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WO2013168945A1 - Novel method for preparing benzoporphyrin derivative and preparation of organic thin film transistor using same - Google Patents

Novel method for preparing benzoporphyrin derivative and preparation of organic thin film transistor using same Download PDF

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Publication number
WO2013168945A1
WO2013168945A1 PCT/KR2013/003919 KR2013003919W WO2013168945A1 WO 2013168945 A1 WO2013168945 A1 WO 2013168945A1 KR 2013003919 W KR2013003919 W KR 2013003919W WO 2013168945 A1 WO2013168945 A1 WO 2013168945A1
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formula
benzoporphyrin
organic solvent
organic
thin film
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French (fr)
Korean (ko)
Inventor
임종선
정승두
전동주
박보근
정석종
조성윤
민복기
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Korea Research Institute of Chemical Technology KRICT
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F1/00—Compounds containing elements of Groups 1 or 11 of the Periodic Table
    • C07F1/08—Copper compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/22—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains four or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/04—Nickel compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/22—Tin compounds
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00—Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30—Coordination compounds
    • H10K85/371—Metal complexes comprising a group IB metal element, e.g. comprising copper, gold or silver
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K10/00—Organic devices specially adapted for rectifying, amplifying, oscillating or switching; Organic capacitors or resistors having potential barriers
    • H10K10/40—Organic transistors
    • H10K10/46—Field-effect transistors, e.g. organic thin-film transistors [OTFT]
    • H10K10/462—Insulated gate field-effect transistors [IGFETs]
    • H10K10/466—Lateral bottom-gate IGFETs comprising only a single gate

Definitions

  • the present invention relates to a novel method for producing a benzoporphyrin derivative and to an organic thin film transistor using the same.
  • TFTs Thin film transistors
  • the TFT has a gate electrode, an insulator layer, and a semiconductor layer in order on a substrate, and has a source electrode and a drain electrode formed at predetermined intervals on the semiconductor layer. A part of the source electrode and the drain electrode is exposed on the surface, and a semiconductor layer is formed on the surface exposed between both electrodes.
  • the semiconductor layer forms a channel region, and the current flowing between the source electrode and the drain electrode is controlled by the voltage applied to the gate electrode to operate on / off.
  • TFTs are manufactured using amorphous or polycrystalline silicon
  • the CVD apparatus used for manufacturing TFTs using such silicon is expensive, and the increase in size of display devices using TFTs greatly increases manufacturing costs.
  • the process of forming amorphous or polycrystalline silicon is performed at a very high temperature, so that the types of materials that can be used as substrates are limited. Accordingly, resin substrates that can be lightweight and flexible and can be freely shaped can be used. There is a problem that cannot be used. If the production of TFTs on a lightweight resin substrate becomes possible, the application to portable electronic devices will also be possible.
  • organic TFT ' a TFT using an organic semiconductor
  • a film forming method used when forming a TFT from an organic semiconductor there are known a vacuum deposition method, a printing method and a coating method capable of a solution process, and in particular, the film forming method by the printing method can realize a larger device while suppressing an increase in manufacturing cost.
  • the process temperature required for the film formation can be made relatively low.
  • Pentacene which is widely known as an organic TFT material, has reported a charge mobility of up to 7 cm V depending on the gate organic insulating film, and vacuum deposition is used as the method for forming the pentacene.
  • vacuum deposition method since the vacuum deposition method is expensive, the development of an organic semiconductor material by a printing method having a low manufacturing cost and an easy large-area process has been proposed.
  • TIPS-pentacene, TES-ADT, diF TES-ADT, etc. in which pentacene and anthracene are substituted with a dissolvable group in an organic solvent, has a charge mobility of 1 cm 2 / V It has been reported above (Thomas N. Jackson, et, al., Appl.
  • polythiophene derivatives have been studied as a polymer semiconductor which is expected to be most suitable in the film forming process by printing method, but the charge mobility has been reported to be less than 0.3 cm 2 / V-s (Beng S. Ong, et. Al. , Chem. Eur J. 14, 4766 (2008)).
  • studies on copper-benzoporphyrin derivatives using copper-benzobenzoporphyrin precursors, which are known to have the best organic TFT characteristics among organometallic compound semiconductors have been reported.
  • the mobility of the prepared organic TFTs is known to be greater than 1 cm V 's (US 2007/0012914 and US 2009/0186490), since they are soluble in low boiling organic solvents such as chloroform, It is difficult to form a thin film and its solubility is low, and it must be well dissolved in an organic solvent having high boiling point to form a film by printing method such as inkjet, gravure, offset, gravure offset and reverse offset printing. There is a problem that it is difficult to manufacture an organic TFT. Therefore, it is difficult to establish suitable printing process conditions.
  • an organic solar cell is known as an application element using an organic semiconductor.
  • the benzoporphyrin precursor In order to prepare the banjo porphyrin derivatives, the benzoporphyrin precursor must be synthesized by reacting phthalimide at a very high temperature (320 ° C) or using isoindole derivatives synthesized from a very complicated step (7 step configuration). There is a problem that is difficult to manufacture. Since the isoindole derivative synthesized by the conventional method includes an ester group, it is cumbersome to involve carboxyl group decarboxylation in order to introduce a substituent at the mesogenic position (LA ⁇ Yakubo, et. Al. , Russ. J. Gen. Chem., 78 (2007) 1255; and S. Ito., Chem. Commun. (1998) 1661).
  • the present inventors are isoindole which is a precursor of the benzoporphyrin derivative While studying a method for preparing a derivative, a benzoporphyrin precursor was synthesized in a simple and high yield from an easy-to-get starting material, and from this, a method for easily preparing a benzoporphyrin derivative and a printing method using a benzoporphyrin precursor were easily prepared.
  • the present invention was completed by discovering a method of manufacturing an organic thin film transistor.
  • Another object of the present invention is to provide a method for producing an organic thin film transistor by a printing method using a benzoporphyrin precursor.
  • Step 1 Preparing a compound represented by Chemical Formula 3 by reacting the compound represented by Chemical Formula 2 with formic acid and then reacting with dienes and Diels-Alder in an organic solvent (Step 1);
  • Step 2 Preparing a compound represented by Chemical Formula 4 by reacting the compound represented by Chemical Formula 3 prepared in Step 1 in an ammonium hydroxide and an organic solvent (Step 2);
  • step 4 of preparing a benzoporphyrin of formula 1 by treating the benzoporphyrin precursor of formula 5 prepared in step 3 at a high temperature:
  • the present invention provides a method for producing an organic thin film transistor comprising the step of introducing the benzoporphyrin precursor represented by the following formula (5) to the organic semiconductor channel using a printing method;
  • the novel method for preparing a benzoporphyrin derivative according to the present invention can economically obtain a benzoporphyrin derivative as a target compound by significantly reducing the production process step compared to a method for preparing a benzoporphyrin derivative known in the art, and also boiling a benzoporphyrin precursor.
  • the organic thin film transistor of high degree of mobility can be manufactured by performing a printing method by dissolving in a mixed organic solvent having different points.
  • Example 1 is a view showing the structure of an organic thin film transistor according to the present invention in Example 64.
  • FIG. 1 The symbols shown in FIG. 1 are as follows:
  • Drain electrode. 2 is in Example 65. A diagram showing the structure of the manufactured organic thin film transistor.
  • Organic gate insulating film is a view showing the structure of an organic thin film transistor according to the present invention in Comparative Examples 1 to 2.
  • Drain electrode. 4 is a current-voltage curve for an organic thin film transistor of which the gate insulating film prepared in Example 64 is Si.
  • 5 is a current ⁇ voltage curve for an organic thin film transistor in which the gate insulating film prepared in Example 65 is an organic insulating film.
  • 6 is a current-voltage curve of an organic thin film transistor in which a thin film is formed using 1% copper benzobenzoporphyrin precursor in Comparative Example 1.
  • FIG. FIG. 7 is a current-voltage curve of an organic thin film transistor in which a thin film is formed using 2% copper-banjo porphyrin precursor in Comparative Example 2.
  • step 1 Reacting the compound represented by the formula (2) with formic acid and then reacting with diene and Dies-Alder in an organic solvent to prepare a compound represented by the formula (3) (step 1);
  • step 4 of preparing a benzoporphyrin of formula 1 by treating the benzoporphyrin precursor of formula 5 prepared in step 3 at a high temperature:
  • R 1 is hydrogen or d or C 12 straight or branched alkyl
  • Step 1 is a reaction of the compound represented by the formula (2) with formic acid (formic acid), and then reacted with dienes (Diels-Alder) in an organic solvent to prepare a compound represented by the formula (3) Step.
