an alkyl group or an aryl group, and X and Y each independently represent a hydrogen atom or a leaving group. And at least one of X and Y is a leaving group, Q ^{1 to} Q ⁴ each independently represents a hydrogen atom, a halogen atom or a monovalent organic group, and Q ^{1 to} Q ⁴ are adjacent to each other. Groups may be bonded to each other to form a ring. When at least one pair of adjacent Q ^{1 to} Q ⁴ is not bonded to form a ring, at least one of Q ^{1 to} Q ⁴ Is a group having a condensed polycyclic aromatic group.

The organic semiconductor compound precursor represented by Formula 1 in the composition for forming an organic semiconductor film of the present invention is synonymous with the compound of the present invention described above, and the preferred embodiments are also the same.
The organic semiconductor compound precursor represented by Formula 1 may be contained singly or in combination of two or more, but from the viewpoint of the mobility of the organic semiconductor film obtained, one kind alone It is preferable to contain.
The content of the organic semiconductor compound precursor represented by Formula 1 in the composition for forming an organic semiconductor film of the present invention is preferably 30 to 100% by mass, and 50 to 100% by mass with respect to the total solid content. More preferably, it is more preferably 70 to 100% by mass. Moreover, when not containing the binder polymer mentioned later, it is preferable that the said content is 90-100 mass% with respect to the total solid, and it is more preferable that it is 95-100 mass%. In addition, solid content is the quantity except volatile components, such as a solvent.

<Binder polymer>
The composition for forming an organic semiconductor film of the present invention preferably further contains a binder polymer.
Moreover, the organic semiconductor element of this invention mentioned later may be an organic semiconductor element which has a layer containing the said organic semiconductor layer and a binder polymer.
The kind in particular of a binder polymer is not restrict | limited, A well-known binder polymer can be used.
Examples of the binder polymer include polystyrene resin, acrylic resin, rubber, and thermoplastic elastomer.
Among these, as the binder polymer, a polymer compound having a benzene ring (a polymer having a monomer unit having a benzene ring group) is preferable. The content of the monomer unit having a benzene ring group is not particularly limited, but is preferably 50 mol% or more, more preferably 70 mol% or more, and still more preferably 90 mol% or more in all monomer units. The upper limit is not particularly limited, but 100 mol% can be mentioned.
Examples of the binder polymer include polystyrene, poly (α-methylstyrene), polyvinyl cinnamate, poly (4-vinylphenyl), poly (4-methylstyrene), and the like.

The 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 1,500,000, and still more preferably 100,000 to 1,000,000.
Moreover, when using the solvent mentioned later, it is preferable that the binder polymer has higher solubility in the solvent used than the specific compound. It is excellent in the mobility and thermal stability of the organic semiconductor obtained as it is the said aspect.
The content of the binder polymer in the composition for forming an organic semiconductor film of the present invention is preferably 1 to 200 parts by mass and more preferably 10 to 150 parts by mass with respect to 100 parts by mass of the specific compound. Preferably, it is 20-120 mass parts. It is excellent in the mobility and thermal stability of the organic semiconductor obtained as it is the said range.

<Solvent>
The composition for forming an organic semiconductor film of the present invention preferably contains a solvent, and more preferably contains an organic solvent.
A known solvent can be used as the solvent.
Specifically, for example, hydrocarbon solvents such as hexane, octane, decane, toluene, xylene, mesitylene, ethylbenzene, decalin, 1-methylnaphthalene, for example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone. Halogenated hydrocarbon solvents such as dichloromethane, chloroform, tetrachloromethane, dichloroethane, trichloroethane, tetrachloroethane, chlorobenzene, dichlorobenzene, chlorotoluene, ester solvents such as ethyl acetate, butyl acetate, amyl acetate, methanol, propanol, Alcohol solvents such as butanol, pentanol, hexanol, cyclohexanol, methyl cellosolve, ethyl cellosolve, ethylene glycol, dibutyl ether Ether solvents such as tetrahydrofuran, dioxane, anisole, amide / imide solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, 1-methyl-2-pyrrolidone, 1-methyl-2-imidazolidinone, Examples thereof include sulfoxide solvents such as dimethyl sulfoxide and nitrile solvents such as acetonitrile.

A solvent may be used individually by 1 type and may be used in combination of multiple.
Among these, aromatic hydrocarbon solvents, halogenated hydrocarbon solvents, ketone solvents and / or ether solvents are preferable, toluene, xylene, mesitylene, tetralin, dichlorobenzene or anisole are more preferable, and toluene is particularly preferable. .
When the solvent is contained, the content of Component A in the composition for forming an organic semiconductor film of the present invention is preferably 0.01 to 80% by mass, and more preferably 0.05 to 10% by mass. The content of component B is preferably 0.01 to 80% by mass, more preferably 0.05 to 10% by mass. More preferably, it is 0.1-5 mass%. Within the above range, the coating property is excellent and the organic semiconductor film can be easily formed.

