JP2007103921A - Semiconductor element - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a semiconductor element having an organic semiconductor layer that is excellent in crystallinity and orientation. <P>SOLUTION: A semiconductor element comprises at least a layer that contains one or more polymer compounds and is formed on a substrate, and an organic semiconductor layer in contact with the layer containing the one or more polymer compounds. At least one of the polymer compounds is a polymer compound having one or more secondary or tertiary aliphatic amino groups. The amino groups of the polymer compound having the aliphatic amino groups exist on a side chain and/or a branched chain. The layer containing the polymer compounds contains polysiloxane compounds. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a semiconductor element having an organic semiconductor.

  The development of thin film transistors using organic semiconductors has been gradually active since the late 1980s. The basic performance of a thin film transistor using an organic semiconductor has recently exceeded the basic performance of a thin film transistor using amorphous silicon. Organic materials are often easy to process and often have a high affinity for a flexible plastic substrate on which a thin film FET (Field Effect Transistor) is formed. Therefore, the organic material is attractive as a material for a semiconductor layer in an element that requires flexibility or lightness. As organic semiconductor materials, the following materials have been studied so far. First, acene-based compounds such as pentacene and tetracene disclosed in Patent Document 1 may be mentioned. Second, phthalocyanines including lead phthalocyanine disclosed in Patent Document 2 can be mentioned. Thirdly, low molecular weight compounds such as perylene and its tetracarboxylic acid derivatives are mentioned. Fourthly, aromatic oligomers represented by thiophene hexamers called α-thienyl or sexual thiophene disclosed in Patent Document 3 as well as polythiophene, polythienylene vinylene, poly-p-phenylene vinylene, and the like. Examples include molecular compounds. Many of these are described in Non-Patent Document 1.

  Characteristics such as nonlinear optical characteristics, conductivity, and semiconductivity required when a device is formed from these compounds as a semiconductor layer greatly depend on crystallinity and orientation as well as material purity. An organic material exhibiting good semiconductor characteristics is generally a compound having an extended π-conjugated system. On the other hand, a compound having an expanded π-conjugated system is usually insoluble or hardly soluble in a solvent. For example, since pentacene has high crystallinity and is insoluble in a solvent, a pentacene thin film is generally formed by using a vacuum evaporation method. Thereby, a pentacene thin film exhibiting high field effect mobility has been obtained. However, when the vacuum deposition method is used, the workability of the organic material is not sufficiently exhibited in that the apparatus becomes large and the film formation takes time.

On the other hand, an FET using a film in which a soluble precursor thin film of pentacene is formed by coating and converted to pentacene by heat treatment has also been reported (see Patent Document 4).
Furthermore, it has been reported that tetrabenzoporphyrin obtained by heating a porphyrin fused with a bulky bicyclo [2.2.2] octadiene skeleton at 210 ° C. or higher can be used as an organic semiconductor (Non-Patent Document 4, Patent Document 5 and Patent Document 6). Although the organic semiconductor layers described in these documents have high field effect mobility, they are only realized on the same silicon substrate or glass substrate as amorphous silicon. On the other hand, in order to realize a flexible device utilizing the characteristics as an organic material, it is important to form an organic semiconductor layer that stably exhibits high mobility even on a resin substrate.

As a method of forming an organic semiconductor layer that stably exhibits high mobility, a method of controlling an interface between a gate insulating layer and an organic semiconductor layer is known. For example, in Patent Document 7, a threshold voltage of an organic semiconductor layer formed thereon is controlled by chemically adsorbing a silane compound having various substituents on a gate insulating layer. However, although a uniform interface can be formed on an inorganic insulating layer such as SiO ₂ , it is difficult to chemically adsorb the silane compound on the surface of the organic insulating layer. Patent Document 8 discloses a field effect transistor in which a layer made of polydimethylsiloxane is formed between a gate insulating layer and an organic semiconductor layer. However, no material has been found that can form a uniform polymer layer on an organic insulating layer and further form an organic semiconductor layer on the organic insulating layer by coating. In order to obtain stable characteristics as an organic semiconductor even on a flexible substrate, it is considered that further studies for obtaining an optimum crystal arrangement are necessary in order to improve carrier mobility.
JP-A-5-55568 Japanese Patent Laid-Open No. 5-190877 JP-A-8-264805 US2003 / 0136964 A1 JP 2003-304014 A JP 2004-6750 A JP 2005-32774 A JP 2005-509299 A Advanced Material, 2002, No. 2, p. 99 to 117 “Japan Journal of Applied Physics”, Applied Physics Society, 1991, Vol. 30, p. 596 to 598 “Nature” Nature Publishing Group, 1999, vol. 401, p. 685 to 687 The 81st Annual Meeting of the Chemical Society of Japan 2002 Preliminary Proceedings II, p. 990 (2F9-14)

  As described above, an organic semiconductor layer having high mobility has been formed by a simple method using a coating method, but it has excellent orientation and crystallinity on a flexible substrate such as a resin substrate. The establishment of a method for forming the provided film has been an issue.

  The present invention has been made to solve this problem, and an object thereof is to provide a semiconductor element having an organic semiconductor layer having high crystallinity and orientation. It is another object of the present invention to provide a field effect transistor exhibiting high field effect mobility.

  The present invention provides, in a semiconductor element having an organic semiconductor layer, a layer containing at least one polymer compound and an organic semiconductor layer in contact with the layer containing at least one polymer compound on a substrate. And at least one of the polymer compounds is a polymer compound having one or more secondary or tertiary aliphatic amino groups, and the amino group of the polymer compound having the aliphatic amino groups is a side chain. The semiconductor element is characterized in that the layer containing the polymer compound present on the branched chain contains a polysiloxane compound. Here, as a high molecular compound, only 1 type may be used and 2 or more types may be mixed and used. Moreover, only 1 type may have an aliphatic amino group among each high molecular compound, and 2 or more types may have an aliphatic amino group. The polymer compound may have a plurality of types of amino groups therein. Of course, as long as the requirements described in the claims are satisfied, the use of a compound having a primary amino group or a compound having no amino group is not excluded.

  Here, the polysiloxane compound is a polymer having a siloxane structure (—Si—O—). The polysiloxane compound used in the present invention preferably has an organosilane structure. The polysiloxane compound is preferably a polymer compound having one or more secondary or tertiary aliphatic amino groups. However, a polysiloxane compound may be used as a polymer compound other than a polymer compound having one or more secondary or tertiary aliphatic amino groups.

  Moreover, this invention is a semiconductor element characterized by at least 1 type of the said polysiloxane compound containing the structure shown by following General formula (1).

Wherein R ₁ to R ₄ are any of substituted or unsubstituted alkyl groups having 1 to 8 carbon atoms, alkenyl groups, substituted or unsubstituted phenyl groups, or siloxane units. R ₁ to R ₄ Each may be the same or different, and n represents an integer of 1 or more.)

  In the present specification and claims, the term “substituted or unsubstituted” means that a hydrogen atom, methyl group or methylene group in the target group or unit is replaced with another atom or group. It indicates that it may be. Here, examples of other atoms or groups include a halogen atom, a hydroxyl group, a cyano group, a phenyl group, a nitro group, a mercapto group, and a glycidyl group. When a methyl group or a methylene group is substituted, the number of carbon atoms means the number of carbon atoms after substitution (that is, actual).

  Moreover, this invention is a semiconductor element characterized by at least 1 type of the said polysiloxane compound containing the structure shown by following General formula (2) or following General formula (3).

(Wherein R ₇ to R ₁₀ are any of a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an alkenyl group, and a substituted or unsubstituted phenyl group. Each of R ₇ to R ₁₀ is the same. Or m and n are integers of 0 or more, and the sum of m and n is an integer of 1 or more.)

(Wherein R ₁₁ to R ₁₄ are any of substituted or unsubstituted alkyl groups having 1 to 8 carbon atoms, alkenyl groups, or substituted or unsubstituted phenyl groups. Each of R ₁₁ to R ₁₄ is (It may be the same or different. P and q are integers of 0 or more, and the sum of p and q is an integer of 1 or more.)
Note that “or” is a concept including “and”. Therefore, the case where at least one of the polysiloxane compounds has both the structure represented by the general formula (2) and the structure represented by the general formula (3) is also included in the present invention. Of course.

  In addition, the present invention is characterized in that at least one of the polysiloxane compounds includes one or more of siloxane structures represented by the following general formula (4), general formula (5), and general formula (6). It is a semiconductor element.

(Wherein R ₁₅ , R ₁₆ , R ₁₉ , R ₂₀ , R ₂₂ , R ₂₅ , R ₂₆ , R ₂₈ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, Any one of an alkenyl group, an alkynyl group, a benzyl group, a phenethyl group, and a styryl group, each of R ₁₅ and R ₁₆ , R ₁₉ and R ₂₀ , R ₁₉ and R ₂₂ , and R ₂₅ and R ₂₆ are bonded to each other; One of R ₁₅ and R ₁₆ is other than a hydrogen atom, and R ₁₇ , R ₂₁ , R ₂₃ , R ₂₇ , and R ₂₉ have 1 to 12 carbon atoms that are not directly bonded to the aromatic ring. divalent organic groups _{.R 18, R 24,} R ₃₀ represents a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, an alkenyl group, an alkynyl group, an alkoxyl group, a benzyl group, Fe Butyl group, a styryl group or .r is either siloxane units,, s, t is an integer of 1 or more, u represents an integer of 2 or more.)

  In the present invention, at least one of the siloxane compounds is one or more of silsesquioxane structures including a skeleton represented by the following general formula (7), general formula (8), or general formula (9). It is a semiconductor element characterized by including.

