JP2012097079A - Method of producing phthalocyanine nano size structure aggregate, and electronic device using the phthalocyanine nano size structure aggregate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of producing a wire or rod shape crystal of phthalocyanines which is a typical organic semiconductor, especially a phthalocyanine nano size structure (nanowire or nano rod) aggregate in which a phthalocyanine nano size structure (nanowire or nano rod) having a structure of the shape of a filament with a nano size of 100 nm or less of a minor axis is arranged in a fixed direction, and further, to provide an electronic device in which characteristics have been improved by using the phthalocyanine nano size structure (nanowire or nano rod) aggregate.SOLUTION: The method of producing a phthalocyanine nano size structure (nanowire or nano rod) aggregate comprises as follows. After dissolving non-substituted phthalocyanine and phthalocyanine which has a substituent in an acid, a complex which has been obtained by being deposited in a poor solvent, is made a fine particle, then is applied on a substrate, the exposure of an organic solvent steam is performed on the substrate.

Description

The present invention relates to a method for producing a phthalocyanine nanosize structure aggregate, and an electronic device using the phthalocyanine nanosize structure aggregate.

In recent years, there has been a demand for a “lightly inexpensive information terminal that is hard to break” that anyone can use in any location. For this realization, it is desired to use a soft material having a cost merit in a transistor which is a key device (most important element) of an information terminal. However, conventionally used inorganic materials such as silicon cannot sufficiently satisfy these demands.

  Under such circumstances, an “organic transistor (OFET)” using an organic substance in the semiconductor portion (semiconductor layer) of the transistor attracts attention (see Non-Patent Document 1). A semiconductor made of such an organic substance (organic semiconductor) is soft and can be processed at a low temperature, and generally has a high affinity with a solvent. For this reason, there is an advantage that a semiconductor layer can be manufactured (film formation) on a flexible plastic substrate using a wet process such as coating or printing at a low price, and it is possible to realize a “lightly and inexpensive information terminal that is hard to break”. Is expected as an indispensable material for next-generation electronic devices.

Phthalocyanines are one of typical organic semiconductors, and are known to exhibit good transistor characteristics by controlling higher-order structures, that is, molecular arrangement and assembly state (see Non-Patent Document 2). . However, since phthalocyanines have low solvent solubility, it is difficult to produce a device by a wet process, and when used for an electronic device, a dry process such as vacuum deposition or sputtering is generally used. Since such a dry process is a complicated and expensive process, it is difficult to provide a low-cost electronic device that is one of the characteristics of an organic semiconductor.

In order to solve this problem, a technique is also disclosed in which a transistor is manufactured by a wet process by introducing a soluble substituent into phthalocyanines to enhance solvent solubility (see Patent Document 1). However, in this method, each molecule of the phthalocyanines is not sufficiently arranged and the higher order structure cannot be controlled, so that the transistor characteristics are inferior as compared with the dry process. In order to show good semiconductor properties, it is important that each molecule has a dimensional crystal structure arranged in a certain direction, and among them, a one-dimensional wire or rod crystal ( A crystalline structure having a long system (major axis) and a minor axis (minor axis) is useful. Further, in order to more suitably develop into an electronic device, the wire or rod-like crystal is a nano-sized structure having a minor axis of μm or less, preferably 100 nm or less (hereinafter referred to as a nano-sized structure of the wire or rod-like crystal). It is preferable that the object is simply expressed as nanowire or nanorod.

Crystals of phthalocyanines are widely used as colorants for paints of printing inks, and many techniques for controlling the crystal size and shape are also known. For example, a solvent salt milling method (for example, Patent Document 2) in which an inorganic salt and an organic solvent are mixed with metal phthalocyanine and the pigment is finely pulverized by a grinding apparatus, or a large amount of the metal phthalocyanine is dissolved in sulfuric acid. A crystallization method in which precipitation is performed in water (for example, Patent Document 3). However, it has not been possible to obtain the above-described nanosize structure made of phthalocyanines using these methods.

On the other hand, as a method for controlling the higher-order structure of phthalocyanines, the present inventors have already disclosed a method for producing phthalocyanine nanowires (Patent Document 4).
However, in applying the nano-sized structures such as phthalocyanine nanowires to various electronic devices, it is advantageous that the formed nano-sized structures have a structure oriented and arranged in a certain direction. There is no known technique for growing nano-sized structures such as phthalocyanine nanowire crystals.

Advanced Materials 2002, No. 14, P.I. 99 Applied Physics Letters 2005, 86, p. 22103 Japanese Laid-Open Patent Publication No. 2008-303383 JP 2002-121420 PR JP 2004-091560 A WO 2010/122921

In view of the above, in the present invention, a phthalocyanine nanosize structure (nanowire or nanorod) having a wire-like or rod-like crystal of phthalocyanine, which is a typical organic semiconductor, in particular, a nano-sized fine wire having a short axis of 100 nm or less is provided. An object of the present invention is to provide a method for producing an aggregate of phthalocyanine nanosize structures (nanowires or nanorods) arranged in a certain direction. It is another object of the present invention to provide an electronic device having improved characteristics by using the phthalocyanine nanosize structure (nanowire or nanorod) aggregate.

As a result of diligent studies to solve the above problems, the present inventors dissolved an unsubstituted phthalocyanine and a substituted phthalocyanine in an acid, and then precipitated the composite obtained in a poor solvent. A phthalocyanine nanosize structure having a nano-sized fine wire structure with a minor axis of 100 nm or less by applying the organic solvent vapor on the substrate after being finely divided, The inventors have found that a phthalocyanine nanosize structure aggregate in which phthalocyanine nanosize structures are grown in a certain direction is obtained, and have completed the present invention.
In addition, the complex obtained by dissolving unsubstituted phthalocyanine and phthalocyanine having a substituent in an acid and then precipitating it in a poor solvent is made into fine particles, and then applied onto the substrate, and in a certain direction on the substrate. The organic solvent vapor is exposed after stress is applied, or the organic solvent vapor is flowed in a certain direction on the substrate to perform exposure, whereby a phthalocyanine nano having a nano-sized fine wire structure with a minor axis of 100 nm or less The present inventors have found that a phthalocyanine nanosize structure aggregate having a size structure, in which the phthalocyanine nanosize structure has grown in a certain direction, has been completed.

  According to the present invention, a nano-sized wire or rod-like crystal having excellent semiconductor properties, in particular, a phthalocyanine nano-sized structure having a nano-sized fine wire structure with a minor axis of 100 nm or less, and the nano-sized It is possible to provide a method for easily producing a phthalocyanine nanosize structure aggregate in which structures are arranged in a certain direction. In addition, since the phthalocyanine nanosize structure aggregate obtained by the manufacturing method has a structure in which phthalocyanine nanosize structures are arranged in a certain direction, it can be suitably used as a template for forming various electronic devices and nanostructures. Is possible.

It is a schematic diagram which shows the flow cell used in Example 1, and the method of solvent vapor exposure. FIG. 6 is a schematic diagram showing a method for applying stress to the micronized composite film performed in Example 5. 6 is an SEM observation image showing the structure of a phthalocyanine nanosize structure aggregate film obtained in Example 5. FIG. 6 is an SEM observation image showing the structure of a phthalocyanine nanosize structure aggregate film obtained in Example 5. FIG. 2 is an SEM observation image showing the structure of a phthalocyanine nanowire assembly film obtained in Comparative Example 1.