The viscosity of the composition for forming an organic semiconductor film of the present invention is not particularly limited, but is preferably 0.1 to 100 mPa · s, more preferably 0.1 to 50 mPa · s, and more preferably 9 to 40 mPa in terms of excellent coating properties. -S is more preferable. In addition, the viscosity in this invention is a viscosity in 25 degreeC.
As a measuring method of a viscosity, it is preferable that it is a measuring method based on JISZ8803.

<Other ingredients>
The composition for forming an organic semiconductor film of the present invention may contain other components in addition to the organic semiconductor compound precursor represented by the formula 1, the binder polymer, and the solvent.
As other components, known additives and the like can be used.
In the composition for forming an organic semiconductor film of the present invention, the content of components other than the organic semiconductor compound precursor represented by Formula 1, the binder polymer, and the solvent is preferably 10% by mass or less, and preferably 5% by mass or less. It is preferably 1% by mass or less, and particularly preferably 0.1% by mass or less. When it is in the above range, the film-forming property is excellent, and the mobility and thermal stability of the obtained organic semiconductor are excellent.

  The manufacturing method of the composition for forming an organic semiconductor film of the present invention is not particularly limited, and a known method can be adopted. For example, a desired composition can be obtained by adding a predetermined amount of an organic semiconductor compound precursor represented by Formula 1 and a binder polymer simultaneously or sequentially in a solvent and appropriately performing a stirring treatment.

(Organic semiconductor film and organic semiconductor element)
The organic semiconductor film of the present invention contains an organic semiconductor compound precursor represented by Formula 1, or contains an organic semiconductor compound obtained by heating the organic semiconductor compound precursor represented by Formula 1. Features.
The organic semiconductor element of the present invention contains an organic semiconductor compound precursor represented by Formula 1 or contains an organic semiconductor compound obtained by heating the organic semiconductor compound precursor represented by Formula 1. Features.

The organic semiconductor element in the first preferred embodiment of the present invention is an organic semiconductor element having an organic semiconductor film formed using the composition for forming an organic semiconductor film of the present invention. In the first embodiment, the film forming property is excellent, and the mobility and driving stability of the obtained organic semiconductor are excellent.
The organic semiconductor element in the 2nd preferable embodiment of this invention is an organic semiconductor element which has a layer containing the said polymer between the layer containing the said organic semiconductor, and an insulating film. In the second embodiment, the productivity and cost are excellent.
The layer containing an organic semiconductor in the second embodiment is preferably a layer made of the organic semiconductor.
The insulating film in the second preferred embodiment is preferably a gate insulating film.
Furthermore, the layer containing the polymer in the second preferred embodiment is preferably a layer made of the polymer.

The organic semiconductor film of the present invention and the organic semiconductor element of the present invention are preferably manufactured using the composition for forming an organic semiconductor film of the present invention.
A method for producing an organic semiconductor film or an organic semiconductor element using the composition for forming an organic semiconductor film of the present invention is not particularly limited, and a known method can be adopted. For example, a method of producing an organic semiconductor film by applying the composition onto a predetermined substrate and subjecting it to a drying treatment as necessary can be mentioned.
The method for applying the composition on the substrate is not particularly limited, and a known method can be adopted, for example, an inkjet printing method, a flexographic printing method, a bar coating method, a spin coating method, a knife coating method, a doctor blade method, or the like. The inkjet printing method and the flexographic printing method are preferable.
In addition, as a flexographic printing method, the aspect using a photosensitive resin plate as a flexographic printing plate is mentioned suitably. In some embodiments, the composition can be printed on a substrate to easily form a pattern.
Especially, the manufacturing method of the organic-semiconductor film of this invention and the manufacturing method of the organic-semiconductor element of this invention are the film-forming process formed into a film with the composition for organic-semiconductor-film formation of this invention, and the said organic-semiconductor film-forming A desorption process in which at least a part of the organic semiconductor compound precursor represented by Formula 1 is aromatized with desorption of a leaving group to form an organic semiconductor active layer by applying an external stimulus to the composition It is particularly preferred that

  The drying process in the film forming step is a process that is performed as necessary, and optimal conditions are appropriately selected depending on the type of the organic semiconductor compound precursor represented by Formula 1 and the solvent used. Among them, the heating temperature is preferably 30 ° C. to 200 ° C., more preferably 50 ° C. to 150 ° C., and the heating time is superior in terms of the mobility and thermal stability of the organic semiconductor obtained and excellent productivity. 10 to 300 minutes are preferable, and 10 to 150 minutes are more preferable.

