KR102590966B1 - Organic compound and organic thin film and electronic device - Google Patents

Abstract

It relates to an organic compound represented by the following formula (1), an organic thin film containing the organic compound, a thin film transistor, and an electronic device.

[Formula 1]

In Formula 1,
A and B are each independently a substituted or unsubstituted C6 to C30 arylene group, a divalent substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof,
Z ¹ to Z ⁶ are each independently hydrogen, a C1 to C10 haloalkyl group or a halogen atom, but at least one of Z ¹ to Z ⁶ is a C1 to C10 haloalkyl group or a halogen atom,
n ¹ and n ² are each independently integers from 0 to 5,
L is a condensed polycyclic group in which six or more rings are fused, and is a group represented by the following formula (2),
[Formula 2]

In Formulas 2 and 3, the definitions of Ar ¹ to Ar ³ , X ¹ , X ² , R ¹ , R ² , R ^a , a, b and * are as described in the specification.

Description

Organic compounds, organic thin films and electronic devices {ORGANIC COMPOUND AND ORGANIC THIN FILM AND ELECTRONIC DEVICE}

It relates to organic compounds, organic thin films, and electronic devices.

Flat panel displays, such as liquid crystal displays (LCD), organic light emitting diode displays (OLED displays), and electrophoretic displays, have multiple pairs of electric field generating electrodes and between them. It contains an electro-optic active layer. In the case of a liquid crystal display device, the electro-optical active layer includes a liquid crystal layer, and in the case of an organic light-emitting display device, the electro-optical active layer includes an organic light-emitting layer.

One of the pair of electric field generating electrodes is usually connected to a switching element to receive an electric signal, and the electro-optical active layer converts this electric signal into an optical signal to display an image.

Flat panel display devices use a three-terminal thin film transistor (TFT) as a switching element, and a gate line that transmits a scanning signal to control the thin film transistor and a signal to be applied to the pixel electrode are used as a switching element. A data line that transmits data is provided in the flat panel display device.

Among these thin film transistors, research is being actively conducted on organic thin film transistors (OTFTs), which contain organic semiconductors such as low molecules or polymers instead of inorganic semiconductors such as silicon (Si).

Organic thin film transistors are attracting attention as a core element of flexible display devices because they can be made into shapes such as fibers or films due to the nature of organic materials. In addition, organic thin film transistors can be manufactured through a solution process such as inkjet printing, so they can be easily applied to large-area flat panel displays where only the deposition process has limitations.

One embodiment provides an organic compound applicable to electronic devices such as organic thin film transistors.

Another embodiment provides an organic thin film containing the organic compound.

Another embodiment provides an electronic device including the organic thin film.

According to one embodiment, an organic compound represented by the following Chemical Formula 1 is provided.

[Formula 1]

In Formula 1,

A and B are each independently a substituted or unsubstituted C6 to C30 arylene group, a divalent substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof,

Z ¹ to Z ⁶ are each independently hydrogen, a C1 to C10 haloalkyl group or a halogen atom, but at least one of Z ¹ to Z ⁶ is a C1 to C10 haloalkyl group or a halogen atom,

n ¹ and n ² are each independently integers from 0 to 5,

L is a condensed polycyclic group in which six or more rings are fused, and is a group represented by the following formula (2),

[Formula 2]

In Formula 2,

Ar ¹ and Ar ² are each independently a substituted or unsubstituted pentagonal ring or a substituted or unsubstituted hexagonal ring,

Ar ³ is or ego,

X ¹ to X ⁴ are each independently O, S, Se, Te or NR ^a ,

R ¹ , R ² , R ^a , R ^x and R ^y are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, or a substituted or unsubstituted C6 to C30 aryl group. group, substituted or unsubstituted C7 to C30 arylalkyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 heterocyclic group, substituted or An unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a hydroxy group, a halogen atom, or a combination thereof,

a and b are each independently an integer of 1 to 3,

* is the connection point,

In Formula 2, Ar ³ is And when a=b=1, L is a group represented by the following formula (3):

[Formula 3]

In Formula 3 above,

Ar ¹ , Ar ² , X ¹ to X ⁴ , R ¹ , R ² and * are as defined in Formula 2 above.

Ar ¹ and Ar ² may each independently be a substituted or unsubstituted benzene ring or a substituted or unsubstituted heterocyclic group.

