KR20190113719A - Crystalline two-dimensional conjugated polymer, thin films using the same, and method for producing the same - Google Patents

Abstract

The present invention relates to: a two-dimensional conjugated polymer synthesizing organic conjugated molecules capable of mutually reversible covalent bonding using a single reaction method; a thin film using the same; and a manufacturing method thereof. The two-dimensional conjugated polymer and the thin film manufactured from the same have excellent electrical and optical properties, thereby having various applicability.

Description

Crystalline two-dimensional conjugated polymer, thin film using the same and manufacturing method thereof {CRYSTALLINE TWO-DIMENSIONAL CONJUGATED POLYMER, THIN FILMS USING THE SAME, AND METHOD FOR PRODUCING THE SAME}

The present invention relates to a two-dimensional conjugated polymer, a thin film using the same, and a method for preparing the organic conjugated molecule capable of mutually reversible covalent bonding using a single reaction method.

In general, in the case of the organic polymer, the arrangement of the molecules forming it is not uniform. In particular, since the formation varies depending on various reaction conditions such as time, temperature and reaction size, it is extremely difficult to control this. This problem, among other things, makes the application difficult by causing difficulties in expressing the physical and electrical properties of the material efficiently and uniformly. In order to solve this problem, research on the development of organic polymers with relatively uniform molecular arrangements using self-reparing to compensate for defects is necessary.

SUMMARY OF THE INVENTION An object of the present invention is to provide a manufacturing method for forming a polymer by maintaining and supplementing a molecular arrangement by the polymer itself using self-reparing, which can compensate for defects.

In addition, an object of the present invention is to provide a two-dimensional conjugated polymer having a higher stability and lowering the negative bonding rate of molecules in a polymer, and a polymer film of a thin film using the same.

Specifically, the present invention is to provide a two-dimensional polymer having a low defect and a thin polymer film using the same by using an imine bond capable of reversible bonding with a triphenylene-based compound having six binding sites.

One aspect of the present invention for achieving the above object is a crystalline two-dimensional conjugated polymer derived from any one or two or more compounds selected from a compound represented by the following formula (1) and a compound represented by the following formula (2) to (4).

[Formula 1]

In Formula 1, L ₁ to L ₆ are each independently selected from a single bond or an alkylene group of C ₁ -C ₂ , and R ₁ to R ₆ are each independently selected from hydrogen or an alkyl group of C ₁ -C 3. )

[Formula 2]

[Formula 3]

[Formula 4]

(In Formulas 2 to 4, R ₇ to R ₁₈ are each independently selected from hydrogen or an alkyl group of C1-C3.)

Another aspect of the invention is a thin film consisting of the above crystalline two-dimensional conjugated polymer.

Another aspect of the present invention is a thin film or a composite substrate having a thin film and an electronic component including the same.

Another embodiment of the present invention is a polymerization composition for preparing a crystalline two-dimensional conjugated polymer comprising a compound represented by Formula 1 and any one or two or more compounds selected from the compounds represented by Formulas 2 to 4, an acid catalyst, and a solvent. .

Another aspect of the present invention is a method for producing a crystalline two-dimensional conjugated polymer thin film comprising applying and heating the polymerization composition.

Another embodiment of the present invention is a crystalline two-dimensional conjugated polymer comprising the step of polymerizing the compound represented by the formula (1) and any one or two or more compounds selected from the compounds represented by the formula (2) to (4) under an acid catalyst It is a manufacturing method of.

The two-dimensional conjugated polymer of the present invention and the film of the thin film prepared therefrom have excellent electrical and optical properties, and thus have various applications, and new two-dimensional organic electronic materials, specifically, organic light emitting diodes (OLEDs) and organic electric fields. It can be applied to various electronic component materials such as effect transistor (OFET).

In addition, it can be applied to light-based electric materials by showing high efficiency of light sensitivity in wide light wavelength range. Based on this, it can be applied to high value-added industries such as semiconductors.

In Figure 1 a is a photograph showing the color of the mixture before and after the reaction, b is 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP), 2,3,6,7,10, UV-Vis spectra of 11-hexaaminotriphenylene (HATP) and C2P-5 are shown.
Figure 2 shows the FT-IR spectra of HHTP, HATP and C2P-5.
Figure 3 shows the X-ray photoelectron spectroscopy (XPS) results of C2P-5.
4 is a photograph evaluating dispersibility after dispersing C2P-5 in N-methyl-2-pyrrolidone.
Figure 5 shows the microscopic characteristics of the prepared C2P-5 thin film.
6 is a result of measuring the thickness of the C2P-5 thin film.
7 is a photograph showing that the thin film is separated by a solvent.
8 shows the crystal structure of the C2P-5 thin film.
9 shows a gas sorption isotherm of the C2P-5 thin film.
10 shows the structure of a stack of C2P-5.
11 shows the electrical properties of C2P-5.
12 shows the CV and UV-VIS spectra of C2P-5.
Figure 13 shows the synthesis and structural properties of C2P-7.
14 is a high resolution XPS spectra of C2P-7.
15 shows the synthesis and structural properties of C2P-9.
16 is a high resolution XPS spectra of C2P-9.