Hereinafter, the present invention will be described in detail.
That is, the present invention includes the following items.

1. (1) Step (a) in which an unsubstituted phthalocyanine and a substituted phthalocyanine are dissolved in an acid, and then precipitated in a poor solvent to obtain a composite (A1)
(2) Step (b) of obtaining a fine particle composite (A2) by making the composite (A1) into fine particles
(3) Step (c) of applying the micronized composite (A2) onto a substrate (substrate) to obtain a micronized composite film (B)
(4) Step (d) of growing the nano-sized structure by exposing the micronized composite film (B) to organic solvent vapor on the base material (substrate).
A process for producing a nano-sized structure aggregate comprising an unsubstituted phthalocyanine and a substituted phthalocyanine, and having a major axis and a minor axis, the minor axis being 100 nm or less .
2. In the step (d), the micronized composite film (B) is exposed to an organic solvent vapor after applying stress in a certain direction on the base material (substrate), or on the base material (substrate). Exposure is performed by flowing organic solvent vapor in a certain direction. The manufacturing method of the nanosize structure aggregate | assembly as described in.
3. 1. An unsubstituted phthalocyanine is represented by the general formula (1) or (2) Or 2. The manufacturing method of the nanosize structure aggregate | assembly as described in.

(Wherein, X is selected from the group consisting of copper atom, zinc atom, cobalt atom, nickel atom, tin atom, lead atom, magnesium atom, silicon atom, iron atom, palladium atom, TiO, VO, and AlCl. Any one.)
4). The phthalocyanine having a substituent is represented by the general formula (3) or (4). ~ 3. The manufacturing method of the nanosize structure aggregate | assembly in any one of.

Ｙ_１からＹ_４は、フタロシアニン骨格とＺ_１〜Ｚ_４を結合させる結合基を表し、Ｙ_１からＹ_４が結合基として存在しない場合には、Ｚ_１〜Ｚ_４は、−Ｎ_３、−ＣＮ、−ＮＣ、−ＮＯ_２、−ＮＲ_２（Ｒは水素、又は置換基を有してもよいアルキル基を表す）、−ＮＲ_３ ^＋（Ｒは水素、又は置換基を有してもよいアルキル基を表す）、−ＯＨ、−Ｏ⁻、−ＳＨ、−Ｓ⁻、−ＳＯ_２Ｈ、−ＳＯ_２ ⁻、−ＳＯ_３Ｈ、−ＳＯ_３ ⁻、−ＣＨＯ、−ＣＯＯＨ、−ＣＯＯ⁻、−Ｂ（ＯＲ）_３（Ｒは水素、又は置換基を有してもよいアルキル基を表す）、−ＳｉＲ_３（Ｒは水素、又は置換基を有してもよいアルキル基を表す）、−Ｓｉ（ＯＲ）_３（Ｒは水素、又は置換基を有してもよいアルキル基を表す）、−Ｐ（＝Ｏ）（ＯＲ）_２（Ｒは水素、又は置換基を有してもよいアルキル基を表す）、−Ｐ（＝Ｏ）（ＯＨ）_２、置換基を有してもよい（オリゴ）アリール基、置換基を有してもよい（オリゴ）ヘテロアリール基、置換基を有してもよい（ポリ）エーテル鎖、置換基を有してもよい（ポリ）アルキレンイミン鎖、置換基を有してもよいフラーレン類、又は置換基を有してもよいフタルイミドであり、
Ｙ_１からＹ_４が、−Ｏ−、−Ｓ−、−Ｃ（＝Ｏ）−、−Ｃ（＝Ｏ）Ｏ−、−ＯＣ（＝Ｏ）−、−ＯＣ（＝Ｏ）Ｏ−、−Ｃ（＝Ｏ）ＮＨ−、−ＮＨＣ（＝Ｏ）−、−ＮＨＣ（＝Ｏ）ＮＨ−、−ＯＣ（＝Ｏ）ＮＨ−、−ＮＨＣ（＝Ｏ）Ｏ−、−Ｓ（＝Ｏ）−、−Ｓ（＝Ｏ）_２−、−ＳＯ_２ＮＨ−、−ＮＨＳＯ_２−、−ＮＨＳＯ_２ＮＨ−、−ＳＯ_３−、−ＯＳ（＝Ｏ）_２−、−Ｎ＝Ｎ−、−Ｃ（＝Ｏ）ＯＣ（＝Ｏ）−、−Ｃ（＝Ｏ）ＮＨＣ（＝Ｏ）−、−（ＣＲ_２）_ｎ−（ｎは１〜１０の整数を、Ｒは水素、又は置換基を有してもよいアルキル基を表す）、−ＣＨ＝ＣＨ−、−Ｃ≡Ｃ−で表される結合基である場合には、Ｚ_１〜Ｚ_４は、置換基を有してもよいアルキル基、置換基を有してもよい（オリゴ）アリール基、置換基を有してもよい（オリゴ）へテロアリール基、置換基を有してもよい(ポリ)エーテル鎖、置換基を有してもよい（ポリ）アルキレンイミン鎖、置換基を有してもよいフラーレン類、置換基を有してもよいフタルイミド、又は−ＳｉＲ_３（Ｒは水素、又は置換基を有してもよいアルキル基を表す）であり、ａ、ｂ、ｃ及びｄは各々独立に０〜４の整数を表すが、そのうち少なくとも一つは０ではない。
Ｘは、銅原子、亜鉛原子、コバルト原子、ニッケル原子、錫原子、鉛原子、マグネシウム原子、珪素原子、鉄原子、パラジウム原子、チタニル（ＴｉＯ）、バナジル（ＶＯ）、塩化アルミニウム（ＡｌＣｌ）からなる群から選ばれる何れかである。）
５．置換基を有してもよいアルキル基が、メチル基、エチル基又はプロピル基であり、置換基を有してもよい（オリゴ）アリール基が、置換基を有してもよい（オリゴ）フェニレン基又は置換基を有してもよい（オリゴ）ナフチレン基であり、置換基を有してもよい（オリゴ）へテロアリール基が、置換基を有してもよい（オリゴ）ピロール基、置換基を有してもよい（オリゴ）チオフェン基、置換基を有してもよい（オリゴ）ベンゾピロール基又は置換基を有してもよい（オリゴ）ベンゾチオフェン基である４．に記載のナノサイズ構造物集合体の製造方法。
６．前記工程（ａ）における酸が、硫酸、クロロ硫酸、メタンスルホン酸又はトリフルオロ酢酸である１．〜５．の何れかに記載のナノサイズ構造物集合体の製造方法。
７．前記工程（ｄ）における有機溶媒がアミド系有機溶媒、ハロゲン系有機溶媒、又は芳香族系有機溶媒である１．〜６．の何れかに記載のナノサイズ構造物集合体の製造方法。
８．前記アミド系有機溶媒がＮ−メチルピロリドン、ジメチルホルムアミド、ジエチルホルムアミド又はＮ，Ｎ−ジメチルアセトアミドである７．に記載のナノサイズ構造物集合体の製造方法。
９．前記ハロゲン系有機溶剤が、クロロホルム、塩化メチレン又はジクロロエタンである７．に記載のナノサイズ構造物集合体の製造方法。
１０．前記芳香族系有機溶媒が、トルエン、キシレン、エチルベンゼン、クロロベンゼン又はジクロロベンゼンである７．に記載のナノサイズ構造物集合体の製造方法。
１１．１．〜１０．の何れかに記載のナノサイズ構造物集合体の製造方法により得られるナノサイズ構造物集合体を含有する電子デバイス。