  • Step 1 As the organic solvent in step 1, ethyl acetate, methylene chloride, acetone nucleic acid, diethyl ether, diisopropyl ether and the like may be used, and methylene chloride may be preferably used.
  • the reaction temperature of step 1 is preferably 4Q to 50 ° C, more preferably 45 ° C. ⁇ If the reaction temperature is lower than the above temperature, there is a problem that the reaction yield is lowered.
  • Step 2 according to the present invention is a step of preparing a compound of Formula 4 by reacting the compound represented by Formula 3 prepared in Step 1 in an ammonium hydroxide and an organic solvent.
  • step 2 diethyl ether, diisopropyl ether ethylene glycol dimethyl ether, and the like may be used, and preferably ethylene glycol dimethyl ether may be used.
  • ammonium hydroxide in step 2 is carried out under a nitrogen atmosphere It is advisable to proceed.
  • the acid used in step 3 is preferably trifluoroacetic acid (TFA) or borontrifluorodiethyl ether.
  • the organic solvent of step 3 may be used alone or in combination of ethyl acetate, methylene chloride, nucleic acid diethyl ether, methane, ethane and the like, preferably methylene chloride may be used.
  • Step 4 according to the present invention is a step of preparing the benzoporphyrin of Formula 1 by treating the benzoporphyrin precursor of Formula 5 prepared at Step 3 at a high temperature.
  • the reaction of step 4 is preferably performed at 200 to 250 ° C. for 5 to 30 minutes, more preferably at 220 ° C. for 10 minutes and at 150 ° C. for 120 minutes.
  • the novel method for preparing a benzoporphyrin derivative according to the present invention can economically obtain a benzoporphyrin derivative, which is a target compound, by significantly reducing the production process step compared to a method for preparing a benzoporphyrin derivative known in the art.
  • the present invention provides a method for producing an organic thin film transistor comprising the step of introducing a benzoporphyrin precursor represented by the formula (5) to the organic semiconductor channel; [Formula 5]
  • the step of introducing the general formula (5) in accordance with the present invention an organic semiconductor channel is the source before using the printing method on the organic insulating film: a step of preparing an organic thin film transistor by introducing the organic semiconductor channel between the poles and the drain electrode.
  • the printing method according to the present invention may use an inkjet printing method, a gravure method, a gravure-eupset method, a screen printing method, a slit-die coating method, a screen printing method, a flexographic printing method, and the like, preferably an inkjet printing method Can be used.
  • the inkjet printing method can simplify the process, lower the equipment cost and manufacturing cost, and deposit the material in the desired pattern position, so that there is no material loss in principle, so there is no waste of raw materials and less environmental load.
  • the photolithography process does not require the development and etching process, so the chemical influence does not deteriorate the characteristics of the substrate or the material, and it is a non-contact printing method, which does not damage the device due to contact. It also has the advantage of being possible.
  • a common organic solvent having different boiling points At least one of the mixed organic solvents should be used with a boiling point of 100 ° C. or higher.
  • the benzoporphyrin precursor prepared in the present invention is dissolved only in an organic solvent having a low boiling point (100 ° C ⁇ ), when the organic solvent having a boiling point of 100 ° C or more is used as a printing method without mixing at least one organic solvent, the nozzle of the printing apparatus It is difficult to jet due to the phenomenon that the nozzle is clogged due to the drying in progress, and the droplets discharged from the nozzle lose the straightness and are difficult to print at a desired position.
  • a solvent in which the porphyrin benzo jeongucheeul dissolved in utilizing the printing method is methylene chloride. Chloroform, ethyl acetate, tetrahydrofuran, ethane, methanol, etc.
  • chloroform can be used.
  • chlorobenzene di Ethylene glycol, trichlorobenzene, dichlorobenzene, orthodichlorobenzene, cyclonuxanone, methyl ethyl ketone, methyl xylene, dimethyl sulfoxide (DMSO), dimethylformamide (DMF) It is possible to use and preferably chlorobenzene.
  • step 1 is 3-
  • the organic layer was separated with distilled water and C3 ⁇ 4C1 2 , dried over anhydrous Na 2 S0 4 , filtered under reduced pressure, and the solvent was removed.
  • Mass spectrometry calculated 907.47, measured 908.01.
  • Steps 1 and 2 4, Preparation of Kyodihydrosene 4, Getano-2H'Isoindole (6a)
  • Step 3 Preparation of Cu (II) -Banzoporphyrin Precursor (5b)
  • a target compound Cu (II) -benzoporphyrin precursor (5b) was prepared by the same method as Step 3 of Example 1, except that formaldehyde was used instead of heptane.
  • Step 4 Preparation of Cu (II) -benzoporphyrin (lb)
  • Example 3 to 21 The compounds of Examples 3 to 21 were prepared in the same manner as in Example 1, except that aldehyde (R-CH0) having a substituent R of Table 1 was used instead of the heptanol used in Step 3 of Example 1. In this case, Examples 19 to 21 used BF 3 ⁇ 0 ⁇ 1 2 as the acid catalyst instead of TFA. Yields and mass spectrometry values are shown in Table 1 below. ⁇ Examples 22 to 42>
  • Example 1 The same procedure as in Example 1 except for using aldehyde (R-CH0) having a substituent R of Table 1 and Cu (0Ac) 2 acid 3 ⁇ 4 (0Ac) 2 instead of the heptanol used in step 3 of Example 1
  • the compound of Examples 22-42 was prepared by the method.
  • the Examples 40 to 42 was used as the BF 3 .0Et 2 as the acid catalyst instead of TFA. Yields and mass spectrometry values are shown in Table 1 below.
  • Example 1 Step 3 heptane to instead appear with an aldehyde (R-CH0) having a substituent R in Table 1 as Cu (0Ac) 2 instead of Ni (0Ac) was added as was used for 2 Excess Et 3 N used in the Except for heating, the compounds of Examples 43 to 63 were prepared in the same manner as in Example 1. In this case, Examples 61 to 63 used BF 3 OEt 2 as an acid catalyst instead of TFA. Yields and mass spectrometry values are shown in Table 1 below.
  • An organic thin film transistor was prepared using the copper ( ⁇ ) -benzoporphyrin precursor obtained in step 3 of Example 2.
  • a 300 nm nanometer silicon dioxide (Si0 2 ) -grown n-doped silicon wafer substrate was used, and the silicon dioxide (Si0 2 ) surface was subjected to UV / ozone treatment. And hydrophobicity by surface treatment with Hexamethyldisioxane (! HMDS).
  • An organic thin film transistor was prepared using the copper ( ⁇ ) -benzoporphyrin precursor obtained in step 3 of Example 2.
  • the ROM 80 by depositing the respective nanometers, 10 nanometers to form a gate electrode.
  • a substrate such as practical example 64
  • silicon dioxide Si0 2
  • an organic insulating film having ohmic contact resistance with an organic semiconductor was used as the gate insulating film.
  • the organic insulating film was prepared by mixing 2,4,6-triallyloxy-1,3,5 ⁇ triazine and pentaerythritol tetrakis with propylene glycol monomethyl ether acetate in a weight ratio of 1.47 to 1, and then using the photoinitiator Igacur 369 ( Shiba GI Co.) was prepared through a photopolymerization composition to which 0.5 wt% was added to the mixed solution. The composition was cured for 30 seconds by spin coating the thin film obtained by 50 milliwatts of ultraviolet light to prepare a gate insulating film.
  • the structure of the prepared organic thin film transistor is shown in FIG.
  • An organic thin film transistor was prepared in the same manner as in Example 65, except that 1 wt.% Of copper ( ⁇ ) -mesophet tetrabutylbenzoporphyrin prepared in 5 was used in toluene. .
  • An organic thin film transistor was prepared using the copper ( ⁇ ) -benzoporphyrin precursor obtained in step 3 of Example 2.
  • Example 64 The same substrate as that used in Example 64 was used, wherein Large amounts of n-doped silicon were gate-wide, and 300 nanometer-thick silicon dioxide (Si) was used as the gate insulating film l ". Copper ( ⁇ ) -benzoporphyrin bulb, dissolved in 1% by weight and 2% by weight in chloroform. The sieve was spin-coated at 1000 rpm in an inert atmosphere and dried at 120 ° C. for 120 minutes at 10 ° C. for 10 minutes at 220 ° C. On the formed precursor film, the channel length and width were 50 micrometers and 1000 micrometers, respectively. A meter-in source / drain electrode was formed of 80 nanometers thick gold by thermal vacuum deposition. The organic thin film transistor structure is shown in FIG. 3.
  • the current-voltage curves of the organic thin film transistors according to the present invention are shown in FIGS. 4 to 7, and the charge mobility and the flashing ratio of the analyzed transistors are shown in Table 2.
  • the performance of the organic thin film transistor using the benzoporphyrin precursor prepared by the present invention and the printing method and the performance of the organic thin film transistor of Comparative Example 1 obtained by using the spin coating method It can be seen that the equivalent level can be obtained in preparation. Accordingly, it can be seen that the organic thin film transistor can be manufactured by using a printing method instead of the conventional spin coating method using the copper (?)-Benzoporphyrin precursor obtained by the method according to the present invention as an organic semiconductor material.
  • the organic semiconductor manufactured according to the present invention has a simple manufacturing process and is advantageous in terms of cost.
  • organic semiconductors for organic solar cells such as dye-sensitized, bulk heterojunction, hetero pn junction, and Schottky types It can be usefully used.
  • tetrabenzoporphyrin derivatives unlike benzoporphyrin precursors, have high solubility regardless of the boiling point of organic solvents and are suitable for the printing process, and also through the introduction of various substituents at the meso positions of benzoporphyrin, This suggests the possibility of manufacturing organic thin film transistor with high flashing ratio.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Thin Film Transistor (AREA)

