KR102097851B1 - Compound, organic transistor and gas sensor containing the same - Google Patents

Abstract

The present specification relates to a compound comprising a unit represented by Chemical Formula 1, an organic transistor and a gas sensor including the same.

Description

Compound, organic transistor and gas sensor including the same {COMPOUND, ORGANIC TRANSISTOR AND GAS SENSOR CONTAINING THE SAME}

The present specification relates to a compound, an organic transistor including the same, and a gas sensor.

Sensors used for the detection of gases, compounds, biomolecules, etc. have received a lot of attention and many research results are being published. Among them, gas sensors have been used in a wide range of fields such as chemical, pharmaceutical, environmental, and medical, and are expected to be more researched in the future. A technology that detects harmful substances and pollutants in the air in real time is indispensable to maintain a good living environment and working environment. Gas sensors are installed in various places and play an important role in monitoring the atmosphere, harmful substances and pollutants in our environment.

The conditions that these gas sensors must have are quickness to show how fast they can react, sensitivity to show how minute they can react when detected, durability to show how long they can operate, and how much consumers It demands characteristics such as economics that show whether the sensor can be used without any burden. In addition, in order to combine with the existing semiconductor process technology, it must have characteristics that are easy to integrate and list. As a practical gas sensor, a domestic gas leak alarm made of tin oxide (SnO ₂ ) is widely used. The operating principle includes a semiconductor type using a resistance value that changes according to a change in the amount of gas, and a vibrator type using a frequency that changes when a gas is adsorbed on a vibrator having a certain frequency. Most gas sensors use a semiconductor type that has a simple circuit and stable thermal properties at room temperature.

The semiconductor-type gas sensor includes an inorganic semiconductor-type gas sensor in which a silicon semiconductor, an inorganic material, forms a semiconductor crystal through covalent bonding between atoms, and an organic semiconductor-type gas sensor combined with a molecular bond of a conductive polymer, that is, a van der Waals interaction. Among these, a gas sensor based on tin oxide requires a high temperature for sensor operation, and a product with a micro heater is commercially available. However, there is a difficulty in thinning due to this problem. In addition, gas concentrations with a sensitivity of 50 ppm or less cannot be measured, which limits the wide range of applications.

Gas sensors based on organic semiconductors can dissolve semiconductor materials in organic solvents and manufacture them in solution through various printing processes, which can significantly reduce the cost of manufacturing existing gas sensors. Therefore, recently, a printing type gas sensor that reports an organic semiconductor as a sensing material through a printing process such as inkjet printing has been actively researched, but research on various organic semiconductor materials for sensing is relatively less conducted.

Korean Patent Application Publication No. 2006-0042013

The present specification provides a novel compound, an organic transistor to which it is applied, and a gas sensor.

An exemplary embodiment of the present specification provides a compound comprising a unit represented by Formula 1 below.

[Formula 1]

In Chemical Formula 1,

X1 to X4 are the same as or different from each other, and each independently CRR ', NR, O, SiRR', PR, S, GeRR ', Se or Te,

n is an integer from 1 to 10,000,

[A1] includes one or a combination of two or more of the following structures,

In the above structure,

X10 to X16 are the same as or different from each other, and each independently CRR ', NR, O, SiRR', PR, S, GeRR ', Se or Te,

a is an integer of 1 or 2,

When a is 2, structures in parentheses are the same as or different from each other,

x is an integer from 1 to 5,

When x is 2 or more, structures in parentheses are the same or different from each other,

R1 to R4, R10 to R12, R and R 'are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Nitrile group; Nitro group; Hydroxy group; Carbonyl group; Ester groups; Imide group; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthioxy group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkyl sulfoxy group; A substituted or unsubstituted aryl sulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In addition, an exemplary embodiment of the present specification is an organic transistor including a gate electrode, a source electrode, a drain electrode, an insulating layer, and an organic semiconductor layer, wherein the organic semiconductor layer includes an organic transistor comprising a compound containing the unit of Formula 1 Provides

In addition, an exemplary embodiment of the present specification is a gas sensor including a gate electrode, a source electrode, a drain electrode, an insulating layer, and an organic semiconductor layer, wherein the organic semiconductor layer is a gas sensor including a compound containing the unit of Formula 1 Provides

The gas sensor according to an exemplary embodiment of the present specification is excellent in detecting effects on gases such as ammonia, ethylene, formaldehyde, hydrofluoric acid, nitrogen oxides, and sulfur oxides.

