KR20200068516A - N-type organic semiconductor material, transistor device comprising the same, and manufacturing method thereof - Google Patents

Abstract

The present invention provides a compound having a structure represented by a chemical Formula 1, used as an N-type organic semiconductor material, an organic field effect transistor device comprising an organic thin film layer containing the compound, and a method of manufacturing the organic field effect transistor device. Therefore, an organic semiconductor material with improved light transmittance can be provided.

Description

An N-type organic semiconductor material, an organic field effect transistor device using the same, and a manufacturing method therefor{N-type organic semiconductor material, transistor device comprising the same, and manufacturing method thereof}

The present invention relates to an N-type organic material semiconductor material, an organic field effect transistor device using the same, and a method of manufacturing the same, more specifically, as an organic compound having a novel structure, an N-type organic material semiconductor material having limited photoreactivity, a transistor device using the same, and It relates to a manufacturing method.

The transistor means a device that converts a voltage signal input to the gate electrode into a current signal output from the source electrode or the drain electrode. The basic operation principle of the transistor is as follows. When a voltage is applied to the gate electrode, a channel is formed between both the source electrode and the drain electrode, and charged particles move between the source electrode and the drain electrode through the channel. At this time, a current signal is output from the source electrode or the drain electrode according to the electric field direction, and the intensity of the current signal is generally proportional to the density of the charged particles.

On the other hand, organic field-effect transistors (Organic Field-effect transistors, OFETs) are a type of transistor, and include an organic semiconductor material having an electrically N-type characteristic and an organic semiconductor material having an electrically P-type characteristic. In particular, the organic field effect transistor forms a channel by utilizing an N-type organic semiconductor material and/or a P-type organic semiconductor material, so that the physical-chemical properties of the organic semiconductor material mainly determine the characteristics, performance, and manufacturing method of the transistor. Will decide.

In detail, the organic field effect transistor has advantages such as improved flexibility, light weight, and ease of manufacture compared to conventional transistors based on inorganic compounds. Advantages as described above can be said to be essential for the manufacture of next-generation electronic products, such as wearable sensors, life-adhesive medical equipment. In addition, in recent years, through the implementation of transparent transistors and power supplies, the manufacture of all-transparent electronic products is considered a short-term goal. However, due to the limitation of the organic semiconductor material as described later, the implementation of the transparent organic field effect transistor is not easy.

For example, the conventional organic semiconductor material has a relatively small HOMO-LUMO gap by simply including a long conjugation bond, so there is a problem that it can absorb light from near infrared (long wavelength) to ultraviolet (short wavelength). Furthermore, when a conventional organic semiconductor material that can be easily excited by a light source is applied to an organic field effect transistor, noise included in the drain current can be significantly observed because the organic semiconductor material is sensitive and excited to the light source.

Therefore, it is necessary to take special measures to fully utilize the advantages of the organic field effect transistor, but also to realize the transparency of the transistor. That is, the excitation characteristics of the organic semiconductor material included in the organic field effect transistor need to be appropriately limited.

Korean Registered Patent No. 10-1069519

The present invention was developed to solve the above-described technical problems, and the present invention aims to provide an organic semiconductor material with improved light transmittance.

In addition, an object of the present invention is to provide an organic semiconductor material with limited photoreactivity.

In addition, an object of the present invention is to provide an organic field effect transistor device that secures high light transmittance and low photoreactivity.

In addition, an object of the present invention is to provide a method for manufacturing an organic field effect transistor device that secures high light transmittance and low light reactivity.

The present inventors have researched to solve the above-mentioned problems, and have come up with an invention comprising the following structures. Specifically, this specification discloses a compound having the structure of Formula 1 below, which is used as an N-type organic semiconductor material.

[Formula 1]

However, in [Formula 1], R ₁ and R ₂ are each one of a straight chain or branched chain saturated carbon chain having 10 to 24 carbon atoms; R ₃ to R ₆ are each -H group or -CH ₃ group; It is preferable that X and Y are each an electron withdrawing group.

In addition, in each compound of the present invention, X is one selected from the group consisting of -NO ₂ group, -CN group, -SO ₃ H group, -CF ₃ group, -CHO group, -COCH ₃ group, Y is H , It is more preferably a carbon chain having 1 to 4 carbon atoms. In addition. In each compound of the present invention, Y is one selected from the group consisting of -NO ₂ group, -CN group, -SO ₃ H group, -CF ₃ group, -CHO group, -COCH ₃ group, X is H, carbon number It is more preferable that it is a carbon chain of 1 to 4.

In addition. In each compound of the present invention, X and Y are more preferably one selected from the group consisting of -NO ₂ group, -CN group, -SO ₃ H group, -CF ₃ group, -CHO group, and -COCH ₃ group, respectively. Do.

In addition. In each compound of the present invention, R ₃ to R ₆ are -H groups, more preferably X and Y are -NO ₂ groups, and in each compound of the present invention, R ₁ and R ₂ are 2-octyldode It is even more preferable to be practical.

On the other hand, the present specification is a substrate; A gate electrode formed on the substrate; A source electrode and a drain electrode formed such that an insulating layer is positioned between the gate electrode; And an organic thin film layer formed to electrically connect the source electrode and the drain electrode, and including an N-type organic semiconductor material having the structure of Chemical Formula 1 below.