Heating is preferable as the external stimulus in the desorption step.
The heating temperature in the desorption step is preferably 100 ° C to 250 ° C, and more preferably 100 ° C to 200 ° C. The heating time is preferably 1 to 300 minutes, more preferably 1 to 150 minutes, and still more preferably 1 to 60 minutes.

  The thickness of the organic semiconductor film to be formed is not particularly limited, but is preferably 10 to 500 nm, more preferably 30 to 200 nm, from the viewpoint of the mobility and driving stability of the obtained organic semiconductor.

The organic semiconductor film produced from the composition of the present invention can be suitably used for an organic semiconductor element, and can be particularly suitably used for an organic transistor (organic thin film transistor).
Although there is no restriction | limiting in particular as an organic semiconductor element, It is preferable that it is a 2-5 terminal organic semiconductor element, and it is more preferable that it is a 2 or 3 terminal organic semiconductor element.
The organic semiconductor element is preferably an element that does not use a photoelectric function.
Examples of the two-terminal element include a rectifying diode, a constant voltage diode, a PIN diode, a Schottky barrier diode, a surge protection diode, a diac, a varistor, and a tunnel diode.
Examples of the three-terminal element include a bipolar transistor, a Darlington transistor, a field effect transistor, an insulated gate bipolar transistor, a unijunction transistor, a static induction transistor, a gate turn thyristor, a triac, and a static induction thyristor.
Among these, a rectifying diode and transistors are preferably exemplified, and a field effect transistor is more preferably exemplified.
As the field effect transistor, an organic thin film transistor is preferably exemplified.

One embodiment of the organic thin film transistor of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic cross-sectional view of one embodiment of the organic semiconductor element (organic thin film transistor (TFT)) of the present invention.
In FIG. 1, an organic thin film transistor 100 includes a substrate 10, a gate electrode 20 disposed on the substrate 10, a gate insulating film 30 covering the gate electrode 20, and a side of the gate insulating film 30 opposite to the gate electrode 20 side. A source electrode 40 and a drain electrode 42 in contact with the surface, an organic semiconductor film 50 covering the surface of the gate insulating film 30 between the source electrode 40 and the drain electrode 42, and a sealing layer 60 covering each member are provided. The organic thin film transistor 100 is a bottom gate-bottom contact type organic thin film transistor.
In FIG. 1, the organic semiconductor film 50 corresponds to a film formed from the above-described composition.
Hereinafter, the substrate, the gate electrode, the gate insulating film, the source electrode, the drain electrode, the organic semiconductor film, the sealing layer, and the respective formation methods will be described in detail.

<Board>
The substrate plays a role of supporting a gate electrode, a source electrode, a drain electrode, and the like described later.
The kind of board | substrate is not restrict | limited in particular, For example, a plastic substrate, a glass substrate, a ceramic substrate etc. are mentioned. Among these, a glass substrate or a plastic substrate is preferable from the viewpoint of applicability to each device and cost.
The material of the plastic substrate may be a thermosetting resin (for example, epoxy resin, phenol resin, polyimide resin, polyester resin (for example, polyethylene terephthalate (PET), polyethylene naphthalate (PEN)) or thermoplastic resin (for example, phenoxy). Resin, polyether sulfone, polysulfone, polyphenylene sulfone, etc.).
Examples of the material for the ceramic substrate include alumina, aluminum nitride, zirconia, silicon, silicon nitride, silicon carbide, and the like.
Examples of the glass substrate material include soda glass, potash glass, borosilicate glass, quartz glass, aluminum silicate glass, and lead glass.

<Gate electrode, source electrode, drain electrode>
Examples of materials for the gate electrode, the source electrode, and the drain electrode include gold (Au), silver, aluminum (Al), copper, chromium, nickel, cobalt, titanium, platinum, tantalum, magnesium, calcium, barium, and sodium. Metal: Conductive oxide such as InO ₂ , SnO ₂ , indium tin oxide (ITO); Conductive polymer such as polyaniline, polypyrrole, polythiophene, polyacetylene, polydiacetylene; Semiconductor such as silicon, germanium, gallium arsenide; Fullerene And carbon materials such as carbon nanotubes and graphite. Among these, a metal is preferable, and silver or aluminum is more preferable.
The thickness of the gate electrode, source electrode, and drain electrode is not particularly limited, but is preferably 20 to 200 nm.

  The method for forming the gate electrode, the source electrode, and the drain electrode is not particularly limited, and examples thereof include a method of vacuum-depositing or sputtering an electrode material on a substrate, and a method of applying or printing an electrode-forming composition. In the case of patterning the electrode, examples of the patterning method include a photolithography method; a printing method such as ink jet printing, screen printing, offset printing, letterpress printing; and a mask vapor deposition method.