DETAILED DESCRIPTION Hereinafter, the present invention will be described in more detail with reference to the accompanying examples or embodiments. However, the following specific examples or examples are only one reference for describing the present invention in detail, but the present invention is not limited thereto and may be implemented in various forms.

Also, unless defined otherwise, all technical and scientific terms have the same meanings as commonly understood by one of ordinary skill in the art to which this invention belongs. The terms used in the description in the present invention are only for effectively describing specific embodiments and are not intended to limit the present invention.

Also, the singular forms used in the specification and the appended claims may be intended to include the plural forms as well, unless the context clearly indicates otherwise.

As used herein, the terms “alkyl” and “alkylene” include both straight and branched chain forms. In addition, the "alkyl" and "alkylene" may be substituted or unsubstituted, and may be unsubstituted unless otherwise stated. Such substitutions may be carried out at the structural backbone of the group or moiety such as halogen, hydroxy, amino, oxo (= 0), thio (= fluoro (F), chloro (Cl), bromo (Br) or iodine (I) radicals). It means that it is further substituted with any one or two or more substituents selected from S) and the like.

One aspect of the present invention is a crystalline two-dimensional conjugated polymer derived from any one or two or more compounds selected from a compound represented by the following formula (1) and a compound represented by the following formulas (2) to (4).

[Formula 1]

In Formula 1, L ₁ to L ₆ are each independently selected from a single bond or an alkylene group of C ₁ -C ₂ , and R ₁ to R ₆ are each independently selected from hydrogen or an alkyl group of C ₁ -C 3. )

[Formula 2]

[Formula 3]

[Formula 4]

(In Formulas 2 to 4, R ₇ to R ₁₈ are each independently selected from hydrogen or an alkyl group of C1-C3.)

In one embodiment of the present invention, Formula 1 is 2,3,6,7,10,11-hexahydroxytriphenylene, and Formula 2 is 2,3,6,7,10,11-hexaaminotree Phenylene, Formula 3 may be 1,2,4,5-benzenetetraamine, Formula 4 may be 2,3,7,8-tetraaminophenazine.

Another aspect of the invention is a thin film consisting of the above crystalline two-dimensional conjugated polymer.

In one aspect of the invention, the thin film may be chemically or physically doped.

Another embodiment of the present invention is a composite substrate having a thin film made of the crystalline two-dimensional conjugated polymer on a substrate.

Another aspect of the invention is an electronic component comprising the thin film or composite substrate.

Another aspect of the present invention is a polymerization composition for preparing a crystalline two-dimensional conjugated polymer comprising a compound represented by the following formula (1) and any one or two or more compounds selected from compounds represented by the following formulas (2) to (4), an acid catalyst and a solvent .

[Formula 1]

In Formula 1, L ₁ to L ₆ are each independently selected from a single bond or an alkylene group of C ₁ -C ₂ , and R ₁ to R ₆ are each independently selected from hydrogen or an alkyl group of C ₁ -C 3. )

[Formula 2]

[Formula 3]

[Formula 4]

(In Formulas 2 to 4, R ₇ to R ₁₈ are each independently selected from hydrogen or an alkyl group of C1-C3.)

In one embodiment of the present invention, Formula 1 is 2,3,6,7,10,11-hexahydroxytriphenylene, and Formula 2 is 2,3,6,7,10,11-hexaaminotree Phenylene, Formula 3 may be 1,2,4,5-benzenetetraamine, Formula 4 may be 2,3,7,8-tetraaminophenazine.

Another aspect of the present invention is a method for producing a crystalline two-dimensional conjugated polymer thin film comprising applying and heating the polymerization composition.

In one aspect of the invention, the production method may be performed under an air or oxygen atmosphere.

In one aspect of the invention, the heating may be performed at a temperature of 150 to 300 ℃.

In one aspect of the invention, after the heating, it may be to further comprise the step of chemically or physically doping.