1 to 4 are diagrams showing an organic transistor according to an exemplary embodiment of the present specification.
5 is a diagram showing an NMR spectrum of compound 1-a.
6 is a diagram showing an MS spectrum of Compound 1-a.
7 is a diagram showing the UV spectrum of Compound 1.
8 is a diagram showing the CV spectrum of Compound 1.
9 is a view showing the UV spectrum of Compound 3.
10 is a diagram showing the CV spectrum of compound 3.
11 is a diagram showing an NMR spectrum of compound 4-b.
12 is a diagram showing an NMR spectrum of compound 4-c.
13 is a diagram showing an MS spectrum of compound 4-c.
14 is a diagram showing an NMR spectrum of compound 4-h.
15 is a diagram showing an NMR spectrum of compound 4-i.
16 is a diagram showing the HPLC spectrum of compound 4-i.
17 is a diagram showing an MS spectrum of compound 4-j.
18 is a diagram showing the UV spectrum of compound 4-j.
19 is a diagram showing the CV spectrum of compound 4-j.
20 is a diagram showing the performance measurement results of the organic transistor prepared in Example 1.
21 is a diagram showing the performance measurement results of the organic transistor prepared in Example 2.
22 is a diagram showing the performance measurement results of the organic transistor prepared in Example 3.
23 is a diagram showing the performance measurement results of the organic transistor prepared in Example 4.
24 is a diagram showing the performance measurement results of the gas sensor prepared in Example 17.
25 is a view showing the performance measurement results of the gas sensor prepared in Example 18.
26 is a view showing the performance measurement results of the gas sensor prepared in Example 19.
27 is a graph showing the gas sensor results according to Examples 17 to 19.

Hereinafter, this specification will be described in detail.

One embodiment of the present specification provides a compound including the unit represented by Chemical Formula 1.

In the present specification, when a part “includes” a certain component, it means that the component may further include other components, not to exclude other components, unless otherwise stated.

In the present specification, when a member is said to be positioned “on” another member, this includes not only the case where one member is in contact with the other member but also another member between the two members.

In the present specification, “combination” means connecting several structures or connecting different types of structures.

In this specification, the term "substituted or unsubstituted" is deuterium; Halogen group; Nitrile group; Nitro group; Imide group; Amide group; Carbonyl group; Ester groups; Hydroxy group; Alkyl groups; Cycloalkyl group; Alkoxy groups; Aryloxy group; Alkyl thioxy group; Arylthioxy group; Alkyl sulfoxy group; Aryl sulfoxyl group; Alkenyl group; Silyl group; Siloxane groups; Boron group; Amine group; Arylphosphine group; Phosphine oxide group; Aryl group; And one or two or more substituents selected from the group consisting of heterocyclic groups, or substituted with two or more substituents among the above-described substituents, or having no substituents. For example, "a substituent having two or more substituents" may be a biphenyl group. That is, the biphenyl group may be an aryl group or may be interpreted as a substituent to which two phenyl groups are connected.

는 다른 치환기 또는 결합부에 결합되는 부위를 의미한다.In this specification,

Means a site that is attached to another substituent or linkage.

In the present specification, the halogen group may be fluorine, chlorine, bromine or iodine.

