KR101046278B1 - Organic semiconductor material and electronic device comprising same - Google Patents

Abstract

The present invention relates to a novel organic semiconductor material and an electronic device including the same, and more particularly, to an organic semiconductor material having a structure in which a thiophene group or a triisopropylsilyl acetylene group are connected with respect to a pyrene group, and an organic thin film transistor including the same; The present invention relates to an organic electronic device such as an organic solar cell.

The organic semiconductor material according to the present invention is thermally stable, has excellent hole mobility as a p-type material of an organic thin film transistor, and has excellent electrical properties as an electron donor material in an organic solar cell.

Organic Semiconductor Materials, Organic Thin Film Transistors, Organic Solar Cells

Description

Organic semiconductor materials and electronic devices containing the same

The present invention relates to a novel organic semiconductor material and an electronic device including the same, and more particularly, to an organic semiconductor material having a structure in which a thiophene group or a triisopropylsilyl acetylene group are connected with respect to a pyrene group, and an organic thin film transistor including the same; The present invention relates to an organic electronic device such as an organic solar cell.

In recent decades, the development of organic materials with semiconductor properties and various application studies using them have been actively conducted. The scope of application research using organic semiconductors such as electromagnetic shielding films, capacitors, OLED displays, organic thin film transistors (OTFTs), solar cells, and memory devices using multiphoton absorption phenomena continues to expand. In particular, the OLED field is expected to commercialize large-scale displays, and thus serves as a catalyst for activating application research using organic materials.It is started as an active driving circuit for OLED and is expected to be applied to next-generation smart cards. There is also a sudden rise. In addition, after the announcement of the electric power generation characteristics using the organic semiconductor as an active layer, it is also attracting a lot of attention to the application as a laser diode. The cost of device fabrication is significantly lower than that of inorganic materials, thus foreseeing a revolution in the solar cell market in the future.

The research on the organic semiconductor thin film transistor has been started since 1980, but in recent years, full-scale research is being conducted worldwide. It is anticipated that electronic circuit boards that are simple to manufacture, inexpensive, and that can be bent or folded without impact are expected to be essential to the industry of the future, and the development of organic transistors to meet these needs is very important. It is emerging as a research field. Organic transistors cannot be used in devices requiring high speeds such as Si or Ge due to their low charge mobility due to the characteristics of organic semiconductors. However, it can be useful when the device needs to be fabricated over a large area, when low process temperatures are required, and when bending is required, especially when low-cost processes are required. Recently, researchers at Philips surprised the world by designing and publishing programmable code generators consisting of 326 transistors using substrates, electrodes, dielectrics (insulators), and semiconductors all using polymers. This completely reverses the stereotype that semiconductors are hard so far, foreshadowing endless applications based on human imagination.

Organic semiconductor transistors are organic semiconductors such as light emitting organic materials used in organic electroluminescent transistors because of the characteristics of the material, so the deposition method is the same, and the physical and chemical properties are similar, so that the device can be manufactured while maintaining the same process conditions. In addition, since both process is possible at room temperature and low temperature (less than 100 ℃), it is possible to manufacture a plastic-based organic electroluminescent device using an organic transistor. In the same vein, it is also possible to use a liquid crystal display device that can be bent using plastic as a substrate. In addition, the driving of electronic paper, which has attracted great attention recently, is not only driving current but driving voltage, and not only a display device requiring high charge mobility or fast switching speed, but also a large area that can be bent. The organic transistor is the most suitable technology because it is applied to. In addition, micro cards for smart cards, which are currently used as silicon bases through semiconductor processes, are expected to be used because organic transistors can be used to reduce costs associated with bonding silicon processors to plastic bases. Furthermore, it is thought that it can be applied to various parts of the computer.

In order to obtain a high performance device, an organic semiconductor must satisfy the following general matters regarding charge injection and current mobility. (Iv) Organic semiconductor materials must have molecular orbital (HOMO / LUMO) energy that facilitates the injection of holes and electrons when an electric field is applied. (Ii) The crystal structure of a substance must have sufficient overlap of frontier orbitals so that effective charge transfer between neighboring molecules can occur. (Iii) Solids must be pure because impurities act as charge traps. (Iii) Molecules should be selectively arranged along the lengthening side-by-side on the device substrate so that effective charge transfer can occur along the direction of intra-molecular pi-pi stacking. (Iii) The crystal region of the organic semiconductor should be covered between the source and drain electrodes in the form of a film with a thin film like single crystal. In addition, it is desirable that the solubility of the organic material is also excellent. Since the solution process can be a low temperature process during device fabrication, a thin film can be easily formed on a plastic substrate, thereby making it possible to fabricate an inexpensive device.

Pentacene, polythiophene, polyacetylene, α-hexathienylene, and fullerene (C60) thin films since OTFT began in earnest since the early 1980s Has been applied in the direction to increase the charge mobility and the flashing ratio, which are important characteristics of the OTFT device. The best p-type channel material at present is pentacene, but has a problem of stability in that electrical properties change due to reaction with oxygen. When the organic semiconductor is oxidized in this manner, the bond is broken and thus the charge mobility is lowered. In addition, lattice distortion occurs in the crystal to form charge traps, and charge scattering caused by these causes a decrease in mobility. In addition, researches to improve charge mobility of organic semiconductors have been conducted to increase the temperature of the substrate during deposition or to induce crystallization of organic molecules using a self-assembly method. But first of all, it is important to design the molecules so that inter-molecular conduction occurs easily.

On the other hand, solar cells are devices that can directly convert solar energy into electrical energy by applying a photovoltaic effect. Typical solar cells are made of p-n junctions by doping crystalline silicon (Si), an inorganic semiconductor. Electrons and holes generated by absorbing light diffuse to the p-n junction and are accelerated by the electric field to move to the electrode. The power conversion efficiency of this process is defined as the ratio of the power given to the external circuit and the solar power entered into the solar cell. However, since the conventional inorganic solar cell has already shown its limitations in terms of economic and material supply and demand, organic semiconductor solar cells having easy processing, low cost, and various functionalities have been spotlighted as alternative energy sources in the long term.

The possibility of an organic solar cell was first proposed in the 1970s, but its efficiency was so low that it was not practical. However, in 1986, Eastman Kodak's Tang showed a double-layer structure using copper phthalocyanine (CuPc) and perylene tetracarboxylic acid derivatives, showing the possibility of practical application as various solar cells. Interest and research on solar cells has increased rapidly and brought about a lot of development. Since 1995, the concept of bulk-heterojunction (BHJ) was introduced by Yu et al., And fullerene derivatives with improved solubility, such as PCBM, were developed as n-type semiconductor materials. there was. In particular, in the case of polymer solar cells, the improvement of efficiency is remarkable due to the change of new device configuration and process conditions in recent 3-4 years, and the donor having low bandgap to replace the existing material. The development of new acceptor materials with good material and charge mobility is constantly being studied.

It is an object of the present invention to provide an organic semiconductor material having a novel structure that is thermally stable as an electrically conductive material and is contained in an active layer such as an organic thin film transistor and an organic solar cell and can exhibit excellent electrical characteristics.

The present invention also provides an organic electronic device such as an organic thin film transistor and an organic solar cell including a new organic semiconductor material.