<Gate insulation film>
Materials for the gate insulating film include polymethyl methacrylate, polystyrene, polyvinylphenol, polyimide, polycarbonate, polyester, polyvinyl alcohol, polyvinyl acetate, polyurethane, polysulfone, polybenzoxazole, polysilsesquioxane, epoxy resin, phenol resin, etc. Examples thereof include oxides such as silicon dioxide, aluminum oxide, and titanium oxide; and nitrides such as silicon nitride. Of these materials, a polymer is preferable in view of compatibility with the organic semiconductor film.
When a polymer is used as the material for the gate insulating film, it is preferable to use a crosslinking agent (for example, melamine) in combination. By using a crosslinking agent in combination, the polymer is crosslinked and the durability of the formed gate insulating film is improved.
The thickness of the gate insulating film is not particularly limited, but is preferably 100 to 1,000 nm.

The method for forming the gate insulating film is not particularly limited, and examples thereof include a method of applying a composition for forming a gate insulating film on a substrate on which a gate electrode is formed, and a method of depositing or sputtering a gate insulating film material. It is done. The method for applying the gate insulating film forming composition is not particularly limited, and known methods (bar coating method, spin coating method, knife coating method, doctor blade method) can be used.
When a gate insulating film forming composition is applied to form a gate insulating film, it may be heated (baked) after application for the purpose of solvent removal, crosslinking, and the like.

<Organic semiconductor film>
The organic semiconductor film of the present invention is a film formed from the composition for forming an organic semiconductor film of the present invention.
The method for forming the organic semiconductor film is not particularly limited, and the above-described composition is applied on the source electrode, the drain electrode, and the gate insulating film, and is subjected to a drying treatment as necessary, thereby obtaining a desired organic semiconductor. A film can be formed.

<Polymer layer>
The organic semiconductor element of the present invention preferably has the polymer layer between the layer containing the organic semiconductor and the insulating film, and more preferably has the polymer layer between the organic semiconductor and the gate insulating film. . The film thickness of the polymer layer is not particularly limited, but is preferably 20 to 500 nm. Although the said polymer layer should just be a layer containing the said polymer, it is preferable that it is a layer which consists of the said polymer.

A method for forming the polymer layer is not particularly limited, and a known method (bar coating method, spin coating method, knife coating method, doctor blade method, ink jet method) can be used.
When the polymer layer-forming composition is applied to form a polymer layer, it may be heated (baked) after application for the purpose of solvent removal, crosslinking, and the like.

<Sealing layer>
The organic thin film transistor of the present invention preferably includes a sealing layer as the outermost layer from the viewpoint of durability. A well-known sealing agent can be used for a sealing layer.
The thickness of the sealing layer is not particularly limited, but is preferably 0.2 to 10 μm.

  The method for forming the sealing layer is not particularly limited. For example, the composition for forming the sealing layer is applied onto the substrate on which the gate electrode, the gate insulating film, the source electrode, the drain electrode, and the organic semiconductor film are formed. Methods and the like. A specific example of the method of applying the sealing layer forming composition is the same as the method of applying the gate insulating film forming composition. When an organic semiconductor film is formed by applying the sealing layer forming composition, it may be heated (baked) after application for the purpose of solvent removal, crosslinking and the like.

FIG. 2 is a schematic cross-sectional view of another embodiment of the organic semiconductor element (organic thin film transistor) of the present invention.
2, the organic thin film transistor 200 includes a substrate 10, a gate electrode 20 disposed on the substrate 10, a gate insulating film 30 covering the gate electrode 20, and an organic semiconductor film 50 disposed on the gate insulating film 30. A source electrode 40 and a drain electrode 42 disposed on the organic semiconductor film 50 and a sealing layer 60 covering each member are provided. Here, the source electrode 40 and the drain electrode 42 are formed using the composition of the present invention described above. The organic thin film transistor 200 is a top contact type organic thin film transistor.
The substrate, gate electrode, gate insulating film, source electrode, drain electrode, organic semiconductor film, and sealing layer are as described above.

1 and 2, the embodiments of the bottom gate-bottom contact type organic thin film transistor and the bottom gate-top contact type organic thin film transistor have been described in detail. However, the composition of the present invention has a top gate-bottom contact type. The present invention can also be applied to a type organic thin film transistor and a top gate-top contact type organic thin film transistor.
In addition, the organic thin-film transistor mentioned above can be used conveniently for electronic paper, a display device, etc.