Description

【명세서】  【Specification】

【발명의 명칭】  [Name of invention]

벤조포르피린 유도체의 신규한 제조방법 및 이를 이용한 유기박막트랜지스 터의 제조  Novel Process for the Preparation of Benzoporphyrin Derivatives and Preparation of Organic Thin Film Transistors Using the Same

【기술분야】 . Technical Field

본 발명은 벤조포르피린 유도체의 신규한 제조방법과 이를 이용한 유기박막 트랜지스터 제조에 관한 것이다. 【배경기술】  The present invention relates to a novel method for producing a benzoporphyrin derivative and to an organic thin film transistor using the same. Background Art

박막 트랜지스터 (이하， "TFT"라 한다.)는 액정 표시장치 등의 표시용 스위칭 소자로서 널리 이용되고 있다. 상기 TFT는 기판 상에 게이트 전극， 절연체층 및 반도체층을 순서로 갖고， 반도체층 상에 소정의 간격을 두고 형성된 소스 전극 및 드레인 전극을 갖고 있다. 소스 전극 및 드레인 전극의 일부는 표면에 노출되고， 양 전극 사이에서 노출되는 면에는 반도체층이 형성되어 있다. 이러한 구성의 TFT에서는， 반도체층이 채널 영역을 이루고 있고， 게이트 전극에 인가되는 전압으로 소스 전극과 드레인 전극 사이에 흐르는 전류가 제어되어 온 /오프 (ON/OFF) 동작한다. 종래, TFT는 비정질이나 다결정의 실리콘을 이용하여 제작되었지만， 이러한 실리콘을 이용한 TFT의 제작에 이용되는 CVD 장치는 고액 (高額)이며， TFT를 이용한 표시장치 등의 대형화는 제조 비용의 대폭적인 증가를 수반한다는 문제점이 있다. 또한， 비정질이나 다결정의 실리콘을 성막하는 프로세스는 매우 높은 온도 하에서 행해지므로 기판으로서 사용 가능한 재료의 종류가 한정되몌 이에 따라 경량이고 또한 유연성의 부여가 가능하며 자유롭게 형상 설계를 할 수 있는 수지 기판 등을 사용할 수 없다는 문제점이 존재한다. 만약 경량의 수지 기판 상에 TFT의 제조가 가능하게 된다면 휴대용 전자 기기에의 응용 또한 가능해질 것이다. 상기와 같은 문제를 해결하기 위해, 유기 반도체를 이용한 TFT (이하， "유기 TFT'라 한다.)가 제안된 바 있다. 유기 반도체로 TFT를 형성할 때에 이용하는 성막 방법으로서 진공 증착법이나 용액공정이 가능한 인쇄법 및 도포법 등이 알려져 있는데， 특히 인쇄법에 의한 성막 방법은 제조 비용의 상승을 억제하면서 소자의 대형화가 실현 가능하게 되고， 성막 시 요구되는 프로세스 온도를 비교적 저온으로 할 수 있다. 또한， 유기 반도체를 이용한 TFT에서는 기판에 이용하는 재료 선택의 제한이 적다는 이점이 있다. 유기 TFT 재료로 널리 알려진 펜타센 (pentacene)은 전하 이동도가 게이트 유기 절연막에 따라 최고 7 cm V 로 보고되었으며 이 펜타센의 성막 방법으로 진 공 증착법이 사용된다. 그러나 진공 증착법은 제조 비용이 고가이므로 제조 비용이 낮고 대면적 공정이 쉬운 인쇄법에 의한 유기 반도체 재료의 개발이 제기된 바 있 다. 이를 위하여 유기 용매에 용해가 가능한 치환기를 펜타센과 안트라센에 도입한 TIPS-펜타센 및 TES-ADT, diF TES-ADT등은 도포법으로 성막한 유기 TFT의 전하 이 동도가 1 cm2/V · s 이상으로 보고되었다 (Thomas N. Jackson, et,al. , Appl. Phys. Lett. , 91권， 063514 (2007)； Thomas N. Jackson, et,al. , Ap l. Phys. Lett. , 93 권， 043301 (2008)； 및 John E. Anthony, et , al . , Adv. mater. , 21권. 1166 (2009)). 그러나 성가 유기 반도체 재료를 인쇄법으로 성막할 경우， 유기 TFT의 전 하 이동 £는 0.5 cm2/V - s 이하로 낮은 수준 ^ᅵ고 재현성의 문제가 여전히 존재함이 밝혀졌다 (J. E. Anthony, et. al., IEEE Electron Device Lett 29권, 1004 (2008)). 또한, 인쇄법으로 성막 공정에서 가장 적합할 것으로 예상되는 고분자 반도 체로 폴리티오펜 유도체가 많이 연구되었으나， 전하 이동도가 0.3 cm2/V - s 이하로 보고되었다 (Beng S. Ong, et. al., Chem. Eur J.14권， 4766 (2008)). 최근에는 유기 금속 화합물 반도체 중 유기 TFT특성이 가장 우수한 것으로 알려진 구리ᅳ벤조포르 피린 전구체를 이용한 구리-벤조포르피린 유도체에 대한 연구가 계속하여 보고되고 있다. 상기 구리-벤조포르피린 전구체를 이용한 유기 TFT의 경우， 유기 용매에 불 용성인 벤조포르피린을 전구체 형태로 합성하여 유기 용매에 용해가 가능한 형태로 제조한 예로 이러한 전구체를 이용하여 용액공정으로 유기 TFT의 제조가 가능하다. 이로부터 제조된 벤조포르피린 전구체 박막은 열처리하여 벤조포르피린 형태로 전 환이 가능하다. 그러나 제조된 유기 TFT의 하 이동도는 1 cm V' s 이상으로 알 려져 있지만 (US 2007/0012914 및 US 2009/0186490), 클로로포름과 같이 끓는점이 낮은 유기 용매에 용해되므로 유기 용매의 빠른 증발 속도에 의해 박막 형성이 어 렵고 그 용해도도 낮을 뿐만 아니라， 잉크젯， 그라비아， 옵셋， 그라비아ᅳ옵셋, 리 버스 옵셋 프린팅 등의 인쇄법으로 성막하기 위해서 끓는점이 높은 유기 용매에 잘 용해가 되어야 하므로 인쇄법에 의한 유기 TFT를 제조하기 어려운 문제가 있다. 따 라서, 적합한 인쇄 공정 조건올 확립하기 어려운 실정이다. 한편， 유기 반도체를 이용한 응용 소자로 유기 태양전지가 알려져 있다. 이는 전극과 광활성충 만으로 이루어져 상기 유기 TFT에 비해 간단한 구성요소를 가지는 장점이 있다. 상기 유기 반도체를 사용한 유기 태양전지의 구조로는 색소 증감형， 벌크 헤테로 접합형， 헤테로 pn 접합형， 쇼트키형 등으로 다양하게 제안되어 있다. 벤조포르피린 유도체를 사용한 태양 전지에 관해서는， 쇼트키 접합형 소자 (K. Yamashita, et.al., Bull. Chem. S0c. Jpn., 60， (1987) 803-805) 또는 페닐렌 유도체를 전자 수용체 충으로 하는 헤테로 접합형 소자 (JP 2003- 304014)가 보고되어 있는데, 벤조포르피린 유도체를 제조하기 까다로워 상용화에 어려움을 겪고 있다. Thin film transistors (hereinafter referred to as "TFTs") are widely used as switching elements for displays, such as liquid crystal displays. The TFT has a gate electrode, an insulator layer, and a semiconductor layer in order on a substrate, and has a source electrode and a drain electrode formed at predetermined intervals on the semiconductor layer. A part of the source electrode and the drain electrode is exposed on the surface, and a semiconductor layer is formed on the surface exposed between both electrodes. In the TFT having such a configuration, the semiconductor layer forms a channel region, and the current flowing between the source electrode and the drain electrode is controlled by the voltage applied to the gate electrode to operate on / off. Conventionally, although TFTs are manufactured using amorphous or polycrystalline silicon, the CVD apparatus used for manufacturing TFTs using such silicon is expensive, and the increase in size of display devices using TFTs greatly increases manufacturing costs. There is a problem with it. In addition, the process of forming amorphous or polycrystalline silicon is performed at a very high temperature, so that the types of materials that can be used as substrates are limited. Accordingly, resin substrates that can be lightweight and flexible and can be freely shaped can be used. There is a problem that cannot be used. If the production of TFTs on a lightweight resin substrate becomes possible, the application to portable electronic devices will also be possible. In order to solve the above problems, a TFT using an organic semiconductor (hereinafter referred to as "organic TFT ') has been proposed. As a film forming method used when forming a TFT from an organic semiconductor, there are known a vacuum deposition method, a printing method and a coating method capable of a solution process, and in particular, the film forming method by the printing method can realize a larger device while suppressing an increase in manufacturing cost. The process temperature required for the film formation can be made relatively low. In addition, there is an advantage that the selection of the material used for the substrate is small in the TFT using the organic semiconductor. Pentacene, which is widely known as an organic TFT material, has reported a charge mobility of up to 7 cm V depending on the gate organic insulating film, and vacuum deposition is used as the method for forming the pentacene. However, since the vacuum deposition method is expensive, the development of an organic semiconductor material by a printing method having a low manufacturing cost and an easy large-area process has been proposed. To this end, TIPS-pentacene, TES-ADT, diF TES-ADT, etc., in which pentacene and anthracene are substituted with a dissolvable group in an organic solvent, has a charge mobility of 1 cm 2 / V It has been reported above (Thomas N. Jackson, et, al., Appl. Phys. Lett., 91, 063514 (2007); Thomas N. Jackson, et, al., Ap l. Phys. Lett., Volume 93 043301 (2008); and John E. Anthony, et, al., Adv. Mater., 21. 1166 (2009)). However, it has been found that when the anionic organic semiconductor material is deposited by printing, the charge transfer £ of the organic TFT is lower than 0.5 cm 2 / V-s and the problem of high reproducibility still exists (JE Anthony, et. al., IEEE Electron Device Lett Vol. 29, 1004 (2008)). In addition, polythiophene derivatives have been studied as a polymer semiconductor which is expected to be most suitable in the film forming process by printing method, but the charge mobility has been reported to be less than 0.3 cm 2 / V-s (Beng S. Ong, et. Al. , Chem. Eur J. 14, 4766 (2008)). Recently, studies on copper-benzoporphyrin derivatives using copper-benzobenzoporphyrin precursors, which are known to have the best organic TFT characteristics among organometallic compound semiconductors, have been reported. In the case of the organic TFT using the copper-benzoporphyrin precursor, an example in which benzoporphyrin insoluble in an organic solvent is synthesized in the form of a precursor and prepared in a form that can be dissolved in an organic solvent. Is possible. The benzoporphyrin precursor thin film prepared therefrom was heat-treated and transferred to the benzoporphyrin form. Exchange is possible. However, although the mobility of the prepared organic TFTs is known to be greater than 1 cm V 's (US 2007/0012914 and US 2009/0186490), since they are soluble in low boiling organic solvents such as chloroform, It is difficult to form a thin film and its solubility is low, and it must be well dissolved in an organic solvent having high boiling point to form a film by printing method such as inkjet, gravure, offset, gravure offset and reverse offset printing. There is a problem that it is difficult to manufacture an organic TFT. Therefore, it is difficult to establish suitable printing process conditions. On the other hand, an organic solar cell is known as an application element using an organic semiconductor. This is made of only the electrode and the photoactive filler has the advantage of having a simple component compared to the organic TFT. As the structure of the organic solar cell using the organic semiconductor, variously proposed as a dye-sensitized type, bulk heterojunction type, hetero pn junction type, Schottky type and the like. As for the solar cell using the benzoporphyrin derivative, a Schottky junction device (K. Yamashita, et. Al., Bull. Chem. S0c. Jpn., 60, (1987) 803-805) or a phenylene derivative is used. A heterojunction device (JP 2003-304014) serving as a receptor charge has been reported, which is difficult to commercialize due to the difficulty in preparing benzoporphyrin derivatives.

상기 밴조포르피린 유도체를 제조하기 위해서는 프탈이미드 (phthalimide)를 매우 높은 고온 (320 °C)에서 반응시키거나 매우 복잡한 단계 (7단계 구성)로부터 합 성된 이소인돌 유도체를 이용하여 벤조포피린 전구체를 합성해야 하는 문제가 있어 제조에 어려움을 겪고 있는 실정이다. 그리고 기존 방법으로 합성된 이소인돌 유도 체는 에스터기를 포함하고 있기 때문에 메소ᅳ위치에 치환기를 도입하기 위해서는 카복실기 이탈 반웅 (decarboxylation)을 수반해야 하는 번거로움이 있다 (L. A. ■Yakubo, et. al . , Russ. J. Gen. Chem. , 78 (2007) 1255； 및 S. Ito. , Chem. Commun. (1998) 1661). 이에， 본 발명자들은 상기 벤조포르피린 유도체의 전구물질인 이소인돌 유도체를 제조하는 방법을 연구하던 중, 얻기 쉬운 출발물질로부터 간단하면서도 높은 수율로 벤조포르피린 전구체를 합성하였으며, 이로부터 벤조포르피린 유도체를 용이하게 제조하는 방법과 벤조포르피린 전구체를 사용하여 인쇄법으로 용이하게 유기박막트랜지스터를 제조하는 방법을 발견하여 본 발명을 완성하였다. In order to prepare the banjo porphyrin derivatives, the benzoporphyrin precursor must be synthesized by reacting phthalimide at a very high temperature (320 ° C) or using isoindole derivatives synthesized from a very complicated step (7 step configuration). There is a problem that is difficult to manufacture. Since the isoindole derivative synthesized by the conventional method includes an ester group, it is cumbersome to involve carboxyl group decarboxylation in order to introduce a substituent at the mesogenic position (LA ■ Yakubo, et. Al. , Russ. J. Gen. Chem., 78 (2007) 1255; and S. Ito., Chem. Commun. (1998) 1661). Therefore, the present inventors are isoindole which is a precursor of the benzoporphyrin derivative While studying a method for preparing a derivative, a benzoporphyrin precursor was synthesized in a simple and high yield from an easy-to-get starting material, and from this, a method for easily preparing a benzoporphyrin derivative and a printing method using a benzoporphyrin precursor were easily prepared. The present invention was completed by discovering a method of manufacturing an organic thin film transistor.

【발명의 상세한 설명】 [Detailed Description of the Invention]

【기술적 과제】 - 본 발명의 목적은 벤조포르피린 유도체의 신규한 제조방법을 제공하는 데 있다.  [Technical problem]-It is an object of the present invention to provide a novel method for producing a benzoporphyrin derivative.

본 발명의 다른 목적은 벤조포르피린 전구체를 이용하여 인쇄법으로 유기박 막트랜지스터의 제조방법을 제공하는데 있다.  Another object of the present invention is to provide a method for producing an organic thin film transistor by a printing method using a benzoporphyrin precursor.

【기술적 해결방법】 Technical Solution

상기 과쎄를 해결하기 위해, : In order to solve the above gwasse:

본 발명은 상기 목적을 달성하기 위하여, 본 발명은 하기 반웅식 1에 나타 난 바와 같이，  The present invention, in order to achieve the above object, the present invention as shown in the following formula 1,

화학식 2로 표시되는 화합물을 포름산 (formic acid)과 반응시킨 후， 유기 용매하에서 디엔 (diene)과 디엘즈알더 (Diels-Alder ) 반응시켜 화학식 3으로 표시되는 화합물을 제조하는 단계 (단계 1);  Preparing a compound represented by Chemical Formula 3 by reacting the compound represented by Chemical Formula 2 with formic acid and then reacting with dienes and Diels-Alder in an organic solvent (Step 1);

상기 단계 1에서 제조된 화학식 3으로 표시되는 화합물을 암모늄하이드록사이드와 유기 용매하에서 반웅시켜 화학식 4의 화합물을 제조하는 단계 (단계 2);  Preparing a compound represented by Chemical Formula 4 by reacting the compound represented by Chemical Formula 3 prepared in Step 1 in an ammonium hydroxide and an organic solvent (Step 2);

상기 단계 2에서 제조된 화학식 4의 화합물을 산 및 유기 용매하에서 알데히드 (R2C(=0)H)와 반웅시켜 화학식 5의 벤조포르피린 전구체를 제조하는 단계 (단계 3); 및 Reacting the compound of Formula 4 prepared in Step 2 with aldehyde (R 2 C (= 0) H) in an acid and an organic solvent to prepare a benzoporphyrin precursor of Formula 5 (step 3); And

상기 단계 3에서 제조된 화학식 5의 벤조포르피린 전구체를 고온에서 처리하여 화학식 1의 벤조포르피린을 제조하는 단계 (단계 4)를 포함하여 이루어지는 벤조포르피린 유도체의 신규한 제조방법을 제공한다:  It provides a novel method for preparing a benzoporphyrin derivative comprising the step (step 4) of preparing a benzoporphyrin of formula 1 by treating the benzoporphyrin precursor of formula 5 prepared in step 3 at a high temperature:

[반웅식 1] [Banungsik 1]

Figure imgf000006_0001
또한 본 발명은 하기 화학식 5로 표시되는 벤조포르피린 전구체를 인쇄법을 아용하여 유기 반도체 채널로 도입시키는 단계를 포함하는 유기박막트랜지스터의 제조방법을 제공한다;
Figure imgf000006_0001
In another aspect, the present invention provides a method for producing an organic thin film transistor comprising the step of introducing the benzoporphyrin precursor represented by the following formula (5) to the organic semiconductor channel using a printing method;

[화학식 5] [Formula 5]

Figure imgf000006_0002
(상기 화학식 5에서， A, R2및 M은 본 명세서에서 기재한 바와 같다).
Figure imgf000006_0002
(In Formula 5, A, R 2 and M are as described herein).