In this specification, the number of carbon atoms of the imide group is not particularly limited, but is preferably 1 to 30 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the nitrogen of the amide group may be substituted with hydrogen, a straight chain, branched or cyclic alkyl group having 1 to 30 carbon atoms, or an aryl group having 6 to 30 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In this specification, the number of carbon atoms of the carbonyl group is not particularly limited, but is preferably 1 to 30 carbon atoms. Specifically, it may be a compound having the following structure, but is not limited thereto.

In the present specification, the carbon or oxygen of the ester group may be substituted with a straight chain, branched or cyclic alkyl group having 1 to 25 carbon atoms or an aryl group having 6 to 30 carbon atoms. Specifically, it may be a compound of the following structural formula, but is not limited thereto.

In the present specification, the alkyl group may be straight chain or branched chain, and carbon number is not particularly limited, but is preferably 1 to 30. Specific examples are methyl, ethyl, propyl, n-propyl, isopropyl, butyl, n-butyl, isobutyl, tert-butyl, sec-butyl, 1-methyl-butyl, 1-ethyl-butyl, pentyl, n-pentyl , Isopentyl, neopentyl, tert-pentyl, hexyl, n-hexyl, 1-methylpentyl, 2-methylpentyl, 4-methyl-2-pentyl, 3,3-dimethylbutyl, 2-ethylbutyl, heptyl, n -Heptyl, 1-methylhexyl, cyclopentylmethyl, cyclohexylmethyl, octyl, n-octyl, tert-octyl, 1-methylheptyl, 2-ethylhexyl, 2-propylpentyl, n-nonyl, 2,2-dimethyl Heptyl, 1-ethyl-propyl, 1,1-dimethyl-propyl, isohexyl, 2-methylpentyl, 4-methylhexyl, 5-methylhexyl, and the like, but is not limited thereto.

In the present specification, the cycloalkyl group is not particularly limited, but preferably has 3 to 30 carbon atoms, specifically cyclopropyl, cyclobutyl, cyclopentyl, 3-methylcyclopentyl, 2,3-dimethylcyclopentyl, cyclohexyl, 3-methylcyclohexyl, 4-methylcyclohexyl, 2,3-dimethylcyclohexyl, 3,4,5-trimethylcyclohexyl, 4-tert-butylcyclohexyl, cycloheptyl, cyclooctyl, and the like. It is not.

In the present specification, the alkoxy group may be a straight chain, branched chain or cyclic chain. The number of carbon atoms of the alkoxy group is not particularly limited, but is preferably 1 to 30 carbon atoms. Specifically, methoxy, ethoxy, n-propoxy, isopropoxy, i-propyloxy, n-butoxy, isobutoxy, tert-butoxy, sec-butoxy, n-pentyloxy, neopentyloxy, Isopentyloxy, n-hexyloxy, 3,3-dimethylbutyloxy, 2-ethylbutyloxy, n-octyloxy, n-nonyloxy, n-decyloxy, benzyloxy, p-methylbenzyloxy, etc. It may be, but is not limited to this.

In the present specification, the amine group is -NH ₂ ; Alkylamine groups; N-aryl alkylamine group; Arylamine group; N-aryl heteroarylamine group; It may be selected from the group consisting of N-alkylheteroarylamine groups and heteroarylamine groups, and the number of carbon atoms is not particularly limited, but is preferably 1 to 30. Specific examples of the amine group are methylamine group, dimethylamine group, ethylamine group, diethylamine group, phenylamine group, naphthylamine group, biphenylamine group, anthracenylamine group, 9-methyl-anthracenylamine group , Diphenylamine group, N-phenylnaphthylamine group, ditolylamine group, N-phenyltolylamine group, triphenylamine group, and the like, but is not limited thereto.

In the present specification, the N-alkylarylamine group means an amine group in which an alkyl group and an aryl group are substituted for N of the amine group.

In the present specification, the N-aryl heteroarylamine group means an amine group in which an aryl group and a heteroaryl group are substituted with N of the amine group.

In the present specification, the N-alkylheteroarylamine group means an amine group in which an alkyl group and a heteroarylamine group are substituted with N of the amine group.