The present invention will be described more specifically with reference to the following examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Unless otherwise specified, “part” and “%” are based on mass.
Compound No. 1 represented by Formula 1 used in the following examples. 1, 3, 8, 12, 19 and 20 are the above-mentioned exemplified compound Nos. 1, 3, 8, 12, 19 and 20.
Moreover, the comparative compounds 1-4 used by the comparative example are compounds shown below.

<Production and evaluation of organic semiconductor elements>
All the materials used for organic semiconductor device production are purified by sublimation, and the purity (254 nm absorption intensity area ratio) is 99.5% or more by high performance liquid chromatography (TSKgel ODS-100Z manufactured by Tosoh Corporation). confirmed.

(Examples 1-6 and Comparative Examples 1-4)
<Forming a semiconductor active layer (organic semiconductor layer) with a compound alone>
As described in Table 3, a compound represented by Formula 1 or a comparative compound (each 10 mg) and toluene (1 mL) were mixed and heated to 60 ° C. to obtain an organic semiconductor-forming composition (coating Solution).
By casting this coating solution on a substrate for FET characteristic measurement heated to 60 ° C. in a nitrogen atmosphere, a precursor composition film is formed, and then the organic semiconductor film is heated at 150 ° C. for 30 minutes (external stimulus is applied). The compound represented by the formula 1 used as a precursor is converted into an organic semiconductor compound by forming an organic semiconductor film (semiconductor active layer) for an organic semiconductor element of each example and comparative example. The organic thin-film transistor elements 1-8 of each Example for characteristic measurement and a comparative example were obtained. The obtained organic thin film transistor elements 1 to 6 were the organic thin film transistor elements of Examples 1 to 6, respectively, and the obtained organic thin film transistor elements 7 and 8 were the organic thin film transistor elements of Comparative Examples 1 and 2, respectively.
The compounds of Comparative Examples 3 and 4 are compounds after the conversion of the precursor compound of Example 4 and have low solubility. Therefore, the compound (1 mg each) and toluene (1 mL) were mixed, and the mixture was heated to 100 ° C. The heated one was used as an organic semiconductor film forming composition (coating solution).
This coating solution is cast on an FET characteristic measurement substrate heated to 60 ° C. in a nitrogen atmosphere, thereby forming an organic semiconductor film (semiconductor active layer) for an organic semiconductor element, that is, a comparative example for measuring FET characteristics. Organic thin film transistor elements 9 and 10 were obtained. The obtained organic thin film transistor elements 9 and 10 were used as the organic thin film transistor elements of Comparative Examples 3 and 4, respectively.
In addition, all the thickness of the said organic-semiconductor film in the obtained organic thin-film transistor element were about 100 nm.
As a substrate for measuring FET characteristics, a bottom provided with chromium / gold (gate width W = 100 mm, gate length L = 100 μm) arranged in a comb shape as source and drain electrodes, and SiO ₂ (thickness 200 nm) as an insulating film A silicon substrate having a contact structure (a schematic diagram of the structure is shown in FIG. 2) was used.

  The FET characteristics of the organic thin film transistor elements of Examples 1 to 6 and Comparative Examples 1 to 4 were measured using a semiconductor parameter analyzer (Agilent, 4156C) connected to a semi-auto prober (manufactured by Vector Semicon Co., Ltd., AX-2000). Evaluation was performed in terms of carrier mobility and mobility change after annealing under normal pressure and nitrogen atmosphere. The results obtained are shown in the table below.

(A) Carrier mobility A voltage of −80 V is applied between the source electrode and the drain electrode of the organic film transistor element (FET element) of each example and comparative example, and the gate voltage is changed in the range of 20 V to −100 V, Formula I _d representing drain current I _d = (w / 2L) μCi (V _g −V _th ) ² (where L is the gate length, W is the gate width, Ci is the capacitance per unit area of the insulating layer, V _g is the gate voltage, V _{t h} was calculated carrier mobility μ using representative.) the threshold voltage. In addition, since the characteristic is too low for the carrier mobility less than 1 × 10 ⁻⁵ cm ² / Vs, evaluation of the threshold voltage change after the subsequent (b) repeated driving is not performed.

(B) Threshold voltage change after repeated driving A voltage of −80 V is applied between the source electrode and the drain electrode of each organic thin film transistor element (FET element), and the gate voltage is repeated 100 times in the range of +20 V to −100 V (a The difference between the threshold voltage V _{before the} repeated driving and the threshold voltage V _after the repeated driving (| V _after −V _before |) was evaluated in the following three stages. The smaller this value, the higher the repeated driving stability of the element, which is preferable.
A: | _After V and _before V | ≦ 5V
B: 5 V <| V _after −V _before | ≦ 10 V
C: | _After V and _before V |> 10V

From Table 3, the organic thin film transistor element using the compound represented by Formula 1 has high carrier mobility, small threshold voltage change after repeated driving, and sufficiently high solubility essential for the coating process. I understood. Therefore, it turned out that the compound represented by Formula 1 is preferably used as an organic semiconductor compound precursor for organic semiconductor elements.
On the other hand, the organic thin-film transistor element using the comparative compounds 1 to 4 has a low carrier mobility. The organic thin film transistor element using Comparative Compounds 2 to 4 had a large threshold voltage change after repeated driving.