Y ₁ to Y ₄ each represent a linking group that binds the phthalocyanine skeleton and Z _{1 to} Z _{4. When} Y ₁ to Y ₄ do not exist as a linking group, Z _{1 to} Z ₄ represent —N ₃ , — CN, —NC, —NO ₂ , —NR ₂ (R represents hydrogen or an alkyl group which may have a substituent), —NR ₃ ⁺ (R may have hydrogen or a substituent) represents an alkyl ^{_{group), - OH, -O -,}} -SH, -S -, -SO 2 H, -SO 2 -, -SO 3 H, -SO 3 -, -CHO, -COOH, -COO -, -B _(oR) 3 (R represents hydrogen or an alkyl group which may have a substituent), - _SiR 3 (R represents hydrogen or an alkyl group which may have a substituent), - Si _(oR) 3 (R represents hydrogen or an alkyl group which may have a substituent), - P (= O) (oR) (R represents hydrogen or an alkyl group which may have a substituent), - P (= O) (OH) 2, an optionally substituted (oligo) aryl group, substituted (Oligo) heteroaryl group which may have, (poly) ether chain which may have a substituent, (poly) alkyleneimine chain which may have a substituent, fullerenes which may have a substituent, Or a phthalimide which may have a substituent,
Y ₁ to Y ₄ are —O—, —S—, —C (═O) —, —C (═O) O—, —OC (═O) —, —OC (═O) O—, — C (═O) NH—, —NHC (═O) —, —NHC (═O) NH—, —OC (═O) NH—, —NHC (═O) O—, —S (═O) — _{, -S (= O) 2 -} , - SO 2 NH -, - NHSO 2 -, - NHSO 2 NH -, - SO 3 -, - OS (= O) 2 -, - N = N -, - C ( = O) OC (= O) -, - C (= O) NHC (= O) -, - (CR 2) n - a (n is an integer of from 1 to 10, R represents a hydrogen, or a substituent Z _{1 to} Z ₄ in the case of a bonding group represented by —CH═CH— or —C≡C—, an alkyl group which may have a substituent, (Oligo) aryl group optionally having substituents, having substituents (Oligo) heteroaryl group, (poly) ether chain which may have a substituent, (poly) alkyleneimine chain which may have a substituent, fullerenes which may have a substituent, substitution Phthalimide which may have a group, or —SiR ₃ (R represents hydrogen or an alkyl group which may have a substituent), and a, b, c and d are each independently 0-4. Represents an integer, at least one of which is not zero.
X is composed of copper atom, zinc atom, cobalt atom, nickel atom, tin atom, lead atom, magnesium atom, silicon atom, iron atom, palladium atom, titanyl (TiO), vanadyl (VO), aluminum chloride (AlCl). Any one selected from the group. )
5. The alkyl group which may have a substituent is a methyl group, an ethyl group or a propyl group, and the (oligo) aryl group which may have a substituent may have a substituent (oligo) phenylene An (oligo) naphthylene group which may have a group or a substituent, and an (oligo) heteroaryl group which may have a substituent may have a (oligo) pyrrole group or a substituent 3. (oligo) thiophene group which may have a substituent, (oligo) benzopyrrole group which may have a substituent or (oligo) benzothiophene group which may have a substituent. The manufacturing method of the nanosize structure aggregate | assembly as described in.
6). 1. The acid in the step (a) is sulfuric acid, chlorosulfuric acid, methanesulfonic acid or trifluoroacetic acid. ~ 5. The manufacturing method of the nanosize structure aggregate | assembly in any one of.
7). 1. The organic solvent in the step (d) is an amide organic solvent, a halogen organic solvent, or an aromatic organic solvent. ~ 6. The manufacturing method of the nanosize structure aggregate | assembly in any one of.
8). 6. The amide organic solvent is N-methylpyrrolidone, dimethylformamide, diethylformamide or N, N-dimethylacetamide The manufacturing method of the nanosize structure aggregate | assembly as described in.
9. 6. The halogen-based organic solvent is chloroform, methylene chloride or dichloroethane. The manufacturing method of the nanosize structure aggregate | assembly as described in.
10. 6. The aromatic organic solvent is toluene, xylene, ethylbenzene, chlorobenzene or dichlorobenzene. The manufacturing method of the nanosize structure aggregate | assembly as described in.
11.1. -10. An electronic device comprising a nanosize structure aggregate obtained by the method for producing a nanosize structure aggregate according to any one of the above.

<Method for producing aggregate of phthalocyanine nanosize structure (nanowire or nanorod)>
One embodiment of the production method of the present invention is characterized by having the following steps.
(1) Step (a) of obtaining a composite (A1) by dissolving an unsubstituted phthalocyanine and a substituted phthalocyanine in an acid, and then precipitating them in a poor solvent.
(2) Step (b) of obtaining a fine particle composite (A2) by making the composite (A1) into fine particles
(3) Step (c) of obtaining the composite film (B) by applying the finely divided composite (A2) on the substrate.
(4) Step (d) of exposing the micronized composite film (B) to an organic solvent vapor to grow a nano-sized structure

・ Process (a)
In general, it is known that phthalocyanines are soluble in an acid solvent such as sulfuric acid. In the method for producing a phthalocyanine nanosize structure of the present invention, first, an unsubstituted phthalocyanine and a phthalocyanine having a substituent are mixed with sulfuric acid, chloro Dissolve in an acid solvent such as sulfuric acid, methanesulfonic acid or trifluoroacetic acid. Thereafter, it is poured into a poor solvent such as water to precipitate a complex (A1) of unsubstituted phthalocyanine and a substituted phthalocyanine.

Here, the mixing ratio of the substituted phthalocyanine to the unsubstituted phthalocyanine is preferably in the range of 5 to 200 mass%, more preferably 30 to 120 mass%. When the mixing ratio is 5% by mass or more, the crystal grows in one direction through the process described later by the action of the substituent (functional group or polymer side chain) of the phthalocyanine having a substituent, and the nanowire or nanorod is satisfactorily obtained. On the other hand, if it is in the range of 200% by mass or less, the functional group and the polymer side chain are not so large as to inhibit the crystal growth. It does not become particulate.
The mixing ratio here is [(mass of substituted phthalocyanine) / (mass of unsubstituted phthalocyanine)] × 100.

  The amount of the unsubstituted phthalocyanine and the substituted phthalocyanine added to the acid solvent is not particularly limited as long as there is no undissolved content and the concentration can be completely dissolved, but the solution has sufficient fluidity. As a range which maintains the viscosity of a grade, 20 mass% or less is preferable.

  When a solution in which the unsubstituted phthalocyanine and the phthalocyanine having the substituent are dissolved is poured into a poor solvent such as water to precipitate the complex of the unsubstituted phthalocyanine and the phthalocyanine having the substituent, The range of 0.01-50 mass% is preferable with respect to a poor solvent. If it is 0.01% by mass or more, the concentration of the complex to be precipitated is sufficiently high, so that solids can be easily recovered. If it is 50% by mass or less, all the unsubstituted phthalocyanines and the substituents are contained. Phthalocyanine precipitates to form a solid composite, which has no dissolved components and can be easily recovered.