In the present specification, the alkyl group in the alkylamine group, the N-arylalkylamine group, the alkylthioxy group, the alkyl sulfoxy group, and the N-alkylheteroarylamine group is the same as the above-described alkyl group. Specifically, the alkyl thioxy group includes a methyl thioxy group, an ethyl thioxy group, a tert-butyl thioxy group, a hexyl thioxy group, and an octyl thioxy group. And the like, but is not limited thereto.

In the present specification, the alkenyl group may be straight chain or branched chain, and the number of carbon atoms is not particularly limited, but is preferably 2 to 30. Specific examples include vinyl, 1-propenyl, isopropenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 3-methyl-1- Butenyl, 1,3-butadienyl, allyl, 1-phenylvinyl-1-yl, 2-phenylvinyl-1-yl, 2,2-diphenylvinyl-1-yl, 2-phenyl-2- ( Naphthyl-1-yl) vinyl-1-yl, 2,2-bis (diphenyl-1-yl) vinyl-1-yl, styrenyl group, styrenyl group, and the like, but are not limited thereto.

In the present specification, the silyl group is specifically trimethylsilyl group, triethylsilyl group, t-butyldimethylsilyl group, vinyldimethylsilyl group, propyldimethylsilyl group, triphenylsilyl group, diphenylsilyl group, phenylsilyl group, etc. However, it is not limited thereto.

In the present specification, the boron group may be -BR ₁₀₀ R ₂₀₀ , wherein R ₁₀₀ and R ₂₀₀ are the same or different, and each independently hydrogen; heavy hydrogen; halogen; Nitrile group; A substituted or unsubstituted monocyclic or polycyclic cycloalkyl group having 3 to 30 carbon atoms; A substituted or unsubstituted, straight or branched chain alkyl group having 1 to 30 carbon atoms; A substituted or unsubstituted monocyclic or polycyclic aryl group having 6 to 30 carbon atoms; And it may be selected from the group consisting of substituted or unsubstituted monocyclic or polycyclic heteroaryl group having 2 to 30 carbon atoms.

In the present specification, the phosphine oxide group is specifically a diphenylphosphine oxide group, a dinaphthyl phosphine oxide, and the like, but is not limited thereto.

In the present specification, the aryl group may be monocyclic or polycyclic.

When the aryl group is a monocyclic aryl group, the number of carbon atoms is not particularly limited, but is preferably 6 to 30 carbon atoms. Specifically, the monocyclic aryl group may be a phenyl group, a biphenyl group, or a terphenyl group, but is not limited thereto.

When the aryl group is a polycyclic aryl group, the number of carbon atoms is not particularly limited. It is preferable that it has 10 to 30 carbon atoms. Specifically, the polycyclic aryl group may be a naphthyl group, anthracenyl group, phenanthryl group, pyrenyl group, perylenyl group, chrysenyl group, fluorenyl group, and the like, but is not limited thereto.

In the present specification, the fluorenyl group may be substituted, and adjacent substituents may combine with each other to form a ring.

,

,

및

등이 될 수 있다. 다만, 이에 한정되는 것은 아니다.When the fluorenyl group is substituted,

,

,

And

It can be back. However, it is not limited thereto.

In the present specification, the aryl group in the aryloxy group, the arylthioxy group, the aryl sulfoxy group, the N-aryl alkylamine group, the N-aryl heteroarylamine group, and the arylphosphine group are the same as those of the above-described aryl group. Specifically, aryloxy groups include phenoxy group, p-toryloxy group, m-toryloxy group, 3,5-dimethyl-phenoxy group, 2,4,6-trimethylphenoxy group, p-tert-butylphenoxy group, 3- Biphenyloxy group, 4-biphenyloxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4-methyl-1-naphthyloxy group, 5-methyl-2-naphthyloxy group, 1-anthryloxy group , 2-anthryloxy group, 9-anthryloxy group, 1-phenanthryloxy group, 3-phenanthryloxy group, 9-phenanthryloxy group, and the like, and arylthioxy groups are phenylthioxy groups, 2- Methylphenyl thioxy group, 4-tert-butylphenyl thioxy group, and the like, but aryl sulfoxy group includes benzene sulfoxy group, p-toluene sulfoxy group, but is not limited thereto.