(Wherein R ₃₁ , R ₃₂ , R ₃₄ , R ₃₅ , R ₃₇ , R ₃₉ , R ₄₀ , R ₄₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, Any one of an alkenyl group, an alkynyl group, a benzyl group, a phenethyl group, and a styryl group A ring structure in which R ₃₁ and R ₃₂ , R ₃₄ and R ₃₅ , R ₃₄ and R ₃₇ , R ₃₉ and R ₄₀ are bonded to each other. One of R ₃₁ and R ₃₂ is other than a hydrogen atom, and R ₃₃ , R ₃₆ , R ₃₈ , R ₄₁ , and R ₄₃ have 1 to 12 carbon atoms that are not directly bonded to the aromatic ring. (It is a divalent organic group. V, w and x are integers of 1 or more, and y is an integer of 2 or more.)

  In addition, the present invention is the semiconductor element characterized in that the organic semiconductor layer is made of a low molecular organic semiconductor.

In addition, the present invention is the semiconductor device, wherein the organic semiconductor layer is made of an acene compound or a porphyrin compound.
In addition, the present invention is a semiconductor element characterized in that the surface of the layer containing one or more polymer compounds facing the surface in contact with the organic semiconductor layer is in contact with the organic resin layer.

Further, the present invention is a semiconductor element, wherein the layer containing one or more polymer compounds is a crystallization promoting layer.
In addition, the present invention is a semiconductor element characterized in that the crystallization promoting layer has a function of promoting bonding between crystal grains.

ADVANTAGE OF THE INVENTION According to this invention, the semiconductor element excellent in crystallinity and orientation can be provided.
The present invention is more effective when a semiconductor element is a field effect transistor, and a semiconductor element having a large field effect mobility is obtained.

  Hereinafter, the present invention will be described in detail by taking a field effect transistor as an example of a semiconductor element. However, the effect of the present invention is applicable not only to field effect transistors but also to semiconductor devices in general. Note that in each drawing to be referred to, the reference numerals given to members that are not described here indicate the same members as the reference numerals used in the drawings that will be described later.

  The field effect transistor according to this embodiment is an element including at least an organic semiconductor, an insulator, and a conductor. The insulator is an insulating film (layer) for covering a conductor as an electrode. An organic semiconductor is an organic semiconductor layer that responds to a stimulus (electric field) generated by such a conductor (electrode). Specifically, it is a layer whose electrical characteristics change with respect to an electric field. More specifically, it is a layer in which the conductivity, that is, the current flowing through the organic semiconductor layer changes according to the change in the electric field.

  FIG. 1A is a schematic schematic cross-sectional view showing an example of a field effect transistor according to the present embodiment. 8 is a base material, 1 is a gate electrode, 2 is a gate insulating layer, 3 is a layer containing a polymer compound, 4 is a source electrode, 5 is a drain electrode, 6 is an organic semiconductor layer, and 7 is a sealing layer. In this element, a gate electrode 1 is provided on the surface of a substrate 8, a gate insulating layer 2 is provided thereon, and a layer 3 containing a polymer compound is provided on the surface of the gate insulating layer 2. A source electrode 4 and a drain electrode 5 are provided on the surface of the layer 3 containing the polymer compound at an interval. An organic semiconductor layer 6 is provided in contact with both the electrodes 4 and 5 on the source electrode 4 and the drain electrode 5 and on the layer 3 containing the polymer compound which is a separation region thereof. The gate insulating layer 2 is provided so as to cover the gate electrode 1. Furthermore, the organic semiconductor layer 6 is covered with a sealing layer 7. Moreover, the base material 8 and the sealing layer 7 can also be replaced.

  In a field effect transistor, when a voltage is applied to a gate electrode, positive or negative charges are induced in a region near the interface between the gate insulating layer and the organic semiconductor layer. (A region where charge is induced in this way is called a channel.) Furthermore, when a voltage is applied between the source electrode and the drain electrode, the charge moves between the two electrodes through the channel, and a current can be obtained. . If a voltage can be uniformly generated in the channel when a voltage is applied to the gate electrode, the barrier is reduced when a voltage is applied between the source electrode and the drain electrode, so that the charge can be efficiently transferred. Can do. That is, high field effect mobility can be shown.

  The inventors of the present invention have intensively studied to find a method for forming a channel in which charges are uniformly generated and the generated charges can efficiently move. As a result, by forming the layer 3 containing a specific polymer compound so as to be adjacent to the channel through which charges move (in FIG. 1, the vicinity of the interface of the organic semiconductor layer 6 on the gate insulating layer 2 side), it is continuous in the channel. In particular, it has become possible to form crystals that are uniform and have few defects, and have found high field-effect mobility.

  A field effect transistor according to a preferred embodiment of the present invention comprises, on a substrate, at least a layer containing one or more polymer compounds and an organic semiconductor layer in contact with the layer containing the one or more polymer compounds, And at least one of the polymer compounds is a polymer compound having one or more secondary or tertiary aliphatic amino groups.

  The layer containing the polymer compound of the present invention only needs to contain a polymer compound having one or more secondary or tertiary aliphatic amino groups, and sufficient uniformity as a layer can be maintained. For example, two or more kinds of polymer compounds may be contained. As an example in the case of containing two or more kinds of polymer compounds, there are cases in which two or more kinds of polymer compounds having one or more secondary or tertiary aliphatic amino groups are contained simultaneously. Further, at least one polymer compound having one or more secondary or tertiary aliphatic amino groups and one or more polymer compounds not having a secondary or tertiary aliphatic amino group are contained at the same time. There is also a case. Other cases are naturally within the scope of the present invention.

  A field effect transistor according to a preferred embodiment of the present invention includes a polymer layer (hereinafter referred to as A layer) containing a polymer compound having one or more secondary or tertiary aliphatic amino groups, and an organic semiconductor layer. (Hereinafter referred to as “B layer”) are preferably laminated in close contact with each other in part or on the entire surface of the device. Here, “adhesion” is a state in which the A layer and the B layer are adjacent to each other at least partially without a gap. Since the A layer is stacked in close contact with the B layer, crystallization of the B layer is promoted, so that the field effect transistor of the present invention exhibits high field effect mobility. Therefore, the A layer can also be generally called a crystallization promoting layer. However, in the claims and specification of the present application, the crystallization promoting layer is defined as a layer that not only promotes crystallization but also has a crystallization promoting function as described later.

  As will be described later, if a solvent-soluble organic semiconductor material or organic semiconductor precursor is used, both the A layer and the B layer can be manufactured using a coating process, and thus it is possible to manufacture an element by a simple process. is there.

  In the present invention, the underlying structure on which the A layer is formed (generally a structure comprising a base material, a gate electrode, and a gate insulating layer. However, the gate insulating layer may be omitted, Depending on the stacking order, it may be only the base material, or other layers may be formed. In the present invention, the crystallization promoting function refers to a function of promoting the stabilization of crystal grains (sometimes accompanied by movement and rotation) and / or the joining of crystal grains, and the crystallization promoting layer is It is a layer that promotes the stabilization of crystal grains (sometimes accompanied by movement and rotation) and / or the bonding between crystal grains.

  In the following, the B layer is formed on the A layer, but the present invention is not limited thereto. However, from the viewpoint of giving influence by the A layer when forming the B layer, it is preferable to form the B layer on the A layer.

The polymer compound of the present invention has one or more secondary or tertiary aliphatic amino groups. Due to the basic effect of the amino group, excess carriers derived from impurities existing at the interface with the gate insulating layer can be trapped. As a result, it is possible to suppress the off current and improve the ON / OFF ratio. However, since the primary aliphatic amino group has high hydrophilicity, the effect of promoting the crystallization of the organic semiconductor layer is lost because the hydrophobicity of the surface of the layer A is lost when an effect is obtained. On the other hand, the secondary or tertiary aliphatic amino group has high hydrophobicity because a group other than hydrogen such as an alkyl group is substituted on the nitrogen atom. For this reason, amino groups are not unevenly distributed on the surface of the A layer, the decrease in hydrophobicity can be prevented, and excess carriers that migrate from the interface with the gate insulating layer can be trapped in the A layer. As a result, the effect of suppressing off current is great. The secondary or tertiary aliphatic amino group described herein is a group shown below, and R is a nitrogen of a direct amino group such as an alkyl group, an alkenyl group, an alkynyl group, a benzyl group, a phenethyl group, or a styryl group. A substituent in which an atom is not connected to an aromatic ring. Furthermore, R can be any substituent unless directly connected to a hydrogen atom, aromatic ring, carbonyl group, or sulfonyl group. Rs may be bonded to form a ring structure, or R and a double bond may be formed to form an imino group. However, when R's are bonded to form a ring structure, aromatic heterocyclic rings such as pyridine ring, pyrazine ring and triazine ring are excluded. At least one of R is a divalent or higher organic group, and an amino group is incorporated into the molecular chain of the polymer via the organic group. Other examples of R include alkyl groups, alkenyl groups, alkynyl groups, benzyl groups, phenethyl groups, styryl groups, and the like. Moreover, it is not limited to it. However, in order to suppress the off-current, the amino group needs to have a certain degree of basicity. Therefore, the basicity constant Kb of the amino group is preferably 1 × 10 ⁻⁷ or more and 1 × 10 ⁻² or less. Therefore, a polymer compound having one or more secondary or tertiary aliphatic amino groups is used for the A layer of the present invention.

  The number of moles of the secondary or tertiary amino group in 100 g of the polymer compound having an aliphatic amino group of the present invention is preferably 0.003 or more and 0.4 or less. If it is less than 0.003, it will be difficult for secondary or tertiary amino groups to be present uniformly on the surface of the A layer, so that the crystal growth of the B layer may be non-uniform. On the other hand, if it exceeds 0.4, the surface of the A layer is hydrophilized and the crystallization promoting effect may be lost.