【유리한 효과】 Advantageous Effects

본 발명에 따른 벤조포르피린 유도체의 신규한 제조방법은 종래에 알려진 벤조포르피린 유도체의 제조방법에 비해 제조공정 단계를 현저히 줄임으로써 목적 화합물인 벤조포르피린 유도체를 경제적으로 얻을 수 있으며, 또한 벤조포르피린 전구체를 끓는 점이 다른 흔합 유기 용매에 용해시켜 인쇄법을 수행함으로써 고이 동도의 유기박막트랜지스터을 제조할 수.있다. 【도면의 간단한 설명】  The novel method for preparing a benzoporphyrin derivative according to the present invention can economically obtain a benzoporphyrin derivative as a target compound by significantly reducing the production process step compared to a method for preparing a benzoporphyrin derivative known in the art, and also boiling a benzoporphyrin precursor. The organic thin film transistor of high degree of mobility can be manufactured by performing a printing method by dissolving in a mixed organic solvent having different points. [Brief Description of Drawings]

도 1은 실시예 64에서 본 발명에 따른 유기박막트랜지스터의 구조를 나타낸 도면이다.  1 is a view showing the structure of an organic thin film transistor according to the present invention in Example 64.

상기 도 1에 나타낸 부호는 하기와 같다:  The symbols shown in FIG. 1 are as follows:

1： 다량의 n도핑된 Si 웨이퍼 기판 (게이트 전극);  1: large amount of n-doped Si wafer substrate (gate electrode);

2： Si02 (300nm) 게이트 절연막; 2: Si0 2 (300 nm) gate insulating film;

3： 본 발명에 따른 유기 반도체 ;  3: organic semiconductor according to the present invention;

4： 소스 전극; 및  4: source electrode; And

5： 드레인 전극. 도 2는 실시예 65에서. 제조된 유기박막트랜지스터의 구조를 나타낸 도면이다.  5: Drain electrode. 2 is in Example 65. A diagram showing the structure of the manufactured organic thin film transistor.

상기 도 2에 나타낸 부호는 하기와 같다:  The symbols shown in FIG. 2 are as follows:

1: 다량의 n도핑된 Si 웨이퍼 및 Si02 ( 300nm)가 성장된 기판; 1: substrate in which a large amount of n-doped Si wafer and Si0 2 (300 nm) were grown;

3: 본 발명에 따른 유기 반도체;  3: organic semiconductor according to the present invention;

4: 소스 전극;  4: source electrode;

5： 드레인 전극;  5: drain electrode;

6： 게이트 전극; 및  6: gate electrode; And

21： 유기 게이트 절연막. 도 3은 비교예 1 내지 비교예 2에서 본 발명에 따른 유기박막트랜지스터의 구조를 나타낸 도면이다. 21: Organic gate insulating film. 3 is a view showing the structure of an organic thin film transistor according to the present invention in Comparative Examples 1 to 2.

상기 도 3에 나타낸 부호는 하기와 같다:  The symbols shown in FIG. 3 are as follows:

1: 다량의 n도핑된 Si 웨이퍼 기판 (게이트 전극);  1: large amount of n-doped Si wafer substrate (gate electrode);

2： Si02 (300nm) 게이트 절연막; 2: Si0 2 (300 nm) gate insulating film;

3： 본 발명에 따른 유기 반도체;  3: organic semiconductor according to the present invention;

4 소스 전극; 및  4 source electrode; And

5： 드레인 전극. 도 4는 실시예 64에서 제조된 게이트 절연막이 Si 인 유기박막트랜지스터에 대한 전류 -전압 곡선이다. 도 5는 실시예 65에서 제조된 게이트 절연막이 유기 절연막인 유기박막트랜지스터에 대한 전류ᅳ전압 곡선이다. 도 6은 비교예 1에서 1 %의 구리ᅳ벤조포르피린 전구체를 사용하여 박막을 형성한 유기박막트랜지스터의 전류 -전압 곡선이다. 도 7은 비교예 2에서 2 %의 구리-밴조포르피린 전구체를 사용하여 박막을 형성한 유기박막트랜지스터의 전류 -전압 곡선이다.  5: Drain electrode. 4 is a current-voltage curve for an organic thin film transistor of which the gate insulating film prepared in Example 64 is Si. 5 is a current ᅳ voltage curve for an organic thin film transistor in which the gate insulating film prepared in Example 65 is an organic insulating film. 6 is a current-voltage curve of an organic thin film transistor in which a thin film is formed using 1% copper benzobenzoporphyrin precursor in Comparative Example 1. FIG. FIG. 7 is a current-voltage curve of an organic thin film transistor in which a thin film is formed using 2% copper-banjo porphyrin precursor in Comparative Example 2. FIG.

【발명의 실시를 위한 최선의 형태】 [Best form for implementation of the invention]

이하， 본 발명을 상세히 설명한다. 본 발땅은 하기 반웅식 1에 나타난 바와 같이，  Hereinafter, the present invention will be described in detail. As shown in Banungsik 1,

화학식 2로 표시되는 화합물을 포름산 (formic acid)과 반웅시킨 후, 유기 용매하에서 디엔 (diene)과 디엘즈알더 (Diels-Alder) 반웅시켜 화학식 3으로 표시되는 화합물을 제조하는 단계 (단계 1);  Reacting the compound represented by the formula (2) with formic acid and then reacting with diene and Dies-Alder in an organic solvent to prepare a compound represented by the formula (3) (step 1);

상기 단계 1에서 제조된 화학식 3으로 표시되는 화합물을 암모늄하이드록사이드와 유기 용매하에서 반웅시켜 화학식 4의 화합물올 제조하는 단계 (단계 2)； Compound represented by Formula 3 prepared in Step 1 Reacting with ammonium hydroxide in an organic solvent to prepare a compound of formula 4 (step 2);

상기 단계 2에서 제조된 화학식 4의 화합물을 산 및 유기 용매하에서 알데히드 (R2C(=0)H)와 반웅시켜 화학식 5의 벤조포르피린 전구체를 제조하는 단계 (단계 3); 및 Reacting the compound of Formula 4 prepared in Step 2 with aldehyde (R 2 C (= 0) H) in an acid and an organic solvent to prepare a benzoporphyrin precursor of Formula 5 (step 3); And

상기 단계 3에서 제조된 화학식 5의 벤조포르피린 전구체를 고온에서 처리하여 화학식 1의 벤조포르피린을 제.조하는 단계 (단계 4)를 포함하여 이루어지는 멘조포르피린 유도체의 신규한 제조방법을 제공한다:  It provides a novel method for preparing a menzoporphyrin derivative comprising the step (step 4) of preparing a benzoporphyrin of formula 1 by treating the benzoporphyrin precursor of formula 5 prepared in step 3 at a high temperature:

[반웅식 1]  [Banungsik 1]

Figure imgf000009_0001
Figure imgf000009_0001

상기 반웅식 1에서

Figure imgf000009_0002
In the reaction 1
Figure imgf000009_0002

R1은 수소 또는 d~C12의 직쇄 또는 측쇄 알킬이고， R 1 is hydrogen or d or C 12 straight or branched alkyl,

R2는 수소， d~C12의 직쇄 또는 측쇄 알킬, 비치환 또는 1 이상의 d Cs의 직쇄 또는 측쇄 알킬, 할로겐， d~C3의 알콕시， d~C3의 알킬에스터로 치환된 페닐， 고리 내 N, 0 또는 S를 포함하는 5원 또는； 6원의 헤테로 아릴， 二 T S 또는 ᅳ"≡— TIPS: 또는ᅳ~ =ᅳ" Z이고， R 2 is hydrogen, d to C 12 straight or branched chain alkyl, unsubstituted or at least one d Cs Straight or branched alkyl, halogen, d-C 3 alkoxy, phenyl substituted by d-C 3 alkylester, 5- or N-membered including N, 0 or S in the ring; 6-membered heteroaryl, 二 TS or ᅳ "≡— TIPS: or ᅳ ~ = ᅳ " Z,

M은 Cu, Ζη또는 Ni이다. 이하， 본 발명에 따른 테트라벤조포르피린 유도체의 제조방법을 단계별로 더욱 구체적으로 설명한다. 먼저， 상기 단계 1은 화학식 2로 표시되는 화합물을 포름산 (formic acid)과 반응시킨 후, 유기 용매하에서 디엔 (diene)과 디엘즈알더 (Diels-Alder) 반응시켜 화학식 3으로 표시되는 화합물을 제조하는 단계이다. M is Cu, Ζη, or Ni. Hereinafter, the method for preparing the tetrabenzoporphyrin derivative according to the present invention will be described in more detail step by step. First, Step 1 is a reaction of the compound represented by the formula (2) with formic acid (formic acid), and then reacted with dienes (Diels-Alder) in an organic solvent to prepare a compound represented by the formula (3) Step.

상기 단계 1에서 유기 용매로는 에틸아세테이트， 메틸렌클로라이드， 아세톤 핵산, 디에틸에테르， 디이소프로필에테르 등을 사용할 수 있고, 바람직하게는 메틸렌클로라이드를 사용할 수 있다. 또한， 상기 단계 1의 반웅온도는 4Q 내지 50 °C가 바람직하고, 45 °C가 더욱 바람직하다. ᅳ 만약, 상기 온도보다 반응 온도가 낮은 경우， 반응 수율이 낮아지는 문제점이 있다. 다음으로， 본 발명에 따른 상기 단계 2는 상기 단계 1에서 제조된 화학식 3으로 표시되는 화합물을 암모늄하이드록사이드와 유기 용매하에서 반웅시켜 화학식 4의 화합물을 제조하는 단계이다. As the organic solvent in step 1, ethyl acetate, methylene chloride, acetone nucleic acid, diethyl ether, diisopropyl ether and the like may be used, and methylene chloride may be preferably used. In addition, the reaction temperature of step 1 is preferably 4Q to 50 ° C, more preferably 45 ° C. ᅳ If the reaction temperature is lower than the above temperature, there is a problem that the reaction yield is lowered. Next, Step 2 according to the present invention is a step of preparing a compound of Formula 4 by reacting the compound represented by Formula 3 prepared in Step 1 in an ammonium hydroxide and an organic solvent.

상기 단계 2의 유기 용매로는 디에틸에테르, 디이소프로필에테르ᅳ 에틸렌글라이콜디메틸에테르 등을 사용할 수 있고， 바람직하게는 에틸렌글라이콜디메틸에테르를 사용할 수 있다. 또한， 상기 단계 2에서 암모늄하이드록사이드의 추가는 질소 분위기하에서 진행하는 것이 바람직하다 . As the organic solvent of step 2, diethyl ether, diisopropyl ether ethylene glycol dimethyl ether, and the like may be used, and preferably ethylene glycol dimethyl ether may be used. In addition, the addition of ammonium hydroxide in step 2 is carried out under a nitrogen atmosphere It is advisable to proceed.

만약， 질소분위기하에서 진행되지 않으면 반응 수율이 낮아지는 문제점이 있다. 본 발명에 따른 상기 단계 3은 상기 단계 2에서 제조된 화학식 5의 화합물을 산 (acid) 및 유기 용매 하에서 알데히드 (R2C(=0)H)와 반응시켜 화학식 5의 밴조포르피린 전구체를 제조하는 단계이다. If it does not proceed in a nitrogen atmosphere, there is a problem that the reaction yield is lowered. Step 3 according to the present invention is to prepare a banjo porphyrin precursor of formula 5 by reacting the compound of formula 5 prepared in step 2 with an aldehyde (R 2 C (= 0) H) in an acid and an organic solvent Step.

상기 단계 3에서 사용되는 산 (acid)은 트리플루오르아세트산 (TFA) 또는 보론트리플루오르디에틸에테르인 것이 바람직하다. 또한， 상기 단계 3의 유기 용매는 에틸아세테이트, 메틸렌클로라이드, 핵산 디에틸에테르， 메탄을， 에탄을 등을 단독으로 또는 흔합하여 사용할 수 있고 바람직하게는 메틸렌클로라이드를 사용할 수 있다. 본 발명에 따른 상기 단계 4는 기 단계 3에서 제조된 화학식 5의 벤조포르피린 전구체를 고온에서 처리하여 화학식 1의 벤조포르피린을 제조하는 단계이다.  The acid used in step 3 is preferably trifluoroacetic acid (TFA) or borontrifluorodiethyl ether. In addition, the organic solvent of step 3 may be used alone or in combination of ethyl acetate, methylene chloride, nucleic acid diethyl ether, methane, ethane and the like, preferably methylene chloride may be used. Step 4 according to the present invention is a step of preparing the benzoporphyrin of Formula 1 by treating the benzoporphyrin precursor of Formula 5 prepared at Step 3 at a high temperature.

