Novel compound for organic p dopant and method for producing same

Abstract

The present invention relates to a novel compound for an organic P dopant and a method for producing same. According to the present invention, in the novel compound produced by reacting a Lewis acid (A) with a precursor having a cyclic conjugated structure including at least two substituents that include at least one among N and O, the Lewis acid binds to two Ns or Os to form an O-A-O, O-A-N or N-A-N bond and thereby form a new ring, whereby the Lewis acid can pull electrons in the conjugated structure to lower the LUMO level and thereby function as a p-dopant or an organic semiconductor. In addition, the method for producing the novel compound consists of a single step and thus has low synthesis costs and excellent price competitiveness, and thus can be effectively used in the field of semiconductor devices.

Description

Novel compounds for organic P dopants and methods for preparing the same

[0001] The present invention relates to a p-dopant compound, and more particularly, to a compound for an organic p-dopant.

[0002] In the semiconductor industry, known as the rice of advanced industries, doping, which intentionally adds impurities to control electrical, optical, and structural properties, is no longer an indispensable technology.

[0003] Recently, much research has been conducted on molecular doping technology that uses dopants, which are similar to doping but are composed of molecules rather than atoms, to form charge carriers by undergoing charge transfer reactions with semiconductors. This technology can be used to improve the electrical conductivity of various organic and inorganic semiconductors, control energy levels, and change absorption characteristics.

[0004] Molecular doping transfers charge through the relative energy difference between the host semiconductor and the guest dopant, so controlling this difference is a key element of the technology. For example, p-doping requires that the semiconductor's highest occupied molecular orbital (HOMO) level be higher than the dopant's lowest unoccupied molecular orbital (LUMO). Satisfying this requirement can enhance the performance of various electronic devices, but the heat inevitably generated during device operation can cause dopant diffusion, hindering operational stability.

[0005] Among various dopant materials, organic dopants, composed of organic compounds, offer the advantage of easily controlling molecular weight, making them advantageous for suppressing thermal diffusion and enhancing operating stability. Organic p-dopants, in particular, are key materials for lowering the operating voltage of organic light-emitting diodes (OLEDs) and thus reducing power consumption due to their excellent operating stability. These organic p-dopants can also be used as a core material for perovskite solar cells, which are expected to form a massive market in the future, and demand for them is expected to further increase.

[0006] Among these commercial organic p-dopants, 2,3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ) has multiple F and CN groups in its quinone ring structure, resulting in a LUMO level of -5.24 eV. NDP-9, a commercial organic p-dopant developed by Novaled in Germany, also has a similar structure and is known to have strong oxidizing properties.

[0007] Another organic p-dopant, hexacyano-trimethylene-cyclopropane (CN6-CP), has a radialene structure in which three carbon atoms form a triangle and are stabilized by CN groups, and has the lowest LUMO level of -5.87 eV among known organic p-dopants.

[0008] In addition, various materials are being developed as dopants, but they have not yet reached a level where they can replace existing commercially available p-dopants.

[0009] Therefore, the problem that the present invention seeks to solve is to provide a novel compound that can replace existing commercialized p-dopants.

[0010] In addition, another problem that the present invention seeks to solve is to provide a method for producing the novel compound.

[0011] The technical problems of the present invention are not limited to the technical problems mentioned above, and other technical problems not mentioned will be clearly understood by those skilled in the art from the description below.

[0012] In order to achieve the above technical task, one aspect of the present invention provides a compound represented by the following chemical formula 1.

[0013] [Chemical Formula 1]

[0014]

[0015] (In the above chemical formula 1,

[0016] Ar is C6~C 20 Aryl, C6~C 20 Heteroaryl and C3~C 10 A cross-conjugated moiety comprising at least one ring selected from the group consisting of cycloalkyl, wherein the heteroaryl contains at least one heteroatom selected from the group consisting of N, O, S, Se and P within the ring,

[0017] X is O or NH,

[0018] Y is O, NH, NR, COO or CONH, R is C1~C4 alkyl,

[0019] A is αβ or αβ2,

[0020] α is selected from the group consisting of B, Al, Zn, Sn, Ru, Ga, Ce, In, Sc, Yb, Er, Dy, Tm, Lu, Tb, Ho, Gd, Sm, La, Eu, Bi, Nd, Hf and Ti,

[0021] β is a halogen element or C6~C regardless of each other 20 It is haloaryl.)