The present inventors have made intensive studies to achieve the above object, and as a result, they have excellent hole mobility and have an aromatic ring and a thiophene group containing sulfur (S) or triisopropylsilyl acetylene containing silicon (Si). Thermally stable new organic semiconductor materials, including triisopropylsilyl acetylene and pyrene groups, which have strong intermolecular-interaction in the solid state with extended π-π stacking In addition, it was confirmed that the present invention can exhibit excellent electrical properties by being included in active layers such as organic thin film transistors and organic solar cells.

The present invention specifically relates to an organic semiconductor compound having a structure represented by the following formula (1) and an organic electronic device comprising the same.

[Formula 1]

[In Formula 1, R ¹ and R ² are independently hydrogen or an alkyl group of C ₁ to C ₂₀ , and n is an integer of 1 to 2,000.]

Hereinafter, the present invention will be described in more detail.

At this time, if there is no other definition in the technical terms and scientific terms used, it has a meaning commonly understood by those of ordinary skill in the art. Repeated descriptions of the same technical constitution and operation as those of the conventional art will be omitted.

The organic semiconductor compound according to the present invention includes a structure of Chemical Formula 1 below as a conductive organic compound.

[Formula 1]

In Formula 1, R ¹ and R ² are independently hydrogen or C ₁ ~ C ₂₀ Alkyl group, n is an integer of 1 to 2,000. When the range of n exceeds 2,000, it is difficult to manufacture under general polymerization conditions.

More specifically, the structure of Formula 1 may be a structure of Formula 2 below.

[Formula 2]

In Formula 2 R ¹ and R ² are independently hydrogen or an alkyl group of a linear or branched C ₁ ~ C _20, n is an integer from 1 to 2,000.

More specifically, the organic semiconductor compound according to the present invention may be a compound represented by the following Chemical Formula 3 as a monomolecular compound, and may be an oligomer including the structure of Chemical Formula 4 as a polymer material.

(3)

[Formula 4]

R ³ in Formulas 3 and 4 And R ⁴ is a C ₁ to C ₂₀ linear or branched alkyl group, m is an integer from 1 to 2,000. Compared to the monomolecular material, the polymer material has an advantage of easily forming an organic semiconductor layer by a solution process.

Taking the compound of Formula 3 as an example among the compounds according to the present invention, the preparation method thereof may be represented by the following Scheme 1. In addition, the method for preparing the polymer compound of Chemical Formula 4 of the compound according to the present invention may be prepared by the method of Scheme 2 below as an example. However, the production method according to the present invention is not limited to the production methods of Schemes 1 and 2 below, and can be variously manufactured using a known organic synthesis method.

Scheme 1

Scheme 2

R ³ , R ⁴ and m in Schemes 1 to 2 are as defined in Formula 3 or Formula 4.

In addition, the present invention further includes the following Chemical Formula 5 and Chemical Formula 6 as an organic semiconductor compound.

[Chemical Formula 5]

[Formula 6]

R ⁵ in Formula 5 is independently hydrogen or a C ₁ ~ C ₂₀ linear or branched alkyl group.

In the compounds according to the present invention, the preparation method of the compounds of Formulas 5 and 6 may be represented by the following Scheme 3 and Scheme 4. However, the production method according to the present invention is not limited to the production methods of Schemes 3 and 4 below, and can be variously manufactured using a known organic synthesis method.

Scheme 3

Scheme 4

The present invention provides an organic electronic device comprising the organic semiconductor compound of the present invention described above. The organic electronic device according to the present invention includes a transistor, a diode, a photodiode, a solar cell, a light emitting diode, a memory, a light emitting transistor, a sensor, and the like. The transistor of the present invention is not particularly limited and includes a bipolar transistor, an electrostatic induction transistor, a field effect transistor, and the like.

As a specific aspect, the present invention provides an organic thin film transistor containing the organic semiconductor compound according to the present invention in an active layer.

The organic thin film transistor according to the present invention includes a source electrode and a drain electrode, an active layer which becomes a current path between these electrodes and contains an organic semiconductor compound according to the present invention, a gate electrode which controls a current passing through the current path, and an active layer and a gate electrode. It comprises an insulating layer disposed between. The structure of the organic thin film transistor may be a top contact method or a bottom contact method, as shown in FIG. 1. In the case of the phase contact structure, the source layer and the drain are located above the channel layer. There is no curvature of, which is more desirable because of less interference with the flow of charge in the source and drain portions.

As another specific aspect, the present invention provides an organic solar cell comprising the organic semiconductor compound according to the present invention as an electron donor material in an active layer.

The organic solar cell has a high work function with a metal / oil-based conductor (photoactive layer) / metal (Metal-Samicondustor or Insulator-Metal (MSM)) structure, and has a low work function with ITO (indium tin oxide) as a transparent electrode. Al or Ca is used as the cathode. Here, the BHT (Bulk-heterojunction) structure using a semiconductor polymer / C60 composite as a donor and an acceptor as an organic semiconductor will be described as an example. First, the polymer / C60 composite solution, which is a photoactive layer, is spin coated, Coating on the ITO layer to a thickness of about 100nm by inkjet printing or the like method. On top of this, Al or Ca metal is vacuum-deposited and used as a cathode, and an extruder blocking layer (EBL) layer is inserted between the electrode and the photoactive layer to enhance the life of the charge as necessary. As the EBL layer, a mixture of PEDOT and PSS may be used.

FIG. 2 is a schematic diagram illustrating a comparison of a bi-layer (B) mode (B) and a bulk-heterojunction (BHT) mode (B) in the structure of an organic solar cell.

In general, the diffusion distance of excitons in organic donors is about 10-30 nm, which is much shorter than the appropriate thickness of donor material for absorbing sunlight (over 100 nm). This is one of the fundamental causes of limiting the efficiency of the organic solar cell, the existing bi-layer (BL) structure is difficult to solve this problem. In addition, since both materials forming the BL (bi-layer) structure are organic monomolecules, deposition is required, and in the case of polymers, it is difficult to manufacture by simple processes such as spin coating. On the other hand, the polymer BHJ structure uses a mixture of donor (D) and acceptor (A) materials, which simplifies the manufacturing process and greatly increases the surface area of the D / A interface. As a result, the charge collection efficiency increases.

The organic solar cell according to the present invention preferably has a BHJ structure, and it is preferable to use the organic semiconductor compound according to the present invention as an electron donor material and mix one or more selected from the following electron acceptor materials to form an active layer. .

Among the electron acceptor materials, it is more preferable to use materials such as PCBM and PCBCR designed to be well dissolved in an organic solvent.

The organic semiconductor compound according to the present invention has an excellent hole mobility and has a strong intermolecular attraction in solid state with an aromatic ring and an thiophene group containing sulfur (S) and extended pi-pie stacking (π-π stacking). The new organic semiconductor material including pyrene group having intermolecular-interaction is thermally stable and is contained in active layers such as organic thin film transistors and organic solar cells, and thus has excellent electrical characteristics.

Hereinafter, the present invention will be described in detail by way of examples. However, the following examples are only for illustrating the present invention, and the content of the present invention is not limited by the following examples.