The polymer compound containing a secondary or tertiary aliphatic amino group has a primary amino group in addition to one or more secondary or tertiary aliphatic amino groups. May be.
The polymer compound having an aliphatic amino group of the present invention refers to an oligomer or polymer having a number average molecular weight of 200 or more. A more preferred number average molecular weight is 500 or more and 1,000,000 or less. The structure of the oligomer or polymer may be any of linear, cyclic, branched, ladder-type, crosslinked, and dendrimer structures, and these structures can be arbitrarily combined.

  The polymer compound having an aliphatic amino group of the present invention may have one or more secondary or tertiary aliphatic amino groups in at least one of the main chain, the side chain, and the branched molecular chain. It ’s fine. Here, the case where the branched chain has an aliphatic amino group refers to a case where it is difficult to say which chain is the main chain or the side chain, such as a polymer compound having a dendritic structure.

  Examples of the polymer compound having a secondary or tertiary aliphatic amino group in the main chain include polyalkyleneamines such as polyethyleneimine or copolymers thereof. The main skeleton of the polymer compound having a secondary or tertiary aliphatic amino group in the side chain includes polyacrylate, polymethacrylate, polyvinyl ether, polystyrene, polycycloolefin, polyether, polyester, polyarylate, polyamide , Polyamideimide, polyimide, polyketone, polysulfone, polyphenylene, polysilicon, polysiloxane, cyclic polysiloxane, ladder-type polysiloxane, or a copolymer obtained by combining these skeletons. Examples of the main skeleton of the polymer compound having a secondary or tertiary aliphatic amino group in the branched chain include polyamidoamine dendrimers and hyperbranched polyamides.

  In the polymer compound having an aliphatic amino group of the present invention, it is more preferable that one or more secondary or tertiary aliphatic amino groups are present on the side chain and / or branched chain. By having a secondary or tertiary aliphatic amino group on the side chain and / or branched chain, the amino group can be present uniformly in the vicinity of the surface of the A layer when the A layer is formed. Therefore, both excess carriers derived from impurities at the interface with the B layer and excess carriers derived from impurities moving from the gate insulating layer can be efficiently trapped. Further, the side chain and / or branched chain having a secondary or tertiary aliphatic amino group exerts an effect of further promoting crystal growth.

  A more preferred example of the polymer compound having an aliphatic amino group of the present invention is a polymer compound having a siloxane skeleton. The polymer compound having a siloxane skeleton is a polymer having a siloxane structure (—Si—O—) and an organosilane structure. That is, as long as it has these structures, the polysiloxane compound may be a copolymer with other organic polymer or inorganic polymer. In the case of a copolymer with another polymer, the siloxane structure or the organic silane structure may exist in the main chain, or may exist in the side chain by graft polymerization or the like. The combination of the siloxane structure (—Si—O—) and the organosilane structure can promote the crystallization promoting effect of the secondary or tertiary aliphatic amino group. The organosilane structure is a structure in which Si and C are directly bonded.

  The polysiloxane compound preferably used in the present invention may have various structures such as a straight chain and a ring. The polysiloxane compound of the present invention more preferably has a high-order crosslinked or branched structure. The higher-order bridged or branched structure described here includes a net-like, ladder-like, cage-like, star-like, and dendritic structure. The crosslinked or branched structure does not necessarily have to be formed via a siloxane structure, but includes a structure in which organic groups such as a vinyl group, an acryloyl group, an epoxy group, and a cinnamoyl group are crosslinked. Moreover, you may include the structure branched through the organic group more than trifunctional.

  The polysiloxane compound layer preferably used in the present invention introduces a secondary or tertiary aliphatic amino group into a highly crosslinked or branched structure during polymerization, whereby amino groups are introduced into the polysiloxane compound. It can be distributed uniformly. Moreover, unlike a monomolecular layer formed by reacting an active group on the substrate surface with octyltrichlorosilane, hexamethyldisilazane, aminopropyltrialkoxysilane, or the like, it is not dependent on the state or shape of the substrate surface. As a result, an amorphous layer can be formed over a wide area. For this reason, the interface between the A layer and the B layer is uniform at least in a wide range beyond the region where the channel is formed. Is formed.

  The polysiloxane compound suitably used for the A layer of the present invention has, for example, the structure represented by the following general formula (1), the main chain is a siloxane unit, and the side chain is an organic group such as a hydrogen atom or a carbon atom. It is the substituent which has.

In the formula, R ₁ to R ₄ are any _one of a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an alkenyl group, a substituted or unsubstituted phenyl group, or a siloxane unit. Each of R ₁ to R ₄ may be the same or different. n is an integer of 1 or more. More preferably, n is an integer of 5 or more and 100,000 or less, and a thin and uniform A layer may not be formed even if n is less than 5 or greater than 100,000.

Substituents R ₁ to R ₄ may be siloxane units as shown below.

Wherein R is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an alkenyl group, a substituted or unsubstituted phenyl group or a siloxane unit represented above, each having the same functionality Or a different functional group.)

  Depending on the type of the substituent in the general formula (1), the polysiloxane may have a linear, cyclic, network, ladder, or cage structure, and any of the polysiloxanes used in the present invention may be used. . A net-like structure, a ladder-like structure or a bowl-like structure is preferable.

  In the present invention, particularly preferred as the polysiloxane compound used in the A layer is at least a specific silsesquioxane skeleton as shown in the following general formula (2) and / or as shown in the following general formula (3). It is a polysiloxane compound having a specific organosiloxane skeleton.

(Wherein R ₇ to R ₁₀ are either substituted or unsubstituted alkyl groups having 1 to 8 carbon atoms, alkenyl groups, or substituted or unsubstituted phenyl groups. Each of R ₇ to R ₁₀ is the same. However, m and n are integers greater than or equal to 0, and the sum of m and n is an integer greater than or equal to 1. The form of copolymerization may be random copolymerization or block copolymerization. good.)

(Wherein R ₁₁ to R ₁₄ are any of substituted or unsubstituted alkyl groups having 1 to 8 carbon atoms, alkenyl groups, or substituted or unsubstituted phenyl groups. Each of R ₁₁ to R ₁₄ is (It may be the same or different. P and q are integers of 0 or more, and the sum of p and q is an integer of 1 or more.)

  The silsesquioxane skeleton represented by the general formula (2) and the organosiloxane skeleton represented by the general formula (6) may include either one or both.

Further, the substituents R ₇ to R ₁₀ and R ₁₁ to R ₁₄ having carbon atoms corresponding to the side chains of the silsesquioxane skeleton and the organosiloxane skeleton are substituted or unsubstituted carbon atoms having 1 to 8 carbon atoms. An alkyl group, an alkenyl group or a substituted or unsubstituted phenyl group; These may be the same functional group or different functional groups depending on the location. For example, an unsubstituted alkyl group such as a methyl group or an ethyl group / an unsubstituted phenyl group / a substituted phenyl group such as a dimethylphenyl group or a naphthyl group. Further, the substituents R ₇ to R ₁₀ may contain various atoms such as oxygen atom, nitrogen atom and metal atom in addition to carbon atom and hydrogen atom.

In the general formula (2), m silsesquioxane units (hereinafter referred to as first units) having substituents R ₇ and R ₈ and a silsesquioxane unit having substituents R ₉ and R ₁₀ are repeated. A structural formula is shown in which n (second unit) repeats are connected. Note that m and n are integers of 0 or more, and m + n is an integer of 1 or more. However, this does not mean that the repetition of the first unit and the repetition of the second unit are separated. Both units may be connected separately or may be connected randomly.

In the general formula (3), p diorganosiloxane units having substituents R ₁₁ and R ₁₂ (hereinafter referred to as first units) and diorganosiloxane units having substituents R ₁₃ and R ₁₄ (hereinafter referred to as “first units”) The structural formula is shown in which q units of the second unit are connected. Note that p and q are integers of 0 or more, and p + q is an integer of 1 or more. However, this does not mean that the repetition of the first unit and the repetition of the second unit are separated. Both units may be connected separately or may be connected randomly.

  Further, the polysiloxane compound used in the present invention includes, for example, at least one of the siloxane structures represented by the following general formula (4), general formula (5), and general formula (6), so that it is secondary. Alternatively, a tertiary amino group can be introduced.

(Wherein R ₁₅ , R ₁₆ , R ₁₉ , R ₂₀ , R ₂₂ , R ₂₅ , R ₂₆ , R ₂₈ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, Any one of an alkenyl group, an alkynyl group, a benzyl group, a phenethyl group, and a styryl group, each of R ₁₅ and R ₁₆ , R ₁₉ and R ₂₀ , R ₁₉ and R ₂₂ , and R ₂₅ and R ₂₆ are bonded to each other; One of R ₁₅ and R ₁₆ is other than a hydrogen atom, and R ₁₇ , R ₂₁ , R ₂₃ , R ₂₇ , and R ₂₉ have 1 to 12 carbon atoms that are not directly bonded to the aromatic ring. divalent organic groups _{.R 18, R 24,} R ₃₀ represents a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, an alkenyl group, an alkynyl group, an alkoxyl group, a benzyl group, Fe Butyl group, a styryl group or .r is either siloxane units,, s, t is an integer of 1 or more, u represents an integer of 2 or more.)

  Particularly preferable as the polysiloxane compound used for the A layer is a polysiloxane compound containing at least one of the silsesquioxane structures represented by the following general formula (7), general formula (8), and general formula (9). It is a siloxane compound.