[Formula 1]

However, in [Formula 1], R ₁ and R ₂ are each one of a straight chain or branched chain saturated carbon chain having 10 to 24 carbon atoms; R ₃ to R ₆ are each -H group or -CH ₃ group; It is preferable that X and Y are each an electron withdrawing group.

On the other hand, the present specification is a substrate; A source electrode and a drain electrode formed on the substrate; An organic thin film layer formed to electrically connect the source electrode and the drain electrode, and including an organic semiconductor material having the structure of Formula 1; An insulating layer formed on the source electrode and the drain electrode; And a gate electrode formed on the insulating layer.

[Formula 1]

However, in [Formula 1], R ₁ and R ₂ are each one of a straight chain or branched chain saturated carbon chain having 10 to 24 carbon atoms; R ₃ to R ₆ are each -H group or -CH ₃ group; It is preferable that X and Y are each an electron withdrawing group.

In addition. In each organic field effect transistor element of the present invention, R ₁ and R ₂ are 2-octyldodecyl groups; R ₃ to R ₆ are -H groups; It is more preferable that X and Y are each selected from the group consisting of -NO ₂ group, -CN group, -SO ₃ H group, -CF ₃ group, -CHO group, and -COCH ₃ group.

In addition. In each organic field effect transistor element of the present invention, it is more preferable that both X and Y are -NO ₂ groups.

In addition. In each organic field effect transistor element of the present invention, the thickness of the organic thin film layer is even more preferably 10 nm or more to 110 nm or less.

Meanwhile, the present specification includes forming a gate electrode on a substrate; Forming an insulating layer on the gate electrode; Forming a source electrode and a drain electrode on the insulating layer; And forming an organic thin film layer including an N-type organic semiconductor material having the structure of Chemical Formula 1 to electrically connect the source electrode and the drain electrode.

[Formula 1]

However, in [Formula 1], R ₁ and R ₂ are each one of a straight chain or branched chain saturated carbon chain having 10 to 24 carbon atoms; R ₃ to R ₆ are each -H group or -CH ₃ group; It is preferable that X and Y are each an electron withdrawing group.

Meanwhile, the present specification includes forming a source electrode and a drain electrode on a substrate; Forming an organic thin film layer including an N-type organic semiconductor material having the structure of Chemical Formula 1 to electrically connect the source electrode and the drain electrode; Forming an insulating layer on the source electrode and the drain electrode; And forming a gate electrode on the insulating layer.

[Formula 1]

However, in [Formula 1], R ₁ and R ₂ are each one of a straight chain or branched chain saturated carbon chain having 10 to 24 carbon atoms; R ₃ to R ₆ are each -H group or -CH ₃ group; It is preferable that X and Y are each an electron withdrawing group.

Through the adoption of the above-described means, the present invention provides an N-type organic semiconductor material capable of securing high light transmittance and low light reactivity in the region of near infrared to visible light.

In addition, the present invention provides an organic field effect transistor device utilizing an organic thin film layer exhibiting high light transmittance and low light reactivity, but also having excellent flashing ratio.

In addition, a manufacturing method capable of producing a large amount of organic field effect transistor devices having the above-described characteristics is provided.

1 is a schematic diagram of a method for synthesizing an N-type organic semiconductor material of the present invention.
Figure 2 shows the results of comparing the ¹ H-NMR spectrum of the organic semiconductor material of the present invention with a theoretical value.
3 is a comparison of the ¹³ C-NMR spectrum of the organic semiconductor material of the present invention with a theoretical value.
4 and 5 are schematic views showing the structure of the organic field effect transistor device of the present invention.
Figure 6 shows the results of comparing the photoreactivity of one embodiment of the present invention and a comparative example.

Terms used in the present application are only used to describe specific examples. Thus, for example, a singular expression includes a plural expression unless the context clearly indicates that it should be singular. In addition, terms such as “include” or “have” as used in the present application are used to clearly indicate the existence of features, steps, functions, elements, or combinations thereof described in the specification, and other features. It should be noted that it is not used to preliminarily exclude the presence of a field or step, function, component, or combination thereof.

On the other hand, unless defined otherwise, all terms used in this specification should be regarded as having the same meaning as generally understood by a person having ordinary skill in the art to which the present invention pertains. Accordingly, unless specifically defined herein, certain terms should not be construed in excessively ideal or formal sense.

Meanwhile, hereinafter, the N-type organic semiconductor material of the present invention is referred to as an organic semiconductor material or abbreviated as a compound. In addition,'straight-chain' refers to a saturated carbon chain that does not have carbon branches. 'Branched chain' refers to a saturated carbon chain with carbon branches. Also,'electron withdrawing group' (EWG) refers to a functional group that draws electrons relative to carbon atoms. The electron pulling method is largely divided into a case by a triggering effect and a case by a resonance effect, and the electron withdrawing machine of the present specification may correspond to both or each. In addition, the'-' symbol added before the functional group is a symbol that refers to an atom that is bonded to the skeleton carbon among the atoms included in the functional group.

<1. Compound of the present invention: organic semiconductor material>

This specification discloses a compound having the structure of Formula 1, which is used as an N-type organic semiconductor material.