[0022] The above Ar is F, Cl, CN, R 1 (Here, R 1 is a C1~C4 alkyl group), NH3, NH2R1 , NHR 1 R 1 , NR 1 R 1 R 1 , Br, CF3, CBr3, CCl3, C(CN)3, OCH3, OSO2CF3, NO2, C6~C 20 Aryl, C6~C 20 Heteroaryl and C3~C 10 It may have a substituent selected from the group consisting of cycloalkyl.

[0023] The compound of the above chemical formula 1 may be selected from the following group.

[0024]

[0025]

[0026]

[0027]

[0028]

[0029]

[0030]

[0031] (At this time, X, Y and A are as defined in the above chemical formula 1,

[0032] Z1 to Z7 are independently F, Cl, CN, R 1 , NH3, NH2R 1 , NHR 1 R 1 , NR 1 R 1 R 1 , Br, CF3, CBr3, CCl3, C(CN)3, OCH3, OSO2CF3 and NO2,

[0033] R 1 is a C1~C4 alkyl.)

[0034] The compound of the above chemical formula 1 may be selected from the group consisting of compounds of the following chemical formulas 1a to 1d.

[0035] [Chemical Formula 1a]

[0036]

[0037] [Chemical Formula 1b]

[0038]

[0039] [Chemical Formula 1c]

[0040]

[0041] [Chemical Formula 1d]

[0042]

[0043] In addition, another aspect of the present invention provides a method for preparing a compound of the above chemical formula 1. The method for preparing a compound of the above chemical formula 1 includes a step of preparing a compound of the above chemical formula 1 by forming a new heterocyclic moiety by refluxing a reaction mixture in which a precursor compound having a cyclic conjugated structure and a Lewis acid are dissolved in an organic solvent, as shown in the following reaction scheme 1.

[0044] [Reaction Formula 1]

[0045]

[0046] (In the above reaction formula 1,

[0047] X, Y and A are as defined in the above chemical formula 1,

[0048] Y' is O, OH, NH2, NHR, COOH or CONH2,

[0049] R is C1~C4 alkyl,

[0050] When Y' is O, Y' forms a double bond with the carbon atom to which it is bonded,

[0051] The above Lewis acid is αβ2 or αβ3,

[0052] The above α and β are as defined in the above chemical formula 1.)

[0053] The precursor compound may comprise a quinone moiety or a radielene moiety.

[0054] The above organic solvent may be anhydrous toluene or anhydrous butyl acetate.

[0055] The above reflux reaction can be carried out in an inert atmosphere.

[0056] A step of purifying the manufactured compound of chemical formula 1 to a high purity may be further included.

[0057] In addition, another aspect of the present invention provides a semiconductor device comprising the compound of the above chemical formula 1 as an organic p-dopant or organic semiconductor.

[0058] The above organic semiconductor may be an electron blocking layer, a hole injection layer, or an n-type organic semiconductor.

[0059] According to the present invention, a novel compound prepared by reacting a precursor having a cyclic conjugated structure including two or more adjacent substituents including at least one of N and O with a Lewis acid (A) forms a new ring by forming an OAO, OAN or NAN bond by the Lewis acid bonding with two Ns or Os, and thereby the Lewis acid can function as a p-dopant or an organic semiconductor by lowering the LUMO level by attracting electrons within the conjugated structure. In addition, since the method for preparing the novel compound consists of a single step, the synthesis cost is low, and thus the novel compound has excellent price competitiveness, and thus can be usefully used in the field of semiconductor devices.

[0060] FIG. 1 is a graph showing the change in absorbance according to wavelength of a P3HT thin film doped with a compound of chemical formula 1 according to one embodiment of the present invention.

[0061] Figure 2 is a graph showing the change in absorbance according to wavelength of a BCF-doped P3HT thin film according to a comparative example of the present invention.

[0062] FIG. 3 is a graph showing the increase ratio compared to the initial surface resistance during heat treatment of a P3HT thin film doped with a compound of chemical formula 1 according to one embodiment of the present invention.

[0063] Figure 4 shows the change in absorbance by wavelength according to the heat treatment temperature when a P3HT thin film doped with a compound of chemical formula 1a according to one embodiment of the present invention is heat treated.