In the present specification, examples of the arylamine group include a substituted or unsubstituted monoarylamine group, a substituted or unsubstituted diarylamine group, or a substituted or unsubstituted triarylamine group. The aryl group in the arylamine group may be a monocyclic aryl group or a polycyclic aryl group. The arylamine group containing two or more aryl groups may include a monocyclic aryl group, a polycyclic aryl group, or a monocyclic aryl group and a polycyclic aryl group at the same time. For example, the aryl group in the arylamine group can be selected from the examples of the aryl group described above.

In the present specification, the heteroaryl group includes one or more non-carbon atoms, heteroatoms, and specifically, the heteroatoms may include one or more atoms selected from the group consisting of O, N, Se, and S. The number of carbon atoms is not particularly limited, but preferably 2 to 30 carbon atoms, and the heteroaryl group may be monocyclic or polycyclic. Examples of the heterocyclic group include thiophene group, furanyl group, pyrrol group, imidazolyl group, thiazolyl group, oxazolyl group, oxadiazolyl group, pyridyl group, bipyridyl group, pyrimidyl group, triazinyl group, tria Jolyl group, acridil group, pyridazinyl group, pyrazinyl group, quinolinyl group, quinazolinyl group, quinoxalinyl group, phthalazinyl group, pyridopyrimidyl group, pyridopyrazinyl group, pyrazino pyrazinyl group , Isoquinolinyl group, indolyl group, carbazolyl group, benzoxazolyl group, benzimidazolyl group, benzothiazolyl group, benzocarbazolyl group, benzothiophene group, dibenzothiophene group, benzofuranyl group, pe Nanthrolyl group (phenanthroline), thiazolyl group, isooxazolyl group, oxadiazolyl group, thiadiazolyl group, benzothiazolyl group, phenothiazinyl group and dibenzofuranyl group, but is not limited thereto.

In the present specification, examples of the heteroarylamine group include a substituted or unsubstituted monoheteroarylamine group, a substituted or unsubstituted diheteroarylamine group, or a substituted or unsubstituted triheteroarylamine group. The heteroarylamine group containing two or more heteroaryl groups may include a monocyclic heteroaryl group, a polycyclic heteroaryl group, or a monocyclic heteroaryl group and a polycyclic heteroaryl group simultaneously. For example, the heteroaryl group in the heteroarylamine group may be selected from the examples of the heteroaryl group described above.

In the present specification, examples of the heteroaryl group in the N-aryl heteroarylamine group and the N-alkylheteroarylamine group are the same as those of the aforementioned heteroaryl group.

In the present specification, the heterocyclic group may be monocyclic or polycyclic, aromatic, aliphatic or aromatic and aliphatic condensed ring, and may be selected from examples of the heteroaryl group.

In one embodiment of the present specification, [A1] includes one or a combination of two or more of the following structures.

In the above structure, X10 to X16 are the same as or different from each other, and each independently CRR ', NR, O, SiRR', PR, S, GeRR ', Se or Te,

a is an integer of 1 or 2,

When a is 2, structures in parentheses are the same or different from each other,

x is an integer from 1 to 5,

When x is 2, the structures in parentheses are the same or different from each other,

R10 to R12, R and R 'are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Nitrile group; Nitro group; Hydroxy group; Carbonyl group; Ester groups; Imide group; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthioxy group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkyl sulfoxy group; A substituted or unsubstituted aryl sulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present specification, [A1] is any one of the following structures.