[Example]

2-Bromothiophene, 3-Bromothiophene, 1,2-Dibromoethane, Pyrene, n-Butyllitium 2.5M in Hexanes), 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborane (2-Isopropoxy-4,4,5,5-tetramethyl-1,3,2 -dioxaborolane, bromine, anhydrous toluene and florisil were purchased from Aldrich Chemical Co. Tetrakis (triphenylphosphine) palladium (0) as catalyst, 1,3-bis (biphenylphosphino) propane nickel (II) chloride (1,3-Bis (biphenylphosphino) propane nickel (II) chloride was purchased from Strem Chemicals, Inc., 1-bromooctane, 1-bromohexane, carbon tetrachloride, toluene (toluene), tetrahydrofuran (purified with sodium wire), anhydrous magnesium sulfate (MgSO ₄ ), potassium carbonate (K ₂ CO ₃ ), sodium hydroxide (NaOH) It was purchased from (Junsei). Silica gel was purchased from Merck and magnesium (Mg, purified diethyl ether) was purchased from Fluka.Chloroform, hexane (Hexane) and methanol (Methanol) were used for the purification of materials. Acetone was purchased from JTBaker. Before the UV and PL measurements of the film (film) was filtered using a 0.45 μm syringe filter was used for spin coating. PCBM ([6,6] -phenyl C61-butyric acid methyl ester) was used as a solar cell acceptor.

^{For 1} H NMR and ¹³ C NMR spectra, Bruker AM-400 was used, and elemental analysis was performed using EA 1110-Fisons. The UV absorption spectrum was Shimadzu UV-3600 and the light emission spectrum was Shimadzu RF 5301 PC Fluorometer. Thermal analysis was carried out using a TGA Q-50 instrument from TGA instruments to measure the decomposition temperature (T _d ) in a heating system at 10 ℃ per minute under nitrogen stream, and T _{g ,} T _m and T of the material using DSC 200F3 from NETZSCH. _c was measured. Cyclic Voltammetry was measured to determine HOMO Level of the material, and AUTOLAB, Poteniostat / Galvanostat Model was used. The electrical characterization of the transistor device was measured by a semiconductor parameter analyzer (Agilent 4155C) and the surface of the active layer of the transistor device by atomic force microscopy (AFM), PSIA XE-100. Was measured. The IV curve of the solar cell was measured using a 1 kW solar simulator (Newport 91192), and the IPCE characteristics were measured using a Solar cell response / Quantum efficiency / IPCE Measurement system (PV Measurements, Inc.).

Example 1 Preparation of D2OBTP [1,6- (di-2-octyl-bithiophenyl) -pyrene]

Preparation of 2,2′-bithiophene [2,2′-bithiophene] (Product 1)

Mount the condenser in a round flask, add Mg (4.473g, 183.9mmol), and vacuum for 2 hours with slight temperature to remove oxygen and moisture. In a glove box, 30 ml of anhydrous tetrahydrofuran was added to the flask containing Mg, and 0.3 ml of 1,2-bromoethane was added to wipe the surface of the Mg. Then, 2-bromothiophene (15 g, 91.95 mmol) was added to reflux for about 2 hours, and cooled to room temperature to prepare a grignard reagent.

To the mixture of Ni (dppp) Cl ₂ (0.33 g, 0.613 mmol), 30 ml of anhydrous THF, and 2-bromothiophene (10 g, 61.3 mmol) was added dropwise the Grignard reagent at 0 ° C., followed by reflux for 24 hours. Let's do it.

After completion of the reaction, methanol was added to terminate the reaction, and then EA (ethyl acetate) and brine (NaCl + distilled water) were added thereto to extract the product, followed by distillation of the solvent to obtain a transparent liquid substance (product 1) (60% yield).

¹ H-NMR (400MHZ, CDCl ₃ ) δ 6.90 (d, 2H), 7.15 (d, 2H), 7.20 (d, 2H)

5- Octyl -2,2′- Vithiophene  [5- Octyl -2,2′- bithiophene Manufacturing of Product  2)

Product 1 (2.85g, 0.017mol) is vacuumed for 1 hour to remove oxygen and water, and then dissolved in 50 ml of dry THF. N-butyllithium (2.5M in hexane, 7.14ml, 0.0178mol) was added slowly at -78 ° C and stirred for 2 hours. Then, 1-bromooctane (3.61 g, 0.017 mol) was slowly added at -78 ° C, stirred for 1 hour, and stirred at room temperature for 2 hours to terminate the reaction. After quenching with methanol, the organic layer is extracted with MC (methylene chloride) and brine, and the remaining water is removed with anhydrous magnesium sulfate (MgSO ₄ ), and the solvent is evaporated and distilled to obtain a liquid substance. (59% yield)

¹ H-NMR (200MHZ, CDCl ₃ ) δ 0.85 (t, 3H), 1.25 (m, 10H), 1.62 (m, 2H), 2.75 (t, 2H), 6.75 (d, 1H), 6.90 (d, 1H), 7.00 (t, 1H), 7.15 (d, 1H), 7.20 (d, 1H)

5- Octyl -5 '-[4,4,5,5- Tetramethyl -1,3,2- Dioxaborolanyl ] -2,2'- Vithiophene  {5- Octyl -5 '-[4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl] -2,2'- bithiophene } Manufacturing ( Product  3)

Product 2 (2.9g, 0.01mol) is vacuumed for 1 hour to remove oxygen and water, and then dissolved in 30 ml of dry THF. N-butyllithium (2.5M in hexane, 4.4ml, 0.011mol) was slowly added at -78 ° C, followed by stirring for 2 hours. 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane again at -78 ° C (2-isopropoxy-4,4,5,5-tetramethyl-1,3 , 2-dioxaborolane) (2.05 g, 0.01 mol) was added slowly, followed by stirring for 2 hours and stirring at room temperature for 40 hours to terminate the reaction. After quenching with methanol, extract the organic layer with MC and brine, remove the remaining water with anhydrous magnesium sulfate (MgSO ₄ ), evaporate the solvent, and remove the liquid substance with column chromatography (using hexane). Get (61% yield)

¹ H-NMR (400 MHz, CDCl ₃ ) δ 0.85 (t, 3H), 1.25 (m, 8H), 1.30 (m, 2H), 1.35 (m, 12H), 1.65 (m, 2H), 2.75 (t, 2H), 6.65 (d, 1H), 7.00 (t, 1H), 7.12 (d, 1H), 7.47 (d, 1H)

1,6- Dibromopyrene  [1,6- dibromopyrene Manufacturing of Product  4)

Prepare a 2L three-necked flask, dissolve pyrene (Pyrene 37.67g, 185.7mmol) in carbon tetrachloride (500ml), and then bromine (bromine 20.0ml, 388mmol) solution in carbon tetrachloride (800ml). Drop-wise over time. After stirring for 12 hours, the white precipitate obtained by terminating the reaction was filtered through a glass filter and dissolved in toluene (1.4 L) at 60 ° C. The toluene solution was washed with 5% NaHCO ₃ (1200 ml) and H ₂ O (600 ml), heated to 100 ° C. and filtered again to remove the brown solid. Product 4 was obtained by removing the solvent, and recrystallized three times with toluene (1400ml, 800ml, 450ml) to obtain Product 4 (1,6-dibromopyrene). (23% yield)

¹ H-NMR (400 MHz, CDCl ₃ ) δ 8.02 (d, 2H), 8.10 (d, 2H), 8.25 (d, 2H), 8.45 (d, 2H)