[0064] Figure 5 shows the change in absorbance by wavelength according to the heat treatment temperature when a P3HT thin film doped with a compound of chemical formula 1b according to one embodiment of the present invention is heat treated.

[0065] Figure 6 shows the change in absorbance by wavelength according to the heat treatment temperature when a P3HT thin film doped with a compound of chemical formula 1c according to one embodiment of the present invention is heat treated.

[0066] Figure 7 shows the change in absorbance by wavelength according to the heat treatment temperature when a P3HT thin film doped with a compound of chemical formula 1a according to one embodiment of the present invention is heat treated.

[0067] Figure 8 shows the compounds manufactured in Manufacturing Examples 1-4 and Comparative Example 1 of the present invention. 19 F NMR spectrum (CDCl3, 600 MHz).

[0068] Hereinafter, embodiments of the present invention will be described in detail with reference to the attached drawings. In describing the present invention, detailed descriptions of related known functions or configurations will be omitted if they are deemed to unnecessarily obscure the gist of the present invention. Furthermore, the terms used in this specification are terms intended to appropriately express preferred embodiments of the present invention and may vary depending on the intentions of the user or operator, or customary practices in the field to which the present invention pertains. Therefore, definitions of these terms should be based on the contents throughout this specification.

[0069] Identical reference numerals in each drawing represent identical elements.

[0070] Throughout the specification, when we say that an element is "on" another element, this includes not only cases where the element is in contact with the other element, but also cases where another element exists between the two elements.

[0071] Throughout the specification, whenever a part is said to "include" a component, this does not mean that it excludes other components, but rather that it may include other components, unless otherwise stated.

[0072] In this specification, “cross conjugation” means that only two of the three pi bonds in a molecule interact by conjugation, and the third pi bond is excluded from the interaction.

[0073] Unless specifically defined herein, "alkyl group" means an aliphatic hydrocarbon group. The alkyl group may be a "saturated alkyl group" that does not contain any double bond or triple bond. Alternatively, the alkyl group may be an "unsaturated alkyl group" that contains at least one double bond or triple bond. The alkyl group, whether saturated or unsaturated, may be branched, straight-chain, or cyclic. The alkyl group is C1~C 30 It can be an alkyl group. More specifically, the alkyl group is C1~C 10 It may be an alkyl group or a C1~C6 alkyl group. For example, the C1~C4 alkyl group may be selected from the group consisting of methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, and t-butyl.

[0074] Additionally, unless specifically defined herein, a "cycloalkyl group" refers to a cyclic saturated hydrocarbon group having 3 to 20 carbon atoms. Specifically, the cycloalkyl group includes a cycloalkyl group having 3 to 6 carbon atoms. Specific examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, or a cyclohexyl group.

[0075] Additionally, unless specifically defined herein, "aryl group (Ar)" means a carbocyclic aromatic radical having 6 to 20 carbon atoms, which comprises one or more rings, wherein the rings may be attached together in a pendant manner or fused together. Specifically, the aryl group includes an aryl group having 6 to 20 carbon atoms, and more specifically, 6 to 12 carbon atoms. Specific examples of the aryl group include a phenyl group, a naphthyl group, or a biphenyl group.

[0076] In addition, unless specifically defined herein, "arylalkyl group" means a functional group (Ar-Ra-) in which a straight-chain or branched alkyl group (Ra) is substituted with an aryl group (Ar), which is an aromatic hydrocarbon group. Specifically, the arylalkyl group includes an arylalkyl group having 7 to 20 carbon atoms, more specifically, 7 to 12 carbon atoms. Specific examples of the arylalkyl group include a benzyl group, a phenethyl group, and the like.

[0077] In addition, unless specifically defined herein, "aryloxy group" means an aryl group (-OAr) bonded to oxygen, wherein the aryl group is as defined above. Specifically, the aryloxy group includes an aryloxy group having 6 to 20 carbon atoms, more specifically, 6 to 12 carbon atoms. Specific examples of the aryloxy group include phenoxy and the like.

[0078] In addition, unless specifically defined herein, "arylamine group" means a functional group (Ar-NH2-) in which an amine group (NH2-) is substituted with an aryl group (Ar), which is an aromatic hydrocarbon group. Specifically, the arylalkyl group includes an arylamine group having 6 to 20 carbon atoms, and more specifically, 6 to 12 carbon atoms.