(Wherein R ₃₁ , R ₃₂ , R ₃₄ , R ₃₅ , R ₃₇ , R ₃₉ , R ₄₀ , R ₄₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, One of an alkenyl group, an alkynyl group, a benzyl group, a phenethyl group, and a styryl group, wherein R ₃₁ and R ₃₂ , R ₃₄ and R ₃₅ , R ₃₄ and R ₃₇ , R ₃₉ and R ₄₀ are bonded to each other; One of R ₃₁ and R ₃₂ is other than a hydrogen atom, and R ₃₃ , R ₃₆ , R ₃₈ , R ₄₁ , and R ₄₃ have 1 to 12 carbon atoms that are not directly bonded to the aromatic ring. (It is a divalent organic group. V, w and x are integers of 1 or more, and y is an integer of 2 or more.)

  These polysiloxane compounds can be used alone or in combination. One polysiloxane compound may have a plurality of types of units described above. One or more polysiloxane compounds may be blended with other high molecular compounds or low molecular compounds.

Hereinafter, a method for forming the A layer of the present invention from the above polysiloxane compound will be described.
A preferred example of the A layer in the present invention mainly contains a polysiloxane compound having a silsesquioxane skeleton and / or an organosiloxane skeleton as shown in the general formula (2) or the general formula (3). In order to form such a layer, for example, a polyorganosilsesquioxane compound represented by the following general formula (10) and / or general formula (11) and / or one of the following general formula (12) and There is a method in which a solution containing the polyorganosiloxane compound represented by the general formula (13) or any one is applied onto a substrate and dried by heating. Also, a sol obtained by hydrolyzing a silicon monomer in which the number of repetitions a, b, c and d is only 1 among the compounds represented by the following general formulas (10), (11), (12) and (13) There is a method of coating the substrate on a substrate and drying it by heating.

  In the former method in which the coating film is dried by heating, the polyorganosilsesquioxane compounds represented by the general formulas (10) and (11) are condensed by dehydration or dealcoholization reaction and connected in a ladder form. On the other hand, the polyorganosiloxane compounds represented by the following general formulas (12) and (13) are similarly condensed by dehydration or dealcoholization reaction to increase the molecular weight. However, at this time, the drying temperature is not so high that the organic matter completely disappears, so that the raw material compound does not have a complete silica structure, and most of the substituents remain in the general formulas (2) and (3) A silsesquioxane skeleton or an organosiloxane skeleton as shown in FIG.

  Commercially available polyorganosilsesquioxane compounds represented by general formula (10) and general formula (11) and polyorganosiloxane compounds represented by general formula (12) and general formula (13) can be used. These polyorganosilsesquioxane compounds and polyorganosiloxane compounds can also be synthesized by the reactions shown in the following reaction formula (14) and reaction formula (15), respectively.

  The reaction formulas (14) and (15) will be described. A trifunctional organosilicon monomer and / or a bifunctional organosilicon monomer having an organic group R ′ is hydrolyzed in a solvent such as alcohol to produce a silanol compound. The silicon monomer shown in the above formula is an alkoxide, and R ″ OH is eliminated by hydrolysis, but chloride can also be used as the silicon monomer. However, hydrogen chloride is generated as a desorbing component in this case. The silanol compound obtained by hydrolysis is further dehydrated and condensed by heating or the like to produce a polyorganosilsesquioxane compound and a polyorganosiloxane compound. By removing the solvent and the catalyst, the polyorganosilsesquioxane compound and the polyorganosiloxane compound are isolated as solids. The structure, molecular weight, type of terminal group, and the like of the resulting compound can be changed depending on the catalyst, solvent, pH, concentration, etc. during the reaction.

(In the formula, each of R ₇ and R ₈ is a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a substituted or unsubstituted phenyl group. Each of R ₇ and R ₈ is the same. R ₄₄ to R ₄₇ are each an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and a is an integer of 1 or more.)

(In the formula, R ₉ and R ₁₀ are each a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a substituted or unsubstituted phenyl group. Each of R ₉ and R ₁₀ is the same. R ₄₈ to R ₅₁ are an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and b is an integer of 1 or more.)

(Wherein R ₁₁ and R ₁₂ are each a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a substituted or unsubstituted phenyl group. Each of R ₁₁ and R ₁₂ is the same. R ₅₂ and R ₅₃ are each an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and c is an integer of 1 or more.)

(In the formula, R ₁₃ and R ₁₄ are each a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a substituted or unsubstituted phenyl group. Each of R ₁₃ and R ₁₄ is the same. R ₅₄ and R ₅₅ are each an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and d is an integer of 1 or more.)

  On the other hand, a method of applying a sol obtained by hydrolyzing a silicon monomer on a substrate and drying by heating will be described. The silicon monomer described here is a trifunctional silicon monomer represented by the following general formula (16) (17) (18) (19) and / or a bifunctional silicon monomer represented by the general formula (20) (21) in a solvent. And stir in the presence of water at room temperature or with heating. A sol is prepared through the same hydrolysis and dehydration condensation reactions as in Reaction Formula (14) and Reaction Formula (15). When the obtained sol coating is heated, silanols and unreacted alkoxides are condensed by dehydration or dealcoholization reaction, resulting in a dense silsesquioxane skeleton or organo group as shown in general formulas (2) and (3). A siloxane skeleton is formed.

(Wherein R ₇ to R ₁₀ are either substituted or unsubstituted alkyl groups having 1 to 8 carbon atoms, alkenyl groups, or substituted or unsubstituted phenyl groups. Each of R ₇ to R ₁₀ is the same. And R ₅₆ to R ₅₉ are each independently an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.)

(Wherein R ₁₁ to R ₁₄ are any one of a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an alkenyl group, or a substituted or unsubstituted phenyl group. Each of R ₁₁ to R ₁₄ is the same. And R ₆₀ and R ₆₁ are each independently an alkyl group having 1 to 4 carbon atoms or a hydrogen atom.)

  Exemplary silicon monomers that can be used to prepare the sol include trifunctional silicon monomers and bifunctional silicon monomers. Examples of trifunctional silicon monomers include methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, butyltrimethoxysilane, vinyltrimethoxysilane, 3-aminopropyltriethoxysilane, and phenyltrimethoxysilane. Is mentioned. Examples of the bifunctional silicon monomer include dimethyldimethoxysilane and diphenyldimethoxysilane.

  Moreover, a small amount of fluorine-containing silicon monomers such as trifluoropropyltrimethoxysilane, heptadecafluorodecyltrimethoxysilane, and tridecafluorooctyltrimethoxysilane can be added.

  For the preparation of the sol, it is preferable to add water. The pH of the solution changes depending on the concentration of the amino group contained in the polymer of the present invention and the amount of added water, and the hydrolysis of the monomer is promoted. The amount of water added is 0.1 equivalent or more and 20 equivalents or less with respect to the OR ″ group of the monomer in the reaction formula (14) or the reaction formula (15).

  Further, the polyorganosilsesquioxane compound represented by the general formula (10), the general formula (11) and the polyorganosiloxane compound represented by the general formula (12) and the general formula (13) and the above reaction formula (14) or the reaction formula The silicon monomer in (15) can also be mixed and used. In this case, water can be added as in the preparation of the sol. The amount of water added is preferably 0.1 equivalents or more and 20 equivalents or less with respect to the OR ″ group of the monomer.

Furthermore, tetrafunctional silicon monomers such as tetramethoxysilane and tetraethoxysilane can be used in combination in order to improve the coating property and solvent resistance after heating.
In addition, a method for introducing a secondary or tertiary amino group into the polysiloxane compound forming the A layer of the present invention will be described.

The general formulas (4), (5), and (6) represent structures included in the polysiloxane forming the A layer, and at least one of the general formulas (4), (5), and (6) is included. It is preferable to contain. R ₁₅ , R ₁₆ , R ₁₉ , R ₂₀ , R ₂₂ , R ₂₅ , R ₂₆ , and R ₂₈ may be different substituents, and R ₁₅ and R ₁₆ , R ₁₉ and R ₂₀ , R ₂₅ and R ₂₆ are They may be bonded to each other to form a ring structure. However, either one of R ₁₅ and R ₁₆ is a substituent other than a hydrogen atom. When two or more structures of the general formulas (4), (5), and (6) are included, two or more different types can be included.

  The structures represented by the general formulas (4), (5), and (6) are formed in the polysiloxane that forms the A layer of the present invention using the silane compounds represented by the following general formulas (22), (23), and (24). Can be introduced.

(Wherein R ₁₅ , R ₁₆ , R ₁₉ , R ₂₀ , R ₂₂ , R ₂₅ , R ₂₆ , R ₂₈ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, An alkenyl group, an alkynyl group, a benzyl group, a phenethyl group, and a styryl group, each having a ring structure in which R ₁₅ and R ₁₆ , R ₁₉ and R ₂₀ , R ₁₉ and R ₂₂ , and R ₂₅ and R ₂₆ are bonded to each other. One of R ₁₅ and R ₁₆ is other than a hydrogen atom, and R ₁₇ , R ₂₁ , R ₂₃ , R ₂₇ , and R ₂₉ are divalent having 1 to 12 carbon atoms that are not directly bonded to the aromatic ring. R ₆₂ , R ₆₄ , and R ₆₆ are an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and R ₆₃ , R ₆₅ , and R ₆₇ are each a hydroxyl group, a substituted or unsubstituted carbon atom having 1 to 4 carbon atoms. 5 al Group, indicates an alkenyl group, an alkynyl group, an alkoxyl group, or substituted or unsubstituted phenyl group .r, s, t is an integer of 1 or more, u is an integer of 2 or more.)