[Formula 1]

However, in [Formula 1], R ₁ and R ₂ are each one of a straight chain or branched chain saturated carbon chain having 10 to 24 carbon atoms; R ₃ to R ₆ are each -H group or -CH ₃ group; It is preferable that X and Y are each an electron withdrawing group. In addition, it is appropriate that the number average molecular weight of the organic semiconductor material of the present invention is about 5,000 to 50,000. Hereinafter, the structure of the organic semiconductor material of the present invention will be described in more detail.

<1.1. Functional groups of organic semiconductor materials>

In each compound of the present invention, at least X is one selected from the group consisting of -NO ₂ group, -CN group, -SO ₃ H group, -CF ₃ group, -CHO group, -COCH ₃ group, or Y is It is preferably one selected from the group consisting of -NO ₂ group, -CN group, -SO ₃ H group, -CF ₃ group, -CHO group, -COCH ₃ group, and the like. Furthermore, it is most preferable that both X and Y are -NO ₂ groups from the viewpoint of ensuring the ease of manufacture and maximizing the planarity and polarity of the organic semiconductor material of the present invention.

On the other hand, the aforementioned -NO ₂ group, -CN group, -SO ₃ H group, -CF ₃ group, -CHO group, and -COCH ₃ group are all strong electron withdrawing groups, and are electrons to the corresponding functional groups through inducing and resonance effects. Is omnipresent. In particular, each of the functional groups described above includes both a partial positive charge and a partial negative charge, and as a result, has a permanent dipole moment. Specifically, a partial negative charge is located at a hetero atom located at the end of each functional group, and a partial positive charge is located at an atom bonded to a skeleton carbon.

Since the electron withdrawing group (X and/or Y) contained in the organic semiconductor material of the present invention has a permanent dipole moment, high light transmittance and low light reactivity of the organic thin film layer containing the organic semiconductor material of the present invention Can be derived. In detail, the exciton generated in the organic thin film layer of the present invention by the incident light is trapped by a functional group having a large dipole moment. Accordingly, as a result of the exciton being quenched by a functional group, it is determined that electrical energy is not generated in the organic thin film layer, and thermal energy due to vibration of the functional group is produced.

Therefore, in addition to the above-mentioned electron withdrawing machine, use of a functional group having a permanent dipole moment of sufficient size is permitted. The correlation between the electron withdrawing group included in the organic semiconductor material of the present invention and the high light transmittance and low light reactivity of the organic thin film layer will be described later.

On the other hand, on the premise that at least one of the X or Y includes an electron withdrawing group, at least one functional group of X or Y may be H or a carbon chain having 1 to 4 carbon atoms. The length of the carbon chain referred to as X or Y is sufficient as long as it does not impair the planarity of the organic semiconductor material of the present invention.

Similarly, in the organic semiconductor compound of the present invention, R ₁ and R ₂ are each one of a straight chain or branched chain saturated carbon chain having 10 to 24 carbon atoms; It is preferable that R ₃ to R ₆ are each -H group or -CH ₃ group. However, the length of R ₁ to R ₆ , the bonding form, and the like are sufficient as long as it does not impair the planarity of the organic semiconductor material of the present invention, and can be freely selected by those skilled in the art.

However, in terms of improving the planarity and symmetry of the organic semiconductor material of the present invention, R1 and R2 are preferably the same functional group. In the same vein, it is preferred that R ₃ and R ₅ , R ₄ and R _{6 are} also the same functional group. On the other hand, from the viewpoint of improving the solubility in the solvent and the like to secure manufacturing ease, R ₁ and R ₂ in each compound of the present invention are preferably carbon chains having 10 or more carbon atoms, and 2-octyldode It is more preferable that it is practical.

<1.2. Synthesis of organic semiconductor material of the present invention>

The organic semiconductor material of the present invention can be synthesized through a coupling reaction between two monomers. Structural formulas of each monomer used in the coupling reaction are as follows [Formula 1-1] and [Formula 1-2].

[Formula 1-1]

[Formula 1-2]

The functional groups included in [Chemical Formula 1-1] and [Chemical Formula 1-2] are <1.1. Functional group of organic semiconductor material>. Specifically, R ₁ and R ₂ are each of a straight chain or branched chain saturated carbon chain having 10 to 24 carbon atoms, respectively; R ₃ to R ₆ are each -H group or -CH ₃ group; It is preferable that X and Y are each an electron withdrawing group.

The -SnMe ₃ functional group of [Formula 1-1] and the -Br functional group of [Formula 1-2] are functional groups introduced for a coupling reaction, and those skilled in the art may use the functional group according to the type of the coupling reaction. You can vary the type of. In addition, the coupling reaction between the compound of [Formula 1-1] and the compound of [Formula 1-2] may be performed under metal catalyst conditions such as Pd, Pt, Ni, and Cu catalysts.

In the synthesis of the organic semiconductor material of the present invention, it is sufficient if the sp ² -sp ² carbon-ed to form a new bond between the carbon mixed in the coupling reaction. As examples of the coupling reaction that satisfies the above conditions, still coupling, negishi coupling, Suzuki coupling, Hiyama coupling reaction, and the like can be considered.

<2. Transistor element comprising the compound of the present invention>

This specification further discloses an organic field effect transistor device including the organic semiconductor material of the present invention. For matters related to the organic semiconductor material, refer to <1.1. Functionality of organic semiconductor material>.