Ar ¹ and Ar ² may be a substituted or unsubstituted benzene ring.

In Formula 2, a=b=1 or a=b=2 may be satisfied.

The L may be any one of the groups listed in Group 1 below.

[Group 1]

In group 1 above,

X ¹ to X ⁴ are each independently O, S, Se, Te or NR ^a ,

R ¹ to R ¹² , and R ^a are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted Ringed C7 to C30 arylalkyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 heterocyclic group, substituted or unsubstituted C2 to C30 heterocyclic group. A C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a hydroxy group, a halogen atom, or a combination thereof,

* is a connection point.

A and B may each independently be any one of the groups listed in Group 2 below.

[Group 2]

X ²¹ to X ²³ are each independently O, S, Se, Te or NR ^a ,

R ²¹ to R ²⁶ , and R ^a are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted Ringed C7 to C30 arylalkyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 heterocyclic group, substituted or unsubstituted C2 to C30 heterocyclic group. A C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a hydroxy group, a halogen atom, or a combination thereof,

* is a connection point.

Z ¹ to Z ⁶ may each independently be a halogen atom.

The organic compound may be any one of those listed in Group 3 below.

[Group 3]

In group 3 above,

X ¹ to X ⁴ are each independently O, S, Se, Te or NR ^a ,

R ^a is each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C7 to C30 arylalkyl group. , substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 heterocyclic group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted It is a ringed C2 to C30 alkynyl group, a hydroxy group, a halogen atom, or a combination thereof.

According to another embodiment, an organic thin film containing the organic compound is provided.

According to another embodiment, an electronic device including the organic thin film is provided.

According to another embodiment, it includes a gate electrode, an organic semiconductor overlapping the gate electrode, and a source electrode and a drain electrode electrically connected to the organic semiconductor, wherein the organic semiconductor is an organic compound represented by Formula 1. Provides a thin film transistor including a.

According to another embodiment, an electronic device including the thin film transistor is provided.

The electronic devices may include solar cells, liquid crystal displays, organic light emitting devices, electrophoresis devices, organic photoelectric devices, and organic sensors.

An organic compound with improved electrical properties such as charge mobility is provided.

Figure 1 is a cross-sectional view showing a thin film transistor according to one implementation.
Figure 2 shows MALDI-TOF mass spectrometry data of the compound according to Synthesis Example 1.
Figure 3 shows MALDI-TOF mass spectrometry data of the compound according to Synthesis Example 2.
Figure 4 is a graph showing the charge mobility of the organic thin film transistor according to Example 1.
Figure 5 is a graph showing the charge mobility of the organic thin film transistor according to Example 2.

Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention. However, the present invention may be implemented in many different forms and is not limited to the embodiments described herein.

Unless otherwise defined herein, 'substituted' means that the hydrogen atom in the compound is a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, an azido group, or an amino group. Dino group, hydrazino group, hydrazono group, carbonyl group, carbamyl group, thiol group, ester group, carboxyl group or its salt, sulfonic acid group or its salt, phosphoric acid or its salt, C1 to C20 alkyl group, C2 to C20 alkenyl group, C2 to C20 alkynyl group, C6 to C30 aryl group, C7 to C30 arylalkyl group, C1 to C30 alkoxy group, C1 to C20 heteroalkyl group, C3 to C20 heteroarylalkyl group, C3 to C30 cycloalkyl group, C3 to C15 cycloalkenyl group, It means substituted with a substituent selected from C6 to C15 cycloalkynyl group, C3 to C30 heterocycloalkyl group, and combinations thereof.

Additionally, unless otherwise defined in the specification, 'hetero' means containing 1 to 3 hetero atoms selected from N, O, S, Se, and P.

Hereinafter, an organic compound according to one embodiment will be described.

The organic compound according to one embodiment may be represented by the following Chemical Formula 1.