There is no particular limitation as long as the non-substituted phthalocyanine and the substituted phthalocyanine are insoluble or hardly soluble with respect to the poor solvent, but the homogeneity of the complex to be precipitated can be kept high, and refinement described later. Water or an aqueous solution containing water as a main component and having a small environmental load suitable for the process can be mentioned as the most preferable poor solvent.
The composite can be filtered using a filter paper and a Buchner funnel to remove acidic water and washed with water until the filtrate becomes neutral to recover the water-containing composite. The recovered complex may be subjected to step (b) by adding a solvent or water in a water-containing state, or after drying to completely remove water, an organic material such as N-methylpyrrolidone or dichlorobenzene is used. You may wet-disperse in a solvent and use for a process (b).

  From the observation result with a transmission electron microscope, it was confirmed that the complex of the unsubstituted phthalocyanine and the substituted phthalocyanine complex (A1) obtained in the step (a) was amorphous.

・ Process (b)
The step (b) is not particularly limited as long as the composite (A1) obtained through the step (a) can be formed into fine particles. There are a dry method and a wet method as the method of microparticulation. However, in view of applying the microparticulate composite (A2) obtained in this step in the subsequent step (c), the composite method is performed by a wet method. It is preferable to make the body (A1) fine particles. For example, the complex (A1) obtained in the step (a) is obtained by using a wet disperser using microbeads such as a bead mill or a paint conditioner, or T.I. K. Using a medialess disperser typified by Fillmix, wet dispersion is performed together with a dispersion solvent such as water or an organic solvent and a water-containing organic solvent, and the composite is made into fine particles. Although there is no restriction | limiting in particular regarding the mass ratio with respect to the dispersion | distribution solvent of this composite here, From a viewpoint of dispersion | distribution efficiency, it is preferable to carry out the dispersion process in the range of 1-30 mass% solid content concentration. In the case of using micromedia such as zirconia beads for the micronization treatment, the bead diameter is preferably in the range of 0.01 to 2 mm in view of the degree of micronization of the composite. In addition, from the viewpoint of the efficiency of microparticulation and recovery efficiency, the micromedia can be most preferably microparticulated in the range of 100 to 1000% by mass with respect to the dispersion of the composite.

  The obtained micronized composite (A2) may be used in the step (c) as it is in the form of water or a solvent dispersion, or may be dried to form a powder after removing moisture or solvent. You may use for (c), or you may use for a process (c), after drying and removing a water | moisture content or a solvent part to make a powder and redispersing in another solvent. Although there is no restriction | limiting in particular about the method of pulverization, Processing by filtration, centrifugation, a rotary evaporator, etc. can be mentioned. Furthermore, you may dry until a water | moisture content and a solvent content are removed completely using a vacuum dryer etc.

The solvent used in the dispersion is not particularly limited as long as it does not have low affinity with phthalocyanines. For example, amide solvents, glycol ester solvents, aromatic organic solvents with high affinity with phthalocyanines And halogen-based organic solvents are preferable, and specifically, N, N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, toluene, xylene, ethylbenzene, chlorobenzene, dichlorobenzene, which have particularly high affinity with phthalocyanine Ethylene glycol monomethyl ether acetate, propylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, chloroform, methylene chloride, or dichloroethane It may be mentioned as suitable dispersing organic solvents. The amide organic solvent, glycol ether organic solvent, aromatic organic solvent, halogen organic solvent can be used alone, but can also be used in a mixture at any ratio, and with other organic solvents It can also be used together.

Regarding the addition amount of the organic solvent with respect to the above-mentioned finely divided composite (A2), the solid content concentration of the finely divided composite (A2) with respect to the organic solvent is 0 from the viewpoint of appropriate fluidity and prevention of aggregation. It is in the range of 1 to 20%, more preferably 1 to 10%.
When the micronized composite (A2) is used as the organic solvent or water dispersion in the step (c), it is micronized by using a dispersion stirrer, homogenizer, ultrasonic homogenizer, wet pulverizer (jet mill), etc. The degree of dispersion of the composite (A2) with respect to the dispersion may be improved.

・ Process (c)
The finely divided composite (A2) obtained through the step (b) is applied to a substrate as a powder or an organic solvent or an aqueous dispersion to obtain a finely divided composite coated substrate. The method for applying the fine composite powder is not particularly limited, and a known and commonly used method can be employed. Specific examples include electrostatic powder coating, a friction transfer method, and a rubbing method. On the other hand, there are no particular limitations on the method of forming the organic solvent or the aqueous dispersion of the micronized composite (A2), and a known and commonly used coating or printing method can be employed. Gravure method, gravure offset method, offset method, letterpress method, letterpress inversion method, screen method, microcontact method, reverse method, air doctor coater method, blade coater method, air knife coater method, roll coater method, squeeze coater method, impregnation coater Method, transfer roll coater method, kiss coater method, cast coater method, spray coater method, electrostatic coater method, ultrasonic spray coater method, die coater method, spin coater method, bar coater method, slit coater method, drop cast method, etc. Can be mentioned.

  The substrate on which the fine particle composite (A2) is applied is not particularly limited as long as the fine particle composite is fixed on the substrate by coating. Metal, inorganic material, glass, inorganic oxide, polymer Materials can be used. Examples of metals that can be used include iron, aluminum, gold, silver, copper, nickel, and tungsten. Examples of inorganic materials and oxides include silicon substrates, aluminum oxide, titanium oxide, zirconium oxide, and oxide. Zinc, silica, etc. can be used, and examples of the polymer material include polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyethersulfone (PES), polyetherimide, polyetheretherketone, polyphenylene sulfide, poly Arylate, polyimide, polycarbonate (PC), cellulose triacetate (TAC), cellulose acetate propionate (CAP), or the like can be used. Among polymer materials, using a plastic film as a base material can reduce the weight as compared with the case of using a substrate made of metal, glass, inorganic oxide, or the like, and can provide flexibility. In addition, a substrate with an electrode can also be used for device formation.

・ Process (d)
A phthalocyanine nanostructure is grown on the substrate obtained by exposing the finely divided composite-coated substrate obtained through the step (c) to vapor of an organic solvent. In the step (d), the organic solvent used for exposure is not particularly limited as long as it does not have low affinity with phthalocyanines. For example, an amide solvent or glycol ester solvent having high affinity with phthalocyanines. , Aromatic organic solvents and halogen-based organic solvents are preferable. Specifically, N, N-dimethylacetamide, N, N-dimethylformamide, N-methylpyrrolidone, toluene, xylene, ethylbenzene, chlorobenzene, dichlorobenzene, chloroform, Methylene chloride, dichloroethane, etc. can be mentioned as the most suitable organic solvent. The amide organic solvent, glycol ester solvent, aromatic organic solvent, and halogen organic solvent can be used alone, but can be used in a mixture at any ratio, and further used in combination with other organic solvents. It can also be used.

  The vapor temperature of the organic solvent is preferably in the range of 0 to 300 ° C, more preferably 20 to 250 ° C. When the vapor temperature is 0 ° C. or higher, an organic solvent vapor having a concentration sufficient for nanowire or nanorod formation can be generated. Further, the exposure time is not particularly limited, but it is preferable to expose at least 10 minutes before the length (major axis) of the phthalocyanine nanosize structure grows to 100 nm or more.