D2OBTP  [1,6- ( di -2- octyl - bithiophenyl ) - pyrene Manufacturing of Product  5)

Vacuum and remove water and oxygen in a round flask equipped with a condenser containing Product 4 (1.0g, 2.8mmol) and Product 3 (2.38g, 5.88mmol), and dissolve by adding anhydrous toluene (10ml). Pd (pph ₃ ) ₄ catalyst (0.03eq) and then THF (20ml) and K ₂ CO ₃ (4eq) is added. The reaction is terminated after stirring at 100 to 120 ° C. for 48 hours. Product 5 was dissolved in chloroform and columned with Florisil and Silicagel to remove Pd (pph ₃ ) ₄ and recrystallized in methanol to obtain a yellow solid, which was purified by Soxhlet using methanol. (85% yield)

¹ H-NMR (200 MHz, CDCl ₃ ) δ 0.85 (t, 6H), 1.25 (m, 20H), 1.62 (m, 4H), 2.75 (t, 4H), 6.75 (d, 4H), 7.07 (d, 4H), 8.08 (d, 2H), 8.12 (d, 2H), 8.18 (d, 2H), 8.58 (d, 2H)

In view of the application of the organic electronic material, it is important that the organic materials used have high thermal stability without being deformed according to the external temperature. The organic semiconductor material (D2OBTP) prepared in this example was well dissolved in chloroform or toluene at room temperature. TGA and DSC were measured to investigate the thermal properties of the synthesized small molecules, and the results are shown in FIGS. 3 and 4. First, TGA was measured by increasing the temperature to 10 ° C. per minute under N ₂ , and the weight reduction of the measured sample was found to be a very thermally stable organic material as the 5% Decomposition Temperature of the initial weight was 435 ° C.

In solids, molecules are constrained to occupy a given position. We call this state that the solid phase has a 'positional order'. In addition, molecules at these particular positions are constrained in the direction they align with each other, and this solid phase is said to have an 'orientative order'. When the solid melts and becomes a liquid, the two kinds of order are completely lost, causing the molecules to move and roll irregularly. Some solid order remains due to the melting of solids, and positional order is called a 'liquid crystal'. The molecules in the liquid crystal phase move freely in exactly the same way as in the liquid state, but the tendency to align in a particular direction remains.

Many molecular structures do not form a liquid crystal phase, but about one in 200 compounds synthesized throughout organic chemistry have a liquid crystal phase. Molecules with the following conditions show good liquid crystallinity. First of all, the shape of the molecule must be long, that is, it must be considerably longer than the width of the molecule. Second, the central part of the molecule must remain firm. Finally, it is even more advantageous if the ends of the molecules are rather bent.

D2OBTP [1,6- (di-2-octyl-bithiophenyl) -pyrene] almost completely satisfies these liquid crystal conditions due to its molecular structure, and heating and cooling rates = 10 ° C / min (Left), 5 ° C / min (Right)] As a result, it was observed that clear liquid crystal characteristics were shown between 223 and 240 ° C. Tg (glass transition temperature) was not found in the range from room temperature to 300 ℃, and melting temperature (Tm) and crystalline temperature (Tc) were found at 223 ℃ and 195 ℃, respectively.

In order to observe and confirm the liquid crystal state in more detail, the state of heating and cooling of D2OBTP from 216 ° C to 250 ° C was observed with a polarizing microscope, and the results are shown in FIG. 3. Referring to FIG. 5, it can be seen that the arrangement of liquid crystals appears well at around 233 ° C. during cooling.

In order to determine the absorbance and fluorescence change of the prepared organic semiconductor material (D2OBTP) dissolved in a CHCl ₃ solvent UV and PL was measured and the results are shown in FIG. The absorption region showed maximum absorption at 410 nm and PL emission at 500 nm.

In addition, the HOMO level of the material was determined by cyclic voltammetry. Ferrocene / ferrocenium redox system (-4.8 eV) was measured in the solid film state as a reference and the HOMO level was calculated to be -5.1 eV, and the UV _edge of the UV spectrum of the chloroform solution. The band gap was calculated using (465 nm) and found to be 2.66 eV. From the HOMO level and the band gap, LUMO level-2.44 eV was obtained.

Example 2 Preparation of P3H5PBT [Poly (3,3'-dihexyl-5-pyrenyl-2,2'-bithiophene)]

3- Hexylthiophene  [3- hexylthiophene Manufacturing of Product  6)

Mount the condenser in a round flask, add Mg (4.473g, 183.9mmol), and vacuum for 2 hours with slight temperature to remove oxygen and moisture. In a glove box, 30 ml of anhydrous tetrahydrofuran was added to the flask containing Mg, and 0.3 ml of 1,2-bromoethane was added to wipe the surface of the Mg. Then, 1-bromohexane (15 g, 91.95 mmol) was added to reflux for about 2 hours, and cooled to room temperature to prepare a grignard reagent.

The Grignard reagent was added dropwise at 0 ° C. to a mixed solution of Ni (dppp) Cl ₂ (0.33 g, 0.613 mmol), anhydrous THF 30 ml, and 3-bromothiophene (10 g, 61.3 mmol), followed by reflux for 24 hours.

After the reaction, methanol was added to terminate the reaction, and then, EA (ethyl acetate) and brine (NaCl + distilled water) were added thereto to extract the product, and then purified by column chromatography (using n-hexane) to obtain a transparent liquid substance. (56% yield)

¹ H-NMR (200MHZ, CDCl ₃ ) δ 0.85 (t, 3H), 1.25 (m, 6H), 1.62 (m, 2H), 2.75 (t, 2H), 6.90 (d, 2H), 7.15 (d, 1H)

2- Bromo -3- Hexylthiophene  [2- bromo -3- hexylthiophene Manufacturing of Product  7)

3-hexylthiophene (5.8 g, 34.5 mmol) synthesized in the previous reaction was placed in a round flask and 50 ml of acetic acid / chloroform (volume ratio 7: 3) and n-bromosuccinimide (6.45 g, 36.2 mmol) was added. The reaction was completed after stirring at 0 ° C. for about 2 hours. The work-up process is performed with MC (methylene chloride) and brine (Brine), but it is necessary to extract enough to remove acetic acid. Water is removed with MgSO ₄ , the solvent is removed and a clear liquid compound is obtained. (89% yield)

¹ H-NMR (200 MHz, CDCl ₃ ) δ 0.85 (t, 3H), 1.25 (m, 6H), 1.62 (m, 2H), 2.75 (t, 2H), 6.90 (d, 1H), 7.15 (d, 1H)

3,3'- Dihexyl -2,2'- Vithiophene  [3,3'- dihexyl -2,2'- bithiophene Manufacturing of Product  8)

Mg (2.26g, 93.0mmol) was put in a round flask equipped with a condenser and vacuumed for about 2 hours while applying a slight temperature to remove moisture and oxygen. In a glove box, 30 ml of anhydrous tetrahydrofuran was added to the flask containing Mg, and 0.3 ml of 1,2-bromoethane was added to wipe the surface of the Mg. Subsequently, 2-bromo-3-hexylthiophene (9.15 g, 37.2 mmol) was added thereto, refluxed for about 2 hours, and cooled to room temperature to prepare a grignard reagent.