Another embodiment of the present invention includes the step of polymerizing a compound represented by the following formula (1) and any one or two or more compounds selected from compounds represented by the following formulas (2) to (4) by heating under an acid catalyst and air or oxygen atmosphere It is a method for producing a crystalline two-dimensional conjugated polymer.

[Formula 1]

In Formula 1, L ₁ to L ₆ are each independently selected from a single bond or an alkylene group of C ₁ -C ₂ , and R ₁ to R ₆ are each independently selected from hydrogen or an alkyl group of C ₁ -C 3. )

[Formula 2]

[Formula 3]

[Formula 4]

(In Formulas 2 to 4, R ₇ to R ₁₈ are each independently selected from hydrogen or an alkyl group of C1-C3.)

In one embodiment of the present invention, Formula 1 is 2,3,6,7,10,11-hexahydroxytriphenylene, and Formula 2 is 2,3,6,7,10,11-hexaaminotree Phenylene, Formula 3 may be 1,2,4,5-benzenetetraamine, Formula 4 may be 2,3,7,8-tetraaminophenazine.

In one aspect of the invention, the heating may be performed at a temperature of 150 to 300 ℃.

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

The inventors of the present invention have found a stable structure by reacting a compound having a triphenylene structure and a compound containing a diamine, as a result of research to develop a polymer material having self-reparing and excellent electrical and optical properties. The present invention has been found to provide a novel polymer material having excellent electrical and optical properties.

In one embodiment of the present invention, the crystalline two-dimensional conjugated polymer is derived from any one or two or more compounds selected from the compound represented by Formula 1 and the compound represented by Formula 2 to Formula 4. To be derived here means to form a polymer by polymerization.

In one embodiment of the present invention, the compound represented by Formula 1 is more specifically, for example, in Formula 1, L ₁ to L ₆ are each independently a single bond, and R ₁ to R ₆ are each independently It may be selected from hydrogen or an alkyl group of C1-C3.

More specifically, for example, in Formula 1, L ₁ to L ₆ may be each independently a single bond, and R ₁ to R ₆ may be each independently hydrogen. Specifically, it may be 2,3,6,7,10,11-hexahydroxytriphenylene represented by 1-1 below, but is not limited thereto.

In one embodiment of the present invention, the compound represented by Formula 2 may be more specifically, for example, in Formula 2, R ₇ to R ₁₂ may be each independently hydrogen. Specifically, it may be 2,3,6,7,10,11-hexaaminotriphenylene represented by 2-1 below, but is not limited thereto.

In one embodiment of the present invention, the compound represented by Formula 3 may be more specifically, for example, in Formula 3, R ₁₃ and R ₁₄ may be each independently hydrogen. Specifically, it may be 1,2,4,5-benzenetetraamine represented by 3-1 below, but is not limited thereto.

In one embodiment of the present invention, the compound represented by Formula 4 may be more specifically, for example, in Formula 4, R ₁₅ and R ₁₈ may be each independently hydrogen. Specifically, it may be 2,3,7,8-tetraaminophenazine represented by 4-1 below, but is not limited thereto.

In one embodiment of the present invention, the two-dimensional conjugated polymer may be derived from the compound of Formula 1 and the compound of Formula 2, and may include the following structure.

[Formula 1]

More specifically, the compound of Formula 1 and the compound of Formula 2 may be polymerized using a 1: 0.8 to 1.2 molar ratio, more specifically 1: 1 molar ratio. Formula 1 uses 2,3,6,7,10,11-hexahydroxytriphenylene as the compound of Formula 1, and 2,3,6,7,10,11-hexaamino as the compound of Formula 2 As an example of the crystalline two-dimensional conjugated polymer in the case of using triphenylene, it is not limited thereto but specifically illustrated.

In one embodiment of the present invention, the two-dimensional conjugated polymer may be derived from the compound of Formula 1 and the compound of Formula 3, and may include the following structure.

[Formula 2]

More specifically, the compound of Formula 1 and the compound of Formula 3 may be polymerized using a 1: 1 to 3 molar ratio, more specifically 1: 1.2 to 1.8 molar ratio, more specifically 1: 1.5 molar ratio. Structural formula 2 uses 2,3,6,7,10,11-hexahydroxytriphenylene as the compound of formula 1, and 1,2,4,5-benzenetetraamine is used as the compound of formula 3 As an example of the crystalline two-dimensional conjugated polymer of, but is not specifically limited to that specifically illustrated.

In one embodiment of the present invention, the two-dimensional conjugated polymer may be derived from the compound of Formula 1 and the compound of Formula 4, and may include the following structure.