In the step (d), the fine composite film (B) obtained in the previous step (c) is subjected to stress in a certain direction on the substrate and then exposed to an organic solvent vapor, or the organic solvent is exposed on the substrate. The organic solvent exposure may be performed by flowing steam in a certain direction. Thereby, it becomes possible to grow phthalocyanine nanowires or nanorods in the stress direction or the airflow direction (in one direction) (an assembly made up of oriented nano-sized structures). When such stress is not applied, the nanowires or nanorods extend in the direction perpendicular to the substrate, so that nanowires or nanorods having a certain orientation in the substrate vertical direction can be obtained (orientated). An assembly of nano-sized structures).
As described above, phthalocyanines such as phthalocyanine or phthalocyanine derivatives are one of typical organic semiconductors, and control higher order structures, that is, molecular arrangement and assembly state, that is, molecules are arranged in a certain direction. In other words, phthalocyanine nanowires or nanorods in which these molecules are arranged in a certain direction are very useful materials as organic semiconductors. Usually, when such a material is used for an electronic device or the like, the phthalocyanine nanowire or nanorod is rarely used alone, and is used as a plurality of aggregates. If the arrangement of the wires or rods is random, the charge transport direction may not be constant, and sufficient capacity may not be exhibited. Therefore, it is important to form a structure in which the phthalocyanine nanowires or nanorods are arranged in a certain direction in order to fully exhibit the ability as a semiconductor.

For example, in the case of spin coating, the stress of the present invention is along the radial liquid flow generated from the center of the substrate to the outer edge during coating rotation. In the case of coating with a bar coat or applicator, the bar or applicator is used. This refers to the stress generated in the direction of movement. Further, after applying the micronized composite (A2) onto the substrate, a stress in a certain direction may be applied to the surface by pressing and moving another substrate from above.

<Phthalocyanines constituting phthalocyanine nano-sized structures (nanowires or nanorods)>
Examples of the phthalocyanine nanosize structure of the present invention include a phthalocyanine nanosize structure composed of unsubstituted phthalocyanine and a substituted phthalocyanine (phthalocyanine derivative).

As the unsubstituted phthalocyanine constituting the phthalocyanine nanosize structure of the present invention, a phthalocyanine represented by the general formula (1) and a metal-free phthalocyanine represented by the formula (2) can be used.

In general formula (1), X is not limited as long as it constitutes phthalocyanine. However, copper atom, zinc atom, cobalt atom, nickel atom, tin atom, lead atom, magnesium atom, silicon atom, iron atom Metal atoms such as palladium atoms, and metal oxides and metal halides such as titanyl (TiO), vanadyl (VO), and aluminum chloride (AlCl), among which copper atoms, zinc atoms, and iron atoms Particularly preferred.

As the phthalocyanine having a substituent constituting the phthalocyanine nanosize structure of the present invention, a phthalocyanine derivative represented by the following general formula (3) or (4) can be used.

In the general formula (3), X is not limited as long as it constitutes phthalocyanine. However, copper atom, zinc atom, cobalt atom, nickel atom, tin atom, lead atom, magnesium atom, silicon atom, iron atom Metal atoms such as palladium atoms, and metal oxides and metal halides such as titanyl (TiO), vanadyl (VO), and aluminum chloride (AlCl), among which copper atoms, zinc atoms, and iron atoms Particularly preferred.

In the general formula (3) or (4), _{Y 4} from _{Y 1} represents a linking group linking the _{Z 4} phthalocyanine skeleton and _{Z 1, Y 4} from _{Y 1} may not exist, from _{Y 1} Y _{When 4} does not exist as a linking group, Z ₁ to Z ₄ are —N ₃ , —CN, —NC, —NO ₂ , —NR ₂ (where R is hydrogen, or alkyl which may have a substituent). represents a group), - _NR ³ + (R represents hydrogen or an alkyl group which may have a substituent ^{group), - OH, -O -,} -SH, -S -, -SO 2 H, -SO ^{_{2 -, -SO 3 H, -SO}} 3 -, -CHO, -COOH, -COO -, -B (oR) 3 (R represents an alkyl group which may have hydrogen or a substituent), - SiR ₃ (R represents hydrogen or an alkyl group which may have a _{substituent), - Si (oR) 3} (R is water Or a substituent represented also alkyl group), - P (= O) (OR) 2 (R represents hydrogen or an alkyl group which may have a substituent), - P (= O) (OH) ₂ , optionally having (oligo) aryl (group), optionally having (oligo) heteroaryl (group), optionally having substituent (poly) It is an ether chain, a (poly) alkyleneimine chain which may have a substituent, a fullerene which may have a substituent, or a phthalimide which may have a substituent.

In the general formula (3) or (4), Y ₁ to Y ₄ can be used without particular limitation as long as they are a linking group that binds the phthalocyanine ring and Z ₁ to Z ₄ . Examples of such linking groups include alkylene groups, arylene groups, heteroarylene groups, vinylene bonds, ethynylene, sulfide groups, ether groups, sulfoxide groups, sulfonyl groups, urea groups, urethane groups, amide groups, amino groups, imino groups. Group, ketone group, ester group and the like. More specifically, —O—, —S—, —C (═O) —, —C (═O) O—, —OC (═O )-, -OC (= O) O-, -C (= O) NH-, -NHC (= O)-, -NHC (= O) NH-, -OC (= O) NH-, -NHC ( _{= O) O -, - S} (= O) -, - S (= O) 2 -, - SO 2 NH -, - NHSO 2 -, - NHSO 2 NH -, - SO 3 -, - OS (= O _{) 2 -, - N = N} -, - C (= O) OC (= O) -, - C (= O) NHC (= O) -, _{(CR 2)} n - (a n is an integer of 1 to 10, R represents hydrogen or an alkyl group which may have a substituent), - CH = CH -, - is C≡C- like.

In the general formula (3) or (4), Z ₁ to Z ₄ are functional groups that can be bonded to the phthalocyanine ring via the bonding groups Y ₁ to Y ₄ .

More specifically, such functional groups include, for example, alkyl groups, alkyloxy groups, amino groups, mercapto groups, carboxy groups, sulfonic acid groups, silyl groups, silanol groups, boronic acid groups, nitro groups, and phosphoric acids. Group, aryl group, heteroaryl group, cycloalkyl group, heterocycloalkyl group, nitrile group, isonitrile group, ammonium salt, fullerenes, phthalimide group, etc., more specifically, phenyl group or naphthyl group An aryl group such as an indoyl group, a heteroaryl group such as an indoyl group and a pyridinyl group, and an alkyl group such as a methyl group. Among these, specifically preferred groups include an alkyl group which may have a substituent, an (oligo) aryl group which may have a substituent, an (oligo) heteroaryl group which may have a substituent, A (poly) ether chain which may have a substituent, a (poly) alkyleneimine chain which may have a substituent, a fullerene which may have a substituent, a phthalimide which may have a substituent, -SiR 3 _(R is hydrogen or an alkyl group which may have a substituent), and the like.

Examples of the alkyl group that may have a substituent include an alkyl group having 1 to 20 carbon atoms, and a lower alkyl group such as a methyl group, an ethyl group, or a propyl group is particularly preferable. Further, an alkyl group having an ether group or an amino group is also preferable.

(M is an integer of 1 to 20, and R and R ′ are each independently an alkyl or aryl group having 1 to 20 carbon atoms.)
The group represented by can also be used.