(Examples 7 to 12 and Comparative Examples 5 and 6)
<Forming a semiconductor active layer (organic semiconductor layer) using a compound together with a binder>
As described in Table 4, the compound represented by Formula 1 or a comparative compound (each 10 mg), PαMS (poly (α-methylstyrene), Mw = 300,000), manufactured by Aldrich) 10 mg, toluene ( 2 mL) was mixed and heated to 60 ° C., and an organic thin film transistor element for measuring FET characteristics was prepared in the same manner as in Example 1 except that the coating solution was used. The same evaluation as in Example 1 was performed. The obtained organic thin film transistor elements 11 to 16 were organic thin film transistor elements of Examples 7 to 12, and the obtained organic thin film transistor elements 17 and 18 were organic thin film transistor elements of Comparative Examples 5 and 6, respectively.
In addition, all the thickness of the said organic-semiconductor film in the obtained organic thin-film transistor element were about 100 nm.
The results obtained are shown in Table 4 below.

From Table 4 above, it was found that the organic thin film transistor element in which the semiconductor active layer was formed using the compound represented by Formula 1 together with the binder polymer had high carrier mobility and small threshold voltage change after repeated driving. Therefore, it turned out that the compound represented by Formula 1 is preferably used as an organic semiconductor compound precursor for organic semiconductor elements.
On the other hand, the organic thin film transistor element in which the semiconductor active layer was formed using the comparative compounds 1 and 2 together with the binder polymer had a low carrier mobility. Moreover, the organic thin-film transistor element which formed the semiconductor active layer using the comparative compound 2 with the binder polymer had a large threshold voltage change after repeated driving.

  Furthermore, when each organic thin-film transistor element obtained in Example 2 was observed with the naked eye and observed with an optical microscope, all the thin films using PαMS as the binder polymer had very high smoothness and uniformity. I understood.

  From the above, in the device of the comparative example, when the semiconductor active layer is formed of a composite system of the binder polymer and the comparative compound, the carrier mobility is very low, whereas in the organic thin film transistor device of the present invention, Even when a semiconductor active layer is formed using a compound with a binder, good carrier mobility is exhibited, a change in threshold voltage after repeated driving is small, and an element with extremely high film smoothness and uniformity can be obtained. I understood.

(Examples 13 to 18 and Comparative Examples 7 and 8)
<Semiconductor active layer (organic semiconductor layer) formation>
A silicon wafer provided with SiO ₂ (thickness: 370 nm) as a gate insulating film was used, and surface treatment was performed with octyltrichlorosilane.
As described in Table 5, a compound represented by Formula 1 or a comparative compound (each 10 mg) and toluene (1 mL) were mixed and heated to 60 ° C. to obtain a coating solution for an organic semiconductor element. . This coating solution was cast on an octylsilane surface-treated silicon wafer heated to 90 ° C. in a nitrogen atmosphere, and then heated at 150 ° C. for 30 minutes to form an organic semiconductor film for an organic semiconductor element.
Furthermore, gold was deposited on the surface of the thin film using a mask to produce source and drain electrodes, and an organic thin film transistor element having a gate width W = 5 mm and a gate length L = 80 μm was obtained. The obtained organic film transistor elements 19 to 24 were organic thin film transistor elements of Examples 13 to 18, respectively, and the obtained organic film transistor elements 25 and 26 were organic thin film transistor elements of Comparative Examples 7 and 8, respectively.
The FET characteristics of the organic thin film transistor elements of Examples and Comparative Examples were measured under normal pressure and nitrogen atmosphere using a semiconductor parameter analyzer (Agilent, 4156C) connected with a semi-auto prober (manufactured by Vector Semicon Co., Ltd., AX-2000). Thus, evaluation was performed from the viewpoint of carrier mobility and threshold voltage change after repeated driving.
The obtained results are shown in Table 5 below.

  From Table 5 above, it was found that the organic thin film transistor element using the compound represented by Formula 1 has high carrier mobility and small threshold voltage change after repeated driving. Therefore, it turned out that the compound represented by Formula 1 is preferably used as an organic semiconductor compound precursor for organic semiconductor elements.

  10: substrate, 20: gate electrode, 30: gate insulating film, 40: source electrode, 42: drain electrode, 50: organic semiconductor film, 60: sealing layer, 100, 200: organic thin film transistor

Claims (25)

An organic semiconductor film forming composition comprising an organic semiconductor compound precursor represented by the following formula 1.