Specifically, the organic field effect transistor of the present invention includes a substrate; A gate electrode formed on the substrate; A source electrode and a drain electrode formed such that an insulating layer is positioned between the gate electrode; And an organic thin film layer formed to electrically connect the source electrode and the drain electrode, and including an N-type organic semiconductor material having the structure of Chemical Formula 1 below.

[Formula 1]

However, in [Formula 1], R ₁ and R ₂ are each one of a straight chain or branched chain saturated carbon chain having 10 to 24 carbon atoms; R ₃ to R ₆ are each -H group or -CH ₃ group; It is preferable that X and Y are each an electron withdrawing group.

On the other hand, the present specification is a substrate; A source electrode and a drain electrode formed on the substrate; An organic thin film layer formed to electrically connect the source electrode and the drain electrode, and including an organic semiconductor material having the structure of Formula 1; An insulating layer formed on the source electrode and the drain electrode; And a gate electrode formed on the insulating layer.

[Formula 1]

However, in [Formula 1], R ₁ and R ₂ are each one of a straight chain or branched chain saturated carbon chain having 10 to 24 carbon atoms; R ₃ to R ₆ are each -H group or -CH ₃ group; It is preferable that X and Y are each an electron withdrawing group.

In addition, in each organic field effect transistor device of the present invention, the substrate is not only an inorganic substance such as glass, but also polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polycarbonate, polycarbonate, poly It may be a flexible plastic substrate such as polyvinylalcohol, polyacrylate, polyimide, cyclic olefin copolymer (COC), polynornornene, and the like. In particular, by using a transparent plastic substrate such as polyethylene terephthalate, polycarbonate, polyimide, and COC, it is possible to secure the flexibility of the organic field effect transistor device of the present invention and also ensure light transmission.

In addition, in each organic field effect transistor device of the present invention, the gate electrode, the source electrode and the drain electrode are independent gold (Au), silver (Ag), aluminum (Al), nickel (Ni), copper (Cu), respectively. It may be manufactured using a metal such as titanium (Ti) or a transparent electrode material such as ITO, IZO, ITSO, In2O3, AlZnO, GaZnO, ZnO.

In addition. In each organic field effect transistor element of the present invention, the thickness of the organic thin film layer is more preferably 10 nm or more to 110 nm or less. On the other hand, it is most preferable that the thickness of the organic thin film layer of the present invention is 50 nm from the viewpoint of maintaining the light transmittance of the organic thin film layer at a certain level or more and maximizing the drain current.

<3. Method for manufacturing transistor device of the present invention>

Meanwhile, the present specification further discloses a method for manufacturing an organic field effect transistor device of the present invention. The description of the organic field effect transistor device of the present invention is described in <2. The same as the organic field effect transistor device of the present invention.

Specifically, a method of manufacturing an organic field effect transistor device includes forming a gate electrode on a substrate; Forming an insulating layer on the gate electrode; Forming a source electrode and a drain electrode on the insulating layer; And forming an organic thin film layer including an N-type organic semiconductor material having the structure of Chemical Formula 1 to electrically connect the source electrode and the drain electrode.

[Formula 1]

However, in [Formula 1], R ₁ and R ₂ are each one of a straight chain or branched chain saturated carbon chain having 10 to 24 carbon atoms; R ₃ to R ₆ are each -H group or -CH ₃ group; It is preferable that X and Y are each an electron withdrawing group.

Meanwhile, a method of manufacturing an organic field effect transistor device includes forming a source electrode and a drain electrode on a substrate; Forming an organic thin film layer including an N-type organic semiconductor material having the structure of Chemical Formula 1 to electrically connect the source electrode and the drain electrode; Forming an insulating layer on the source electrode and the drain electrode; And forming a gate electrode on the insulating layer.

[Formula 1]

However, in [Formula 1], R ₁ and R ₂ are each one of a straight chain or branched chain saturated carbon chain having 10 to 24 carbon atoms; R ₃ to R ₆ are each -H group or -CH ₃ group; It is preferable that X and Y are each an electron withdrawing group. Hereinafter, each step constituting the manufacturing method of the organic field effect transistor device of the present invention will be described in detail.

The step of forming the organic thin film layer containing the N-type organic semiconductor material of the present invention is any one of a process of thermal deposition in a vacuum atmosphere using a mask, a spin coating process, a drop-casting process, and an inkjet printing process. It can be performed using. In addition, the step of forming the organic thin film layer may be performed at temperature conditions of, for example, room temperature, 50°C, 70°C, 90°C, and 110°C, but is not particularly limited thereto.

On the other hand, in each organic field effect transistor device of the present invention, the gate electrode, the source electrode and the drain electrode are independent gold (Au), silver (Ag), aluminum (Al), nickel (Ni), copper (Cu), It may be made of a metal such as titanium (Ti), or a transparent electrode material such as ITO, IZO, ITSO, In ₂ O ₃ , AlZnO, GaZnO, ZnO.

In addition, in the step of forming the source electrode and the drain electrode of the present invention and the step of forming the gate electrode, the gate electrode, the source electrode, and the drain electrode can be manufactured by a conventional manufacturing method that is well known in the art. .

In addition, in the step of forming an insulating layer on top of the source electrode and the drain electrode or on the top of the gate electrode, use of an insulator having a high dielectric constant, which is commonly used, is permitted, and a person skilled in the art can appropriately consider the type of substrate. It is possible to choose.