  The (oligo) aryl group which may have a substituent is preferably a phenyl group which may have a substituent, a naphthyl group which may have a substituent, or a substituent. Examples thereof include an oligophenylene group and an oligonaphthyl group which may have a substituent. Examples of the substituent include known and commonly used substituents that can be substituted on the aryl group.

  The (oligo) heteroaryl group which may have a substituent is preferably a pyrrole group which may have a substituent, a thiophene group which may have a substituent, or a substituent. Examples thereof include a good oligopyrrole group and an oligothiophene group which may have a substituent. Examples of the substituent include known and commonly used substituents that can be substituted on the heteroaryl group.

  In addition, examples of the fullerenes which may have a substituent include unsubstituted fullerenes and fullerenes having known and commonly used substituents, such as C60 fullerene, C70 fullerene, [6,6] -phenyl. Examples thereof include C61 butyric acid methyl ester (PCBM).

Examples of the phthalimide group that may have the substituent include:

(Where q is an integer from 1 to 20)
The group represented by these can be mentioned. Examples of the substituent include known and commonly used substituents that can be substituted on the phthalimide group.

Examples of the (poly) ether chain which may have a substituent include polyalkylene oxide copolymers represented by the general formula (Chemical Formula 7), that is, ethylene oxide polymers and ethylene oxide / propylene oxide copolymers. Any polyalkylene oxide can be used, either block polymerized or randomly polymerized.

Here, Q ′ in the general formula (Chemical Formula 7) may be either a linear hydrocarbon group or a branched hydrocarbon group as an acyclic hydrocarbon group having 1 to 30 carbon atoms, and the hydrocarbon group is saturated. Either a hydrocarbon group or an unsaturated hydrocarbon group may be used. Examples of such an acyclic hydrocarbon group include a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, n-pentyl group, n-hexyl group, n-octyl group, 2 Examples thereof include linear or branched saturated hydrocarbon groups such as -ethyl-hexyl group, n-dodecyl group, stearyl group, n-tetracosyl group and n-triacontyl group.

In addition, as the linear or branched unsaturated hydrocarbon group, the hydrocarbon group may have a double bond or a triple bond, for example, a vinyl group, a propenyl group, an isopropenyl group, a butenyl group, a pentenyl group. Linear or branched unsaturated hydrocarbon groups such as isoprene group, hexenyl group, heptenyl group, octenyl group, decenyl group, geranyl group, ethynyl group, 2-propynyl group, 2-pentene-4-ynyl group, etc. be able to.

The number of repeating n of the polyalkylene oxide moiety is not particularly limited, but is preferably 4 or more and 100 or less from the viewpoint of the affinity with the dispersion solvent, that is, the dispersion stability of the resulting nanosized structure, Preferably they are 5 or more and 80 or less, More preferably, they are 10 or more and 50 or less.

(Here, n is an integer of 4 to 100, Q is each independently a hydrogen atom or a methyl group, and Q 'is an acyclic hydrocarbon group having 1 to 30 carbon atoms.)

In general formula (3) or (4), a, b, c and d each independently represents an integer of 0 to 4, and represents the number of substituents Y ₁ Z ₁ to Y ₄ Z ₄ substituted on the phthalocyanine ring. Note that at least one of the numbers a to d of the substituents substituted on the phthalocyanine ring is not zero.

Specific examples of the phthalocyanine having a substituent represented by the general formula (3) include, but are not limited to, the following. Here, the numbers next to the parentheses in the formula of the substituted phthalocyanine represent the average number of substituents introduced into the phthalocyanine molecule. The reason why this number is a decimal number is that although the number of substituents introduced for each molecule is an integer, different numbers of substituents are introduced in actual use.

(Here, X is a copper atom or a zinc atom, n is an integer of 1 to 20, and m is a numerical value of 0 to 4 representing the average number of substituents introduced.)

(Where X is a copper atom or zinc atom, n is an integer of 1 to 20, m is a numerical value of 0 to 4 representing the average number of substituents introduced, and R ₁ to R ₄ are each independently a hydrogen atom. Represents a halogen, an alkyl group having 1 to 20 carbon atoms, an alkyloxy group or an alkylthio group.)

(Where X is a copper atom or zinc atom, n is an integer from 1 to 20, m is a numerical value from 0 to 4 representing the average number of substituents introduced, and R ₁ to R ₂ are each independently a hydrogen atom. Represents a halogen, an alkyl group having 1 to 20 carbon atoms, an alkyloxy group or an alkylthio group.)

(However, in the formula, Q and R represent a hydrogen atom or a methyl group. N is a numerical value of 4 to 100. In addition, the number m of polyalkylene oxide chains bonded to the phthalocyanine through a sulfamoyl bond is included in the phthalocyanine. (It is a numerical value of 0 to 4 representing the average number of introductions for four benzene rings.)

Moreover, as a specific compound represented by General formula (4), the phthalocyanine derivative which does not have a center metal in the said Formula (Chemical Formula 8)-(Chemical Formula 18) can be mentioned.

<Electronic device>
The electronic device is not particularly limited as long as it is a generally known device composed of an organic semiconductor, and includes an organic EL, an organic field effect transistor, an organic solar cell, an organic photodiode, an organic sensor, an organic laser, an organic thyristor, and the like. Can be mentioned.
Hereinafter, the present invention will be described more specifically based on examples. In addition, this invention is not limited to the following Example.

Example 1
<Manufacture of phthalocyanine nano-sized structure aggregate (film)>
・ Process (a)
Copper phthalocyanine (Fastogen Blue 5380E (trade name, manufactured by DIC)) 1.0 g

で表される銅フタロシアニン誘導体化合物０．８３ｇを濃硫酸（関東化学製）８１ｇに投入して完全に溶解させ、濃硫酸溶液を調製した。続いて蒸留水７３０ｇを１０００ｍＬのビーカーに投入し、これを氷水で十分、冷却した後、該蒸留水を撹拌しながら、先に調製した濃硫酸溶液を投入し、銅フタロシアニンと前記銅フタロシアニン誘導体化合物とからなる複合体を析出させた。

Was added to 81 g of concentrated sulfuric acid (manufactured by Kanto Chemical Co., Inc.) to completely dissolve it to prepare a concentrated sulfuric acid solution. Subsequently, 730 g of distilled water was put into a 1000 mL beaker, and this was cooled sufficiently with ice water, and then the concentrated sulfuric acid solution prepared above was added while stirring the distilled water, and copper phthalocyanine and the copper phthalocyanine derivative compound were added. A composite consisting of was deposited.

  Subsequently, the obtained composite was filtered using a filter paper, washed sufficiently with distilled water, and the composite containing water was recovered.

・ Process (b)
12.4 g of a hydrous composite containing 2.5 g of the composite comprising the copper phthalocyanine obtained in the step (a) and the copper phthalocyanine derivative compound is put into a polypropylene container having a capacity of 50 mL, and 4.3 g of distilled water is further added. Then, the weight ratio of the composite to water was 15%, and then 60 g of zirconia beads having a diameter of 0.5 mm were added, followed by treatment for 2 hours using a paint shaker. Subsequently, the composite finely divided (fine) by the treatment is separated and recovered from the zirconia beads, and further distilled water is added thereto to add a 50 g finely divided composite aqueous dispersion (solids concentration 5%) (microparticulated composite). A body water dispersion (1)) was obtained.

・ Process (c)
The finely divided composite aqueous dispersion obtained in the step (b) was cast on a glass plate and dried.