[0079] Additionally, unless specifically defined herein, a “heteroaryl group” means a monocyclic aromatic compound or a polycyclic aromatic compound composed of fused aromatic rings, containing at least one heteroatom selected from the group consisting of N, O, S, Se, and P in at least one ring, the remaining members being carbon.

[0080] Also, in this specification, "C x -C y ", it should be interpreted that it also describes cases where the number of carbon atoms is a number corresponding to all integers between carbon atoms x and carbon atoms y.

[0081]

[0082] One aspect of the present invention provides a novel compound represented by the following chemical formula 1.

[0083] [Chemical Formula 1]

[0084]

[0085] (In the above chemical formula 1,

[0086] Ar is C6~C 20 Aryl, C6~C 20 Heteroaryl and C3~C 10 A cross-conjugated moiety comprising at least one ring selected from the group consisting of cycloalkyl, wherein the heteroaryl contains at least one heteroatom selected from the group consisting of N, O, S, Se and P within the ring,

[0087] X is O or NH,

[0088] Y is O, NH, NR, COO or CONH, R is C1~C4 alkyl,

[0089] A is αβ or αβ2,

[0090] α is selected from the group consisting of B, Al, Zn, Sn, Ru, Ga, Ce, In, Sc, Yb, Er, Dy, Tm, Lu, Tb, Ho, Gd, Sm, La, Eu, Bi, Nd, Hf and Ti,

[0091] β is a halogen element or C6~C regardless of each other 20 It is haloaryl.)

[0092] The above Ar is F, Cl, CN, R 1 (Here, R 1 is a C1~C4 alkyl group), NH3, NH2R 1 , NHR 1 R 1 , NR 1 R 1 R 1 , Br, CF3, CBr3, CCl3, C(CN)3, OCH3, OSO2CF3, NO2, C6~C 20 Aryl, C6~C 20 Heteroaryl and C3~C 10 It may be substituted with a substituent selected from the group consisting of cycloalkyl.

[0093] Specifically, the compound of the above chemical formula 1 can be selected from the following group.

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101] (At this time, X, Y and A are as defined in the above chemical formula 1,

[0102] Z1 to Z7 are independently F, Cl, CN, R 1 , NH3, NH2R 1 , NHR 1 R 1 , NR 1 R 1 R 1 , Br, CF3, CBr3, CCl3, C(CN)3, OCH3, OSO2CF3 and NO2,

[0103] R 1 is a C1~C4 alkyl.)

[0104] As an example, the compound of formula 1 according to the present invention may be selected from the group consisting of compounds of formulae 1a to 1d below.

[0105] [Chemical Formula 1a]

[0106]

[0107] [Chemical Formula 1b]

[0108]

[0109] [Chemical Formula 1c]

[0110]

[0111] [Chemical Formula 1d]

[0112]

[0113] The compound of chemical formula 1 according to the present invention is characterized in that a substituent containing N or O as two substituents adjacent to a cross-conjugated moiety having a cyclic conjugated structure forms a new heterocyclic moiety by bonding with a Lewis acid (A) to form an OAO, OAN or NAN bond.

[0114] At least one heterocyclic moiety formed through the OAO, OAN or NAN bond may be formed in the compound of formula 1, and for example, one, two or three may be formed in the compound.

[0115] The compound of chemical formula 1 according to the present invention can function as a p-dopant or organic semiconductor by lowering the LUMO level by the Lewis acid attracting electrons within the conjugated structure through the OAO, OAN or NAN bond formed by combining O or N formed on two carbons in the conjugated structure with a Lewis acid (A), and exhibiting thermal stability.

[0116] Specifically, the organic semiconductor may be an electron blocking layer, a hole injection layer, or an n-type organic semiconductor.

[0117]

[0118] In addition, another aspect of the present invention provides a method for preparing a compound represented by the following chemical formula 1.

[0119] The method for producing a compound represented by the above chemical formula 1 includes a step of producing a compound of the chemical formula 1 by refluxing a reaction mixture in which a precursor compound having a cyclic conjugated structure and a Lewis acid are dissolved in an organic solvent to form a new heterocyclic moiety, as shown in the following reaction scheme 1.

[0120] [Reaction Formula 1]

[0121]

[0122] (In the above reaction formula 1,

[0123] X, Y and A are as defined in the above chemical formula 1,

[0124] Y' is O, OH, NH2, NHR, COOH or CONH2,

[0125] R is C1~C4 alkyl,

[0126] When Y' is O, Y' forms a double bond with the carbon atom to which it is bonded,

[0127] The above Lewis acid is αβ2 or αβ3,

[0128] The above α and β are as defined in the above chemical formula 1.)