[Formula 1]

In Formula 1,

A and B are each independently a substituted or unsubstituted C6 to C30 arylene group, a divalent substituted or unsubstituted C2 to C30 heterocyclic group, or a combination thereof,

Z ¹ to Z ⁶ are each independently hydrogen, a C1 to C10 haloalkyl group or a halogen atom, but at least one of Z ¹ to Z ⁶ is a C1 to C10 haloalkyl group or a halogen atom,

n ¹ and n ² are each independently integers from 0 to 5,

L is a condensed polycyclic group in which six or more rings are fused, and is a group represented by the following formula (2),

[Formula 2]

In Formula 2,

Ar ¹ and Ar ² are each independently a substituted or unsubstituted pentagonal ring or a substituted or unsubstituted hexagonal ring,

Ar ³ is or ego,

X ¹ to X ⁴ are each independently O, S, Se, Te or NR ^a ,

R ¹ , R ² , R ^a , R ^x and R ^y are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, or a substituted or unsubstituted C6 to C30 aryl group. group, substituted or unsubstituted C7 to C30 arylalkyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 heterocyclic group, substituted or An unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a hydroxy group, a halogen atom, or a combination thereof,

a and b are each independently an integer of 1 to 3,

* is the connection point,

In Formula 2, Ar ³ is And when a=b=1, L is a group represented by the following formula (3).

[Formula 3]

In Formula 3 above,

Ar ¹ , Ar ² , X ¹ to X ⁴ , R ¹ , R ² and * are as defined in Formula 2 above.

The organic compound is a low-molecular compound in which L, a condensed polycyclic group in which six or more rings are fused, is located in the core, a halogen atom is contained in the terminal portion, and the core portion and the terminal portion are connected to a predetermined ring group. The organic compound can increase the planarity of the compound by appropriately adjusting the number of fused rings in the core portion, thereby increasing packing and stacking between molecules. In addition, the organic compound contains halogen atoms at the end portions, thereby increasing not only the interaction between the end portions but also the pi-pi interaction between the core portions due to the action of Van der Waals Force between halogen atoms. This can improve intermolecular interactions or intermolecular space structure.

Ar ¹ and Ar ² may each independently be a substituted or unsubstituted benzene ring or a substituted or unsubstituted heterocyclic group.

For example, L may be a fusion of a substituted or unsubstituted benzene ring and a substituted or unsubstituted heterocyclic group, and for example, Ar ¹ and Ar ² may be a substituted or unsubstituted benzene ring.

As an example, when Ar ¹ or Ar ² is a substituted or unsubstituted heterocyclic group, Ar ¹ or Ar ² includes O, S, Se, Te, or NR ^a . It may be a heterocyclic group, where R ^a is hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C3 to C30 aryl group. C7 to C30 arylalkyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 heterocyclic group, substituted or unsubstituted C2 to C30 alkyl group. It may be a nyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a hydroxy group, a halogen atom, or a combination thereof.

As an example, the condensed polycyclic group represented by L may have a symmetrical structure, for example, a and b may be 1 at the same time, or a and b may be 2 at the same time, but the present invention is not limited thereto.

The L may be one of the groups listed in Group 1 below, but is not limited thereto.

[Group 1]

In group 1 above,

X ¹ to X ⁴ are each independently O, S, Se, Te or NR ^a ,

R ¹ to R ¹² , and R ^a are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted Ringed C7 to C30 arylalkyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 heterocyclic group, substituted or unsubstituted C2 to C30 heterocyclic group. A C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a hydroxy group, a halogen atom, or a combination thereof,

* is a connection point.

As described above, the organic compound contains at least one halogen atom at an end, and the at least one halogen atom may be contained at one end or both ends of the organic compound. For example, the halogen atom may be fluorine. For example, in Formula 1, Z ¹ to Z ⁶ may each independently be a halogen atom such as fluorine (F), chlorine (Cl), bromine (Br), or iodine (I), for example, Z ¹ to Z ⁶ may all be fluorine. For example, in Formula 1, n ¹ and n ² may each independently be integers from 1 to 5, for example, 1 or 2, but are not limited thereto.

Meanwhile, in Formula 1, A and B may each independently be, for example, any one of the substituted or unsubstituted groups listed in Group 2 below, but are not limited thereto.

[Group 2]

X ²¹ to X ²³ are each independently O, S, Se, Te or NR ^a ,

R ²¹ to R ²⁶ , and R ^a are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, substituted or unsubstituted Ringed C7 to C30 arylalkyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 heterocyclic group, substituted or unsubstituted C2 to C30 heterocyclic group. A C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkynyl group, a hydroxy group, a halogen atom, or a combination thereof,

* is a connection point.