・ Process (d)
The fine composite-coated glass plate obtained in step (c) was placed in a flow cell, and dichlorobenzene vapor was flowed with nitrogen gas at room temperature, and exposed from one direction of the substrate for 1 hour (see FIG. 1). . When this glass plate was taken out and observed using a scanning electron microscope, nanowires grown to a short diameter of about 100 nm and a ratio of the length to the short diameter of 10 or more grew in the vapor flow direction (orientation). (Phthalocyanine nanowire aggregate (film) (1)).

<Manufacture and evaluation of transistors>
A source / drain electrode made of a gold thin film was patterned on the oriented phthalocyanine nanowire aggregate (film) (1) obtained in Example 1 by vapor deposition so that the orientation direction was a channel (channel length: 75 μm, channel width: 5 mm). Further, a parylene film was formed thereon as a gate insulating film by a chemical vapor deposition method (CVD method). The parylene film is made by using diXC made by Sanka Chemical Co., Ltd. as a raw material, sublimated at a temperature of 100 to 170 ° C. under reduced pressure, and subsequently introduced into a pyrolysis furnace (pyrolysis furnace temperature: 650 ° C.). The phthalocyanine nanowire aggregate (film) was introduced into a film formation chamber provided with a substrate (film thickness: 1 μm).
Finally, platinum was deposited to 30 nm using an ion coater, and a bottom contact top gate type transistor (1) was produced.
The transistor characteristics of each organic transistor were measured. The transistor characteristic is measured by using a digital multimeter (237, manufactured by Keithley), sweeping 0 to -80V voltage (Vg) to the gate electrode, and applying -80V applied current (Id) between the source and drain electrodes. This was done by measuring. The mobility was determined by a known method from the slope of √Id−Vg. The unit is cm ² / V · s. These results are shown in Table 1.

(Example 2)
In the same manner as in Example 1, except that the gate insulating film material in Example 1 was changed to parylene and changed to polyimide (Sunever (trade name, manufactured by Nissan Chemical Industries)), a bottom contact top gate type transistor (2 ) Was produced. The evaluation results are shown in Table 1.

(Example 3)
A source / drain electrode made of a titanium / gold laminated thin film was patterned on a glass substrate by vapor deposition (channel length: 75 μm, channel width: 5 mm) (substrate (3)). In addition, the thickness of each layer was taken as lower layer: titanium layer 5 nm, upper layer: gold layer 30 nm.
The glass substrate in the step (c) of Example 1 is changed to the substrate (3), and the gas flow direction in the step (d) is the same as the channel direction formed on the substrate (3). Thus, a top contact top gate type transistor (3) was manufactured. The evaluation results are shown in Table 1.

Example 4
The surface layer of the n-type silicon substrate was thermally oxidized to form a silicon oxide (300 nm) layer on the silicon substrate (substrate (4)).
An aligned phthalocyanine nanowire aggregate (film) was obtained in the same manner as in Example 1 except that the glass substrate in the step (c) of Example 1 was changed to the substrate (4).
Thereafter, on the phthalocyanine aggregate (film), a source / drain electrode made of a gold thin film is patterned by vapor deposition so that the orientation direction is a channel (channel length: 75 μm, channel width: 5 mm), A top contact bottom gate type transistor (4) was obtained. The evaluation results of the transistor are shown in Table 1.

(Example 5)
<Manufacture of phthalocyanine nanowire assembly (film)>
After performing steps (a) to (c) in the same manner as in Example 1, the finely divided composite-coated glass plate was sandwiched between the glass plates from above and applied with stress by sliding in one direction (see FIG. 2) at room temperature and placed in a glass bottle saturated with dichlorobenzene vapor, and allowed to stand for 1 hour. When this glass plate was taken out and observed using a scanning electron microscope, the nanowire grown to a minor axis of about 20 nm and a ratio of the length to the minor axis of 10 or more was in the stress direction (right direction in FIGS. 3 and 4). (See FIGS. 3 and 4) (Oriented phthalocyanine nanowire aggregate (film) (5)).

<Manufacture and evaluation of transistors>
A transistor was fabricated in the same manner as in Example 1 except that the phthalocyanine nanowire aggregate (film) (5) was used instead of the phthalocyanine nanowire aggregate (film) (1). The evaluation results are shown in Table 1.

(Example 6)
<Manufacture and evaluation of solar cells>
An ITO transparent conductive layer serving as a positive electrode was deposited to a thickness of 100 nm on a glass substrate by a sputtering method, and this was patterned into a strip shape having a width of 2 mm by a photolithography method. The obtained glass substrate with pattern ITO was ultrasonically washed three times for 15 minutes each in the order of neutral detergent, distilled water, acetone, and ethanol, then UV / ozone treatment for 30 minutes, and PEDOT: PSS aqueous dispersion on this A buffer layer 1 made of PEDOT: PSS was formed to a thickness of 60 nm by spin coating (trade name AI4083, manufactured by HC Starck). This was heated and dried with a hot plate at 100 ° C. for 5 minutes, and then the finely divided composite aqueous dispersion (solid) obtained by the steps (a) and (b) of Example (1) on the PEDOT: PSS layer. Material concentration 5%) (fine particle composite aqueous dispersion (1)) was spin-coated to form a fine particle composite film having a thickness of 100 nm. This was put into a glass bottle saturated with dichlorobenzene vapor at room temperature, and allowed to stand for 1 hour to produce a phthalocyanine nanowire aggregate (film) (6). Thereafter, 2 wt% PCBM-orthodichlorobenzene was spin-coated on the phthalocyanine nanowire aggregate (film) (6) to deposit an electron-accepting material layer, and this was deposited on a metal mask for vapor deposition (2 mm width strip). (For pattern formation) in a vacuum deposition apparatus, the degree of vacuum in the apparatus is increased to 5 × 10 ⁻⁴ Pa, and then the negative electrode aluminum is formed into a 2 mm wide strip pattern by resistance heating. Vapor deposition was performed (film thickness: 80 nm). As described above, a photoelectric conversion element (6) having an area of 2 mm × 2 mm (a portion where the strip-like ITO layer and the aluminum layer intersect) was produced.

The positive and negative electrodes of the photoelectric conversion element (6) thus obtained are connected to a digital multimeter (trade name 6241A, manufactured by ADC), and simulated sunlight (simple solar simulator XES151S, manufactured by Mitsunaga Electric Manufacturing Co., Ltd.). , Spectrum shape: AM1.5, intensity: 100 mW / cm ² ) (irradiation from the ITO layer side), the voltage was swept from −0.1 V to +0.8 V in the atmosphere, and the current value was measured. At this time, the short-circuit current density (value of the current density when the applied voltage is 0 V. Hereinafter, J _sc ) is 5.33 mA / cm ² , and the open circuit voltage (value of the applied voltage when the current density is 0. V _oc ) was 0.55 V, the fill factor (FF) was 0.33, and the photoelectric conversion efficiency (PCE) calculated from these values was 0.98%. FF and PCE were calculated by the following formula.

FF = JV _max / (J _sc × V _oc )
(Here, JV _max is the product of the current density and the applied voltage at the point where the product of the current density and the applied voltage is maximum between the applied voltage of 0 V and the open circuit voltage value.)