상기 단계 4의 반웅은 200 내지 250 °C에서 5 내지 30분간 진행되는 것이 바람직하고, 220 °C에서 10분간， 150°C에서 120분간 진행하는 것이 더욱 바람직하다. 본 발명에 따른 벤조포르피린 유도체의 신규한 제조방법은 종래에 알려진 벤조포르피린 유도체의 제조방법에 비해 제조공정 단계를 현저히 줄임으로써 목적 화합물인 벤조포르피린 유도체를 경제적으로 얻을 수 있다. 또한 본 발명은 하기 화학식 5로 표시되는 벤조포르피린 전구체를 유기 반도체 채널로 도입시키는 단계를 포함하는 유기박막트랜지스터의 제조방법을 제공한다; 【화학식 5] The reaction of step 4 is preferably performed at 200 to 250 ° C. for 5 to 30 minutes, more preferably at 220 ° C. for 10 minutes and at 150 ° C. for 120 minutes. The novel method for preparing a benzoporphyrin derivative according to the present invention can economically obtain a benzoporphyrin derivative, which is a target compound, by significantly reducing the production process step compared to a method for preparing a benzoporphyrin derivative known in the art. In another aspect, the present invention provides a method for producing an organic thin film transistor comprising the step of introducing a benzoporphyrin precursor represented by the formula (5) to the organic semiconductor channel; [Formula 5]

Figure imgf000012_0001
Figure imgf000012_0001

(상기 화학식 5에서, A, R2및 M은 상기 반웅식 1에서 정의된 바와 같다). 본 발명에 따른 상기 화학식 5를 유기 반도체 채널로 도입하는 단계는 유기절연막 위에 인쇄법을 이용하여 소스 전:극과 드레인 전극 사이에 유기 반도체 채널을 도입하여 유기박막트랜지스터를 제조하는 단계이다. (In Formula 5, A, R 2 and M are as defined in Banung Formula 1). The step of introducing the general formula (5) in accordance with the present invention an organic semiconductor channel is the source before using the printing method on the organic insulating film: a step of preparing an organic thin film transistor by introducing the organic semiconductor channel between the poles and the drain electrode.

상기 단계에서 소스 전극과 드레인 전극 사이에 반도체 채널을 인쇄법으로 도입하는 것은 대면적 공정이 쉽고， 제조 비용이 낮으며， 복잡한 패턴도 형성할 수 있어 유용하다. 본 발명에 따른 상기 인쇄법은 잉크젯 프린팅법， 그라비아법 , 그라비아- 읍셋법， 스크린 인쇄법, 슬릿 -다이 코팅법, 스크린 인쇄법， 플렉소 인쇄법 등을 사용할 수 있고, 바람직하게는 잉크젯 프린팅법을 사용할 수 있다.  In this step, the introduction of the semiconductor channel between the source electrode and the drain electrode by the printing method is easy because a large area process is easy, the manufacturing cost is low, and a complicated pattern can be formed. The printing method according to the present invention may use an inkjet printing method, a gravure method, a gravure-eupset method, a screen printing method, a slit-die coating method, a screen printing method, a flexographic printing method, and the like, preferably an inkjet printing method Can be used.

잉크곗 프린팅법은 공정이 간단하고 설비 비용 ·제조 비용을 낮출 수 있고 재료를 원하는 패턴 위치에 퇴적시켜서 원칙적으로 재료의 손실이 없어서 원료의 낭비가 없고, 환경적인 부하가 적다. 또한 포토 리소그래픽과 같이 현상ᅳ에칭 등의 공정이 필요 없기 때문에 화학적 영향으로 기판이나 재료의 특성이 열화되는 경우가 없을 뿐만 아니라 비접촉식 인쇄 방식이어서 접촉에 의한 디바이스 손상이 없으며 요철이 있는 기판으로의 패턴도 가능하다는 장점이 있다. 또한 본 발명에 따른 벤조포르피린 전구체를 상기 인쇄법으로 유기박막트랜지스터를 제조하기 위해서는 끓는점이 서로 다른 흔합 유기 용매를 사용하여야 하며， 바람직하게는 흔합 유기 용매 증 1종 이상은 그 끓는점이 100 °c 이상인 것을 사용하여야 한다. The inkjet printing method can simplify the process, lower the equipment cost and manufacturing cost, and deposit the material in the desired pattern position, so that there is no material loss in principle, so there is no waste of raw materials and less environmental load. In addition, the photolithography process does not require the development and etching process, so the chemical influence does not deteriorate the characteristics of the substrate or the material, and it is a non-contact printing method, which does not damage the device due to contact. It also has the advantage of being possible. In addition, in order to prepare an organic thin film transistor using the printing method of the benzoporphyrin precursor according to the present invention, a common organic solvent having different boiling points At least one of the mixed organic solvents should be used with a boiling point of 100 ° C. or higher.

본 발명에서 제조된 벤조포르피린 전구체는 끓는점이 낮은 (100 °C<) 유기 용매에만 용해되기 때문에 끓는점이 100 °C 이상인 유기 용매를 1종 이상 흔합하지 않고 인쇄법으로 사용했을 때， 인쇄장치의 노즐에서 건조가 진행되어 노즐이 일부 막히는 현상으로 인해 젯팅하기 어렵고， 또 노즐에서 토출된 액적이 직진성을 잃어 원하는 위치에 프린팅하기 어려운 단점이 있다. 상기 인쇄법을 이용하는 단계에서 벤조포르피린 전구체을 용해시키는 용매로는 메틸렌클로라이드， . ；클로로포름, 에틸아세테이트， 테트라하이드로퓨란 (tetrahydrofuran), 에탄을, 메탄올 등을 단독으로 또는 흔합하여 사용할 수 있고 바람직하게는 클로로포름을 사용할 수 있으며， 끓는점이 100 °C 이상인 유기 용매로는 클로로벤젠， 디에틸렌글리콜， 트리클로로벤젠， 다이클로로벤젠， 오르쏘다이클로로벤젠, 사이클로핵사논， 메틸에틸케톤， 메틸자일렌, 디메틸설폭사이드 (DMSO: Dimethyl sulfoxide), 디메틸포름아미드 (DMF: Dithylformamide)등을 흔합하여 사용할 수 있고 바람직하게는 클로로벤젠을 사용할 수 있다. Since the benzoporphyrin precursor prepared in the present invention is dissolved only in an organic solvent having a low boiling point (100 ° C <), when the organic solvent having a boiling point of 100 ° C or more is used as a printing method without mixing at least one organic solvent, the nozzle of the printing apparatus It is difficult to jet due to the phenomenon that the nozzle is clogged due to the drying in progress, and the droplets discharged from the nozzle lose the straightness and are difficult to print at a desired position. A solvent in which the porphyrin benzo jeongucheeul dissolved in utilizing the printing method is methylene chloride. Chloroform, ethyl acetate, tetrahydrofuran, ethane, methanol, etc. can be used alone or in combination. Preferably chloroform can be used. As an organic solvent having a boiling point of 100 ° C. or higher, chlorobenzene, di Ethylene glycol, trichlorobenzene, dichlorobenzene, orthodichlorobenzene, cyclonuxanone, methyl ethyl ketone, methyl xylene, dimethyl sulfoxide (DMSO), dimethylformamide (DMF) It is possible to use and preferably chlorobenzene.

【발명의 실시를 위한 형태】 [Form for implementation of invention]

이하， 본 발명을 실시예 및 실험예에 의하여 상세히 설명한다.  Hereinafter, the present invention will be described in detail by Examples and Experimental Examples.

단， 하기 실시예 및 실험예는 본 발명을 구체적으로 예시하는 것이며， 본 발명의 내용이 실시예 및 실험예에 의해 한정되는 것은 아니다.  However, the following Examples and Experimental Examples specifically illustrate the present invention, and the content of the present invention is not limited to the Examples and Experimental Examples.

하기 실시예에서 출발물질로 사용된 1-브로모ᅳ4, 4-디에특시 -2ᅳ부타인 (2)은 참고문헌 미국등록특허 US48004769 A1에 따 제조되었다.. 1-Bromox4, 4-Dietex-2zbutane (2), used as starting material in the following examples, was prepared according to reference US Pat. No. 4,800,471 A1.

<실시예 1> Cu(II)ᅳ메조—테트라핵실벤조포르피린 (la)의 제조 단계 1： 3- (브로모메틸)바이사이클로 [2.2.2]옥타 -2， 5-디엔 -2- 카바알데하이드 (3a)의 제조 Example 1 Preparation of Cu (II) ᅳ meso-tetranuxylbenzoporphyrin (la) Step 1: 3- (bromomethyl) bicyclo [2.2.2] octa-2,5-diene-2- Preparation of Carbaaldehyde (3a)

Figure imgf000014_0001
Figure imgf000014_0001

질소 하에서' 화학식 2의 1-브로모 -4, 4-디에특시 -2-부타인 (5.6 g, 0.026 mole)을 포믹산 (formic acid)(6.0 mL, 0.16 mole)에 녹인 다음 45 °C에서 2.5시간 동안 교반하였다. 이어서 메틸렌클 I로라이드 (C¾C12)(50 mL)와 1，3- 사이클로핵사디엔 (4.0 mL, 0.042 mole)을 : 첨가하고 48시간 동안 45 °C에서 교반하고, 실은으로 냉각시킨 다음 증류수와 메틸렌클로라이드로 유기층을 분리하였다. 무수 Na2S04로 유기층을 건조시킨 후 감압여과하고 용매를 제거하였다. 실리카겔 컬럼 크로마토그래피 (C¾C12)로 분리하여 목적화합물인 3- (브로모메틸)바이사이클로 [2.2.2]옥타 -2，5—디엔 -2-카바알데하이드 (3a)를 4 ' 1-bromo of the formula (2) under nitrogen, 4-diethoxy-2-butanone in particular (5.6 g, 0.026 mole) of PO acid (formic acid) (6.0 mL, 0.16 mole) and then dissolved in 45 ° C Stirred for 2.5 h. Then methylene class I low-grade (C¾C1 2) (50 mL) and 1,3-cyclo hex-diene (4.0 mL, 0.042 mole) of: was added and stirred at 45 ° C for 48 hours, cooled to and then distilled water and in fact The organic layer was separated by methylene chloride. The organic layer was dried over anhydrous Na 2 SO 4 , filtered under reduced pressure and the solvent was removed. Separation was carried out by silica gel column chromatography (C¾C1 2 ) to prepare 3- (bromomethyl) bicyclo [2.2.2] octa-2,5—diene-2-carbaaldehyde (3a) as a target compound.

얻었다 (수율 2.7 g, 46%). Obtained (yield 2.7 g, 46%).