  The method of forming the A layer of the present invention from the polysiloxane having the structure represented by the general formulas (4), (5), and (6) includes the polyorganosilsesquioxane compound represented by the general formula (2) This is the same as the method for forming the A layer composed of the polyorganosiloxane compound represented by the general formula (3). Specifically, there are the following two methods. First, at least one of the silane compounds represented by the general formulas (22), (23), and (24) is converted into a polyorganosilsesquioxane compound and / or the general formula (12) represented by the general formula (12). The polyorganosiloxane compound shown in 13) is mixed in a solvent, and the resulting solution is applied onto a substrate and dried by heating. The other is a sol obtained by hydrolyzing a solution in which at least one of the compounds represented by the general formulas (22), (23) and (24) is mixed with other silicon monomers on a substrate. It is a method of applying and drying by heating.

Formula (22) (23) a silane compound represented by (24) is _{R 63, R 65, R 67} is a hydroxyl group or an alkoxyl group trifunctional silane monomers or _{R 63, R 65, R 67} is a hydroxyl group or an alkoxyl It can be roughly classified into bifunctional silane monomers other than the group. As trifunctional silane monomer,

  As bifunctional silane monomer,

Is a preferred example, but is not limited thereto.
A preferable heat treatment temperature when forming the A layer of the present invention from the polysiloxane is 120 ° C. or higher, more preferably 140 ° C. or higher and 230 ° C. or lower. If it is heated below 120 ° C., the hydrolysis reaction may be insufficient.

  The contact angle of pure water on the surface of the layer A of the present invention is preferably in the range of 70 ° to 95 °. More preferably, it is not less than 75 ° and not more than 90 °. If it is less than 70 °, the effect of promoting the crystal growth of the B layer is small, and sufficient transistor characteristics may not be obtained. Further, if it exceeds 95 °, the adhesion between the A layer and the B layer is remarkably lowered, and peeling may occur, or when the B layer is formed by solution coating, it may be repelled and cannot be applied. .

In the process of cross-linking reaction and solvent removal, the stabilizer that does not evaporate, volatilize or burn out in the temperature region is removed from the solution system as much as possible.
Arbitrary things, such as alcohol and ester, can be used for the solvent of a coating solution. In order to promote the reaction, a solvent may be selected in consideration of wettability to the substrate.

  The method for applying the raw material solution for the A layer is not particularly limited. It is applied by a conventional coating method such as spin coating method, casting method, spray coating method, doctor blade method, die coating method, dipping method, printing method, ink jet method, dropping method and the like. Examples of the printing method include screen printing, offset printing, gravure printing, flexographic printing, and micro contact printing. Among these coating methods, a preferable method in that a film can be formed with a desired film thickness by controlling the coating amount is a spin coating method, a dipping method, a spray coating method, or an ink jet method. Further, in order to maintain the insulating properties of the obtained film, it is important that dust and the like are not mixed in the coating solution as much as possible, and it is desirable to filter the raw material solution with a membrane filter in advance.

  It is preferable to adjust the liquid concentration so that the thickness of the A layer is 1 nm to 100 nm, preferably 3 nm to 50 nm. If it is less than 1 nm, it is difficult to obtain a uniform film and the mobility may be lowered. On the other hand, if the thickness exceeds 100 nm, the apparent dielectric film thickness increases, which may require a higher driving voltage.

Before applying the A layer, the surface of the substrate may be modified by ultrasonic treatment with an alkaline solution, UV irradiation or the like in order to improve the wettability of the substrate surface.
Next, the preferable aspect of B layer of this invention is demonstrated. The constituent material of the B layer may be a low molecular compound or a high molecular compound as long as it is a compound showing organic semiconductor characteristics.

From the viewpoint of obtaining a highly crystalline B layer in combination with the crystallization promoting effect of the A layer, the constituent material of the B layer is more preferably a low molecular organic semiconductor having a molecular weight of 2000 or less.
Examples of the low molecular weight compound include acene compounds, thiophene oligomer derivatives, phenylene derivatives, phthalocyanine compounds, porphyrin compounds, and cyanine dyes. Examples of the polymer compound include polyacetylene derivatives, polythiophene derivatives, polyphenylene vinylene derivatives, and the like, but it is particularly preferable to contain an acene compound or a porphyrin compound in order to obtain a high mobility transistor.

  Although an example of an acene type compound is shown below, the compound of the present invention is not limited to these.

  The porphyrin compound is preferably a porphyrin compound represented by the following general formula (25).

In the formula, R ₆₈ to R ₇₅ are each independently at least one selected from a hydrogen atom, a halogen atom, a hydroxyl group, or an alkyl group having 1 to 12 carbon atoms, an oxyalkyl group, a thioalkyl group, and an alkyl ester group. Indicates. R ₆₈ to R ₇₅ may be the same or different. R ₆₈ and R ₆₉ , R ₇₀ and R ₇₁ , R ₇₂ and R ₇₃ , or R ₇₄ and R ₇₅ may be bonded to each other to form an aromatic ring. Examples of the aromatic ring formed include a benzene ring, a naphthalene ring, and an anthracene ring. Any of the formed aromatic rings may have a substituent or may be linked to another porphyrin ring. R ₇₆ may be a hydrogen atom or a group such as an alkyl group, an alkoxyl group, or a halogen atom. X represents a hydrogen atom or a metal atom. As an example of the X, H, Cu, Zn, Ni, Co, Mg, and various metals such as Fe, is AlCl, TiO, FeCl, atomic group such as SiCl ₂ like. X is not particularly limited, but is particularly preferably two hydrogen atoms or a copper atom. Here, when X is two hydrogen atoms, it becomes a metal-free porphyrin compound. Examples thereof include a compound represented by the following general formula (29).

  An example of a porphyrin compound is shown below. Although the structure of an unsubstituted and metal-free body is mainly shown, the substituent, the central metal, and the central atomic group are not limited. Of course, the compound of this invention is not limited to these.

  These acene compounds and porphyrin compounds can be formed on the substrate on which the A layer is formed by a general method such as a vacuum deposition method, a dispersion coating method, or a solution coating method. A solution coating method is preferred.

  In order to form the B layer by the solution coating method, it is preferable to pass through a solvent-soluble precursor. The application method is not particularly limited. It can apply | coat by a conventional coating method, for example, a spin coating method, a cast method, a spray coating method, a doctor blade method, a die coating method, a dipping method, a printing method, an inkjet method, a dripping method etc. Examples of the printing method include screen printing, offset printing, gravure printing, flexographic printing, and micro contact printing. Among these coating methods, a preferable method is a spin coating method, a dipping method, a spray coating method, and an ink jet method in that a film thickness of a desired film thickness can be formed by controlling the coating amount. Generally, after a precursor is dissolved in a solvent, a coating film is formed by solution coating, and an organic semiconductor crystal layer is formed by heating or the like. The precursor is a compound having a bulky substituent, and is preferably converted into an organic semiconductor compound having high planarity with the elimination of the bulky substituent moiety. This method makes it possible to achieve both solution coating and formation of a highly crystalline B layer. Further, from the viewpoint that the elimination reaction is completed and the elimination component is hardly volatilized and remains, it is preferable to use the reverse Diels-Alder reaction from the viewpoint of facilitating use of the coating process.

  Here, the Diels-Alder reaction is an organic chemical reaction in which a double bond called dienophile is added to a conjugated diene to form a cyclic structure. The reverse Diels-Alder reaction is a reverse reaction of the Diels-Alder reaction and is a reaction in which a cyclic structure formed by the Diels-Alder reaction is converted into a conjugated diene and a dienophile.

  In order to perform the reverse Diels-Alder reaction, it is preferable to apply energy by heating, ultraviolet rays, visible light, infrared rays, X-rays, electron beams, laser irradiation, or the like. A plurality of these energy application methods can be combined. That is, these application methods can be used in combination simultaneously or sequentially.

  A bicyclo skeleton is generally used as a substituent for the precursor capable of reverse Diels-Alder reaction. An example of the bicyclo skeleton is shown in the reaction formulas (26) to (28).

(R ₇₇ and R ₇₈ are each independently a hydrogen atom, halogen atom, hydroxyl group, alkyl group, alkoxyl group, etc. R ₇₇ and R ₇₈ may be bonded to each other to form a ring structure.)

In the reactions shown in the reaction formulas (26) and (27), the reverse Diels-Alder reaction is caused mainly by heat, and the reactions shown in the general formula (28) are mainly caused by light irradiation.
Examples of organic semiconductor precursors having a bicyclo skeleton represented by reaction formulas (26) to (28) (hereinafter referred to as “bicyclo forms”) are shown below.

  As a method for producing the B layer when the bicyclo body is used as a precursor, the bicyclo body is dissolved in an organic solvent, and then applied to the substrate on which the A layer is formed, and then heated and / or irradiated with light. Thus, a method of obtaining a crystallized film of an organic semiconductor compound is preferable.

It is sufficient that the A layer and the B layer are in close contact with each other, and another element component such as a partial electrode may exist between the A layer and the B layer.
Before applying the B layer, the surface of the A layer may be modified using a general method as necessary.

  Moreover, it is desirable to filter the precursor solution with a filter such as a membrane filter in advance in order to prevent dust and the like from entering the semiconductor layer as much as possible. This is because insoluble matters and external dust contamination prevent uniform orientation and may cause an increase in OFF current and a decrease in ON / OFF ratio. In addition, it can be pre-dried at a temperature of 130 ° C. or lower when the bicyclo coating is applied.

  The bicyclo skeleton formed by coating causes a reverse Diels-Alder reaction by heating and / or light irradiation. As shown in the reaction formulas (26) to (28), the aromatic ring (benzo) is removed along with the elimination of the elimination component. Convert to Simultaneously with the generation of the aromatic ring, crystal growth is caused by stacking organic semiconductor molecules, and a crystallized film of the organic semiconductor compound is obtained. Further, when the elimination reaction is carried out only by heating, heating at 140 ° C. or higher is necessary in most cases. The heating temperature for obtaining higher field effect mobility is preferably 150 ° C. or higher and 280 ° C. or lower, and more preferably 170 ° C. or higher and 230 ° C. or lower. If it is less than 150 ° C., a crystallized film with sufficient crystal growth may not be obtained. If it exceeds 280 ° C., cracks may occur due to rapid film shrinkage.