PCE = [(J _sc × V _oc × FF) / pseudo sunlight intensity (100 mW / cm ² )] × 100 (%)

(Comparative Example 1)
The steps (a) to (b) were carried out in the same manner as in Example (1) except that the finely divided composite was separated and recovered from the zirconia beads, and then the aqueous dispersion was not produced but filtered. Got the body.
This finely divided complex was dispersed in 60 g of dichlorobenzene and stirred for 2 hours, and then 60 g of N-methylpyrrolidone was further added and stirred for 2 hours. The dispersion was heated using an oil bath and heated to 145 ° C. over 90 minutes. After reaching 145 ° C., heating was continued for 30 minutes at the same temperature. The dispersion after heating was filtered using a membrane filter (pore size: 0.1 μm), and the residue was thoroughly washed with dichlorobenzene. The filter residue was cast on a glass substrate (phthalocyanine nanowire aggregate (film) (1) ′) and subjected to SEM observation, and it was observed that fibrous phthalocyanine nanowires were randomly aggregated. (FIG. 5).

  A transistor (1) 'was produced in the same manner as in Example (1) except that the phthalocyanine nanowire aggregate (film) (1)' was used instead of the phthalocyanine nanowire aggregate (film) (1). The evaluation results are shown in Table (1). From the table, it can be said that the effect of the present invention is remarkable.

  By the production method of the present invention, it is possible to produce an aggregate (film) made of aligned (orientated) phthalocyanine nanosize structures (arranged (orientated) phthalocyanine nanowires or nanorods) having excellent semiconductor characteristics.

(A) Fine particle composite coated glass plate (b) Flow cell (c) Dichlorobenzene (d) Dichlorobenzene vapor (e) Glass plate (f) Stress application direction

Claims (11)

(1) Step (a) in which an unsubstituted phthalocyanine and a substituted phthalocyanine are dissolved in an acid, and then precipitated in a poor solvent to obtain a composite (A1)
(2) Step (b) of obtaining a fine particle composite (A2) by making the composite (A1) into fine particles
(3) Step (c) of applying the micronized composite (A2) onto a substrate to obtain a micronized composite film (B)
(4) Step (d) of growing a nano-sized structure by exposing the micronized composite film (B) to an organic solvent vapor on a substrate.
A process for producing a nano-sized structure aggregate comprising an unsubstituted phthalocyanine and a substituted phthalocyanine, and having a major axis and a minor axis, the minor axis being 100 nm or less . In the step (d), the micronized composite film (B) is exposed to the organic solvent vapor after applying a stress in a certain direction on the substrate, or the organic solvent vapor is directed in a certain direction on the substrate. The method for producing a nano-sized structure aggregate according to claim 1, wherein the exposure is performed by flowing in a flow. The method for producing a nano-sized structure aggregate according to claim 1 or 2, wherein the unsubstituted phthalocyanine is represented by the general formula (1) or (2).

(Wherein, X is selected from the group consisting of copper atom, zinc atom, cobalt atom, nickel atom, tin atom, lead atom, magnesium atom, silicon atom, iron atom, palladium atom, TiO, VO, and AlCl. Any one.) The method for producing a nanosize structure aggregate according to any one of claims 1 to 3, wherein the phthalocyanine having a substituent is represented by the general formula (3) or (4).

(However, in the formula, Y ₁ to Y ₄ represent a linking group for bonding the phthalocyanine skeleton and Z _{1 to} Z _4, and when Y ₁ to Y ₄ are not present as a linking group, Z _{1 to} Z ₄ are , —N ₃ , —CN, —NC, —NO ₂ , —NR ₂ (R represents hydrogen or an alkyl group which may have a substituent), —NR ₃ ⁺ (R represents hydrogen or a substituent) represents an alkyl group which may _{^{have), - OH, -O -,}} -SH, -S -, -SO 2 H, -SO 2 -, -SO 3 H, -SO 3 -, -CHO, - ^{COOH, -COO -, -B (oR} ) 3 (R represents an alkyl group which may have hydrogen or a substituent), - _SiR 3 (R is hydrogen, or an optionally substituted alkyl represents a _{group), - Si (oR) 3} (R represents hydrogen or an alkyl group which may have a substituent), - P ( O) _(OR) 2 (R represents hydrogen or an alkyl group which may have a substituent), - P (= O) (OH) 2, an optionally substituted (oligo) aryl group A (oligo) heteroaryl group which may have a substituent, a (poly) ether chain which may have a substituent, a (poly) alkyleneimine chain which may have a substituent, and a substituent Fullerenes that may be, or phthalimide that may have a substituent,
Y ₁ to Y ₄ are —O—, —S—, —C (═O) —, —C (═O) O—, —OC (═O) —, —OC (═O) O—, — C (═O) NH—, —NHC (═O) —, —NHC (═O) NH—, —OC (═O) NH—, —NHC (═O) O—, —S (═O) — _{, -S (= O) 2 -} , - SO 2 NH -, - NHSO 2 -, - NHSO 2 NH -, - SO 3 -, - OS (= O) 2 -, - N = N -, - C ( = O) OC (= O) -, - C (= O) NHC (= O) -, - (CR 2) n - a (n is an integer of from 1 to 10, R represents a hydrogen, or a substituent Z _{1 to} Z ₄ in the case of a bonding group represented by —CH═CH— or —C≡C—, an alkyl group which may have a substituent, (Oligo) aryl group optionally having substituents, having substituents (Oligo) heteroaryl group, (poly) ether chain which may have a substituent, (poly) alkyleneimine chain which may have a substituent, fullerenes which may have a substituent, substitution Phthalimide which may have a group, or —SiR ₃ (R represents hydrogen or an alkyl group which may have a substituent), and a, b, c and d are each independently 0-4. Represents an integer, at least one of which is not zero.
X is composed of copper atom, zinc atom, cobalt atom, nickel atom, tin atom, lead atom, magnesium atom, silicon atom, iron atom, palladium atom, titanyl (TiO), vanadyl (VO), aluminum chloride (AlCl). Any one selected from the group. ) The alkyl group which may have a substituent is a methyl group, an ethyl group or a propyl group, and the (oligo) aryl group which may have a substituent may have a substituent (oligo) phenylene An (oligo) naphthylene group which may have a group or a substituent, and an (oligo) heteroaryl group which may have a substituent may have a (oligo) pyrrole group or a substituent The (oligo) thiophene group which may have a substituent, the (oligo) benzopyrrole group which may have a substituent or the (oligo) benzothiophene group which may have a substituent Manufacturing method of size structure aggregate. The method for producing a nano-sized structure aggregate according to any one of claims 1 to 5, wherein the acid in the step (a) is sulfuric acid, chlorosulfuric acid, methanesulfonic acid, or trifluoroacetic acid. The method for producing a nano-sized structure aggregate according to any one of claims 1 to 6, wherein the organic solvent in the step (d) is an amide organic solvent, a halogen organic solvent, or an aromatic organic solvent. The method for producing a nano-sized structure aggregate according to claim 7, wherein the amide organic solvent is N-methylpyrrolidone, dimethylformamide, diethylformamide, or N, N-dimethylacetamide. The method for producing a nano-sized structure aggregate according to claim 7, wherein the halogen-based organic solvent is chloroform, methylene chloride, or dichloroethane. The method for producing a nano-sized structure aggregate according to claim 7, wherein the aromatic organic solvent is toluene, xylene, ethylbenzene, chlorobenzene, or dichlorobenzene. The electronic device containing the nanosize structure aggregate obtained by the manufacturing method of the nanosize structure aggregate in any one of Claims 1-10.

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