The organic compound may be, for example, any one of the compounds listed in Group 3 below, but is not limited thereto.

[Group 3]

In group 3 above,

X ¹ to X ⁴ are each independently O, S, Se, Te or NR ^a ,

R ^a is each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C7 to C30 arylalkyl group. , substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 heterocyclic group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted It is a ringed C2 to C30 alkynyl group, a hydroxy group, a halogen atom, or a combination thereof.

The organic compound may be implemented as an organic thin film through a deposition or solution process. The organic thin film can be applied to various devices including organic semiconductors. For example, the organic compound can be applied to a thin film transistor and as a charge transport layer and/or an active layer in electronic devices such as solar cells, liquid crystal displays, organic light-emitting displays, electrophoretic devices, organic photoelectric devices, and organic sensors.

Hereinafter, an example of a thin film transistor containing the organic compound will be described with reference to the drawings.

In the drawing, the thickness is enlarged to clearly express various layers and regions. Throughout the specification, similar parts are given the same reference numerals. When a part of a layer, membrane, region, plate, etc. is said to be “on” another part, this includes not only cases where it is “directly above” the other part, but also cases where there is another part in between. Conversely, when a part is said to be “right on top” of another part, it means that there is no other part in between.

Figure 1 is a cross-sectional view showing a thin film transistor according to one implementation.

A gate electrode 124 is formed on a substrate 110 made of transparent glass, silicon, or plastic. The gate electrode 124 is connected to a gate line (not shown) that transmits the gate signal. The gate electrode 124 is made of gold (Au), copper (Cu), nickel (Ni), aluminum (Al), molybdenum (Mo), chromium (Cr), tantalum (Ta), titanium (Ti), alloys thereof, or It can be made with a combination of these.

A gate insulating film 140 is formed on the gate electrode 124. The gate insulating film 140 may be made of an organic material or an inorganic material. Examples of organic materials include polyvinyl alcohol-based compounds, polyimide-based compounds, polyacryl-based compounds, and polystyrene ( Examples of soluble polymer compounds include polystyrene-based compounds and benzocyclobutane (BCB), and examples of inorganic materials include silicon nitride (SiN _x ) and silicon oxide (SiO ₂ ).

A source electrode 173 and a drain electrode 175 are formed on the gate insulating film 140. The source electrode 173 and the drain electrode 175 face each other with the gate electrode 124 at the center. The source electrode 173 is connected to a data line (not shown) that transmits data signals. The source electrode 173 and the drain electrode 175 are gold (Au), copper (Cu), nickel (Ni), aluminum (Al), molybdenum (Mo), chromium (Cr), tantalum (Ta), and titanium (Ti). ), alloys thereof, or combinations thereof.

An organic semiconductor 154 is formed on the source electrode 173 and the drain electrode 175. The organic semiconductor 154 may be made of the organic compounds described above. The organic semiconductor 154 may be formed by preparing the above-described organic compounds in solution form and using a solution process such as spin coating, slit coating, or inkjet printing. However, the present invention is not limited to this and the above-mentioned organic compounds can also be formed through a dry process such as vapor deposition.

Here, a bottom gate structure thin film transistor is described as an example of a thin film transistor, but it is not limited to this and can be equally applied to thin film transistors of any structure, including a top gate structure thin film transistor.

The thin film transistor may be applied as a switching element or driving element to various electronic devices, and the electronic devices may include, for example, a liquid crystal display device, an organic light emitting display device, an electrophoretic display device, an organic photoelectric device, and an organic sensor.

The above-described implementation example will be described in more detail through examples below. However, the following examples are for illustrative purposes only and do not limit the scope of the present invention.

synthesis of organic compounds

Synthesis example One

(Synthesis of Compound P1)

In a 2000 ml two-neck flask, 8g (33mmol) of 2,4-dibrom thiophene, 7.52g (39.6 mmol) of 4-(trifluoromethyl)boronic acid, 8.66g (66 mmol) of potassium carbonate, tetrakisb (triphenylphosphine)palladium(0) 0.953 g (0.825 mmol), 640 ml of THF and 40 ml of water were refluxed at a temperature of 65°C for 12 hours. Afterwards, the reaction is terminated with water and chloroform and work-up is performed. Afterwards, the compound P1 is obtained by purifying it using column chromatography with hexane. (Yield: 71%)