For example, as an example of the insulating layer of the present invention, a polymer material such as Al ₂ O ₃ , HfO ₂ or BZT (Barium Zirconate Titanate), or an inorganic insulating layer such as SiO ₂ or Si ₃ N ₄ may be used, and polyimide ( Use of polymer materials such as polyimide, benzocyclobutane (BCB), parylene, polyvinylalcohol, polyvinylphenol, polymethyl methacrylate, etc. You can consider In addition, a mixture of the inorganic insulating layer and the polymer material as described above may be used as the insulating layer, or a plurality of insulating layers may also be included.

The insulating layer may also be performed using any one of a process of thermal deposition in a vacuum atmosphere, a spin coating process, a drop-casting process, and an inkjet printing process.

{Example and evaluation}

Hereinafter, with reference to the accompanying drawings and embodiments will be described in more detail with respect to what the specification claims. However, the drawings or examples presented in the present specification may be modified in various ways by a person skilled in the art and have various forms, and the description of the present specification is not limited to the specific disclosure form. It should be considered as including all equivalents or substitutes included in the spirit and scope of the present invention. In addition, the accompanying drawings are provided to help a person skilled in the art to more accurately understand the present invention and may be illustrated as exaggerated or reduced than actual.

Example 1: Organic semiconductor material of the invention

1 is a schematic diagram of a method for synthesizing an N-type organic semiconductor material of the present invention. In order to prepare the organic semiconductor material of the present invention, precursor 2Sn-ODTPPD(2,5-bis(2-octyldodecyl)-3,6-bis-(5-trimethylstannanyl-thiophen-2-yl)-2, 5- Equivalent to dihydro-pyrrolo[3,4-c]pyrrole-1,4-dione, manufactured by Derthon OPV Co. Ltd.) and 2Br-DNT (2,5-dibromo-3,4-dinitrothiophene, manufactured by Sigma-Aldrich) And the coupling reaction was carried out under catalytic conditions. Specifically, Pd ₂ (dba) ₃ and P(o-tol) ₃ were added as catalysts. The solvent of the reaction was toluene.

After the precursor and the catalyst were dissolved in a solvent and uniformly mixed, the coupling reaction was performed for 72 hours at 100°C in an inert atmosphere. After the reaction was completed, toluene was evaporated to obtain a thick solution. After re-dissolving the concentrated solution in chlorobenzene, the catalyst was extracted using deionized water. The organic semiconductor material of the present invention dissolved in chlorobenzene was filtered and washed with an organic solvent such as methanol. The obtained filtrate was heated in a vacuum oven at 60° C. for 24 hours to obtain a bluish green powder.

Evaluation 1: yield evaluation of the organic semiconductor material of the present invention

The results of taking the ¹ H NMR Spectrum and ¹³ C NMR spectrum of the turquoise powder are as follows. By comparing the theoretically predicted chemical shift value of the target material with the actual measured value, it was confirmed that the organic semiconductor material of the present invention was correctly synthesized. The yield was 65%.

Figure 2 shows the results of comparing the ¹ H-NMR spectrum of the organic semiconductor material of the present invention with a theoretical value. Referring to FIG. 2, the chemical shift values shown on the 1H-NMR spectrum are summarized as follows. Hereinafter, the lowercase alphabet shown in parentheses is for showing the position of the atom where the peak is observed in the structural formula. ¹ H NMR spectrum (500 MHz, CDCl ₃ , ppm): δ = 0.88-0.90 (CH ₃ , e), 1.22-1.26 (CH ₂ , d), 2.04 (CH ₂ , c), 2.18 (CH ₂ , b ), 7.89 (CH, a).

3 is a comparison of the ¹³ C-NMR spectrum of the organic semiconductor material of the present invention with a theoretical value. Referring to FIG. 3, the chemical shift values shown on the ¹³ C NMR spectrum are summarized as follows. Hereinafter, the lowercase alphabet shown in parentheses is for showing the position of the atom where the peak is observed in the structural formula. ¹³ C NMR Spectrum (500 MHz, CDCl ₃ , ppm): δ = 13.85-31.95 (CH ₃ , h), 50.29 (CH ₂ , g), 114.52 (C, f), 124.77 (CH, e), 140.04- 146.73 (C, bd), 165.83 (C, a)

Manufacturing Example: Organic field effect transistor device of the present invention

4 and 5 are schematic views showing the structure of the organic field effect transistor device of the present invention. 4, the organic field effect transistor device 1 of the present invention includes a substrate 10; A gate electrode 41 formed on the substrate 10; A source electrode 42 and a drain electrode 43 formed such that an insulating layer 20 is positioned between the gate electrode 41; And an organic thin film layer 30 formed to electrically connect the source electrode 42 and the drain electrode 43, and includes an N-type organic semiconductor material having the structure of Formula 1 described above.

Referring to FIG. 5 on the other hand, the organic field effect transistor element 2 of the present invention includes a substrate 10; A source electrode 42 and a drain electrode 43 formed on the substrate; An organic thin film layer 30 formed to electrically connect the source electrode 42 and the drain electrode 43, and includes an organic semiconductor material having the structure of Formula 1 described above; An insulating layer 20 formed on the source electrode 42 and the drain electrode 43; And a gate electrode 41 formed on the insulating layer. However, hereinafter, the method for manufacturing the organic field effect transistor element of the present invention will be described in detail based on the organic field effect transistor element 2 having the structure as shown in FIG. 5.