[Formula 3]

More specifically, the compound of Formula 1 and the compound of Formula 4 may be polymerized by using 1: 1.5 to 5 molar ratio, more specifically 1: 2 to 3 molar ratio, more specifically 1: 2.5 molar ratio. Structural formula 2 uses 2,3,6,7,10,11-hexahydroxytriphenylene as a compound of formula 1, and 2,3,7,8-tetraaminophenazine as a compound of formula 4 As an example of the crystalline two-dimensional conjugated polymer in the case, it is not limited thereto but specifically illustrated.

In one embodiment of the present invention, the method for producing the crystalline two-dimensional conjugated polymer is a compound represented by the formula (1), and any one or two or more compounds selected from compounds represented by the formula (2) to formula (4) under an acid catalyst It may be to include a step of polymerization.

The heat polymerization may be performed in an air or oxygen atmosphere, but is not necessarily limited thereto.

More specifically, Formula 1 is 2,3,6,7,10,11-hexahydroxytriphenylene, Formula 2 is 2,3,6,7,10,11-hexaaminotriphenylene Formula 3 may be 1,2,4,5-benzenetetraamine, and Formula 4 may be 2,3,7,8-tetraaminophenazine, but is not limited thereto.

At this time, the mixing ratio of any one or two or more compounds selected from the compound represented by Formula 1 and the compound represented by Formula 2 to Formula 4 is not limited, but may be added in a 1: 0.8 to 5 molar ratio. More specifically, for example, the compound of Formula 1 and the compound of Formula 2 may be polymerized using a 1: 0.8 to 1.2 molar ratio, more specifically 1: 1 molar ratio. In addition, the compound of Formula 1 and the compound of Formula 3 may be polymerized using a 1: 1 to 3 molar ratio, more specifically 1: 1.2 to 1.8 molar ratio, more specifically 1: 1.5 molar ratio. In addition, the compound of Formula 1 and the compound of Formula 4 may be polymerized using a 1: 1.5 to 5 molar ratio, more specifically 1: 1: 2 to 3 molar ratio, more specifically 1: 2.5 molar ratio.

In one aspect of the invention, the acid catalyst is used to induce a polymerization reaction, the content of the acid catalyst relative to the compound represented by the formula (1) is 1: 1 to 2 molar ratio, more specifically 1: 1.2 to 1.6 molar ratio may be used, but is not limited thereto. Specifically, for example, trifluoroacetic acid, toluenesulfonic acid and methanesulfonic acid, acetic acid, hydrochloric acid, sulfuric acid, and the like may be used, but is not limited thereto.

In one aspect of the present invention, the polymerization is preferably carried out by heating in the air or oxygen atmosphere to polymerize, the heating may be carried out at a temperature of 150 to 300 ℃, more specifically 160 to 250 ℃. In addition, performing the reaction in an air or oxygen atmosphere is preferred because it induces oxidation of the compound, but is not limited thereto. In this case, the reaction time may be performed for 10 to 72 hours, more specifically for 24 to 36 hours, but is not limited thereto.

The polymerization may be carried out by adding a solvent, and the organic solvent may dissolve a monomer, although it is not limited. Specifically, for example, N-methyl-2-pyrrolidone (NMP) and dimethylformamide (DMF). ), Dimethylacetamide (DMAC) and dimethylsulfoxide (dimethylsulfoxide, DMSO), isopropyl alcohol and the like can be used, but is not limited thereto. In addition, the polymerization may further include a process of removing monomers and oligomers using the solvent.

Another embodiment of the present invention is a polymerization composition for preparing a crystalline two-dimensional conjugated polymer comprising a compound represented by Formula 1 and any one or two or more compounds selected from the compounds represented by Formulas 2 to 4, an acid catalyst, and a solvent. .

More specifically, Formula 1 is 2,3,6,7,10,11-hexahydroxytriphenylene, Formula 2 is 2,3,6,7,10,11-hexaaminotriphenylene Formula 3 may be 1,2,4,5-benzenetetraamine, and Formula 4 may be 2,3,7,8-tetraaminophenazine, but is not limited thereto. Their content is the same as described above. In addition, the type and content of the acid catalyst and the solvent are the same as described above.

Another aspect of the present invention is a method for producing a crystalline two-dimensional conjugated polymer thin film comprising applying and heating the polymerization composition. The heating may be performed in an air or oxygen atmosphere, but is not limited thereto.

The method of applying the polymerization composition may be performed through a method selected from knife coating, roll coating, die coating, curtain coating and casting coating. It is possible to, but is not limited to.