¾ NMR: δ 9.89 (s, 1H), 6.40—6.34 (m, 2H) , 4.53-4.44 (m, 2H), 4.31- 4.28(m, 1H), 3.79-3.76(m, 1H) , 1.52-1.21 (m, 4H) . 단계 2: 4,7—디하이드로 -4,그에타노 -2Hᅳ이소인돌 (4a)의 제조  ¾ NMR: δ 9.89 (s, 1H), 6.40—6.34 (m, 2H), 4.53-4.44 (m, 2H), 4.31- 4.28 (m, 1H), 3.79-3.76 (m, 1H), 1.52-1.21 (m, 4 H). Step 2: Preparation of 4,7-Dihydro-4, Getano-2H ᅳ isoindole (4a)

Figure imgf000014_0002
Figure imgf000014_0002

상기 단계 1에서 ' ¾은 화학식 3a의 3- ' ¾ in step 1 is 3-

(브로모메틸)바이사이클로 [2.2.2]옥타 -2， 5-디엔 -2-카바알데하이드를 에틸렌 글라이콜 디메틸 에테르 (15 mL, 0.49 M)에 녹인 다음 질소 하에서 N¾0H(4.2 mL, 30 腿 ole)를 첨가하였다. 실온에서 2시간 동안 교반하고, 증류수와 CH2C12로 유기층을 분리하였다. 무수 Na2S04로 유기층올 건조시킨 후 감압여과하고 용매를 제거하였다. 실리카겔 컬럼 크로마토그래피 (C¾C12)로 분리하여 목적화합물인 4，그 디하이드로ᅳ4，7-에타노 -2H-이소인돌 (4a)을 얻었다 (수율 0.73 g, 68%). Έ NMR: δ 7.53 (br s, 1H), 6.52 (d, 1H), 6.50 (d, 1H)， 6.45 (d, 1H) 3.85(m, 2H), 1.54(m, 4H). 단계 3: Cu(II)-메조 -테트라핵실벤조포르피린 전구체 (5a)의 제조 (Bromomethyl) bicyclo [2.2.2] octa-2,5-diene-2-carbaaldehyde was dissolved in ethylene glycol dimethyl ether (15 mL, 0.49 M) and then N¾0H (4.2 mL, 30 腿) under nitrogen. ole) was added. After stirring for 2 hours at room temperature, the organic layer was separated with distilled water and CH 2 C1 2 . The organic layer was dried over anhydrous Na 2 SO 4 , filtered under reduced pressure and the solvent was removed. Separation was carried out by silica gel column chromatography (C¾C1 2 ) to obtain the title compound 4, dihydrox4,7-ethano-2H-isoindole (4a) as a target compound (yield 0.73 g, 68%). NMR: δ 7.53 (br s, 1H), 6.52 (d, 1H), 6.50 (d, 1H), 6.45 (d, 1H) 3.85 (m, 2H), 1.54 (m, 4H). Step 3: Preparation of Cu (II) -Meso-tetranuxylbenzoporphyrin Precursor 5a

Figure imgf000015_0001
Figure imgf000015_0001

상기 단계 2에서 얻은 화학식 4a의 4，그디하이드로-4，그에타노-211- 이소인돌 (0.43 g, 3.0 麵 ole)을 CH2C12(300 mL, 0.01 M)에 녹인 다음 헵타날 (0.42 mL, 3.0醒 ole)과 TFA (0.022 mL, 0.3賺 ole)를 첨가하고 12시간 동안 교반시켰다. 이어서 2 ,3-디클로로 -5， 6-디시아노 -1， 4—벤조퀴논 (DDQ) (0.74 g, 3.3 隱 ole)을 첨가하고 1시간 동안 다시 교반시켰다. 반응 용액을 알루미나 컬럼 크로마토그래피 (CH2C12:THF = 9:1)로 통과시킨 후 용매를 제거하고， C¾C12와 메탄올을 9:1로 흔합한 용액 (60 mL, 0.05 에 다시 녹인 다음 Cu(0Ac)2(0.54 g 3.0 隱 ole)를 첨가하고 15분 동안 교반 ¼였다. 증류수와 C¾C12로 유기층을 분리하였고， 무수 Na2S04로 유기층을 건조시킨 후 감압여과하고 용매를 제거하였다. 실리카겔 컬럼 크로마토그래피 (C¾C12:핵산 = 3:7)로 분리하여 목적 화합물인 Cu(II)ᅳ메조 -테트라핵실벤조포르피린 전구체 (5a)를 얻었다 (수율 0.17 g, 22%) . 4, Gdihydro-4, etano-211-isoindole (0.43 g, 3.0 麵 ole) of Chemical Formula 4a obtained in step 2 was dissolved in CH 2 C1 2 (300 mL, 0.01 M), and then heptane (0.42 mL). , 3.0 醒 ole) and TFA (0.022 mL, 0.3 賺 ole) were added and stirred for 12 hours. Then 2,3-dichloro-5, 6-dicyano-1, 4-benzoquinone (DDQ) (0.74 g, 3.3 dl ole) was added and stirred again for 1 hour. Pass the reaction solution through alumina column chromatography (CH 2 C1 2 : THF = 9: 1), remove the solvent, dissolve C¾C1 2 and methanol in 9: 1 solution (60 mL, 0.05 again, and then Cu (0Ac) 2 (0.54 g 3.0 ole) was added and stirred for 15 minutes. The organic layer was separated with distilled water and C¾C1 2 , dried over anhydrous Na 2 S0 4 , filtered under reduced pressure, and the solvent was removed. Separation was carried out by silica gel column chromatography (C¾C1 2 : nucleic acid = 3: 7) to obtain Cu (II) ᅳ mezo-tetranuxylbenzoporphyrin precursor (5a) as a target compound (yield 0.17 g, 22%).

질량분석: 계산값 1019.60， 측정값 1020.12 단계 4: Cu( II)—메조 -테트라핵실벤조포르피린 (la)의 제조 Mass spectrometry: calculated value 1019.60, measured value 1020.12 Step 4: Preparation of Cu (II) —meso-tetranuxylbenzoporphyrin (la)

Figure imgf000016_0001
Figure imgf000016_0001

상기 단계 3에서 얻은 화학식 5a의 Cu(II)—메조ᅳ테트라핵실벤조포르피린 전구체 (0.056 g, 0.049腿 ole)를 220 °C에서 10 분간 가열하고 실온으로 넁각시킨 다음 실리카겔 컬럼크로마토그래피 (C¾Cl2:Hexanes = 3:7)로 분리하여 목적 화합물인 Cu(II)-메조ᅳ테트라핵실벤조포르피린 (la)을 얻었다 (수율 0.049 g, 99%) . Cu (II) —Mezothet tetranuxylbenzoporphyrin precursor (0.056 g, 0.049 腿 ole) of Formula 5a obtained in step 3 was heated at 220 ° C. for 10 minutes, cooled to room temperature, and then silica gel column chromatography (C¾Cl 2 : Hexanes = 3: 7) to obtain Cu (II) -mesophet tetranucleosilbenzoporphyrin (la) as a target compound (yield 0.049 g, 99%).

질량분석: 계산값 907.47， 측정값 908.01.  Mass spectrometry: calculated 907.47, measured 908.01.

<실시예 2> Cu( II)-벤조포르피린의 제조 Example 2 Preparation of Cu (II) -benzoporphyrin

단계 1 및 단계 2: 4，교디하이드로ᅳ 4,그에타노 -2Hᅳ이소인돌 (6a)의 제조

Figure imgf000016_0002
Steps 1 and 2: 4, Preparation of Kyodihydrosene 4, Getano-2H'Isoindole (6a)
Figure imgf000016_0002

상기 실시예 1의 단계 1 및 단계 2와 동일한 방법에 의해 목적 화합물인 4 ,그디하이드로ᅳ4，그에타노 -2H-이소인돌 (4a)을 제조하였다. 단계 3: Cu(II)-밴조포르피린 전구체 (5b)의 제조

Figure imgf000017_0001
In the same manner as in Step 1 and Step 2 of Example 1, 4, gdihydro @ 4 and etano-2H-isoindole (4a) as target compounds were prepared. Step 3: Preparation of Cu (II) -Banzoporphyrin Precursor (5b)
Figure imgf000017_0001

5 b  5 b

헵타날 대신 포름알데하이드를 사용한 것을 제외하고는 상기 실시예 1의 단계 3와 동일한 방법에 의해 목적 화합물인 Cu(II)-벤조포르피린 전구체 (5b)를 제조하였다. 단계 4: Cu(II)-벤조포르피린 (lb)의 제조  A target compound Cu (II) -benzoporphyrin precursor (5b) was prepared by the same method as Step 3 of Example 1, except that formaldehyde was used instead of heptane. Step 4: Preparation of Cu (II) -benzoporphyrin (lb)

Figure imgf000017_0002
Figure imgf000017_0002

상기 실시예 1의 단계 4와 동일한 방법에 의해 목적 화합물인 Cu(II)- 벤조포르피린 (lb)을 제조하였다.  In the same manner as in Step 4 of Example 1, Cu (II) -benzoporphyrin (lb) as a target compound was prepared.

<실시예 3내지 실시예 21> <Example 3 to Example 21>

실시예 1의 단계 3에서 사용한 헵타날 대신 하기 표 1의 치환기 R을 갖는 알데하이드 (R-CH0)를 사용한 것을 제외하고， 상기 실시예 1과 동일한 방법으로 실시예 3 내지 21의 화합물을 제조하였다. 이때, 실시예 19 내지 21은 TFA 대신 산촉매로 BF3 ·0Ε12를 사용하였다. 수율 및 질량 분석값은 하기 표 1에 나타내었다. <실시예 22 내지 42> The compounds of Examples 3 to 21 were prepared in the same manner as in Example 1, except that aldehyde (R-CH0) having a substituent R of Table 1 was used instead of the heptanol used in Step 3 of Example 1. In this case, Examples 19 to 21 used BF 3 · 0Ε1 2 as the acid catalyst instead of TFA. Yields and mass spectrometry values are shown in Table 1 below. <Examples 22 to 42>

실시예 1의 단계 3에서 사용한 헵타날 대신 하기 표 1의 치환기 R을 갖는 알데하이드 (R-CH0)를 사용한 것과 Cu(0Ac)2 대산 ¾(0Ac)2를 사용한 것을 제외하고 상기 실시예 1과 동일한 방법으로 실시예 22 내지 42의 화합물을 제조하였다. 이때 실시예 40 내지 42은 TFA 대신 산촉매로 BF3.0Et2를 사용하였다. 수율 및 질량 분석값은 하기 표 1에 나타내었다. Example 1 The same procedure as in Example 1 except for using aldehyde (R-CH0) having a substituent R of Table 1 and Cu (0Ac) 2 acid ¾ (0Ac) 2 instead of the heptanol used in step 3 of Example 1 The compound of Examples 22-42 was prepared by the method. The Examples 40 to 42 was used as the BF 3 .0Et 2 as the acid catalyst instead of TFA. Yields and mass spectrometry values are shown in Table 1 below.

<실시예 43 내지 63> <Examples 43 to 63>

실시예 1의 단계 3에서 사용한 헵타날 대신 하기 표 1의 치환기 R을 갖는 알데하이드 (R-CH0)를 사용한 것과 Cu(0Ac)2 대신 Ni(0Ac)2를 사용한 것과 과량의 Et3N을 첨가하고 가열한 것을 제외하고， 상기 실시예 1과 동일한 방법으로 실시예 43 내지 63의 화합물을 제조하였다. 이때， 실시예 61 내지 63은 TFA 대신 산 촉매 로 BF3OEt2를 사용하였다. 수율 및 질량 분석값은 하기 표 1에 나타내었다. Example 1 Step 3 heptane to instead appear with an aldehyde (R-CH0) having a substituent R in Table 1 as Cu (0Ac) 2 instead of Ni (0Ac) was added as was used for 2 Excess Et 3 N used in the Except for heating, the compounds of Examples 43 to 63 were prepared in the same manner as in Example 1. In this case, Examples 61 to 63 used BF 3 OEt 2 as an acid catalyst instead of TFA. Yields and mass spectrometry values are shown in Table 1 below.

[표 1】 ' [Table 1] '

Figure imgf000018_0001
Figure imgf000018_0001

Figure imgf000019_0001
Figure imgf000019_0001

Figure imgf000020_0001
Figure imgf000021_0001
Figure imgf000020_0001
Figure imgf000021_0001

<실시예 64> 인쇄법에 의한 구리 (Π)-벤조포르피린의 유기박막트랜지스터의 제조 Example 64 Preparation of Organic Thin Film Transistors of Copper (Π) -Benzoporphyrin by Printing Method

상기 실시예 2의 단계 3에서 얻어진 구리 (Π)-벤조포르피린 전구체를 이용하여 유기박막트랜지스터를 제조하였다.  An organic thin film transistor was prepared using the copper (Π) -benzoporphyrin precursor obtained in step 3 of Example 2.

유기박막트랜지스터 소자의 제작을 위해 통상적으로 사용되는 300 나노미터 두께의 이산화규소 (Si02)가 성장된 n 도윙 실리콘 웨이퍼 기판을 사용하였고, 그 이산화규소 (Si02) 표면을 자외선 /오존 처리한 후, 핵사메틸다이실록산 (Hexamethyldisioxane; ！ HMDS)로 표면처리하여 소수성을 가지도록 하였다. For the fabrication of the organic thin film transistor device, a 300 nm nanometer silicon dioxide (Si0 2 ) -grown n-doped silicon wafer substrate was used, and the silicon dioxide (Si0 2 ) surface was subjected to UV / ozone treatment. And hydrophobicity by surface treatment with Hexamethyldisioxane (！ HMDS).