In summary, the method of manufacturing an organic field effect transistor device of the present invention includes forming a source electrode and a drain electrode on a substrate; Forming an organic thin film layer including an N-type organic semiconductor material having the structure of Chemical Formula 1 to electrically connect the source electrode and the drain electrode; Forming an insulating layer on the source electrode and the drain electrode; And forming a gate electrode on the insulating layer.

Specifically, the organic semiconductor material of Example 1 was prepared at different concentrations. For uniform mixing of the organic semiconductor material, the mixture was stirred for 24 hours at 60°C. Similarly, a PMMA solution with a concentration of 20 mg/mL (weight average molecular weight: 120 kDa, polydispersity index: 2.2, manufactured by Sigma Aldrich) and a PVA solution with a concentration of 90 mg/mL (weight average molecular weight: 89 to 98 kDa, manufactured by Sigma Aldrich) The mixture was stirred at 60°C for 24 hours.

The surface of the glass substrate having a thickness of 0.7 mm was washed with acetone and alcohol, and then treated with UV-Ozone. The source electrode (Ag) and the drain electrode (Ag) were placed on the cleaned glass substrate using a shadow mask. The length of the source electrode and the drain electrode was 70 μm, respectively, the width was 2 mm, and the thickness was 60 nm. Both the source electrode and the drain electrode located on the substrate were heated at 140°C for 20 minutes.

Thereafter, the organic semiconductor material prepared on the organic substrate, the source electrode, and the drain electrode was spin-coated, and then left at a temperature of 70° C. and an inert atmosphere for about 15 minutes to form an organic thin film layer. In addition, the prepared PMMA solution and PVA solution were spin coated on the top of the organic thin film layer in the order of PMMA solution and PVA solution. The thickness of the PMMA layer was 100 nm, and the thickness of the PVA layer was 300 nm. After the spin coating of the PVA layer was completed, the organic field effect transistor device, before the gate electrode was formed, was left for about 12 hours at 70°C temperature conditions and an inert atmosphere. Thereafter, a gate electrode (Al) was deposited on the PVA layer. The thickness of the gate electrode was 80 nm.

Preparation Example 1: Organic field effect transistor device having an organic thin film layer thickness of 20 nm

According to the manufacturing method of the organic field effect transistor device described in the above production example, the organic semiconductor material having a concentration of 3 mg/mL was spin coated to obtain an organic field effect transistor device having a thickness of the organic thin film layer of 20 nm.

Preparation Example 2: Organic field effect transistor device with an organic thin film layer having a thickness of 35 nm

According to the manufacturing method of the organic field effect transistor device described in the above production example, the organic semiconductor material having a concentration of 5 mg/mL was spin coated to obtain an organic field effect transistor device having a thickness of the organic thin film layer of 35 nm.

Preparation Example 3: An organic field effect transistor device having an organic thin film layer thickness of 50 nm

According to the manufacturing method of the organic field effect transistor device described in the above production example, the organic semiconductor material having a concentration of 7 mg/mL was spin coated to obtain an organic field effect transistor device having a thickness of the organic thin film layer of 50 nm.

Preparation Example 4: Organic field effect transistor device with an organic thin film layer thickness of 75 nm

According to the manufacturing method of the organic field effect transistor device described in the above production example, the organic semiconductor material having a concentration of 10 mg/mL was spin coated to obtain an organic field effect transistor device having a thickness of the organic thin film layer of 75 nm.

Preparation Example 5: Organic field effect transistor device with an organic thin film layer having a thickness of 95 nm

According to the manufacturing method of the organic field effect transistor device described in the above production example, the organic semiconductor material having a concentration of 12 mg/mL was spin coated to obtain an organic field effect transistor device having a thickness of the organic thin film layer of 95 nm.

Preparation Example 6: Organic field effect transistor device with an organic thin film layer thickness of 110 nm

According to the manufacturing method of the organic field effect transistor device described in the above production example, the organic semiconductor material having a concentration of 15 mg/mL was spin coated to obtain an organic field effect transistor device having a thickness of the organic thin film layer of 110 nm.

Comparative Example: Organic field effect transistor device comprising an organic thin film layer containing P3HT

According to the method of manufacturing the organic field effect transistor device described in the above manufacturing example, using a solution containing a known P3HT (Poly(3-hexylthiophene)) in place of the organic semiconductor material of the present invention, the organic field effect transistor device It was prepared.

On the other hand, with respect to the method of manufacturing an organic field effect transistor device of the present invention, from the viewpoint of improving the transparency of the device, the following method of manufacturing an organic field effect transistor device can be considered. A method of manufacturing an organic field effect transistor device of the present invention includes forming a gate electrode on a substrate; Forming an insulating layer on the gate electrode; Forming an organic thin film layer containing an N-type organic semiconductor material having the structure of Formula 1 described above to electrically connect the source electrode and the drain electrode; And forming a source electrode and a drain electrode on the insulating layer.