The thickness of the thin film may be 0.1 to 100 nm, more specifically 1 to 50 nm, and more specifically 2 to 10 nm as a dried thickness, and may be applied to electronic components of various thin films in the above range. It doesn't happen.

In one aspect of the invention, the method of forming the thin film may be to apply the polymerization composition on a substrate, and to heat to a temperature of 150 to 300 ℃, more specifically 160 to 250 ℃. In this case, the reaction time may be performed for 10 to 72 hours, more specifically for 24 to 36 hours, but is not limited thereto.

Alternatively, the polymerization composition may be polymerized by heating to 150 to 300 ° C., more specifically, 160 to 250 ° C. in a reactor, and then dispersing the prepared polymer in an organic solvent to apply the coating onto a substrate. The reaction time during the polymerization may be performed for 10 to 72 hours, more specifically for 24 to 36 hours, but is not limited thereto. At this time, the organic solvent for dispersing the polymer is not limited as long as it is an organic solvent capable of dissolving the polymer, specifically, for example, N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF), dimethyl Acetamide (DMAC), dimethylsulfoxide (DMSO), isopropyl alcohol, and the like can be used, but are not limited thereto.

The substrate is not limited, and specifically, may be any one selected from glass, silicon wafer, plastic, metal, composite metal, metal oxide, metal nitride, metal carbide, metal sulfide, and the like.

In one aspect of the present invention, the method for separating the prepared thin film from the substrate may be to detach the interface by a solvent immersion method. Specifically, for example, when immersed in a mixed solution of N-methyl-2-pyrrolidone (NMP) and isopropyl alcohol may be separated by itself. More specifically, for example, N-methyl-2-pyrrolidone (NMP): isopropyl alcohol may be to be separated by dipping in a mixed solution of 1: 1 to 20 (v / v).

As described above, the composite substrate having a thin film made of a two-dimensional conjugated polymer of one embodiment of the present invention on a substrate may be applied to an electronic component. More specifically, for example, the organic semiconductor, an electrode material, an optical sensor, a hydrogen generating photocatalyst or an additive thereof may be variously applied.

In one embodiment of the present invention, the thin film made of the crystalline two-dimensional conjugated polymer may have an average charge mobility of 2 cm ² V ^-1 s ^-1 or more, more specifically 2.5 cm ² V ^-1 s ^-1 or more, More specifically, it can satisfy the physical properties of 2 to 5 cm ² V ^-1 s ^{- 1} shows very high charge mobility compared to the previously reported organic thin film. In addition, it has high photosensitivity properties in the UV, Vis and IR wavelength fields.

In one aspect of the invention, the thin film made of the crystalline two-dimensional conjugated polymer may be doped further comprising chemically or physically doping. By further including the doping step may be to further improve the electrical properties.

At this time, the type of dopant solution used for the chemical doping is not limited and may be used without limitation as long as it is generally used in the art. The dopant is specifically, for example, iron chloride (III) (FeCl _3), nitro, sodium hexafluorophosphate (NOPF _6), bis-trifluoromethyl sulfonyl already pyridinium a _{((CF 3 SO 2) 2} N -) , Gold (III) chloride (AuCl ₃ ), 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4-TCNQ) and the like, but is not limited thereto. It doesn't happen.

The dopant solution may be a doping using a coating method such as spin coating, it may be to adjust the amount of the dopant in the doped conjugated polymer film by adjusting the concentration of the dopant solution, but is not limited thereto. .

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following Examples and Comparative Examples are only examples for explaining the present invention in more detail, the present invention is not limited by the following Examples and Comparative Examples.

Example 1

1) Preparation of two-dimensional conjugated polymer (hereinafter referred to as "C2P-5")

4.0 mg (1.2 mM) of 2,3,6,7,10,11-hexahydroxytriphenylene, 6.6 mg (1.2 mM) of 2,3,6,7,10,11-hexaaminotriphenylene and tri 1 μl (1.3 mM) of fluoroacetic acid was dissolved in 10 mL of N-methyl-2-pyrrolidone and placed in a pressure tube. The mixture was tightly sealed, sonicated for 10 minutes and then heated at 180 ° C. for 2 days under oxygen atmosphere. The reaction turned from an initial clear yellow solution to a brown solution. After 2 days, the reaction mixture was cooled slowly over 3 hours and subjected to three dialysis using a regenerated cellulose separator with N-methyl-2-pyrrolidone solution to remove unreacted monomers, oligomers and acid catalysts. It was. Thereafter, after washing with methanol, it was finally dried to obtain a crystalline two-dimensional conjugate (hereinafter referred to as 'C2P-5') as a dark brown solid.

Yield 75%.