  Heating is generally performed on a hot plate in a hot air circulation oven, a vacuum oven, or the like, but the heating method is not limited. In order to obtain uniform alignment, a method of instantaneously heating on a hot plate is preferable. It is also possible to heat with an infrared lamp or the like.

  On the other hand, when the elimination reaction occurs by light irradiation as in the reaction shown in the reaction formula (28), it is preferable to irradiate light having a wavelength of 300 nm to 500 nm. When light of less than 300 nm is irradiated, side reactions other than the desired elimination reaction may occur. When light having a wavelength of 500 nm or more is irradiated, the transistor characteristics may be deteriorated due to side reactions such as oxidation of the generated organic semiconductor.

  For light irradiation, a high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, a xenon lamp, a xenon flash light, a XeCl excimer lamp, or the like can be used as a light source. In order to use only the wavelength necessary for irradiation, to adjust the irradiation intensity, or to cut the heat from the light source, various optical filters and heat cut filters are sandwiched between the light source and the B layer of the present invention. can do.

  Further, crystallization can be promoted by heating at the same time as the light irradiation or after the light irradiation. The heating temperature for obtaining higher field effect mobility is preferably 50 ° C. or higher and 180 ° C. or lower, and particularly preferably in the range of 80 ° C. or higher and 150 ° C. or lower.

  Further, in order to obtain higher crystallinity, a rubbing treatment in which the coating film before heating is lightly rubbed with a cloth or the like can be performed. The cloth used for the rubbing treatment includes, but is not limited to, rayon, cotton, silk and the like.

  The thickness of the B layer obtained by these operations is preferably 10 nm to 200 nm, more preferably 20 nm to 150 nm. The film thickness can be measured with a surface roughness meter or a step gauge.

It is also conceivable to replace the B layer with another general organic semiconductor compound such as phthalocyanine.
The organic film obtained in the present invention is most preferably used for a field effect transistor, but can be applied to other devices.

  FIGS. 1B and 1C are schematic cross-sectional views showing another example of the field-effect transistor of the present invention partially enlarged. A field effect transistor shown in FIGS. 1B and 1C includes a base material 8, a gate electrode 1, a gate insulating layer 2, a layer 3 containing a polymer compound (A layer), a source electrode 4, and a drain electrode 5. And an organic semiconductor layer 6 (B layer).

  The gate electrode, source electrode, and drain electrode are not particularly limited as long as they are conductive materials. Platinum, gold, silver, nickel, chromium, copper, iron, tin, antimony lead, tantalum, indium, aluminum, zinc, magnesium , And alloys thereof, conductive metal oxides such as indium / tin oxide, or inorganic and organic semiconductors whose conductivity has been improved by doping, such as silicon single crystal, polysilicon, amorphous silicon, germanium, graphite, Examples include polyacetylene, polyparaphenylene, polythiophene, polypyrrole, polyaniline, polythienylene vinylene, polyparaphenylene vinylene, and the like. Examples of the method for producing the electrode include a sputtering method, a vapor deposition method, a printing method from a solution and a paste, an ink jet method, and a dipping method. Further, among the electrode materials mentioned above, those having low electric resistance at the contact surface with the semiconductor layer are preferable.

  The insulating layer may be anything as long as the A layer can be applied uniformly, but preferably has a high dielectric constant and low conductivity. Examples include inorganic oxides and nitrides such as silicon oxide, silicon nitride, aluminum oxide, titanium oxide, tantalum oxide, polyacrylate, polymethacrylate, polyethylene terephthalate, polyimide, polyether, polyamide, polyamideimide, polybenzoxazole, Examples thereof include organic insulating materials such as polybenzothiazole, phenol resin, polyvinyl phenol, and epoxy resin. From the viewpoint that a flexible and lightweight substrate can be produced, an organic insulating material is preferable. Moreover, in order to apply | coat A layer uniformly on an insulating layer, it is necessary to form an insulating layer with high surface smoothness. In that case, the surface of the insulating layer can be smoothed without selecting the base of the insulating layer (for example, the gate electrode), and from the viewpoint of not being attacked by the solvent when forming the A layer, heat using a phenol resin, polyvinyl phenol, or epoxy resin A curable resin is preferred.

  Examples of the base material 8 suitably used in the present invention include those obtained by processing silicon, glass, metal, resin or the like into a plate shape, foil shape, film shape or sheet shape. In particular, a resin base material is preferable from the viewpoints of flexibility and processability. The resin base material used is polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyimide (PI), polyetherimide (PEI), polyethersulfone (PES), polysulfone (PSF), polyphenylene sulfide. (PPS), polyetheretherketone (PEEK), polyarylate (PAR), polyamideimide (PAI), polycycloolefin resin, acrylic resin, polystyrene, ABS, polyethylene, polypropylene, polyamide resin, polycarbonate resin, polyphenylene ether resin, A cellulose resin is mentioned. An organic-inorganic composite material base material in which inorganic oxide fine particles are mixed with these resin materials or an inorganic material is bonded may be used. Note that in FIG. 1B, in the case where the gate electrode functions as a base material, a field effect transistor can be formed without using the base material.

  The field effect transistor structure in the present invention may be any of a top contact electrode type, a bottom contact electrode type, and a top gate electrode type. Also, it is not limited to the horizontal type, but also a vertical type (a structure in which one of the source electrode and the drain electrode is on the surface of the organic semiconductor layer on the substrate side and the other is on the surface of the organic semiconductor layer on the side opposite to the substrate) Good.

Synthesis Examples and Examples are shown below, but the present invention is not limited to these Examples.
Synthesis example 1
Step 1-1
A mixture of 3.16 g (39.5 mmol) of 1,3-cyclohexadiene, 10.5 g (34.1 mmol) of trans-1,2-bis (phenylsulfonyl) ethylene and 200 ml of toluene was refluxed for 7 hours. Then, the reaction mixture was obtained by cooling and concentrating under reduced pressure. The crude reaction product was recrystallized (chloroform / hexane) to give 5,6-bis (phenylsulfonyl) -bicyclo [2.2.2] oct-2-ene (13.8 g, 35.6 mmol, yield 90). %).

Step 1-2
The reaction system of the obtained mixture of 5,6-bis (phenylsulfonyl) -bicyclo [2.2.2] oct-2-ene (7.76 g, 20 mmol) and anhydrous tetrahydrofuran (50 ml) was purged with nitrogen. Thereafter, 2.425 ml (22 mmol) of ethyl isocyanoacetate was added and cooled to 0 ° C. Potassium t-butoxide (50 ml / 1 M THF (tetrahydrofuran) solution) was added dropwise over 2 hours, followed by stirring at room temperature for 3 hours. After completion of the reaction, dilute hydrochloric acid was added, and the reaction mixture was washed with a saturated aqueous sodium hydrogen carbonate solution, distilled water and saturated brine in that order, and dried over anhydrous sodium sulfate. Purification by silica gel column chromatography (chloroform) gave ethyl-4,7-dihydro-4,7-ethano-2H-isoindole-1-carboxylate (3.5 g, 16 mmol, 80% yield).

Step 1-3
Under an argon atmosphere, a mixed solution of the obtained ethyl-4,7-dihydro-4,7-ethano-2H-isoindole-1-carboxylate 0.42 g (1.92 mmol) and anhydrous THF 50 ml was cooled to 0 ° C. . Thereafter, 0.228 g (6 mmol) of lithium aluminum hydride powder was added and stirred for 2 hours. Then, THF was removed, extracted with chloroform, washed with a saturated aqueous sodium hydrogen carbonate solution, distilled water and saturated brine in that order, and dried over anhydrous sodium sulfate. This reaction solution was filtered, purged with argon, protected from light, 10 mg of p-toluenesulfonic acid was added, and the mixture was stirred at room temperature for 12 hours. Further, 0.11 g of p-chloranil was added and stirred at room temperature for 12 hours. The extract was washed with a saturated aqueous sodium hydrogen carbonate solution, distilled water, and saturated brine in that order, and dried over anhydrous sodium sulfate. After the solution was concentrated, a metal-free tetrabicyclo compound represented by the following general formula (29) was obtained by alumina column chromatography (chloroform) and recrystallization (chloroform / methanol) (0.060 g, 0.097 mmol, yield 20). %).

Step 1-4
A solution of 0.02 g (0.032 mmol) of the obtained metal-free tetrabicyclo and 0.019 g (0.1 mmol) of copper (II) acetate monohydrate in 30 ml of chloroform and 3 ml of methanol was stirred at room temperature for 3 hours. The reaction solution was washed with distilled water and saturated brine, and then dried over anhydrous sodium sulfate. The solution was concentrated and recrystallized with chloroform / methanol to obtain a tetrabicyclocopper complex represented by the following general formula (30) (0.022 g, yield 100%).

Synthesis example 2
Step 2-1
Pentacene (1.39 g, 5.0 mmol), vinylene carbonate (0.32 g, 5.0 mmol), and xylene (95 ml) were placed in an autoclave and stirred at 180 ° C. for 72 hours. After the reaction, the compound represented by the following general formula (31) was obtained by concentration and drying under reduced pressure (1.78 g, 98%).

Step 2-2
The compound (1 g, 2.7 mmol) obtained in step 2-1 was put in a reaction vessel and dissolved in 1,4-dioxane (30 ml). (4M) NaOH (11.3 ml) was added thereto, and the mixture was refluxed for 1 hour. After completion of the reaction, the reaction product was poured into water and extracted with ethyl acetate. The organic layer was washed with water and saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. As a result, 6,13-Dihydro-15,16-dihydroxy-6,13-ethanolpentene represented by the following general formula (32) was obtained (0.91 g, 100%).