(Synthesis of Compound P2)

Add 0.515 g (1.68 mmol) of compound P1 to a 100 ml one-necked flask and dissolve in 20 ml of THF. Afterwards, the temperature is lowered to -78°C, and 0.84 m (1.68 mmol) of LDA is added. Afterwards, 0.15 g (0.765 mmol) of thieno[3,2-b]thiophene-2,5-dicarbaldehyde was added. After 12 hours, the reaction is terminated with sodium hydrogen carbonate and work-up is performed with chloroform. Afterwards, recrystallization is performed using chloroform to obtain compound P2. (Yield: 46%)

(Synthesis of Compound P3)

Add 0.38 g (0.468 mmol) of compound P2, 0.44 g (3.52 mmol) of sodium cyanoborohydride (NaCNBH ₃ ), and zinc iodide (ZnI ₂ ) into a 250 ml two-necked flask. Add 70 ml of 1,2 dichloroethane, reflux the temperature to 40℃, and leave it overnight. Slowly pour 50 ml of water into the reaction vessel, and then slowly add 1N HCl to complete the reaction. After work-up with chloroform, the precipitate is captured and purified with methanol to obtain compound P3 (yield: 80%).

(Synthesis of Compound P4)

1.0 g of compound P3, 0.6 g of CuCN and 20 ml of NMP were placed in a 50 ml vial and reacted at a temperature of 180° C. for 1 hour and 30 minutes in a microwave reactor. Afterwards, the reaction was terminated with 1 N HCl solution and work-up was performed using DCM. Afterwards, the precipitate is captured and purified using ethyl acetate to obtain compound P4 (yield: 85%).

(Synthesis of Compound P5)

Dissolve 1.82 g (2.72 mmol) of compound P4 in 200 ml of DCM and lower the temperature to -10°C. Afterwards, slowly add 8.5 ml (8.16 mmol) of DIBAL-H. After 2 hours at -10°C, 1N HCl (MeOH (3): H2O (1)) is slowly injected. After that, slowly raise the temperature to room temperature. Afterwards, the organic layer is separated using water and DCM. Compound P5 is obtained by separation and purification using column chromatography using chloroform. (Yield: 39%)

(Synthesis of Compound P6)

Add 1.0 g of compound P5, 1.0 g of Amberlyst 15 (manufactured by Sigma-adrich), and 20 ml of 1,2-Dichorobenzene, and react at 120°C for 14 hours in a microwave reactor. Afterwards, the temperature is lowered to room temperature and then separated and purified by decant using ethyl acetate to obtain compound P6. (Yield: 50%)

Next, the actual structure of the final compound (compound P6) obtained in Synthesis Example 1 was confirmed by MALDI-TOF mass spectrometry.

Figure 2 shows MALDI-TOF mass spectrometry data of the final compound obtained in Synthesis Example 1 (m/z = 639.898). Referring to Figure 2, it can be confirmed that the compound of the synthesis example was actually obtained.

Synthesis example 2

(Synthesis of Compound P2')

Dissolve 0.5g (2.63mmol) of Benzo[1,2-b:4,5-b']dithiophene in 30ml of THF, drop the temperature to -78°C under a nitrogen atmosphere, and then add lithium diisopropylamine (LDA) solution ( 2.0 M, 3.0 ml, 5.8 mmol, 2.2 equiv.) was carefully injected. Afterwards, when the temperature reaches 0 ℃, drop the temperature again to -78 ℃ and inject Anhydrous dimethylformamide (0.6 ml, excess). When room temperature is reached, 1N HCl solution is injected and stirred for 20 minutes. Afterwards, PH is neutralized by injecting 1N concentration of NaHCO ₃ . Afterwards, the organic layer was extracted with dicholromethane, moisture was removed using MgSO ₄ and dried. Afterwards, the compound P2' is obtained by purification using column chromatography (yield: 80%).

(Synthesis of compound P3')

1.35 g (4.4 mmol) of compound P1 obtained in the process of Synthesis Example 1 was placed in a 100 ml one-neck flask and dissolved in 30 ml of THF. Afterwards, the temperature is lowered to -78°C, and 2.2 ml (4.4 mmol) of LDA is added. Afterwards, 0.5 g (2.0 mmol) Benzo[1,2-b:4,5-b']dithiophene-dicarbaldehyde is added. After 12 hours, the reaction is terminated with sodium hydrogen carbonate and work-up is performed with chloroform. Afterwards, the above compound P3' was obtained by recrystallization using chloroform (yield: 65%).