The Grignard reagent was added dropwise at 0 ° C. to a mixed solution of Ni (dppp) Cl ₂ (0.17 g, 0.31 mmol), 30 ml of anhydrous THF, and 3-bromothiophene (10 g, 61.3 mmol), followed by reflux for 24 hours.

After completion of the reaction, methanol was added to terminate the reaction, and then EA (ethyl acetate) and brine (NaCl + distilled water) were added to extract the product, and then the solvent was removed to obtain a transparent liquid substance. (60% yield)

¹ H-NMR (400 MHz, CDCl ₃ ) δ 0.85 (t, 6H), 1.25 (m, 12H), 1.52 (m, 4H), 2.45 (t, 4H), 6.93 (d, 2H), 7.25 (d, 2H)

3,3'- Dihexyl -5,5 '-[di-4,4,5,5- Tetramethyl -1,3,2- Dioxaborolanyl ] -2,2'- Vithiophene  {3,3'- dihexyl Preparation of -5,5 '-[di-4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl] -2,2'-bithiophene} Product  9)

The 3,3'-dihexyl-2,2'-bithiophene (4.36g, 13.0mmol) synthesized above was vacuumed for about 1 hour to remove oxygen and water, and then dissolved in 30 ml of THF. N-butyllithium (2.5M in hexanes, 17.1 ml, 27.37 mmol) was slowly added at −78 ° C., followed by stirring for 2 hours. Again, 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (5.32 g, 28.6 mmol) was slowly added at -78 ° C, followed by stirring for 2 hours and 40 hours. After stirring at room temperature, the reaction is terminated. After the reaction, methanol was added to terminate the reaction, methyl chloride and brine were added thereto, the organic layer was extracted, the remaining water was removed with anhydrous magnesium sulfate, and the solvent was evaporated. Purification by column chromatography (using n-hexane) gives a liquid material. (40% yield)

¹ H-NMR (400 MHz, CDCl ₃ ) δ 0.85 (t, 6H), 1.20 (m, 8H), 1.26 (m, 4H), 1.30 (m, 24H), 1.48 (m, 4H), 2.45 (t, 4H), 7.50 (s, 2H)

P3H5PBT  [Poly (3,3'- dihexyl -5- pyrenyl -2,2'- bithiophene )] ( Polymer Manufacturing

Product 9 (1.5g, 2.558mmol) and Product 4 (0.921g, 2.588mmol) are placed in a round flask equipped with a condenser and vacuumed to remove moisture and oxygen, and then dissolved by adding anhydrous toluene (10ml). THF (10ml) and K ₂ CO ₃ after adding Pd (0) catalyst (0.084mmol) Aqueous solution (4eq) is added. Finally, add Aliquit (0.103g, 0.2558mmol) and stir at 100-120 ℃ for 48 hours, add 0.1 g of 2-bromothiophene, and after 6 hours, 0.1g of 2-thiopheneboronic acid 6 hours later, the reaction is terminated. The product was dissolved in chloroform, columned with Florisil to remove Pd (pph ₃ ) ₄ , and then recrystallized in methanol to obtain a red solid, which was purified by Soxhlet extractor using methanol, hexane and acetone. It was.

GPC: Mn 4300, Mw 7300,

¹ H-NMR (400 MHz, CDCl ₃ ) δ 0.85 (t, 6H), 1.25 (m, 8H), 1.45 (m, 4H) 1.75 (m, 4H), 2.85 (t, 4H), 7.32 (s, 2H ), 8.02 (d, 2H), 8.10 (d, 2H), 8.25 (d, 2H), 8.45 (d, 2H),

¹³ C-NMR (400MHZ, CDCl ₃ ) δ 17.0, 21.5, 24.5, 25.0, 25.5, 120.5, 125.5, 126.0, 126.5, 128.0, 129.0, 129.5, 130.0, 131.0, 132.0

The synthesized polymer (P3H5PBT) was well dissolved in chloroform, THF and toluene, which are common organic solvents at room temperature. In order to evaluate the thermal stability of the synthesized polymer (P3H5PBT) TGA and DSC were measured and the results are shown in FIG. TGA N ₂ It was measured by increasing the temperature to 10 ℃ per minute under the weight loss of the sample was found to be a very thermally stable organic material with a 5% Decomposition Tempertature of the original weight of 370 ℃. However, as shown in the DSC analysis results (FIG. 7 (b)), no distinct Tg or Tm was found in the section from the apparent room temperature to 300 ℃.

In order to determine the absorbance and fluorescence change of the synthesized polymer (P3H5PBT), UV and PL were measured in a solution in which P3H5PBT was dissolved in chloroform and spin-coated at a concentration of 1w%, and the results are shown in FIG. 8. In the UV absorption spectra of the solution state and the solid film state, the solution state showed the maximum absorption at 397 nm and the film state at 401 nm, but there was no significant difference. However, in the PL emission, the solution state was 525 nm and the film state was 550 nm, showing a red-shift of about 25 nm. In solution, the molecules are distributed over a wide range and can move relatively freely; in the solid film state, the tendency of aggregation of pyrene groups and the coplanar due to pyrene in the film It is presumed to be the result of intermolecular stacking due to the influence of coplanar configuration and neighboring 3-hexylthiophene.

In addition, the HOMO level of the material was determined by cyclic voltammetry. Ferrocene / ferrocenium redox system (-4.8 eV) was measured in the solid film state as a reference, HOMO level was calculated as -5.48 eV, UV _edge of the UV spectrum of the solid film state The band gap was calculated using (470 nm) and found to be 2.64 eV. From the HOMO level and the band gap, LUMO level-2.84 eV was obtained.

Example 3 1,6- (di-2- [3,7-dimethyl] octyl-2,2'-bithiopetyl) -pyrene {1,6- (di-2- [3,7- dimethyl] octyl-2,2'-bithiophenyl) -pyrene}

3,7-dimethyl- Octyl bromide  [3,7- dimethyl - octylbromide Manufacture of

Triphenylphosphine (27.3 g, 0.1042 mol) and 3,7-dimethyloctanol (3,7-dimethyloctanol (15 g, 0.09477 mol) were methylated in a 500 ml 2-neck round flask under an ice bath. Dissolve in 100 ml of chloride. N-bromosuccinimide (N-Bromosuccinimide, 20.25g, 0.1137mol) was added little by little (heat generation), and then stirred at room temperature for 12 hours to terminate the reaction. The organic layer was extracted with methyl chloride and brine, and the remaining water was removed with anhydrous magnesium sulfate (MgSO ₄ ), followed by rotary evaporation to filter out solids formed by adding hexane. Finally, distillation gives a product in the liquid state. (80% yield)

¹ H-NMR (400MHZ, CDCl ₃ ): 0.86 (d, 6H), 0.92 (d, 3H), 1.12 (m, 4H), 1.26 (m, 2H), 1.50 (m, 1H), 1.62 (m, 2H), 1.85 (m, 1H), 3.42 (m, 2H)

5- [3,7-dimethyl] Octyl -2,2′- Vithiophene  {5- [3,7- dimethyl ] octyl -2,2′-bithiophene} Preparation