In detail, the step of depositing the ITO electrode (1 mm X 12 mm), which is a gate electrode, on a glass substrate having a thickness of 0.7 mm through photolithography is preferentially performed. Thereafter, the organic substrate on which the ITO electrode is deposited is washed with acetone and alcohol, and treated with UV-Ozone. Next, a PMMA layer as an insulating layer is stacked on the glass substrate and the gate electrode. The PMMA solution may be prepared at a concentration of 90 mg/mL, and a spin coating method may be employed for lamination. In addition, the thickness of the PMMA layer may be 500 nm. In addition, annealing for 30 minutes at a temperature condition of 100°C may be involved. After the annealing is completed, an organic thin film layer is stacked on the insulating layer. The solution used for laminating the organic thin film may be prepared at a concentration of 3 mg/mL. The organic thin film layer may also be laminated through a spin coating method. After the lamination of the organic thin film layer is completed, a gate electrode Ag is deposited on the organic thin film layer. The gate electrode may have a thickness of 15 nm.

Evaluation 2: Light transmittance evaluation

In order to evaluate the light transmittance of the organic thin film layers included in Preparation Examples 1 to 6 described above, a UV-vis-NIR spectrometer (Lambda 750, manufactured by PerkinElmer) was used. The measurement results are summarized in Table 1 below.

parameter Organic thin film layer Preparation Example 1 Preparation Example 2 Preparation Example 3 Preparation Example 4 Preparation Example 5 Preparation Example 6 Light transmittance (520nm, %) 95.14 93.93 90.73 88.81 86.84 84.24 Light transmittance (780nm, %) 86.21 77.50 60.95 55.36 48.36 42.02

Referring to Table 1, when the thickness of the organic thin film layer of the present invention is 20 nm, the transmittance exceeds 95% in the visible region (520 nm) and the transmittance exceeds 85% in the near infrared region (780 nm). You can confirm that In addition, since the organic thin film layer of the present invention transmits most of the light in the visible light region (about 85%) even when its thickness is 110 nm (Production Example 6), transparency in visual observation can be secured relatively freely in thickness. . On the other hand, when the thickness of the organic thin film layer of the present invention is 75 nm (Production Example 3), it can be seen that not only transmits light in the visible region 90% or more, but also transmits light in the near infrared region 60% or more. In other words, the organic thin film layer containing the organic semiconductor material of the present invention is not easily excited by light belonging to the visible or near infrared region, and thus it is determined that light absorption is limited.

Evaluation 3: Evaluation of photoreactivity with and without light source

Figure 6 shows the results of comparing the photoreactivity of one embodiment of the present invention and a comparative example. The x-axis of FIG. 6 represents the thickness of the organic thin film layer in each production example. The y-axis of Figure 6 photoreactive (Photoresponsivity, R _C (unit: mA / W)) for each manufacturing the organic thin film layer shows a.

6, the thickness is 20 nm (Production Example 1), 35 nm (Production Example 2), 50 nm (Production Example 3), 75 nm (Production Example 4), 95 nm (Production Example 5), 110, respectively. The photoreactivity at nm (Preparation Example 6) was all shown to converge to zero. On the other hand, in the case of the organic thin film layer containing P3HT corresponding to the comparative example, the photoreactivity was also increased as the thickness of the organic thin film layer increased.

The above observation means that the organic thin film layer containing the organic semiconductor material of the present invention is not additionally excited by an external light source, unlike the conventional organic thin film layer. In addition, as a result, the change in drain current was negligible by an external light source.

Specific measurement data according to changes in the thickness of the external light source and the organic thin film layer are shown in Table 2 below. The intensity of the light source having a wavelength of 520 nm and the light source having a wavelength of 780 nm was 0.27 mW/cm ² , and the intensity of white light (LED) was 69.6 mW/cm ² . The intensity of the light source was measured using a silicon photodiode (818-UV, manufactured by Newport).

parameter λ (nm) Organic thin film layer Preparation Example 1 Preparation Example 2 Preparation Example 3 Preparation Example 4 Preparation Example 5 Preparation Example 6 I _D,MAX
(nA) 520 nm 187 205 212 269 253 221 780 nm 192 212 223 279 262 234 white light 194 214 225 285 271 244 R _c
(mA/W) 520 nm 0.39 0.32 0.31 0.73 0.31 0.28 780 nm 1.94 2.23 2.02 1.45 2.23 1.2 white light 0.6 0.02 0.21 0.29 0.02 0.18 I _D,OFF
(pA) 520 nm 12.01 9.42 0.48 1.35 3.68 21.15 780 nm 31.29 24.51 1.59 8.54 27.07 12.38 white light 42.43 2.43 0.97 18.15 23.87 1.24 R _ON/OFF
(10 ⁴ ) 520 nm 1.56 2.17 44.17 19.93 6.88 1.04 780 nm 6.14 0.86 14.03 3.27 0.27 1.89 white light 4.57 8.81 23.2 1.57 1.14 19.68

In the above table, I _D,MAX means the maximum drain current value, and R _C means the photoreactivity as described above. In addition, I _D,OFF means the leakage current value (Off current), and R _ON/OFF means the ON/OFF ratio. The output and transfer curves of the organic field effect transistor device were measured using a semiconductor parameter analyzer (2636B, Keithley).

