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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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• 2012
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