The 2,2'-bithiophene (4.0 g, 0.024 mol) is kept in vacuum for about 1 hour and then dissolved in THF. N-butyllithium (n-butyllitium 2.5M in hexanes, 10.08ml, 0.0252mol) was slowly added at -78 ° C, followed by stirring for 2 hours. Again, 3,7-dimethyl-octylbromide (5.84 g, 0.0264 mol) was slowly added at -78 ° C, and then stirred for 1 hour, and stirred at room temperature for 2 hours to terminate the reaction. After cooling with methanol, the organic layer was extracted with methyl chloride and brine, and the remaining moisture was removed with anhydrous magnesium sulfate (MgSO ₄ ). After rotary evaporation, the final product was distilled to obtain a liquid product. (50% yield)

¹ H-NMR (400MH _Z , CDCl ₃ ): 0.86 (d, 6H), 0.89 (d, 3H), 1.12 (m, 4H), 1.28 (m, 2H), 1.49 (m, 3H), 1.67 (m , 1H), 2.75 (m, 2H), 6.75 (d, 1H), 6.90 (d, 1H), 7.00 (t, 1H), 7.15 (d, 1H), 7.20 (d, 1H)

5- [3,7-dimethyl] Octyl -5 '-[4,4,5,5- Tetramethyl -1,3,2- Dioxaborolanyl ] 2,2′- Vithiophene  {5- [3,7-dimethyl] octyl-5 '-[4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl] -2,2'- bithiophene } Manufacturing

5- [3,7-dimethyl] octyl-2,2'-bithiophene (3.7 g, 0.01207 mol) is vacuumed for about 1 hour and then dissolved in THF. N-butyllithium (n-butyllitium 2.5M in hexanes, 5.31ml, 0.01328mol) was added slowly under -78 ° C and stirred for 2 hours. Again, 2-isopropoxy-4,4,5,5-tetramethyll-1,3,2-dioxaborolane (2.47 g, 0.01328 mol) was added slowly at -78 ° C, followed by stirring for 2 hours and 40 The reaction is terminated after stirring at room temperature for time. After cooling with methanol, the organic layer was extracted with methyl chloride and brine, and the remaining water was removed with anhydrous magnesium sulfate (MgSO ₄ ), followed by rotary evaporation, and finally column with hexane to obtain a liquid product. (45% yield)

¹ H-NMR (400MH _Z , CDCl ₃ ): 0.86 (d, 6H), 0.89 (d, 3H), 1.12 (m, 4H), 1.28 (m, 2H), 1.32 (s, 12H), 1.49 (m , 3H), 1.67 (m, 1H), 2.75 (m, 2H), 6.65 (d, 1H), 7.02 (d, 1H), 7.12 (d, 1H), 7.48 (d, 1H)

1,6- (di-2- [3,7-dimethyl] Octyl -2,2′- Vithiopetyl ) - Pyrene  {1,6- ( di -2- [3,7- dimethyl ] octyl -2,2'-bithiophenyl) -pyrene}

1,6-dibromopyrene (0.832g, 0.00231mol) and 5- [3,7-dimethyl] octyl-5 '-[4,4,5,5-tetramethyl-1,3,2-di In a round flask equipped with a condenser prepared with oxaborolanyl] -2,2'-bithiophene (2.0 g, 0.00462 mol), a vacuum was taken and dissolved in anhydrous toluene (about 10 ml). Add Pd (0) catalyst (0.08g, 0.03eq) and add THF (10ml) and potassium carbonate (K ₂ CO ₃ , 6ml, 4eq). The reaction is terminated after stirring for 48 hours at 100 ~ 120 ℃ temperature. The compound was dissolved in chloroform and columned with Florisil to remove Pd (pph ₃ ) _4, and then recrystallized in methanol to obtain a yellow solid, and then purified by Soxhlet in hexane. (40% yield)

¹ H-NMR (400MH _Z , CDCl ₃ ): 0.86 (d, 12H), 0.89 (d, 6H), 1.12 (m, 8H), 1.28 (m, 4H), 1.49 (m, 6H), 1.67 (m , 2H), 2.80 (m, 4H), 6.65 (d, 4H), 7.05 (d, 4H), 8.07 (d, 2H), 8.09 (d, 2H), 8.16 (d, 2H), 8.59 (d, 2H)

Example 4 1,6- (di- (2- [3,7-dimethyl] octyl) thieno (3,2-b) thiophene) pyrene {1,6- (di- (2- [ 3,7-dimethyl] octyl) thieno (3,2-b) thiophene) -pyrene}

3- Bromothiophene -2- Carbaldehyde  [3- Bromothiophene -2- carbaldehyde Manufacturing of Product  10)

In a 500 ml round flask, 3-bromothiophene (16.3 g, 0.1 mol) was evacuated for 1 hour to remove oxygen and water, and then dissolved in 250 ml of dry THF. Lithium diisopropylamide (Lithium diisopropylamide 2M in THF, 50ml, 0.001mol) was added slowly at 0 ° C. and stirred for 1 hour. Again, N-formylpiperidine (11.11ml, 0.001mol) was slowly added at 0 ° C, stirred for 3 hours, and the reaction was terminated. The reaction was terminated with 20% aqueous ammonium chloride solution and the organic layer was extracted with diethyl ether and brine. The remaining water was removed with anhydrous magnesium sulfate (MgSO ₄ ), the solvent was evaporated and fractional distillation to obtain a liquid substance. . (68% yield)

¹ H-NMR (400MHZ, CDCl ₃ ): δ 7.11 (d, 1H), 7.69 (d, 1H), 9.92 (d, 1H)

ethyl Thieno (3,2-b) thiophene -2- Carboxylate  [ Ethyl thieno  (3,2-b) thiophene -2- carboxylate Manufacturing of Product  11)

Add Product 10 (12.5g, 0.0654mol), 125ml DMF and K ₂ CO ₃ (12.21g, 0.0883mol) and stir for 1 hour. Ethyl sulfanyl acetate (7.99 g, 0.0665 mol) was added slowly, followed by stirring for 72 hours and the reaction was terminated. After completion of the reaction with distilled water, the organic layer was extracted with methyl chloride and brine, and the remaining water was removed with anhydrous magnesium sulfate (MgSO ₄ ), the solvent was evaporated and fractional distillation to obtain a liquid substance. (85% yield)

¹ H-NMR (400MH _Z , CDCl ₃ ): δ 1.37 (t, 3H), 4.34 (m, 2H), 7.24 (d, 1H), 7.55 (d, 1H), 7.97 (s, 1H)

Thieno (3,2-b) thiophene -2- Carbaldehyde  [ Thieno (3,2-B) thiophene-2- carbaldehyde Manufacturing of Product  12)

115.975ml of an aqueous solution of sodium hydroxide (4.639g, 0.1159mol) and 116ml of THF were added to Product 11 (12.31g 0.0579mol), followed by stirring at 70 ° C for 3 hours to terminate the reaction. Evaporation of the solvent and addition of 232 ml of 1M HCl at 0 ° C. resulted in a white solid precipitate. The precipitate is filtered, and the filtrate is again poured into 300 ml of distilled water, stirred for 24 hours, and then filtered again and dried in a vacuum oven. (55% yield)

¹ H-NMR (400MHZ, CDCl ₃ ) δ 7.50 (d, 1H), 7.91 (d, 1H), 8.09 (s, 1H)