[0129] In the above manufacturing method, the precursor compound may include a quinone moiety or a radielene moiety, but is not limited thereto.

[0130] In the above manufacturing method, the organic solvent may include, but is not limited to, anhydrous toluene or anhydrous butyl acetate.

[0131] In the above manufacturing method, the reaction can be performed in an inert atmosphere, and the solution is heated to the boiling point and refluxed. At this time, if the reaction occurs, the color of the solution darkens, allowing the completion of the reaction to be identified.

[0132] In the above manufacturing method, it is preferable that the reaction time be sufficiently long, at least 3 hours. If the reaction time is less than 3 hours, the reaction may not proceed sufficiently, resulting in the generation of numerous by-products.

[0133] The manufactured compound of Chemical Formula 1 may further include a step of purifying it to a high purity through column chromatography or recrystallization. This purification process can effectively remove impurities and improve the lifespan and efficiency of a device containing the purified compound.

[0134] The compound of chemical formula 1 manufactured can be utilized as an organic p-dopant or organic semiconductor for doping a semiconductor in a semiconductor device, and as an example of the organic semiconductor, it can be utilized as an electron blocking layer, a hole injection layer, or an n-type organic semiconductor.

[0135]

[0136] According to the present invention, a compound of formula 1 prepared by reacting a precursor having a cyclic conjugated structure including two or more adjacent substituents including at least one of N and O with a Lewis acid (A) forms a new ring by allowing the Lewis acid to bond with two Ns or Os to form an OAO, OAN or NAN bond, thereby allowing the Lewis acid to lower the LUMO level by attracting electrons within the conjugated structure, thereby functioning as a p-dopant or an organic semiconductor. In addition, since the method for preparing the compound of formula 1 is comprised of a single step, the synthesis cost is low, and thus the compound has excellent price competitiveness, and thus can be usefully used in the field of semiconductor devices.

[0137]

[0138] Hereinafter, preferred manufacturing examples and experimental examples are presented to aid in understanding the present invention. However, the following examples and experimental examples are provided solely to aid in understanding the present invention, and the present invention is not limited to the following manufacturing examples and experimental examples.

[0139]

[0140] Manufacturing Example 1-4: Manufacturing of a novel compound for organic p-dopant

[0141] [Manufacturing Example 1]

[0142]

[0143] In a glove box filled with N2, 0.2 mmol of chloranilic acid and 0.4 mmol of tris(pentafluorophenyl)borane were weighed and placed in a round flask, and 10 mL of anhydrous toluene or anhydrous butyl acetate was injected to prepare a reaction mixture.

[0144] Next, the above reaction mixture was heated in a heating mantle under N2 and refluxed for 3 to 24 hours. The solution after the reaction was completed was dried in a vacuum oven for more than 12 hours to obtain a compound of chemical formula 1a (yield 47.2%, purity 77.7%).

[0145]

[0146] [Manufacturing Example 2]

[0147]

[0148] In Manufacturing Example 1, 2,3-Dichloro-5,8-dihydroxy-1,4-naphthoquinone was used instead of chloranilic acid in the reactant, and the same method as Manufacturing Example 1 was performed to obtain a compound of chemical formula 1b. (Yield 52.0%, purity 91.2%)

[0149]

[0150] [Manufacturing Example 3]

[0151]

[0152] In Manufacturing Example 1, 0.2 mmol of quinoclamine and 0.2 mmol of tris(pentafluorophenyl)borane were used as the reaction mixture, and the same method as Manufacturing Example 1 was performed to obtain a compound of chemical formula 1c. (Yield 36.9%, purity 39.2%)

[0153]

[0154] [Manufacturing Example 4]

[0155]

[0156] In Manufacturing Example 1, 0.2 mmol of cyclohexanehexone octahydrate and 0.6 mmol of tris(pentafluorophenyl)borane were used as a reaction mixture, and the same method as Manufacturing Example 1 was performed to obtain a compound of chemical formula 1c. (Yield 31.6%, purity 4.3%)

[0157]

[0158] [Comparative Example 1]

[0159] Tris(pentafluorophenyl)borane (BCF) was used alone.