Step 2-3
The reaction vessel was purged with nitrogen, and dimethyl sulfoxide (8.6 ml, 93.5 mmol) and methylene chloride (48 ml) were added. The reaction vessel was cooled to −60 ° C., trifluoroacetic anhydride (11.7 ml, 84.3 mmol) was added, and the mixture was stirred for 10 minutes. After stirring, the reaction was performed by dissolving 6,13-Dihydro-15,16-dihydroxy-6,13-ethanolpentene (0.96 g, 2.7 mmol) obtained in step (2) in dimethyl sulfoxide (4 ml). Slowly dropped into the solution. After the dropwise addition, the mixture was stirred at -60 ° C. for 1.5 hours, and triethylamine (27.5 ml) was added. The mixture was further stirred for 1.5 hours and then returned to room temperature. The reaction solution was poured into 150 ml of 10% hydrochloric acid and extracted with methylene chloride. The organic layer was washed with water and saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The obtained crude product was washed with ethyl acetate to obtain 6,13-Dihydro-6,13-ethanolpentene-15,16-dione represented by the following general formula (33) (0.45 g, 50% ).

Synthesis example 3
Next, 2,6-Dianthryl-9, 10-dihdro-9, 10-ethanolanthracene-11, 12-dione will be described as an example.

Step 3-1
2,6-Dibromoanthracene (2.41 mmol, 0.67 g), vinylene carbonate (3.80 mmol, 0.21 ml) and anhydrous xylene (10 ml) were placed in an autoclave and reacted at 180 ° C. for 3 days. Then, it returned to room temperature and concentrated under pressure reduction. The obtained crude product was purified by silica gel column chromatography. Thereby, 2,6-dibromo-9,10-dihydro-9,10-ethanolanthracene-cis-11,12-diyl carbonate represented by the following general formula (34) was obtained (0.73 g, 72%).

Step 3-2
2,6-dibromo-9,10-dihydro-9,10-ethanolanthracene-cis-11,12-diyl carbonate (0.58 mmol, 0.24 g) obtained in step 3-1, literature (K. Ito, Boric obtained by the method described in T. Suzuki, Y. Sakamoto, D. Kubota, Y. Inoue, F. Sato, S. Tokyo, Angew. Chem. Int. Ed. ester (1.33mmol, 0.40g), tetrakis (triphenylphosphine) palladium (0) (0.066mmol, 0.077g), off the toluene _{(202ml), 1N Na 2 CO} 3 (8.5ml) Put in a score, it was purged with nitrogen, and the mixture was refluxed for 18 hours. Then, after returning to room temperature, cerite filtration was carried out, and the residue was washed with toluene. Thereafter, the filtrate was concentrated under reduced pressure, and the resulting crude product was produced by silica gel chromatography. As a result, 2,6- (2′-Anthryl) -9,10-dihydro-9,10-ethanolanthracene-cis-11,12-diyl carbonate represented by the following general formula (35) was obtained (0. 089 g, 25%).

Step 3-3
2,6- (2′-Anthryl) -9,10-dihydro-9,10-ethanolanthracene-cis-11,12-diyl carbonate (0.11 mmol, 0.067 g) obtained in Step 3-2 was converted to 4N. The mixture was placed in a mixed solution of NaOH (2 ml) and 1,4-dioxane (4 ml) and purged with nitrogen. Thereafter, the mixture was refluxed for 1 hour and returned to room temperature. Water was added thereto and extracted with chloroform. The organic layer was washed with water and saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to obtain a diol. The obtained diol was subjected to Swern oxidation in the same manner as in Synthesis Example 1 (Step 1-3). Thereby, 2,6-Dianthryl-9,10-dihydro-9,10-ethanolanthracene-11,12-dione represented by the following general formula (36) was obtained (0.046 g, 69%).

Preparation of polymer solutions a to e 0.7 g of commercially available flaky methylsilsesquioxane (MSQ) (trade name GR650, manufactured by Showa Denko) was dissolved in a mixed solvent consisting of 49.5 g of ethanol and 49.5 g of 1-butanol. I let you. To this solution were added 0.25 g of methyltrimethoxysilane, 0.05 g of alkoxysilane having an amino group, and 0.05 g of distilled water, and the mixture was stirred at room temperature for 48 hours. Polymer solutions a to e were prepared by passing the obtained solution through a PTFE membrane filter having a pore size of 0.2 μm. Table 1 shows the types of alkoxysilanes having amino groups.

Preparation of Polymer Solution f 0.7 g of commercially available flaky methylsilsesquioxane (MSQ) (trade name GR650, manufactured by Showa Denko) was dissolved in a mixed solvent composed of 49.5 g of ethanol and 49.5 g of 1-butanol. . To this solution, 0.3 g of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane and 0.3 g of distilled water were added and stirred at room temperature for 48 hours. A polymer solution f was prepared by passing the obtained solution through a PTFE membrane filter having a pore size of 0.2 μm.

Preparation of polymer solution g 0.7 g of commercially available flaky methylsilsesquioxane (MSQ) (trade name GR650, manufactured by Showa Denko) was dissolved in a mixed solvent composed of 49.5 g of ethanol and 49.5 g of 1-butanol. . To this solution, 0.25 g of methyltrimethoxysilane, 0.05 g of 3-aminopropyltriethoxysilane, and 0.05 g of distilled water were added and stirred at room temperature for 48 hours. The obtained solution was passed through a PTFE membrane filter having a pore diameter of 0.2 μm to prepare a polymer solution g.

Preparation of polymer solution h Oily polydimethylsiloxane (made by Toray Dow Corning Silicone, trade name Dow Corning 200) was completely dissolved in 99 g of toluene, and the resulting solution was passed through a PTFE membrane filter having a pore size of 0.2 μm. Polymer solution h was prepared.

Preparation of silica sol i Distilled with a mixed solvent consisting of 49.5 g of ethanol and 49.5 g of 1-butanol, 0.95 g of methyltrimethoxysilane, 0.05 g of N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, 0.05 g of water was added. Thereafter, the mixture was stirred at room temperature for 48 hours to prepare silica sol i.

Preparation of Silane Solution j 1 g of 3-aminopropyltriethoxysilane was added to 99 g of ethanol to obtain a uniform solution. A silane solution j was prepared by passing the obtained solution through a PTFE membrane filter having a pore diameter of 0.2 μm.

Examples 1 to 11
(Create resin substrate)
A silver nanoparticle paste (manufactured by Nippon Paint Co., Ltd., Finesphere SVE102) was coated on a PET substrate in which a 3 μm thick phenol resin planarizing layer was provided on the surface of a 188 μm thick PET substrate. Then, the gate electrode with a film thickness of 130 nm was formed by heating in a hot air circulating oven for 180 ° C./30 minutes. Furthermore, poly (p-vinylphenol) (weight average molecular weight 12,000) / melamine cross-linking agent (manufactured by Sanwa Chemical Co., Ltd., trade name Nicalak MX-750LM) / 1-butanol / ethanol = 7/3 / A 63/27 (weight ratio) thermosetting resin composition was coated. Then, the insulating layer 2 with a film thickness of 500 nm was formed by heating in a hot air circulating oven at 180 ° C./60 minutes. After coating the entire surface with a fluororesin and setting the pure water contact angle on the surface to 115 ° or more, the source-drain electrode pattern was irradiated with ultraviolet rays, and the pure water contact angle of the irradiated area was lowered to 50 ° or less. Thereafter, the above-mentioned silver particle paste (Nippon Paint Co., Ltd., Finesphere SVE102) is supplied to the source-drain electrode pattern, and the source-drain silver electrode is formed by heating in a hot air circulating oven at 180 ° C./30 minutes. Formed. Further, the entire surface was irradiated with ultraviolet rays to remove the fluorine coat, thereby preparing an evaluation resin substrate 1 on which a source-drain silver electrode having a channel length L = 50 μm and a channel width W = 3 mm was formed.

(Formation of layer [B layer] containing a polymer compound)
The polymer solution a to f or silica sol i was applied to the surface of the evaluation resin substrate by a spin coating method (rotation speed: 5000 rpm). Next, the coating film thus obtained was heated and cured in a hot air circulating oven at 180 ° C./30 minutes. The film thickness was about 10 nm as measured with a stylus profilometer. The contact angle of water on the substrate surface was measured with a fully automatic dynamic contact angle meter (trade name DCA-WZ, manufactured by Kyowa Interface Science). Further, when the silanol and unreacted alkoxide in the polymer solution are condensed by dehydration or dealcoholization reaction to become a polymer having a silsesquioxane skeleton or an organosiloxane skeleton, it has solvent resistance. Therefore, whether or not the polymer was sufficiently cured and became a compound having a siloxane skeleton or a compound having a silsesquioxane skeleton was judged by solvent resistance to chloroform. Table 2 shows the pure water contact angle on the substrate surface and the solvent resistance evaluation results. Here, the solvent resistance was evaluated by visually observing the surface of the B layer after dropping chloroform.

(Formation of organic semiconductor layer [A layer])
Formation of Organic Semiconductor Layer A-1 A coating film was formed on this substrate by spin coating from a 1 wt% chloroform solution of a metal-free tetrabicyclo compound (general formula (29)) synthesized in Synthesis Example 1 (rotation speed: 1000 rpm) ). After removing unnecessary films other than those on the channel with a nonwoven fabric soaked with chloroform, the substrate is heated at 200 ° C./5 minutes to form an organic semiconductor layer A-1 made of a benzo compound represented by the following general formula (37) did. The film thickness of the organic semiconductor layer A-1 was about 80 nm.