(Synthesis of compound P4')

Add 3.8 g (4.42 mmol) of P3', 4.44 g (70.72 mmol) of sodium cyanoborohydride (NaCNBH ₃ ), and 5.64 g (17.68 mmol) of zinc iodide (ZnI ₂ ) into a 1000 ml two-neck flask. Add 600 ml of 1,2 dichloroethane, reflux the temperature to 40℃, and leave overnight. Slowly pour 50 ml of water into the reaction vessel, and then complete the reaction by slowly adding 1N HCl. After work-up with chloroform, the precipitate is captured and purified with methanol to obtain the above compound P4' (yield: 80%).

(Synthesis of compound P5')

1.0 g of P4', 0.45 g of CuCN, and 20 ml of NMP were placed in a 50 ml vial, and reacted in a microwave reactor at a temperature of 180°C for 1 hour and 30 minutes. Afterwards, the reaction was terminated with 1 N HCl solution and work-up was performed using DCM. Afterwards, the precipitate is separated using ethyl acetate to obtain the compound P5' (yield: 60%).

(Synthesis of Compound P6')

Dissolve 1.0 g (1.38 mmol) of P5' in 120 ml of DCM and then drop the temperature to -10°C. Afterwards, slowly add 4.13 ml (4.13 mmol) of DIBAL-H. After 2 hours at -10°C, slowly inject 1 N HCl (MeOH (3): H2O (1)). After that, slowly raise the temperature to room temperature. Afterwards, the organic layer is separated using water and DCM. The above compound P6' was obtained by purification by column chromatography using chloroform (yield: 50%).

(Synthesis of compound P7')

Add 1.0 g of P6', 1.0 g of Amberlyst 15, and 20 ml of 1,2-Dichorobenzene into a vial, and react at 120°C for 10 hours in a microwave reactor. Afterwards, the temperature is lowered to room temperature and then separated and purified by decanting using ethyl acetate to obtain the above compound P7' (yield: 50%).

Next, the actual structure of the final compound (compound P7 ' ) obtained in Synthesis Example 2 was confirmed by MALDI-TOF mass spectrometry.

Figure 3 shows MALDI-TOF mass spectrometry data of the final compound obtained in Synthesis Example 2 (m/z = 690.017). Referring to Figure 3, it can be confirmed that the compound of the synthesis example was actually obtained.

Fabrication of organic thin film transistors

Example One

First, the cleaned silicon wafer substrate covered with 3000Å of SiO ₂ is exposed to O ₂ plasma, and then immersed in an octadecyltrichlorosilane solution diluted in hexane to a concentration of 10mM to change the surface to hydrophobicity. Next, the organic compound obtained in Synthesis Example 1 was deposited to a thickness of 700 Å through a vacuum vapor deposition method while changing the temperature of the substrate from room temperature to 200°C. Then, using a shadow mask, source and drain electrodes are deposited with Au to a thickness of 1000 Å to produce an organic thin film transistor.

Example 2

An organic thin film transistor was manufactured in the same manner as Example 1, except that the organic compound obtained in Synthesis Example 2 was used instead of the organic compound obtained in Synthesis Example 1.

evaluation

Calculate the charge mobility of the organic thin film transistor according to Example 1.

The charge mobility of the organic thin film transistor was obtained from the saturation region current equation by obtaining a graph with (I _SD ) ^1/2 and V _GS as variables and the slope ^:

In the above equation, I _SD is the source-drain current, m or m _FET is the charge mobility, C ₀ is the capacitance of the gate dielectric, W is the channel width, L is the channel length, V _GS is the gate voltage, and , V _T is the threshold voltage.

The blocking leakage current (I _off ) is the current that flows when in the off state, and was obtained from the current ratio as the minimum current in the off state. The current blink ratio (I _on /I _off ) was obtained as the ratio of the maximum current value in the on state and the minimum current value in the off state.

The results are shown in Figures 4 and 5 and Table 1.