Elemental analysis [[C ₁₈ H ₆ N ₃ ) (CH ₃ OH) ₄ (H ₂ O) _6.2 ] _n : C 52.42, H 6.88, N 8.34; found: C 52.42, H 6.32, N 7.99. Scheme 1 is shown below.

Scheme 1

In Figure 1 a is a photograph showing the color of the mixture before and after the reaction, the left is a photograph of the mixture before the reaction, the right shows that the polymer turned brown after the reaction. b is UV of 2,3,6,7,10,11-hexahydroxytriphenylene (HHTP), 2,3,6,7,10,11-hexaaminotriphenylene (HATP) and C2P-5 -Vis spectra. It can be seen that the absorption spectrum of C2P-5 has a longer wavelength and a band wider than that of the monomer, and the polymerization occurs because of the good π-bonding.

Figure 2 shows the FT-IR spectra of HHTP, HATP and C2P-5. Nearly complete loss of stretching bands associated with the -NH ₂ group of HATP at 3385 cm ^-1 and the -OH group of HHTP at 3350 cm ^-1 , characterized by newly formed pyrazine motifs at 1250 and 1350 cm ^-1 C = N stretching bands appear, indicating polymerization.

Figure 3 shows the X-ray photoelectron spectroscopy (XPS) results of C2P-5. X-ray photoelectron spectroscopy (XPS) results of C2P-5 showed N1s and C1s peaks. At 400.2 eV and 285.4 eV, respectively, further confirming the formation of pyrazine. In addition, the atomic ratios of N and C obtained by elemental analysis are 1: 6.3, which is in agreement with the ideal 1: 6 value. The experimentally slightly excess nitrogen content may arise from the unreacted amino group at the edge, consistent with the presence of a small peak of 399.3 eV corresponding to the sp ³ -hybridized nitrogen atom in the XPS spectrum of C2P-5. All the above observations are in agreement with each other, and it was confirmed that the polymerization reaction between HHTP and HATP was well performed to enable formation of pyrazine motif and consequently extension of π-junction.

2) Preparation of Thin Film

C2P-5 synthesized in 1) was redispersed in N-methyl-2-pyrrolidone, and a thin film was formed on a silicon wafer on which a 300 nm oxide layer was formed by a drop casting method.

4 is a photograph evaluating dispersibility after dispersing C2P-5 in N-methyl-2-pyrrolidone. As shown in Figure 4, it was confirmed that well dispersed in N-methyl-2-pyrrolidone, the left side of a is a picture of C2P-5 dispersed in N-methyl-2-pyrrolidone, the right side UV The picture was taken under light. As a result of evaluating dispersibility, it was confirmed that the dispersion was stable for more than 6 months. b is a photograph of the state of the powder of C2P-5, the right is a photograph taken in the state dispersed in N-methyl-2-pyrrolidone and shaken at room temperature.

Figure 5 shows the microscopic characteristics of the prepared C2P-5 thin film. Optical microscope (OM) (a), scanning electron microscope (SEM) (b), atomic force microscope (AFM) (c), transmission electron microscope (TEM) (d), HR-TEM (e) image of C2P-5 And microscopic properties of various EDP (f) microscopic techniques. SEM images showed thin films with lateral size of several tens of micrometers. The SEM and AFM images showed a further wave of the ultrathin surface and showed flexibility. The AFM height profile of C2P-5 showed that the film thickness was in the range of about 0.7-4 nm, indicating the presence of C2P-5 film laminated from monolayer to several layers in solution.

6 is a result of measuring the thickness of the C2P-5 thin film, Figure 6a shows the thickness of the representative AFM image and the peak profile of the C2P-5 thin film. b is a histogram of the thickness distribution of the C2P-5 thin film. Extensive AFM studies showed that the statistical distribution of single, double, triple and multilayer C2P-5 films was 10%, 10%, 12% and 68%, respectively.

7 is a photograph showing that the thin film is separated by a solvent. Interestingly, the thin film applied to the Si wafer was immersed in a 1:10 (v / v) mixed solution of NMP and isopropyl alcohol to peel off to form a single layer film. 7 is a schematic diagram showing that the peeling, peeling at 2nm of the left side of b was confirmed to be peeled off by confirming that 0.7nm as shown on the right.