In the above structure, the definitions of X10 to X16, R10 to R12, a and x are the same as described above,

X10 ', X13', X14 ', X20 and X20' are the same or different from each other, and are each independently CRR ', NR, O, SiRR', PR, S, GeRR ', Se or Te,

a ', b and b' are each an integer of 1 or 2,

When a ', b and b' are 2 or more, structures in parentheses are the same or different from each other,

x ', y and y' are each an integer from 1 to 5,

When x ', y and y' are 2 or more, the structures in parentheses are the same or different from each other,

R10 ', R20 and R20' are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Nitrile group; Nitro group; Hydroxy group; Carbonyl group; Ester groups; Imide group; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthioxy group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkyl sulfoxy group; A substituted or unsubstituted aryl sulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

이고, X11 및 X12는 전술한 바와 같다.In one embodiment of the present specification, [A1] is

And X11 and X12 are as described above.

이고, X10 내지 X12, X10', R10, R10', x, x', a 및 a'은 전술한 바와 같다.In one embodiment of the present specification, [A1] is

And X10 to X12, X10 ', R10, R10', x, x ', a and a' are as described above.

이고, X10, X10', X13, X14, R10, R10', x, x', a 및 a'는 전술한 바와 같다.In one embodiment of the present specification, [A1] is

And X10, X10 ', X13, X14, R10, R10', x, x ', a and a' are as described above.

이고, X10, X10' X13 내지 X16, X13', X14', X20, X20', R10 내지 R12, R10', R20, R20' x, x', y, y', a, a', b 및 b'은 전술한 바와 같다. In one embodiment of the present specification, [A1] is

, X10, X10 'X13 to X16, X13', X14 ', X20, X20', R10 to R12, R10 ', R20, R20' x, x ', y, y', a, a ', b and b 'Is as described above.

In one embodiment of the present specification, Chemical Formula 1 may be represented by the following Chemical Formulas 1-1 to 1-4.

[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In the above Chemical Formulas 1-1 to 1-4,

The definitions of X1 to X4, X10 to X16, R1 to R4, R10 to R12, a, x and n are the same as described above,

X10 ', X13', X14 ', X20 and X20' are the same or different from each other, and are each independently CRR ', NR, O, SiRR', PR, S, GeRR ', Se or Te,

a ', b and b' are each an integer of 1 or 2,

When a ', b and b' are 2 or more, structures in parentheses are the same or different from each other,

x ', y and y' are each an integer from 1 to 5,

When x ', y and y' are 2 or more, the structures in parentheses are the same or different from each other,

R10 ', R20 and R20' are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Nitrile group; Nitro group; Hydroxy group; Carbonyl group; Ester groups; Imide group; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthioxy group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkyl sulfoxy group; A substituted or unsubstituted aryl sulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present specification, X1 to X4 are the same as or different from each other, and each independently, CRR ', NR, O, SiRR', PR, S, GeRR ', Se, or Te.

In one embodiment of the present specification, X1 to X4 are the same as or different from each other, and each independently, CRR ', NR, or S.

In one embodiment of the present specification, X1 to X4 are S.

X10 to X16 are the same as or different from each other, and are each independently CRR ', NR, O, SiRR', PR, S, GeRR ', Se or Te.

In one embodiment of the present specification, X10 to X16 are the same as or different from each other, and each independently CRR ', NR, or S.

In one embodiment of the present specification, X10 is S.

In one embodiment of the present specification, X11 is S.

In one embodiment of the present specification, X12 is NR and R is a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, X13 is NR and R is a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, X14 is NR, and R is a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, X15 is S.

In one embodiment of the present specification, X16 is S.

In one embodiment of the present specification, R1 to R4 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Nitrile group; Nitro group; Hydroxy group; Carbonyl group; Ester groups; Imide group; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthioxy group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkyl sulfoxy group; A substituted or unsubstituted aryl sulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present specification, R1 to R4 are the same as or different from each other, and each independently hydrogen; Ester groups; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted amine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present specification, R1 to R4 are the same as or different from each other, and each independently hydrogen; A substituted or unsubstituted alkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present specification, R1 to R4 are the same as or different from each other, and each independently an substituted or unsubstituted aryl group.