In Formula 1, Z represents NR ¹ , an oxygen atom, a sulfur atom or a selenium atom, R ¹ represents a hydrogen atom, an alkyl group or an aryl group, and X and Y each independently represent a hydrogen atom or a leaving group. And at least one of X and Y is a leaving group, Q ^{1 to} Q ⁴ each independently represents a hydrogen atom, a halogen atom or a monovalent organic group, and Q ^{1 to} Q ⁴ are adjacent to each other. Groups may be bonded to each other to form a ring. When at least one pair of adjacent Q ^{1 to} Q ⁴ is not bonded to form a ring, at least one of Q ^{1 to} Q ⁴ Is a group having a condensed polycyclic aromatic group.   The composition for forming an organic semiconductor film according to claim 1, wherein the leaving group is a leaving group that is directly bonded to a ring structure through a nitrogen atom, an oxygen atom, a sulfur atom, or a silicon atom.   The composition for forming an organic semiconductor film according to claim 1, wherein one of the X and Y is a leaving group and the other is a hydrogen atom. The composition for forming an organic semiconductor film according to any one of claims 1 to 3, wherein the leaving group is a group represented by any one of formulas X-1 to X-10.

In formulas X-1 to X-10, R ″ each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, a trialkylsilyl group, an alkenyl group, or an alkynyl group.   The composition for organic-semiconductor film formation of any one of Claims 1-4 whose said Z is a sulfur atom. One or more of Q ¹ and Q ² , Q ² and Q ³ , or a combination of Q ³ and Q ⁴ are combined to form a ring. The composition for organic semiconductor film formation of description. The organic-semiconductor compound precursor represented by the said Formula 1 is an organic-semiconductor compound precursor represented by either the following formula 1-1-Formula 1-6, The organic-semiconductor film formation of Claim 4 Composition.

In Formula 1-1 to Formula 1-4, X ′ and Y ′ each independently represent a hydrogen atom or a group represented by Formula X-1 to Formula X-10, and Q ′ ^{1 to} Q ′ ⁴ represent Each independently represents a hydrogen atom, a halogen atom or a monovalent organic group, ring A, ring B and ring C each independently represent a benzene ring, an azole ring, a furan ring or a thiophene ring, and k1 each independently , Represents an integer of 0 to 4, and when k1 is an integer of 2 to 4, a plurality of rings B may be the same or different.

In Formula 1-5 and Formula 1-6, X ″ and Y ″ each independently represent a hydrogen atom or a group represented by Formula X-1 to Formula X-10, and Q ″ ^{1 to} Q ″ ⁴ represent Each independently represents a hydrogen atom, a halogen atom or a monovalent organic group, ring D, ring E and ring F each independently represent a benzene ring, an azole ring, a furan ring or a thiophene ring, and k2 each independently , 1 to 6 and k2 is an integer of 2 to 6, the plurality of rings E may be the same or different. The Q ¹ and Q ³ are groups represented by the following formula Q-1, or the Q ² and Q ⁴ are groups represented by the following formula Q-1. The composition for organic-semiconductor film formation of any one of these.
-LR (Q-1)
In formula Q-1, L is represented by any of the divalent linking groups represented by any of the following formulas L-1 to L-25 or any of the following formulas L-1 to L-25. R represents a divalent linking group in which two or more divalent linking groups are bonded, and R is a hydrogen atom, an alkyl group, an oligooxyethylene group having a repeating number v of oxyethylene units of 2 or more, and a silicon atom number of 2 It represents the above oligosiloxane group or trialkylsilyl group.

In Formula L-1 to Formula L-25, * represents the R-side bond position, the wavy line represents the other bond position, and Formula L-1, Formula L-2, Formula L-6, and Formula L- each R 'independently in 13 formula L-24, represent a hydrogen atom or a substituent, R ^N represents a hydrogen atom or a substituent in the formula L-20 and formula L-24, R ^si in formula L-25 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group. The organic semiconductor film according to claim 8, wherein the Q ¹ and Q ³ are an alkyl group, an aryl group, or a thioaryl group, or the Q ² and Q ⁴ are an alkyl group, an aryl group, or a thioaryl group. Forming composition.   The composition for organic-semiconductor film formation of any one of Claims 1-9 which further contains an organic solvent.   The composition for forming an organic semiconductor film according to claim 10, wherein the organic solvent is an aromatic hydrocarbon solvent, a halogenated hydrocarbon solvent, a ketone solvent and / or an ether solvent.   The composition for forming an organic semiconductor film according to claim 1, further comprising a binder polymer. A film forming step of forming a film with the composition for forming an organic semiconductor film according to any one of claims 1 to 12,
An external stimulus is given to the composition for forming an organic semiconductor film, and at least a part of the organic semiconductor compound precursor represented by the formula 1 is aromatized with elimination of a leaving group, and the organic semiconductor layer A desorption step to form
A method for producing an organic semiconductor film.   The method for producing an organic semiconductor film according to claim 13, wherein the external stimulus is heating at 100 ° C. or higher.   The method for producing an organic semiconductor film according to claim 13, wherein the film forming step is a step of forming a film by a solution coating method. A compound represented by the following formula 1.