8 is a unit cell parameter measurement of a C2P-5 thin film. 8 shows an HR-TEM image, and b shows an FFT-pattern. c is a mask filtered TEM image after applying superimposed P 3 symmetry into a tomographic model structure. d is a table showing the reciprocal distance and index of each spot number of the FFT-pattern. As shown in Figure 8, the high resolution TEM (HR-TEM) and electron diffraction pattern (EDP) layered C2P-5 has a highly ordered internal structure with hexagonal lattice (P6, a = b = 1.637 nm, γ = 120 °) Proved to have. It has also been found that monolayer C2P-5 is sensitive to too many electron beams, resulting in a sharp image.

Taken together all these results, it can be seen that the crystalline single to water layer C2P-5 can be obtained by lateral expansion of the crystalline π-junction.

9 shows a gas sorption isotherm of the C2P-5 thin film. The N ₂ adsorption capacity of C2P-5 at 77K was measured. The specific surface area was 20 m 2 / g.

Although HR-TEM analysis is a holed structure of monolayer C2P-5, multilayer C2P-5 typically did not have any 1D channels found in 2D-COF with an AA stacked array obscured. Consistent with negligible N ₂ adsorption capacity.

Figure 10 shows the structure for the crystallinity of C2P-5. 10A is a mask filtered HR-TEM image showing the overlap of monolayer structure and cell parameters (a = b = 1.637 (10) nm). b is a Fast Fourier transform pattern showing a mutual hexagonal lattice system. c is a Synchrotron powder X-ray diffraction (PXRD) pattern using a radiation wavelength of 1.5178 kHz. d is the surface potential energy map calculated by the X-translational offset and Y-translational offset of the second layer with respect to the pyrazine center of the first layer maintained at a constant interlayer distance (3.45 kHz). Zones I, II and III are marked in yellow, red and black. e denotes a periodic arrangement of nine stack types considered for a bilayer unit cell. f and g are perspective views of the stacking model. As shown by the powder X-ray diffraction (PXRD) of C2P-5 in FIG. 10, weak peaks of 8.96 GHz, 12.62 °, 15.54 ° and 17.82 ° except for the most intense signal at 25.4 °, which corresponds to 3.45 mW of interlayer separation. Could observe.

11 shows the electronic characteristics of C2P-5. 11 a is the calculated GGA band structure of monolayer C2P-5. b is the HOMO and LUMO electron density map. c is a typical transfer curve for Vds of 10 V in an OFET device fabricated using C2P-5 and Au as electrodes on a Si / SiO ₂ substrate. As shown in a, the electronic structure of single layer C2P-5 has a direct band gap of 0.94 eV at the Γ point of the Brillouin region. For more accurate estimation, the finite band gap of approximately 1.53 eV was estimated using the Heyd, Scuseria and Ernzerhof (HSE) hybrid functions. The band gaps obtained from the UV-Vis spectra (1.4 eV) and the cyclic voltammetry (1.2 eV) studies fall between the two theoretical values and confirm that the defects in the film are minimized (see FIG. 12, a being blank (grey). ) And the cyclic voltammogram of the C2P-5 coated Pt electrode (black), b is the UV-Vis spectrum of C2P-5 coated on the quartz surface). The band structure of C2P-5 showed significantly greater curvature for the valence and conduction band near the Γ point, in stark contrast to the flat band structure found in the previously reported 2D conjugated polymer. This would result in a lower effective mass of C2P-5 charge carriers and thus higher carrier mobility. And in fact, the effective mass of electrons and holes is the C2P-5, respectively 0.27m and 0.41m _{0 0} (m ₀ is the free electron mass), which is comparable to an electron and a hole of a single-layered transition metal chalcogenides radical (dichalcogenides). Moreover, the frontier molecular orbitals, consisting of p _z orbitals on carbon and nitrogen atoms, are expected to be non-diffused in the entire 2D network of C2P-5, suggesting that C2P-5 exhibits high charge carrier mobility.

To measure the charge carrier mobility of C2P-5, a conventional top contact OFET device was fabricated on a Si wafer where C2P-5 is used as the active semiconductor layer and Au is used as the electrode. Typical transfer curves showed well-defined field effect behavior under hole-enhanced operation (see Figure 11c).

The average hole mobility of C2P-5 calculated from 30 devices was 2.5 cm ² V ^-1 s ^-1 , and the maximum value reached 4.0 cm ² V ^-1 s ^-1 .

Example 2

1) Preparation of two-dimensional conjugated polymer (hereinafter referred to as "C2P-7")

6.0 mg (1.8 mM) of 2,3,6,7,10,11-hexahydroxytriphenylene, 7.7 mg (2.7 mM) of 1,2,4,5-benzenetetraamine tetrahydrochloride and trifluoroacetic acid It was prepared in the same manner as in Example 1 except that 1 μl (1.3 mM) was dissolved in N-methyl-2-pyrrolidone. Crystalline two-dimensional conjugated polymer (hereinafter referred to as 'C2P-7') was obtained as a dark brown solid. Yield 67%. The analysis method of the polymer was performed or carried out similarly to Example 1, and confirmed.