FIG. 4 is a graph showing the charge mobility of the organic thin film transistor according to Example 1, and FIG. 5 is a graph showing the charge mobility of the organic thin film transistor according to Example 2.

Charge mobility (cm ² /Vs) Maximum current value in on state (A) Current blink ratio (I _on /I _off ) Example 1 11.48 6.66 ×10 ^-4 3.00 × 10 ⁹ Example 2 14.63 3.81 ×10 ^-4 3.50 × 10 ⁹

Referring to Figures 4 and 5 and Table 1, it can be seen that the organic thin film transistor according to Example 1 has excellent characteristics by securing a charge mobility of about 11 cm ² /Vs or more and a current blink ratio of 10 ⁹ or more.

Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements can also be made by those skilled in the art using the basic concept of the present invention as defined in the following claims. It falls within the scope of invention rights.

110: substrate 124: gate electrode
140: gate insulating film 154: organic semiconductor
173: source electrode 175: drain electrode

Claims (13)

Organic compound represented by the following formula (1):
[Formula 1]

In Formula 1,
A and B are each independently a substituted or unsubstituted C6 to C30 arylene group,
Z ¹ to Z ⁶ are each independently hydrogen, a C1 to C10 haloalkyl group or a halogen atom, but at least one of Z ¹ to Z ⁶ is a C1 to C10 haloalkyl group or a halogen atom,
n ¹ and n ² are each independently integers from 1 to 5,
L is a condensed polycyclic group in which six or more rings are fused, and is a group represented by the following formula (2),
[Formula 2]

In Formula 2,
Ar ¹ and Ar ² are each independently a substituted or unsubstituted hexagonal ring,
Ar ³ is ego,
X ¹ to X ⁴ are each independently O, S, Se or Te,
R ¹ , R ² , R ^x and R ^y are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C7 to C30 arylalkyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 heterocyclic group, substituted or unsubstituted C2 to C30 alkenyl group, substituted or unsubstituted C2 to C30 alkynyl group, hydroxy group, halogen atom, or a combination thereof,
a and b are each independently integers from 1 to 3,
* is a connection point.
In paragraph 1:
Ar ¹ and Ar ² are each independently a substituted or unsubstituted benzene ring.
delete In paragraph 1:
Organic compounds that satisfy a=b=1 or a=b=2.
In paragraph 1:
An organic compound wherein L is any one of the groups listed in Group 1 below:
[Group 1]



In group 1 above,
X ¹ to X ⁴ are each independently O, S, Se or Te,
R ¹ to R ¹² are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C7 to C30 aryl group. C30 arylalkyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 heterocyclic group, substituted or unsubstituted C2 to C30 alkenyl group, A substituted or unsubstituted C2 to C30 alkynyl group, a hydroxy group, a halogen atom, or a combination thereof,
* is a connection point. In paragraph 1:
A and B are each independently any of the groups listed in Group 2:
[Group 2]

In group 2 above,
R ²¹ to R ²⁶ are each independently hydrogen, a substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, or a substituted or unsubstituted C7 to C30 aryl group. C30 arylalkyl group, substituted or unsubstituted C1 to C30 heteroalkyl group, substituted or unsubstituted C2 to C30 heterocycloalkyl group, substituted or unsubstituted C2 to C30 heterocyclic group, substituted or unsubstituted C2 to C30 alkenyl group, A substituted or unsubstituted C2 to C30 alkynyl group, a hydroxy group, a halogen atom, or a combination thereof,
* is a connection point. In paragraph 1:
Z ¹ to Z ⁶ are each independently a halogen atom. In paragraph 1:
Organic compounds that are one of those listed in Group 3 below:
[Group 3]


In group 3 above,
X ¹ to X ⁴ are each independently O, S, Se or Te.
An organic thin film comprising the organic compound according to any one of claims 1, 2, and 4 to 8.
gate electrode,
an organic semiconductor overlapping the gate electrode and comprising the organic compound according to any one of claims 1, 2, and 4 to 8, and
A source electrode and a drain electrode electrically connected to the organic semiconductor.
A thin film transistor containing a.
An electronic device comprising the thin film transistor according to claim 10. In paragraph 11:
Electronic devices including solar cells, liquid crystal displays, organic light-emitting devices, electrophoresis devices, organic photoelectric devices, or organic sensors.
An electronic device comprising the organic thin film according to claim 9.

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