Thieno (3,2-b) thiophene  Thieno (3,2-B) thiophene Manufacturing of Product  13)

Copper powder is added to Product 12 (5.7g, 0.0309mol), vacuumed for 2 hours to remove acid and moisture, and then dissolved in quinoline (50ml). The reaction is terminated after stirring at 180 ° C. for 4 hours. After completion of the reaction with diethyl ether, the organic layer was extracted with diethyl ether and 1M HCl, the remaining water was removed with anhydrous magnesium sulfate (MgSO ₄ ), the solvent was evaporated when evaporated, and the liquid phase was purified by column chromatography (using Petroleum ether). Get the material. (53% yield)

¹ H-NMR (400MH _Z , CDCl ₃ ) δ 7.25 (d, 2H), 7.37 (d, 2H)

2,5- Dibromo Thieno (3,2-b) thiophene  [2,5- Dibromo  thieno (3,2-b) thiophene Manufacturing of Product  14)

Dissolve Product 13 (2.4 g, 0.0171 mol) in 80 ml of acetic acid and 20 ml of chloroform. After adding N-bromosuccinimide (6.09 g, 0.0342 mol) at 0 ° C., the mixture was stirred for 6 hours and the reaction was terminated. Extract the organic layer with methyl chloride and brine, remove the remaining moisture with anhydrous magnesium sulfate (MgSO ₄ ), evaporate the solvent when evaporated, recrystallize with methanol for 12 hours, filter, and dry in a vacuum oven. (82% yield)

¹ H-NMR (400MH _Z , CDCl ₃ ): δ 6.96 (s, 2H)

2- [3,7- Dimethyloctyl ] -5- Bromo Thieno (3,2-b) thiophene  {2- [3,7- dimethyloctyl ] -5- bromo  Preparation of thieno (3,2-b) thiophene} Product  15)

In a glove box, 2,5-dibromo dieno (3,2-B) thiophene (Dibromo thieno (3,2-B) thiophene, 2.0 g, 6.71 mmol) is dissolved in THF. N-butyllithium (n-butyllitium 2.5M in hexanes, 2.8ml, 7.0mmol) was slowly added at -78 ° C and stirred for 2 hours. Again, 3,7-dimethyloctylbromide (1.63g, 7.3mmol) was slowly added at -78 ° C, stirred for 1 hour, and stirred at room temperature for 2 hours, and then terminated. After cooling with methanol, the organic layer was extracted with methyl chloride and brine, and the remaining moisture was removed with anhydrous magnesium sulfate (MgSO ₄ ), followed by rotary evaporation, and finally fractional distillation to obtain a liquid product. (67% yield)

¹ H-NMR (400MHZ, CDCl ₃ ): δ 0.86 (d, 6H), 0.89 (d, 3H), 1.12 (m, 4H), 1.28 (m, 2H), 1.49 (m, 3H), 1.67 (m , 1H), 2.75 (m, 2H), 6.65 (s, 1H), 6.96 (s, 1H)

5- [3,7-dimethyl] Octyl -5 '-[4,4,5,5- Tetramethyl -1,3,2- Dioxaborolanyl ]- Thieno (3,2-b) thiophene  Preparation of 5- [3,7-dimethyl] octyl-5 '-[4,4,5,5-tetramethyl-1,3,2-dioxaborolanyl] -thieno (3,2-B) thiophene} (Product 16)

In a glove box, 2- [3,7-dimethyloctyl] -5-bromo thieno (3,2-B) thiophene (2.0 g, 5.56 mmol) is added and dissolved in THF. Under -78 ° C, n-butyllitium 2.5M in hexanes (2.45ml, 6.12mmol) was slowly added and stirred for 2 hours. Then again 2-isopropoxy-4,4,5,5-tetramethyl-1,3,2-dioxaborolane (1.25ml, 6.12mmol) was slowly added at -78 ° C, then stirred for 2 hours and 40 hours. After stirring at room temperature, the reaction is terminated. After cooling with methanol, the organic layer was extracted with methyl chloride and brine, and the remaining water was removed with anhydrous magnesium sulfate (MgSO ₄ ), rotary evaporation, and finally columned with hexane to obtain a liquid product. (55% yield)

¹ H-NMR (400MHZ, CDCl ₃ ): δ 0.86 (d, 6H), 0.89 (d, 3H), 1.12 (m, 4H), 1.28 (m, 2H), 1.32 (s, 12H), 1.49 (m , 3H), 1.67 (m, 1H), 2.75 (m, 2H), 6.65 (s, 1H), 6.96 (s, 1H)

1,6- (di- (2- [3,7-dimethyl] Octyl ) Tieno (3,2-b) thiophene) Pyrene  {1,6- ( di -(2- [3,7- dimethyl ] octyl ) Preparation of thieno (3,2-b) thiophene) -pyrene}

1,6-dibromopyrene (0.886 g, 2.46 mmol) and 5- [3,7-dimethyl] octyl-5 '-[4,4,5,5-tetramethyl-1,3,2-di Vacuum in a round flask equipped with a condenser prepared with oxaborolanyl] -thieno (3,2-B) thiophene (2.0 g, 4.92 mmol) and dissolved in anhydrous toluene (about 10 ml). Pd (0) catalyst (0.085g, 0.03eq) was added and THF (10ml) and K ₂ CO ₃ (6ml, 4eq) were added. The reaction is terminated after stirring for 48 hours at 100 ~ 120 ℃ temperature. The compound was dissolved in chloroform and columned with Florisil to remove Pd (pph ₃ ) _4, and then recrystallized in methanol to obtain a yellow solid, and purified by Soxhlet in hexane, acetone, and methanol. (67% yield)

¹ H-NMR (400MH _Z , CDCl ₃ ) δ 0.86 (d, 12H), 0.89 (d, 6H), 1.12 (m, 8H), 1.28 (m, 4H), 1.49 (m, 6H), 1.67 (m , 2H), 2.80 (m, 4H), 6.65 (s, 2H), 7.05 (s, 2H), 8.07 (d, 2H), 8.09 (d, 2H), 8.16 (d, 2H), 8.59 (d, 2H)

Example 5 Preparation of TIPS-Pyrene [1,6-bis [(triisopropylsilyl) ethynyl] pyrene]

Dry NF (10ml) and triisopropylsilyl acetylene (4.11ml, 18.33mmol) under N ₂ into a dried 250ml round bottom flask, cool to 0 ° C and then t-BuLi (11.76ml, 20.0mmol) Slowly inject into the syringe. After the reaction was stirred for 2 hours, anhydrous THF (120ml) and 1,6-dibromopyrene (3g, 8.33mmol) were added thereto, and the reaction was terminated by stirring at room temperature for 24 hours. After cooling with H ₂ O, an organic layer was extracted with ammonium chloride and ethyl acetate and washed with brine. Remove the remaining water with anhydrous magnesium sulfate (MgSO ₄ ), rotary evaporate, and dissolve the compound in THF (100ml) and add SnCl ₂ · 2H ₂ O (15g, 66.5mmol, in 50ml 50% acetic acid). After stirring the compound at room temperature for 12 hours, the organic layer was extracted again with ethyl acetate and brine, and the remaining moisture was removed with anhydrous magnesium sulfate (MgSO ₄ ). After rotary evaporation and columning with hexane, finally recrystallization from petroleum ether to obtain a solid. (45% yield)