상기 기판 위에 게이트 절연막으로 이산화규소 (Si02)를 표면처리한 후 클로로포름 /클로로벤젠 =4/1 비율의 흔합 유기 용매에 1 중량 %의 구리 (Π)- 벤조포르피린를 녹여 잉크젯 프린팅법으로 채널층을 형성하였다. 그 위에 소스 /드레인 전극으로 금 (80 나노미터)를 증착하여 도 1과 같은 트랜지스터 구조의 유기박막트랜지스터를 제조하였다. <실시예 65> 인쇄법에 의한 구리 (Π)-벤조포르피린의 유기박막트랜지스터의 제조 After surface-treating silicon dioxide (Si0 2 ) on the substrate with a gate insulating film, a channel layer was formed by dissolving 1 wt% of copper (Π)-benzoporphyrin in a mixed organic solvent in a ratio of chloroform / chlorobenzene = 4/1. Formed. Gold (80 nanometers) was deposited on the source / drain electrodes to prepare an organic thin film transistor having a transistor structure as shown in FIG. 1. Example 65 Preparation of Organic Thin Film Transistors of Copper (Π) -Benzoporphyrin by Printing Method

상기 실시예 2의 단계 3에서 얻어진 구리 (Π)-벤조포르피린 전구체를 이용하여 유기박막트랜지스터를 제조하였다.  An organic thin film transistor was prepared using the copper (Π) -benzoporphyrin precursor obtained in step 3 of Example 2.

실지예 64와 같은 기판 위에 금과 크 :롬을 각각 80 나노미터, 10나노미터를 증착시켜 게이트 전극을 형성하였다. 게이트 절연막은 이산화규소 (Si02) 대신에 유기 반도체와 오움 접촉 저항을 이루는 유기 절연막을 사용하였다. 이 유기 절연막은 2，4，6-트리알릴옥시-1,3,5ᅳ트리아진과 펜타에리트리올테트라키스를 1.47 대 1의 중량비로 프로필렌글리콜모노메틸에테르아세테이트에 흔합한 후 광개시제 이가큐르 369(시바가이기사)를 상기 흔합 용액에 0.5 중량 %로 첨가한 광중합 조성물을 통해 제조되었다. 상기 조성물은 스핀코팅하여 얻은 박막을 50 밀리와트 세기의 자외선으로 30 초간 경화하여 게이트 절연막을 제조하였다. 이 절연막 위에 1 중량 ¾의 구리 (Π)-벤조포르피린 전구체를 클로로포름 /클로로벤젠 =4/1 비율의 흔합 유기 용매로 용해시켜 잉크젯 프린팅 법으로 채널 충을 형성하고 그 위에 소스 /드레인 전극을 금 (80 나노미터)을 증착하여 형성하였다. 제조된 유기박막트랜지스터의 구조는 도 2와 같다. Gold and greater on a substrate, such as practical example 64: the ROM 80 by depositing the respective nanometers, 10 nanometers to form a gate electrode. Instead of silicon dioxide (Si0 2 ), an organic insulating film having ohmic contact resistance with an organic semiconductor was used as the gate insulating film. The organic insulating film was prepared by mixing 2,4,6-triallyloxy-1,3,5 리아 triazine and pentaerythritol tetrakis with propylene glycol monomethyl ether acetate in a weight ratio of 1.47 to 1, and then using the photoinitiator Igacur 369 ( Shiba GI Co.) was prepared through a photopolymerization composition to which 0.5 wt% was added to the mixed solution. The composition was cured for 30 seconds by spin coating the thin film obtained by 50 milliwatts of ultraviolet light to prepare a gate insulating film. A 1 ¾ copper (Π) -benzoporphyrin precursor was dissolved on the insulating film in a mixed organic solvent in a ratio of chloroform / chlorobenzene = 4/1 to form a channel filling by inkjet printing, and a source / drain electrode was formed thereon. 80 nanometers). The structure of the prepared organic thin film transistor is shown in FIG.

<실시예 66 내지 실시예 67> 인쇄법에 의한 구리 (Π)-테트라벤조포르피린 유도체의 유기박막트랜지스터의 제조 Examples 66 to 67 Preparation of Organic Thin Film Transistors of Copper (Π) -Tetrabenzoporphyrin Derivative by Printing Method

상기 실시예 1에서 제조된 구리 (Π)-메조-테트라핵실벤조포르피린과 실시예 Copper (Π) -meso-tetranuxylbenzoporphyrin prepared in Example 1 Example

5에서 제조된 구리 (Π)-메조ᅳ테트라부틸벤조포르피린을 를루엔에 1 중량 %을 사용한 것을 제외하고는 실시예 65와 동일한 방법으로 수행하여 유기박막트랜지스터를 제조하였다. . <비교예 1 내지 비교예 2> 스핀코팅에 의한 구리 (Π)-벤조포르피린의 유기박막트랜지스터 제조 An organic thin film transistor was prepared in the same manner as in Example 65, except that 1 wt.% Of copper (Π) -mesophet tetrabutylbenzoporphyrin prepared in 5 was used in toluene. . <Comparative Example 1 to Comparative Example 2> Preparation of organic thin film transistor of copper (Π) -benzoporphyrin by spin coating

상기 실시예 2의 단계 3에서 얻어진 구리 (Π)-벤조포르피린 전구체를 이용하여 유기박막트랜지스터를 제조하였다.  An organic thin film transistor was prepared using the copper (Π) -benzoporphyrin precursor obtained in step 3 of Example 2.

상기 실시예 64에서 사용한 기판과 동일한 기판을 사용하였으며， 이때 다량의 n 도핑된 실리콘은 게이트 전국으로, 300 나노미터 두께의 이산화규소 (Si )는 게이트 절연막으로 사용 l"였다. 그 위에 클로로포름에 1 중량 %， 2 증량 % 녹인 구리 (Π)—벤조포르피린 전구'체를 비활성 분위기에서 1000 rpm의 속도로 스핀코팅하고 150 °C에서 120 분, 220 °C에서 10 분간 건조하여 박막을 형성하였다. 형성된 전구체 박막 위에 채널 길이와 폭이 각각 50 마이크로미터 와 1000 마이크로미터인 소스 /드레인 전극을 열 진공 증착으로 80 나노미터 두께의 금으로 형성하였다 이 유기박막트랜지스터 구조는 도 3과 같다. The same substrate as that used in Example 64 was used, wherein Large amounts of n-doped silicon were gate-wide, and 300 nanometer-thick silicon dioxide (Si) was used as the gate insulating film l ". Copper (Π) -benzoporphyrin bulb, dissolved in 1% by weight and 2% by weight in chloroform. The sieve was spin-coated at 1000 rpm in an inert atmosphere and dried at 120 ° C. for 120 minutes at 10 ° C. for 10 minutes at 220 ° C. On the formed precursor film, the channel length and width were 50 micrometers and 1000 micrometers, respectively. A meter-in source / drain electrode was formed of 80 nanometers thick gold by thermal vacuum deposition. The organic thin film transistor structure is shown in FIG. 3.

<실험예 1>유기박막트랜지스터의 전하 이동도 및 점멸비 측정 Experimental Example 1 Measurement of Charge Mobility and Flashing Ratio of Organic Thin Film Transistor

실시예 64 내지 실시예 65 및 비교예 1 내지 비교예 2에서 제조된 유기박막트렌지스터의 전하이동도 및 점멸비를 알아보기 위하여 다음과 같이 실험하였다. 제조된 각각의 유기박막트랜지스터의 전류 -전압 특성을 반도체매개변수분석기 (4155C)로 측정하였다. 측정된 전류 -전압 곡선으로부터 유기박막트랜지스터의 전하이동도를 계산하였다.  In order to determine the charge mobility and the flashing ratio of the organic thin film transistors prepared in Examples 64 to 65 and Comparative Examples 1 to 2, the following experiments were carried out. The current-voltage characteristics of each organic thin film transistor prepared were measured by a semiconductor parameter analyzer (4155C). The charge mobility of the organic thin film transistor was calculated from the measured current-voltage curve.

본 발명에 따른 각각의 유기박막트랜지스터의 전류 -전압 곡선을 도 4 내지 도 7에 나타내었으며， 분석된 트랜지스터의 전하이동도 및 점멸비는 표 2에 나타내었다.  The current-voltage curves of the organic thin film transistors according to the present invention are shown in FIGS. 4 to 7, and the charge mobility and the flashing ratio of the analyzed transistors are shown in Table 2.

【표 2】  Table 2

Figure imgf000023_0001
Figure imgf000024_0001
도 4 내지 도 7 및 표 2에 나타난 바와 같이， 본 발명에 따라 제조된 벤조포르피린 전구체 및 인쇄법을 이용한 유기박막트랜지스터의 성능은 스핀코팅법을 이용하여 얻어진 비교예 1의 유기박막트랜지스터의 성능과 대비하여 동등한 정도의 수준으로 얻어질 수 있음을 알 수 있다. 따라서， 본 발명은 유기 반도체 물질로서 본 발명에 따른 방법으로 얻어진 구리 (Π)-벤조포르피린 전구체를 이용하여 종래 스핀코팅법 대신 인쇄법을 적용하여 유기박막트랜지스터를 제조할 수 있음을 알 수 있다. 본 발명에 따라 제조된 상기 유기 반도체는 제조공정이 간단하고 비용면에서 유리한 바, 유기박막트랜지스터 이외에도, 색소 증감형， 벌크 해테로 접합형, 헤테로 pn 접합형， 쇼트키형 등의 유기 태양전지용 유기 반도체로 유용하게 사용될 수 있다.
Figure imgf000023_0001
Figure imgf000024_0001
As shown in Figures 4 to 7 and Table 2, the performance of the organic thin film transistor using the benzoporphyrin precursor prepared by the present invention and the printing method and the performance of the organic thin film transistor of Comparative Example 1 obtained by using the spin coating method It can be seen that the equivalent level can be obtained in preparation. Accordingly, it can be seen that the organic thin film transistor can be manufactured by using a printing method instead of the conventional spin coating method using the copper (?)-Benzoporphyrin precursor obtained by the method according to the present invention as an organic semiconductor material. The organic semiconductor manufactured according to the present invention has a simple manufacturing process and is advantageous in terms of cost. In addition to organic thin film transistors, organic semiconductors for organic solar cells such as dye-sensitized, bulk heterojunction, hetero pn junction, and Schottky types It can be usefully used.

<실험예 2>유기박막트랜지스터의 전하 이동도 및 점멸비 측정 Experimental Example 2 Measurement of Charge Mobility and Flashing Ratio of Organic Thin Film Transistor

실시예 66 내지 실시예 67에서 제조된 유기박막트렌지스터의 전하이동도 및 점멸비를 알아보기 위하여 상기 실험예 1과 동일한 방법에 의해 실시하고 그 결과를 표 3에 나타내었다.  In order to determine the charge mobility and the flashing ratio of the organic thin film transistors prepared in Examples 66 to 67, the same procedure as in Experimental Example 1 was performed and the results are shown in Table 3.

【표 3】 Table 3

Figure imgf000024_0002
표 3과 나타난 바와 같이， 본 발명에 따른 벤조포르피린 제조방법으로 제조된 테트라벤조포르피린 유도체를 이용하여 인쇄법으로 제조된 유기박막트랜지스터는 벤조포르피린 전구체를 이용하여 인쇄법으로 제조된 유기박막트랜지스터보다는 전하이동도 및 점멸비가 상대적으로 낮은 것을 알 수 있다.
Figure imgf000024_0002
As shown in Table 3, using the tetrabenzoporphyrin derivative prepared by the method for producing benzoporphyrin according to the present invention prepared by the printing method The organic thin film transistor can be seen that the charge mobility and the flashing ratio is relatively lower than the organic thin film transistor prepared by the printing method using the benzoporphyrin precursor.