[0160]

[0161] Compounds manufactured in Manufacturing Examples 1-4 and Comparative Example 1 19 The F NMR spectrum (CDCl3, 600 MHz) is shown in Fig. 8.

[0162]

[0163] Manufacturing Example 5-8, Comparative Example 2: Manufacturing of a conductive polymer thin film doped with an organic p-dopant

[0164] Poly(3-hexyl thiophene) [P3HT] was dissolved in 1,2-dichlorobenzene at a concentration of 10 mg / mL and spin-coated on a washed glass substrate at 1000 rpm for 60 seconds to form a P3HT thin film with a thickness of several tens of nm.

[0165] While the formed thin film was rotated at 4000 rpm in a spin coater, 50 μL of a p-dopant solution, in which the p-dopant synthesized in Manufacturing Examples 1 to 4 was dissolved in an organic solvent, was sprayed to cause doping. The doping was confirmed to have occurred through a color change in the thin film.

[0166]

[0167] [Experimental Example 1: Measurement of the change in absorbance of a conductive polymer thin film depending on the presence or absence of doping with organic p-dopant]

[0168] In order to investigate the change in the characteristics of the conductive polymer thin film depending on the doping of the organic p-dopant of the present invention, the absorbance of the P3HT thin film not doped with the organic p-dopant and the P3HT thin film doped with the organic p-dopant of Preparation Examples 5-7 was measured, and the results are shown in Fig. 1. In addition, as a comparative example, the absorbance of the P3HT thin film doped solely with tris(pentafluorophenyl)borane (BCF) was measured, and the results are shown in Fig. 2.

[0169] FIG. 1 is a graph showing the change in absorbance according to wavelength of a P3HT thin film doped with an organic p-dopant according to an embodiment of the present invention, and FIG. 2 is a graph showing the change in absorbance according to wavelength of a P3HT thin film doped with BCF according to a comparative example of the present invention.

[0170] As shown in Fig. 1, the P3HT thin film not doped with an organic p-dopant exhibited light absorption only at a wavelength of 600 nm and no absorbance in other wavelength ranges, whereas the P3HT thin film doped with the compound according to the present invention showed a decrease in absorbance of the neutral peak (600 nm) while a significant increase in the doped polaron peak (> 700 nm) appearing in the near-infrared region, confirming that p-type doping was successfully achieved.

[0171] However, as shown in Fig. 2, the P3HT thin film treated with BCF alone showed an absorbance peak only at 600 nm, similar to the P3HT thin film not doped with dopant, confirming that p-type doping did not occur.

[0172] Therefore, the compound according to the present invention can be usefully used as an organic p-dopant by doping into a conductive polymer thin film to change the properties of the thin film, such as absorbance, over a wide wavelength range.

[0173]

[0174] [Experimental Example 2: Thermal Stability Test of a Conductive Polymer Thin Film Doped with a Novel Compound]

[0175] In order to determine the thermal stability of a conductive polymer thin film doped with a novel compound according to the present invention, the following experiment was conducted.

[0176] Specifically, the P3HT thin films doped with the novel compounds manufactured in Manufacturing Examples 5 to 8 were heat-treated at various temperatures from room temperature to 180°C for 1 hour each, and the increase ratio (R / R0) compared to the initial sheet resistance was measured, which is shown in Fig. 3, and the change in absorbance by wavelength for each thin film is shown in Figs. 4 to 7.

[0177] FIG. 3 is a graph showing the increase ratio compared to the initial surface resistance when a P3HT thin film doped with a novel compound according to one embodiment of the present invention is heat-treated.

[0178] As shown in Fig. 3, it can be seen that the conductive polymer thin film doped with the novel compound according to the present invention exhibits doping thermal stability as the increase in sheet resistance is low even when heat-treated at 100°C. In particular, it was confirmed that the conductive polymer thin film doped with the novel compound manufactured in Manufacturing Example 8 exhibits excellent doping thermal stability even when heat-treated at 180°C.

[0179]

[0180] In addition, FIGS. 4 to 7 show changes in absorbance by wavelength according to the heat treatment temperature when heat-treating P3HT thin films doped with the novel compounds manufactured in Manufacturing Examples 5 to 8. Specifically, FIG. 4 shows a case where the compound of Chemical Formula 1a is doped, FIG. 5 shows a case where the compound of Chemical Formula 1b is doped, FIG. 6 shows a case where the compound of Chemical Formula 1c is doped, and FIG. 7 shows a case where the compound of Chemical Formula 1d is doped.