¹ H-NMR (400MHZ, CDCl ₃ ) δ 1.25 (m, 42H), 8.07 (d, 2H), 8.09 (d, 2H), 8.06 (d, 2H), 8.40 (d, 2H)

Example 6 Fabrication of Organic Thin Film Transistor

An organic thin film transistor (OTFT) was manufactured as shown in FIG. 9 using the organic semiconductor material (D2OBTP) prepared in Example 1. Three kinds of top-contact / bottom-gate organic thin film transistor (OTFT) devices were fabricated with different gate electrodes and insulator materials. a) The device used an n-Si wafer coated with SiO ₂ as an insulator as a gate electrode. The active layer deposited organic semiconductor material (D2OBTP) at a rate of 0.5 dl / s in a high vacuum state, the substrate temperature was 70 ℃ during deposition and the thickness of the prepared active layer is 100 nm. Au was deposited on the 80 nm vacuum at a rate of 1 dB / s. b) and c) were fabricated using PVP [poly (vinylphenol)] and PVA [poly (vinylalcohol)] as insulators on ITO-coated glass used as gate electrodes, respectively. The vacuum deposition of the active layer and the source-drain electrode was performed by a shadow mask in N ₂ atmosphere, and the channel length was 40 and the width was 1000.

In a p-channel FET fabricated using D2OBTP, the carrier is a hole and the source-drain voltage is negative (in the case of n-channel, the carrier is electronically positive). Therefore, holes flow from the source to the drain and I _D becomes negative. The fabricated transistor device was measured with a hole mobility of 0.7 cm ² / Vs and a blink rate of 10 ⁸ , showing similar mobility to the device fabricated using pentacene under the same conditions. In the design of molecular structure, thiophene derivatives, which are well known as high charge mobility materials, are connected to both sides of the conjugated aromatic ring pyrene, which has a more planar structure, from which the expansion of π-π stacking and Intermolecular conduction appears to be the result of more ease.

Example 7 Fabrication of Organic Solar Cell Device

To investigate the photovoltaic characteristics of an organic solar cell device made using a new electron donor polymer, as shown in FIG. 11, [ITO / PEDOT: PSS / Polymer (P3H5PBT) + PCBM (C ₆₀₎ or C ₇₀ ) / LiF / Al] structure solar cell device.

First, UV-O ₃ was treated on a cleanly washed indium tin oxide (ITO) glass, and the PEDOT: PSS layer was spin coated to a thickness of about 54 nm. Polymer (P3H5PBT) and PCBM (C ₇₀ ) (or PCBM (C ₆₀ )) were added to chlorobenzene in a ratio of 1: 3 (by weight) and then stirred at 50 ° C. for 20 hours for sufficient mixing of the two materials to prepare a mixed solution. It was. The glass substrate coated with PEDOT: PSS in a glove box (Ar gas) was baked at 140 ° C. for 10 minutes to form an EBL layer of about 100 nm. The mixed solution was spin coated on the EBL layer and heat-treated again at 120 ° C. for 10 minutes to form an active layer of about 100 nm, followed by high temperature deposition of LiF (0.6 nm) / Al (144 nm).

The solar cell device uses polymer (P3H5PBT) + PCBM (C ₇₀ ) and polymer (P3H5PBT) + PCBM (C ₆₀ ) in the active layer to examine the effect of photoelectric efficiency characteristics according to the absorption of acceptor. The fabrication of the photovoltaic characteristics was investigated.

In order to investigate the photovoltaic characteristics of the fabricated device, 100 mW solar power under AM 1.5 was generated using a solar simulator and a radiant power meter, and a 1kW solar simulator (Newport 91192) was used. The current density-voltage characteristics of the organic solar cell device were measured, and the results are shown in FIG. 12.

Both devices showed a high open-circuit value relative to the short-circuit current, and the maximum energy conversion efficiency was relatively high compared to the low FF value. As shown in FIG. 13, the maximum energy conversion efficiency value of the P3H5PBT + PCBM (C ₆₀ ) device and the P3H5PBT + PCBM (C ₇₀ ) device is more than doubled, which is illustrated in FIG. 14. The acceptor PCBM (C ₇₀ ) has a wider visible light absorption area than the PCBM (C ₆₀ ) and is considered to be due to the increase of the total light absorption area of the mixed active layer.

FIG. 1 shows the structure of an organic thin film transistor (OTFT) and shows a structure of an upper contact (a) and a lower contact (b) type.

FIG. 2 is a schematic diagram illustrating a comparison of a bi-layer (BL) mode (a) and a bulk-heterojunction (BHT) mode (b) of an organic solar cell.

3 is a result of analysis of the thermogravimetric analysis (TGA) of the compound prepared in Example 1 (D2OBTP).

4 is a DSC analysis result of the compound (D2OBTP) prepared in Example 1.

FIG. 5 is a cross-polarized optical micrographes (x250) of the compound (D2OBTP) prepared in Example 1. FIG.

6 is a UV spectrum and a PL spectrum of the compound (D2OBTP) prepared in Example 1. FIG.

7 shows TGA (a) and DSC (b) results of the polymer semiconductor material (P3H5PBT) prepared in Example 2. FIG.

8 is a UV and PL spectrum of the polymer semiconductor material (P3H5PBT) prepared in Example 2.

FIG. 9 is a first measurement result of current-voltage (I _D -V _D ) characteristics of organic thin film transistors (OTFTs) prepared in Example 3. FIG.

FIG. 10 is a secondary measurement result of mobility characteristics of an organic thin film transistor when an SiO ₂ dielectric is used among the organic thin film transistors prepared in Example 3. FIG.

FIG. 11 is a schematic diagram of a bulk-heterojunction (BHT) solar cell of the polymer semiconductor material (P3H5PBT) prepared in Example 2. FIG.

12 is a J-V characteristic curve of the organic solar cell prepared in Example 4.

FIG. 13 illustrates an Incident Photon to Current Efficiency (IPCE) of the organic solar cell prepared in Example 4. FIG.

14 is a UV-vis absorption spectrum of PCBM (C ₆₀ ) thin film and PCBM (C ₇₀ ) thin film.

Claims (10)

An organic semiconductor compound having a structure represented by the following formula (1) or (3). [Formula 1]

[In Formula 1, R ¹ and R ² are independently hydrogen or a C ₁ to C ₂₀ linear or branched alkyl group, n is an integer of 1 to 2,000.] (3)

[In Formula 3, R ³ is a C ₁ ~ C ₂₀ linear or branched alkyl group.] The method of claim 1, The organic semiconductor compound is an organic semiconductor compound having a structure of formula (2). [Formula 2]

[In Formula 2, R ¹ and R ² are independently hydrogen or a C ₁ to C ₂₀ linear or branched alkyl group, n is an integer of 1 to 2,000.] delete An organic electronic device comprising the organic semiconductor compound according to claim 1. The method of claim 4, wherein The organic electronic device is an organic thin film transistor containing the organic semiconductor compound in an active layer. The method of claim 4, wherein The organic electronic device is an organic electronic device comprising an organic solar cell containing the organic semiconductor compound as an electron donor material in an active layer. The method of claim 6, The organic layer of the organic solar cell further comprises one or more selected from the following electron acceptor materials.

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