In summary, in the case of Preparation Example 3 in which the thickness of the organic thin film layer is 50 nm, high light transmittance and low light reactivity can be maintained in a wide wavelength band of visible and near infrared regions. In addition, it can be seen that a remarkably improved flashing ratio can also be secured.

1, 2: Organic field effect transistor device
10: substrate
20: insulating layer
30: organic thin film layer
41: gate electrode
42: source electrode
43: drain electrode

Claims (16)

A compound having the structure of Formula 1, used as an N-type organic semiconductor material:
[Formula 1]

(However, in the above [Formula 1],
R ₁ and R ₂ are each one of a straight chain or branched chain saturated carbon chain having 10 to 24 carbon atoms;
R ₃ to R ₆ are each -H group or -CH ₃ group;
X and Y are each characterized by an electron withdrawing group.)
According to claim 1,
The X is one selected from the group consisting of -NO ₂ group, -CN group, -SO ₃ H group, -CF ₃ group, -CHO group, -COCH ₃ group, Y is H, carbon having 1 to 4 carbon atoms A compound characterized by being a chain.
According to claim 1,
The Y is one selected from the group consisting of -NO ₂ group, -CN group, -SO ₃ H group, -CF ₃ group, -CHO group, -COCH ₃ group, X is H, carbon having 1 to 4 carbon atoms A compound characterized by being a chain.
According to claim 1,
The X and Y are each a compound selected from the group consisting of -NO ₂ group, -CN group, -SO ₃ H group, -CF ₃ group, -CHO group, -COCH ₃ group.
The method of claim 4,
R ₃ to R ₆ are -H groups
The X and Y are compounds characterized in that -NO ₂ group.
The method of claim 5,
R ₁ and R ₂ is a 2-octyl dodecyl group, characterized in that the compound.
Board;
A gate electrode formed on the substrate;
A source electrode and a drain electrode formed so that an insulating layer is positioned between the gate electrode; And
An organic field effect transistor device comprising an organic thin film layer including an N-type organic semiconductor material having a structure of Formula 1 below, which is formed to electrically connect the source electrode and the drain electrode:
[Formula 1]

(However, in the above [Formula 1],
R ₁ and R ₂ are each one of a straight chain or branched chain saturated carbon chain having 10 to 24 carbon atoms;
R ₃ to R ₆ are each -H group or -CH ₃ group;
X and Y are each characterized by an electron withdrawing group.)
The method of claim 7,
R ₁ and R ₂ are 2-octyldodecyl groups;
R ₃ to R ₆ are -H groups;
The X and Y are each selected from the group consisting of -NO ₂ group, -CN group, -SO ₃ H group, -CF ₃ group, -CHO group, and -COCH ₃ group.
The method of claim 8,
The X and Y are -NO ₂ organic field effect transistor device characterized in that the group.
The method of claim 9,
The thickness of the organic thin film layer is an organic field effect transistor device, characterized in that 10nm to 110nm or less.
Board;
A source electrode and a drain electrode formed on the substrate;
An organic thin film layer formed to electrically connect the source electrode and the drain electrode, and including an organic semiconductor material having the structure of Formula 1;
An insulating layer formed on the source electrode and the drain electrode; And
A transistor device including a gate electrode formed on the insulating layer:
[Formula 1]

(However, in the above [Formula 1],
R ₁ and R ₂ are each one of a straight chain or branched chain saturated carbon chain having 10 to 24 carbon atoms;
R ₃ to R ₆ are each -H group or -CH ₃ group;
X and Y are each characterized by an electron withdrawing group.)
The method of claim 11,
R ₁ and R ₂ are 2-octyldodecyl groups;
R ₃ to R ₆ are -H groups;
The X and Y are each selected from the group consisting of -NO ₂ group, -CN group, -SO ₃ H group, -CF ₃ group, -CHO group, and -COCH ₃ group.
The method of claim 12,
The X and Y are -NO ₂ organic field effect transistor device characterized in that the group.
The method of claim 13,
The thickness of the organic thin film layer is an organic field effect transistor device, characterized in that 10nm to 110nm or less.
Forming a gate electrode on the substrate;
Forming an insulating layer on the gate electrode;
Forming a source electrode and a drain electrode on the insulating layer; And
A method of manufacturing an organic field effect transistor device comprising forming an organic thin film layer including an N-type organic semiconductor material having the structure of Formula 1 to electrically connect the source electrode and the drain electrode:
[Formula 1]

(However, in the above [Formula 1],
R ₁ and R ₂ are each one of a straight chain or branched chain saturated carbon chain having 10 to 24 carbon atoms;
R ₃ to R ₆ are each -H group or -CH ₃ group;
X and Y are each characterized by an electron withdrawing group.)
Forming a source electrode and a drain electrode on the substrate;
Forming an organic thin film layer including an N-type organic semiconductor material having the structure of Chemical Formula 1 to electrically connect the source electrode and the drain electrode;
Forming an insulating layer on the source electrode and the drain electrode; And
A method of manufacturing an organic field effect transistor device comprising the step of forming a gate electrode on top of the insulating layer:
[Formula 1]

(However, in the above [Formula 1],
R ₁ and R ₂ are each one of a straight chain or branched chain saturated carbon chain having 10 to 24 carbon atoms;
R ₃ to R ₆ are each -H group or -CH ₃ group;
X and Y are each characterized by an electron withdrawing group.)

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