그러나， 테트라벤조포르피린 유도체는 벤조포르피린 전구체와 다르게 유기 용매의 끓는점에 관계없이 높은 용해도를 가지고 있어 인쇄 공정에 적합하고， 벤조 포르피린의 메조 위치에 다양한 치환기의 도입을 통해 인쇄법을 통해서도 전하이동 도 및 점멸비가 높은 유기박막트랜지스터를 제조할 수 있다는 가능성을 제시한다.  However, tetrabenzoporphyrin derivatives, unlike benzoporphyrin precursors, have high solubility regardless of the boiling point of organic solvents and are suitable for the printing process, and also through the introduction of various substituents at the meso positions of benzoporphyrin, This suggests the possibility of manufacturing organic thin film transistor with high flashing ratio.

Claims

【청구의 범위】 【청구항 11 하기 반웅식 1에 나타난 바와 같이 , 화학식 2로 표시되는 화합물을 포름산 (formic acid)과 반응시킨 후, 유기 용매하에서 디엔 (diene)과 디엘즈알더 (Dielsᅳ Alder ) 반웅시켜 화학식 3으로 표시되는 화합물을 제조하는 단계 (단계 1); 상기 단계 1에서 제조된 화학식 3으로 표시되는 화합물을 암모늄하이드록사이드와 유기 용매하에서 반응시켜 화학식 4의 화합물을 제조하는 단계 (단계 2); 상기 단계 2에서 제조된 화학식 4의 화합물을 산 및 유기 용매하에서 알데히드 (R2C(=0)H)와 반응시켜 화학식 5의 벤조포르피린 전구체를 제조하는 단계 (단계 3); 및 상기 단계 3에서 제조된 화학식 5의 벤조포르피린 전구체를 고은에서 처리하여 화학식 1의트라벤조포르피린을 제조하는 단계 (단계 4)를 포함하여 이루어지는 벤조포르피린 유도체의 신규한 제조방법 : [Claim] [Claim 11] As shown in the following reaction formula 1, after reacting the compound represented by the formula (2) with formic acid, diene and Diels Alder under an organic solvent. Reacting to prepare a compound represented by Chemical Formula 3 (Step 1); Preparing a compound of Chemical Formula 4 by reacting the compound represented by Chemical Formula 3 prepared in Step 1 with an ammonium hydroxide in an organic solvent (Step 2); Reacting the compound of formula 4 prepared in step 2 with an aldehyde (R 2 C (= 0) H) in an acid and an organic solvent to prepare a benzoporphyrin precursor of formula 5 (step 3); And a step (step 4) of treating the benzoporphyrin precursor of formula (5) prepared in step 3 in silver to produce a tribenzoporphyrin of formula (1): [반응식 1]Scheme 1
Figure imgf000026_0001
Figure imgf000026_0001
 (상기 반웅식 1에서,
Figure imgf000027_0001
(In the above reaction 1,
Figure imgf000027_0001
 R1은수소 또는 d C^의 직쇄 또는 측쇄 알킬이고, R 1 is hydrogen or straight or branched chain alkyl of d C ^, R2는 수소, d~C12의 직쇄 또는 측쇄 알킬， 비치환 또는 1 이상의 d~C3의 직쇄 또는 측쇄 알킬， 할로겐， (：广^의 알콕시， d~C3의 알킬에스터로 치환된 페닐， 고리 내 N, 0 또는 S를 포함하는 5원 또는 6원의 헤테로 아릴， = TMS 또는 二 TIPS
Figure imgf000027_0002
R 2 is hydrogen, d-C 12 linear or branched alkyl, unsubstituted or at least one d-C 3 linear or branched alkyl, halogen, (: alkoxy of alkoxy, phenyl substituted with d-C 3 alkylester) Or 5- or 6-membered heteroaryl containing N, 0 or S in the ring, = TMS or 2 TIPS
Figure imgf000027_0002
 M은 Cu, Zn또는 Ni이다.)  M is Cu, Zn or Ni.) 【청구항 2】 [Claim 2] 제 1항에 있어서， 상기 단계 1의 유기 용매는 에틸아세테이트， 메틸렌클로라이드， 아세톤， 핵산, 디에틸에테르, 디이소프로필에테르로 이루어지는 군으로부터 선택되는 유기 용매인 것을 특징으로 하는 벤조포르피린 유도체의 신규한 제조방법 .  The method of claim 1, wherein the organic solvent of step 1 is an organic solvent selected from the group consisting of ethyl acetate, methylene chloride, acetone, nucleic acid, diethyl ether, diisopropyl ether, a novel benzoporphyrin derivative Manufacturing method. 【청구항 3】 [Claim 3] 제 1항에 있어서, 상기 단계 1의 반옹은 40 내지 60 °C에서 2.5시간 동안 포믹산과 반웅시킨 후, 48시간 동안 디엘즈알더 반응시키는 것을 특징으로 하는 벤조포르피린 유도체의 신규한 제조방법. The method of claim 1, wherein the reaction of step 1 is a reaction with a formic acid for 2.5 hours at 40 to 60 ° C, followed by a Diels Alder reaction for 48 hours. 【청구항 4】 [Claim 4] 제 1항에 있어서， 상기 단계 :2의 유기 용매는 디에틸에테르， 디이소프로필에테르， 에틸렌글라이콜디메틸에테르로 이루어지는 군으로부터 선택되는 유기 용매인 것을 특징으로 하는 벤조포르피린 유도체의 신규한 제조방법.  The method of claim 1, wherein the organic solvent of step 2 is an organic solvent selected from the group consisting of diethyl ether, diisopropyl ether and ethylene glycol dimethyl ether. . 【청구항 5】 [Claim 5] 제 1항에 있어서， 상기 단계 2의 반웅은 상온에서 내지 3시간 동안 진행되는 것을 특징으로 하는 벤조포르피린 유도체의 신규한 제조방법. The reaction of claim 1, wherein the reaction of Step 2 is performed at room temperature for 3 hours. Novel method for producing a benzoporphyrin derivative, characterized in that proceeding. 【청구항 6】 [Claim 6] 제 1항에 있어서， 상기 단계 3의 산 (acid)은 트리플루오르아세트산 (TFA) 또는 보론트리플루오르디에틸에테르인 것을 특징으로 하는 벤조포르피린 유도체의 신규한 제조방법 .  The method of claim 1, wherein the acid of step 3 is trifluoroacetic acid (TFA) or boron trifluorodiethyl ether. 【청구항 7】 [Claim 7] 거 U항에 있어서， 상기 단계 3의 유기 용매는 에틸아세테이트， 메틸렌클로라이드， 핵산， 디에틸에테르, 메탄올， 에탄을로 이루어진 군으로부터 선택되는 1종 또는 2종의 용매인 것을 특징으로 하는 벤조포르피린 유도체의 신규한 제조방법 .  According to claim U, wherein the organic solvent of step 3 is benzoporphyrin derivative, characterized in that one or two solvents selected from the group consisting of ethyl acetate, methylene chloride, nucleic acid, diethyl ether, methanol, ethane New production method of. 【청구항 8】 [Claim 8] 제 1항에 있어서， 상기 단계 4의 반웅은 200 내지 250 °C에서 5 내지 30분간 진행하는 것을 특징으로 하는 벤조포르피린 유도체의 신규한 제조방법. According to claim 1, wherein the reaction of step 4 is a novel method for producing a benzoporphyrin derivative, characterized in that for 5 to 30 minutes at 200 to 250 ° C. 【청구항 9】 [Claim 9] 하기 화학식 5로 표시되는 테트라벤조포르피린 전구체를 인쇄법을 이용하여 유기 반도체 채널로 도입시키는 단계를： 포함하는 유기 박막 트랜지스터의 제조방법:  A method of manufacturing an organic thin film transistor comprising: introducing a tetrabenzoporphyrin precursor represented by Formula 5 into an organic semiconductor channel using a printing method: [화학식 5] [Formula 5]
Figure imgf000029_0001
Figure imgf000029_0001
 (상기 화학식 5에서， A, R2 및 M은 제 1항의 반웅식 1에서 정의된 바와 같다). (In Formula 5, A, R 2 and M are as defined in Banung 1 of claim 1). 【청구항 10] [Claim 10] 제 9항에 있어서，  The method of claim 9, 상기 화학식 5의 벤조포르피린 전구체 화합물은 하기 반응식 2에 나타난 바와 같이，  The benzoporphyrin precursor compound of Chemical Formula 5 is represented by Scheme 2 below, 화학식 2로 표시되는 화합물을 포름산 (formic acid)과 반응시킨 후， 유기 용매하에서 디엔 (diene)과 디엘즈알더 (Diels-Alder) 반웅시켜 화학식 3으로 표시되는 화합물을 제조하는 단계 (단계 1);  Reacting the compound represented by the formula (2) with formic acid and then reacting with diene and Dies-Alder in an organic solvent to prepare a compound represented by the formula (3) (step 1); 상기 단계 1에서 제조된 화학식 3으로 표시되는 화합물을 암모늄하이드록사이드와 유기 용매하에서 알데히드 (R2C( ))H)와 반웅시켜 화학식 4의 화합물을 제조하는 단계 (단계 2); Reacting the compound represented by Chemical Formula 3 prepared in Step 1 with aldehyde (R 2 C ()) H) in an ammonium hydroxide and an organic solvent to prepare a compound of Chemical Formula 4 (step 2); 상기 단계 2에서 제조된 화학식 4의 화합물을 산 및 유기 용매하에서 반응시켜 화학식 5의 벤조포르피린 전구체를 제조하는 단계 (단계 3); 및  Preparing a benzoporphyrin precursor of Chemical Formula 5 by reacting the compound of Chemical Formula 4 prepared in Step 2 under an acid and an organic solvent (Step 3); And 상기 단계 3에서 제조된 화학식 5의 벤조포르피린 전구체를 인쇄법에 의해 유기 반도체 채널로 도입하는 단계 (단계 4)를 포함하는 유기 박막트랜지스터 제조방법 .  Method for preparing an organic thin film transistor comprising the step (step 4) of introducing the benzoporphyrin precursor of formula (5) prepared in step 3 by the printing method. [반웅식 2] [Bungungsik 2]
Figure imgf000030_0001
Figure imgf000030_0001
 5 5 (상기 반웅식 2에서ᅳ A, R1, R2, 및 M은 제 1항의 반웅식 1에서 정의된 바와 같다). (A, R 1 , R 2 , and M in the above formula 2 are as defined in the formula 1 of claim 1). 【청구항 11】 [Claim 11] 제 9항에 있어서，  The method of claim 9, 상기 인쇄법은 잉크젯 프린팅법， 그라비아법， 그라비아ᅳ옵셋법， 스크린 인쇄법， 스크린 인쇄법， 플렉소 인쇄법으로 이루어진 군으로부터 선택 되어지는 1종인 것을 특징으로 하는 유기박막트랜지스터 제조방법.  And the printing method is one selected from the group consisting of an inkjet printing method, a gravure method, a gravure offset method, a screen printing method, a screen printing method, and a flexographic printing method. 【청구항 12】 [Claim 12] 거 19항에 있어서， ；  According to claim 19, 상기 벤조포르피린 전구체는 인쇄법을 이용하기 위해 2종 이상의 끓는 점아 서로 다른 흔합 유기 용매에 용해시켜 사용하되， 상기 2종 이상의 흔합 유기 용매의 끓는점은 적어도 1종 이상 ere 이상인 것을 특징으로 하는 유기박막트랜지스터 제조방법 . 【청구항 13] The benzoporphyrin precursor is used by dissolving in two or more different boiling organic solvents in order to use the printing method, the boiling point of the two or more mixed organic solvents is at least one organic thin film transistor, characterized in that more than ere Manufacturing method. [Claim 13] 제 12항에 있어서，  The method of claim 12, 상기 흔합 유기 용매는 메틸렌클로라이드, 클로로포름， 에틸아세테이트， 에 탄을 및 메탄올로 이루어지는 군으로부터 선택되는 1종 이상의 용매와 클로로벤젠， 사이클로핵사논 및 디에틸렌글리콜로 이루어 ;지는 군으로부터 선택되는 1종 이상의 용매의 흔합인 것을 특징으로 하는 유기박막트랜지스터 제조방법. The mixed organic solvent comprises one or more solvents selected from the group consisting of methylene chloride, chloroform, ethyl acetate, ethane and methanol, and chlorobenzene, cyclonucleanone and diethylene glycol ; The process for producing an organic thin film transistor, characterized in that the mixture of at least one solvent selected from the group.
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