In Formula 1, Z represents NR ¹ , an oxygen atom, a sulfur atom or a selenium atom, R ¹ represents a hydrogen atom, an alkyl group or an aryl group, and X and Y each independently represent a hydrogen atom or a leaving group. And at least one of X and Y is a leaving group, Q ^{1 to} Q ⁴ each independently represents a hydrogen atom, a halogen atom or a monovalent organic group, and Q ^{1 to} Q ⁴ are adjacent to each other. The groups may be bonded to each other to form a ring. When at least one pair of adjacent Q ^{1 to} Q ⁴ is not bonded to form a ring, at least one of Q ^{1 to} Q ⁴ Is a group having a condensed polycyclic aromatic group. The compound according to claim 16 , wherein the leaving group is a leaving group directly bonded to the ring structure through a nitrogen atom, an oxygen atom, a sulfur atom or a silicon atom. The compound according to claim 16 or 17 , wherein one of the X and Y is a leaving group and the other is a hydrogen atom. The compound according to any one of claims 16 to 18 , wherein the leaving group is a group represented by any one of the formulas X-1 to X-10.

In formulas X-1 to X-10, R ″ each independently represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, a trialkylsilyl group, an alkenyl group, or an alkynyl group. The compound according to any one of claims 16 to 19 , wherein Z is a sulfur atom. 21. In any one of claims 16 to 20 , wherein one or more of Q ¹ and Q ² , Q ² and Q ³ , or a combination of Q ³ and Q ⁴ are bonded to form a ring. The described compound. The compound of Claim 19 represented by either the following formula 1-1-formula 1-6.

In Formula 1-1 to Formula 1-4, X ′ and Y ′ each independently represent a hydrogen atom or a group represented by Formula X-1 to Formula X-10, and Q ′ ^{1 to} Q ′ ⁴ represent Each independently represents a hydrogen atom, a halogen atom or a monovalent organic group, ring A, ring B and ring C each independently represent a benzene ring, an azole ring, a furan ring or a thiophene ring, and k1 each independently , Represents an integer of 0 to 4, and when k1 is an integer of 2 to 4, a plurality of rings B may be the same or different.

In Formula 1-5 and Formula 1-6, X ″ and Y ″ each independently represent a hydrogen atom or a group represented by Formula X-1 to Formula X-10, and Q ″ ^{1 to} Q ″ ⁴ represent Each independently represents a hydrogen atom, a halogen atom or a monovalent organic group, ring D, ring E and ring F each independently represent a benzene ring, an azole ring, a furan ring or a thiophene ring, and k2 each independently , 1 to 6 and k2 is an integer of 2 to 6, the plurality of rings E may be the same or different. Above for ^{Q 1} in and ^{Q 3} are either a group represented by the following formula Q-1, or, the ^{Q 2} and ^{Q 4} is a group represented by the following formula Q-1, claim 16-22 The compound of any one of these.
-LR (Q-1)
In formula Q-1, L is represented by any of the divalent linking groups represented by any of the following formulas L-1 to L-25 or any of the following formulas L-1 to L-25. R represents a divalent linking group in which two or more divalent linking groups are bonded, and R is a hydrogen atom, an alkyl group, an oligooxyethylene group having a repeating number v of oxyethylene units of 2 or more, and a silicon atom number of 2 It represents the above oligosiloxane group or trialkylsilyl group.

In Formula L-1 to Formula L-25, * represents the R-side bond position, the wavy line represents the other bond position, and Formula L-1, Formula L-2, Formula L-6, and Formula L- each R 'independently in 13 formula L-24, represent a hydrogen atom or a substituent, R ^N represents a hydrogen atom or a substituent in the formula L-20 and formula L-24, R ^si in formula L-25 Each independently represents a hydrogen atom, an alkyl group, an alkenyl group or an alkynyl group. The compound according to claim 23 , wherein the Q ¹ and Q ³ are an alkyl group, an aryl group, or a thioaryl group, or the Q ² and Q ⁴ are an alkyl group, an aryl group, or a thioaryl group. The compound according to any one of claims 16 to 24 , which is an organic semiconductor compound precursor.