2) Preparation of Thin Film

A thin film was formed on a silicon wafer on which a 300 nm oxide layer was formed in the same manner as in Example 1, except that C2P-7 prepared in 1) was used.

Figure 13 shows the synthesis and physical properties of C2P-7. a is a reaction scheme and b is an OM image. c is an SEM image (scale bar: 100 mu m) d is a TEM image (scale bar: 5 nm) e is a structure showing 2.3 nm pore size of C2P-7.

14 is a high resolution XPS spectra of C2P-7.

Example 3

1) Preparation of two-dimensional conjugated polymer (hereinafter referred to as "C2P-9")

5.0 mg (1.5 mM) of 2,3,6,7,10,11-hexahydroxytriphenylene, 8.9 mg (2.25 mM) of 2,3,7,8-tetraaminophenazine tetrahydrochloride and trifluoro It was prepared in the same manner as in Example 1 except that 1 μl of acetic acid (1.3 mM) was dissolved in N-methyl-2-pyrrolidone and used. Crystalline two-dimensional conjugated polymer (hereinafter referred to as 'C2P-9') was obtained as a dark brown solid. Yield 62%. The analysis method of the polymer was performed or carried out similarly to Example 1, and confirmed.

2) Preparation of Thin Film

A thin film was formed on a silicon wafer on which a 300 nm oxide layer was formed in the same manner as in Example 1, except that C2P-9 prepared in 1) was used.

15 shows the synthesis and physical properties of C2P-9. a is a reaction scheme and b is an OM image. c is an SEM image (scale bar: 100 mu m) d is a TEM image (scale bar: 5 nm) e is a structure showing a pore size of 3.3 nm of C2P-7.

16 is a high resolution XPS spectra of C2P-9.

Claims (7)

A two-dimensional conjugate comprising applying and heating a polymerization composition comprising a compound represented by the following Chemical Formula 1 and any one or two or more compounds selected from the compounds represented by the following Chemical Formulas 2 to 4, an acid catalyst, and a solvent Method for producing a polymer thin film.
[Formula 1]

In Formula 1, L ₁ to L ₆ are each independently selected from a single bond or an alkylene group of C ₁ -C ₂ , and R ₁ to R ₆ are each independently selected from hydrogen or an alkyl group of C ₁ -C 3. )
[Formula 2]

[Formula 3]

[Formula 4]

(In Formulas 2 to 4, R ₇ to R ₁₈ are each independently selected from hydrogen or an alkyl group of C1-C3.) The method of claim 1,
Formula 1 is 2,3,6,7,10,11-hexahydroxytriphenylene,
Formula 2 is 2,3,6,7,10,11-hexaaminotriphenylene, Formula 3 is 1,2,4,5-benzenetetraamine, Formula 4 is 2,3,7, Method for producing a two-dimensional conjugated polymer thin film that is 8-tetraaminophenazine. The method of claim 1,
The heating is a method of producing a two-dimensional conjugated polymer thin film will be carried out at a temperature of 150 to 300 ℃. The method of claim 1,
After the heating, the method of manufacturing a two-dimensional conjugate polymer thin film further comprising the step of chemically or physically doping. A method for producing a two-dimensional conjugated polymer comprising the step of polymerizing a compound represented by the following Chemical Formula 1 and any one or two or more compounds selected from the compounds represented by the following Chemical Formulas 2 to 4 under an acid catalyst.
[Formula 1]

In Formula 1, L ₁ to L ₆ are each independently selected from a single bond or an alkylene group of C ₁ -C ₂ , and R ₁ to R ₆ are each independently selected from hydrogen or an alkyl group of C ₁ -C 3. )
[Formula 2]

[Formula 3]

[Formula 4]

(In Formulas 2 to 4, R ₇ to R ₁₈ are each independently selected from hydrogen or an alkyl group of C1-C3.) The method of claim 5,
Formula 1 is 2,3,6,7,10,11-hexahydroxytriphenylene,
Formula 2 is 2,3,6,7,10,11-hexaaminotriphenylene, Formula 3 is 1,2,4,5-benzenetetraamine, Formula 4 is 2,3,7, A method for producing a two-dimensional conjugated polymer which is 8-tetraaminophenazine. The method of claim 5,
The heating is a method of producing a two-dimensional conjugated polymer that is carried out at a temperature of 150 to 300 ℃.

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