Formation of Organic Semiconductor Layer A-2 A coating film was formed on this substrate by spin coating from a 1 wt% chloroform solution of the tetrabicyclocopper complex (general formula (30)) synthesized in Synthesis Example 1 (rotation speed: 1000 rpm). . After removing unnecessary films other than on the channel with a nonwoven fabric soaked with chloroform, the substrate is heated at 200 ° C./15 minutes to form an organic semiconductor layer A-2 composed of a benzo compound represented by the following general formula (38) did. The film thickness of the organic semiconductor layer A-2 was about 80 nm.

Formation of organic semiconductor layer A-3 Spin coating method from 1.5 wt% chloroform solution of 6,13-Dihydro-6,13-ethanolpentene-15,16-dione (general formula (33)) synthesized in Synthesis Example 2 Was used to form a coating film (rotation speed: 1000 rpm). Unnecessary films other than on the channel were removed with a nonwoven fabric soaked with chloroform. Thereafter, the substrate was further placed on a hot plate set at 130 ° C., and irradiated with light from a metal halide lamp (PCS-UMX250) manufactured by Nippon P.I. Co., Ltd. whose wavelength was cut with a heat absorption filter and a blue filter for 5 minutes. Thereby, an organic semiconductor layer A-3 made of pentacene was formed. The film thickness of the organic semiconductor layer A-3 was about 100 nm.

Formation of Organic Semiconductor Layer A-4 1.5% by weight of 2,6-Dianthryl-9, 10-dihydro-9, 10-ethanolanthracene-11, 12-dione (general formula (36)) synthesized in Synthesis Example 3 A coating film was formed from the chloroform solution by spin coating (rotation speed: 1000 rpm). Unnecessary films other than on the channel were removed with a nonwoven fabric soaked with chloroform. Thereafter, the substrate was placed on a hot plate set at 130 ° C., and irradiated with light from a metal halide lamp (PCS-UMX250) manufactured by Nippon P-I Co., Ltd. whose wavelength was cut by a heat absorption filter and a blue filter for 5 minutes. Thereby, an organic semiconductor layer A-4 made of a compound represented by the following general formula (39) was formed. The film thickness of the organic semiconductor layer A-4 was about 100 nm.

(Evaluation of transistor characteristics)
_V d _-I d of the transistor that was _created, the V g -I _d curve was measured using a parameter analyzer 4156C of Agilent Technologies Inc. (Ltd.) (trade name).

The mobility μ (cm ² / Vs) was calculated according to the following formula (1).

Here, Ci is the capacitance per unit area of the gate insulating film (F / cm ² ), and W and L are the channel width (mm) and channel length (μm) shown in the examples, respectively. I _d , V _g , and V _th are a drain current (A), a gate voltage (V), and a threshold voltage (V), respectively. Further, the ratio of V _g = −40 V and I _d of 0 V when V _d = −40 V was defined as the ON / OFF ratio. The results are shown in Table 2.

Comparative Examples 1 and 2
The polymer solution g was applied to the surface of the evaluation resin substrate by spin coating (rotation speed: 5000 rpm). Next, this coating film was heat-cured in a hot air circulating oven at 180 ° C./30 minutes. The film thickness was about 10 nm as measured with a stylus profilometer. The contact angle of water on the substrate surface and the solvent resistance against chloroform were evaluated in the same manner as in the examples.

  Further, an organic semiconductor layer was formed by the same method as the organic semiconductor layer B or the organic semiconductor layer C, and transistor characteristics were evaluated by the method described above. The results are shown in Table 2.

Comparative Example 3
The polymer solution h was applied to the surface of the evaluation resin substrate by a spin coating method (rotation speed: 5000 rpm). Next, this coating film was heat-cured in a hot air circulating oven at 180 ° C./30 minutes. When the surface of the coating film was observed with an optical microscope, it was observed that the polymer was non-uniformly dispersed and clouded. When the solvent resistance to chloroform was confirmed, the organic semiconductor layer could not be formed because it was dissolved at room temperature.

Comparative Examples 4 to 5
The silane compound was applied by a dip coating method in which the glass substrate 1 for evaluation or the resin substrate 2 for evaluation was immersed in the silane solution j and then slowly pulled up. Next, this coating film was baked in a hot air circulating oven at 180 ° C./30 minutes. The film thickness was measured with a stylus profilometer, but could not be measured accurately at 5 nm or less. The contact angle of water on the substrate surface and the solvent resistance against chloroform were evaluated in the same manner as in the examples.

  Further, an organic semiconductor layer was formed by the same method as the organic semiconductor layer B or the organic semiconductor layer C, and transistor characteristics were evaluated by the method described above. The results are shown in Table 2.

  Since the semiconductor element of the present invention is excellent in crystallinity and orientation, it can be used for various organic semiconductor devices. In addition, since the field effect transistor of the present invention has high field effect mobility, it can be used for plastic IC cards, information tags, displays, and the like.

It is typical sectional drawing which shows the example of the field effect transistor which is a suitable form of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Gate electrode 2 Gate insulating layer 3 Layer containing a high molecular compound 4 Source electrode 5 Drain electrode 6 Organic-semiconductor layer 7 Sealing layer 8 Base material

Claims (10)

  In a semiconductor device having an organic semiconductor layer, the substrate includes at least a layer containing one or more polymer compounds and an organic semiconductor layer in contact with the layer containing one or more polymer compounds, At least one of the molecular compounds is a polymer compound having one or more secondary or tertiary aliphatic amino groups, and the amino group of the polymer compound having an aliphatic amino group has a side chain and / or a branch. A semiconductor element, wherein the layer which is present on a chain and contains the polymer compound contains a polysiloxane compound. 2. The semiconductor element according to claim 1, wherein at least one of the polysiloxane compounds includes a structure represented by the following general formula (1).

Wherein R ₁ to R ₄ are any of substituted or unsubstituted alkyl groups having 1 to 8 carbon atoms, alkenyl groups, substituted or unsubstituted phenyl groups, or siloxane units. R ₁ to R ₄ Each may be the same or different, and n represents an integer of 1 or more.) 3. The semiconductor element according to claim 1, wherein at least one of the polysiloxane compounds includes a structure represented by the following general formula (2) or the following general formula (3).

(Wherein R ₇ to R ₁₀ are any of a substituted or unsubstituted alkyl group having 1 to 8 carbon atoms, an alkenyl group, and a substituted or unsubstituted phenyl group. Each of R ₇ to R ₁₀ is the same. Or m and n are integers of 0 or more, and the sum of m and n is an integer of 1 or more.)

(Wherein R ₁₁ to R ₁₄ are any of substituted or unsubstituted alkyl groups having 1 to 8 carbon atoms, alkenyl groups, or substituted or unsubstituted phenyl groups. Each of R ₁₁ to R ₁₄ is (It may be the same or different. P and q are integers of 0 or more, and the sum of p and q is an integer of 1 or more.) At least one of the polysiloxane compounds is a compound containing one or more of siloxane structures represented by the following general formula (4), general formula (5), and general formula (6). Item 4. The semiconductor element according to any one of Items 1 to 3.

(Wherein R ₁₅ , R ₁₆ , R ₁₉ , R ₂₀ , R ₂₂ , R ₂₅ , R ₂₆ , R ₂₈ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, Any one of an alkenyl group, an alkynyl group, a benzyl group, a phenethyl group, and a styryl group, each of R ₁₅ and R ₁₆ , R ₁₉ and R ₂₀ , R ₁₉ and R ₂₂ , and R ₂₅ and R ₂₆ bonded to each other; One of R ₁₅ and R ₁₆ is other than a hydrogen atom, and R ₁₇ , R ₂₁ , R ₂₃ , R ₂₇ , and R ₂₉ have 1 to 12 carbon atoms that are not directly bonded to the aromatic ring. divalent organic groups _{.R 18, R 24,} R ₃₀ represents a hydroxyl group, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, an alkenyl group, an alkynyl group, an alkoxyl group, a benzyl group, Fe Butyl group, a styryl group or .r is either siloxane units,, s, t is an integer of 1 or more, u represents an integer of 2 or more.) At least one of the siloxane compounds is a compound containing one or more silsesquioxane structures represented by the following general formula (7), general formula (8), and general formula (9). The semiconductor element according to claim 1.

(Wherein R ₃₁ , R ₃₂ , R ₃₄ , R ₃₅ , R ₃₇ , R ₃₉ , R ₄₀ , R ₄₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, One of an alkenyl group, an alkynyl group, a benzyl group, a phenethyl group, and a styryl group, wherein R ₃₁ and R ₃₂ , R ₃₄ and R ₃₅ , R ₃₄ and R ₃₇ , R ₃₉ and R ₄₀ are bonded to each other; One of R ₃₁ and R ₃₂ is other than a hydrogen atom, and R ₃₃ , R ₃₆ , R ₃₈ , R ₄₁ , and R ₄₃ have 1 to 12 carbon atoms that are not directly bonded to the aromatic ring. (It is a divalent organic group. V, w and x are integers of 1 or more, and y is an integer of 2 or more.)   The semiconductor element according to claim 1, wherein the organic semiconductor layer is made of a low molecular organic semiconductor.   The semiconductor element according to claim 1, wherein the organic semiconductor layer is made of an acene-based compound or a porphyrin compound.   8. The surface according to claim 1, wherein the surface of the layer containing the one or more polymer compounds that faces the surface in contact with the organic semiconductor layer is in contact with the organic resin layer. Semiconductor element.   9. The semiconductor element according to claim 1, wherein the layer containing one or more polymer compounds is a crystallization promoting layer.   The semiconductor element according to claim 9, wherein the crystallization promoting layer has a function of promoting bonding between crystal grains.

Images