[0181] As shown in FIGS. 4 to 7, the novel compounds according to the present invention exhibited a thermal de-doping phenomenon as the absorbance decreased as the heat treatment temperature increased. However, compared to the doping of the compound of chemical formula 1a, the compounds of chemical formula 1b and chemical formula 1d exhibited a smaller range of de-doping phenomenon, confirming excellent thermal stability in particular.

[0182]

[0183] Above, the present invention has been described in detail with reference to preferred embodiments, but the present invention is not limited to the above embodiments, and various modifications and changes can be made by those skilled in the art within the technical spirit and scope of the present invention.

Claims

1. A compound represented by the following chemical formula 1. [Chemical Formula 1] (In the above chemical formula 1, Ar is C6~C 20 Aryl, C6~C 20 Heteroaryl and C3~C 10 A cross-conjugated moiety comprising at least one ring selected from the group consisting of cycloalkyl, wherein the heteroaryl contains at least one heteroatom selected from the group consisting of N, O, S, Se and P within the ring, X is O or NH, Y is O, NH, NR, COO or CONH, R is C1~C4 alkyl, A is αβ or αβ2, α is selected from the group consisting of B, Al, Zn, Sn, Ru, Ga, Ce, In, Sc, Yb, Er, Dy, Tm, Lu, Tb, Ho, Gd, Sm, La, Eu, Bi, Nd, Hf and Ti, β is a halogen element or C6~C regardless of each other 20 It is haloaryl.) 2. In paragraph 1, The above Ar is F, Cl, CN, R 1 (Here, R 1 is a C1~C4 alkyl group), NH3, NH2R 1 , NHR 1 R 1 , NR 1 R 1 R 1 , Br, CF3, CBr3, CCl3, C(CN)3, OCH3, OSO2CF3, NO2, C6~C 20 Aryl, C6~C 20 Heteroaryl and C3~C 10 A compound characterized in that it is substituted with a substituent selected from the group consisting of cycloalkyl.

3. In paragraph 1, A compound characterized in that the compound of the above chemical formula 1 is selected from the following group. (At this time, X, Y and A are as defined in chemical formula 1, Z1 to Z7 are independently F, Cl, CN, R 1 , NH3, NH2R 1 , NHR 1 R 1 , NR 1 R 1 R 1 , Br, CF3, CBr3, CCl3, C(CN)3, OCH3, OSO2CF3 and NO2, R 1 is a C1~C4 alkyl.) 4. In paragraph 1, A compound characterized in that the compound of the above chemical formula 1 is selected from the group consisting of compounds of the following chemical formulas 1a to 1d. [Chemical Formula 1a] [Chemical Formula 1b] [Chemical Formula 1c] [Chemical Formula 1d] 5. As shown in the following reaction formula 1, A method for producing a compound of claim 1, comprising a step of producing a compound of formula 1 by refluxing a reaction mixture in which a precursor compound having a cyclic conjugated structure and a Lewis acid are dissolved in an organic solvent to form a new heterocyclic moiety. [Reaction Formula 1] (In the above reaction formula 1, X, Y and A are as defined in paragraph 1, Y' is O, OH, NH2, NHR, COOH or CONH2, R is C1~C4 alkyl, When Y' is O, Y' forms a double bond with the carbon atom to which it is bonded, The above Lewis acid is αβ2 or αβ3, The above α and β are as defined in the first paragraph.) 6. In paragraph 5, A method for producing a compound, characterized in that the precursor compound comprises a quinone moiety or a radielene moiety.

7. In paragraph 5, A method for producing a compound, characterized in that the organic solvent is anhydrous toluene or anhydrous butyl acetate.

8. In paragraph 5, A method for producing a compound, characterized in that the above reflux reaction is performed in an inert atmosphere.

9. In paragraph 5, A method for producing a compound, characterized in that it further comprises a step of purifying the manufactured compound of chemical formula 1 to a high purity.

10. A semiconductor device containing the compound of paragraph 1 as an organic p-dopant or organic semiconductor.

11. In paragraph 10, A semiconductor device characterized in that the organic semiconductor is an electron blocking layer, a hole injection layer, or an n-type organic semiconductor.

Images