In one embodiment of the present specification, R1 to R4 are the same as or different from each other, and each independently a substituted or unsubstituted phenyl group.

In one embodiment of the present specification, R1 to R4 are the same as or different from each other, and are each independently a phenyl group substituted with an alkyl group.

In one embodiment of the present specification, R10 to R12 are the same as or different from each other, and each independently hydrogen; heavy hydrogen; Halogen group; Nitrile group; Nitro group; Hydroxy group; Carbonyl group; Ester groups; Imide group; Amide group; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted aryloxy group; A substituted or unsubstituted alkylthioxy group; A substituted or unsubstituted arylthio group; A substituted or unsubstituted alkyl sulfoxy group; A substituted or unsubstituted aryl sulfoxy group; A substituted or unsubstituted alkenyl group; A substituted or unsubstituted silyl group; A substituted or unsubstituted boron group; A substituted or unsubstituted amine group; A substituted or unsubstituted arylphosphine group; A substituted or unsubstituted phosphine oxide group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present specification, R10 to R12 are the same as or different from each other, and each independently hydrogen; Ester groups; A substituted or unsubstituted alkyl group; A substituted or unsubstituted cycloalkyl group; A substituted or unsubstituted alkoxy group; A substituted or unsubstituted amine group; A substituted or unsubstituted aryl group; Or a substituted or unsubstituted heterocyclic group.

In one embodiment of the present specification, R10 to R12 are the same as or different from each other, and each independently hydrogen; Or a substituted or unsubstituted alkyl group.

In one embodiment of the present specification, R10 is hydrogen.

In one embodiment of the present specification, R11 and R12 are the same as or different from each other, and each independently an substituted or unsubstituted alkyl group.

In one embodiment of the present specification, R11 and R12 are the same as or different from each other, and each independently an alkyl group.

In one embodiment of the present specification, x is 1.

In one embodiment of the present specification, x is 2.

In one embodiment of the present specification, x is 3.

In one embodiment of the present specification, x is 4.

In one embodiment of the present specification, x is 5.

In one embodiment of the present specification, Chemical Formula 1 is represented by any one of the following Compounds 1 to 4.

[Compound 1]

[Compound 2]

 [Compound 3]

[Compound 4]

In the compounds 1 to 4, n is an integer of 1 to 10,000.

In one embodiment of the present specification, the number average molecular weight of the compound represented by Chemical Formula 1 is preferably 1,000,000 g / mol or less.

In one embodiment of the present specification, the number average molecular weight of the compound of the compound represented by Chemical Formula 1 is 5,000 g / mol to 1,000,000 g / mol. More specifically, the number average molecular weight of the compound represented by Formula 1 is 5,000 g / mol to 500,000 g / mol. In this case, by having a solubility of more than a certain level, it is advantageous for the application of the solution coating method.

One embodiment of the present specification is an organic transistor including a gate electrode, a source electrode, a drain electrode, an insulating layer, and an organic semiconductor layer, wherein the organic semiconductor layer provides an organic transistor including a compound containing the unit of Formula 1 do.

One embodiment of the present specification is a gas sensor including a gate electrode, a source electrode, a drain electrode, an insulating layer, and an organic semiconductor layer, wherein the organic semiconductor layer provides a gas sensor including a compound containing the unit of Formula 1 do.

In one embodiment of the present specification, the gas sensor may be based on an organic transistor. Specifically, the gas sensor may be used by exposing the organic transistor to a specific gas, so that the organic semiconductor layer of the organic transistor changes electrical characteristics through contact with the gaseous material.

In one embodiment of the present specification, the gas sensor is ammonia (NH ₃ ), ethylene (C ₂ H ₄ ), formaldehyde (HCHO), hydrofluoric acid (HF), nitrogen oxides (NOx), sulfur oxides (SOx) or Ethanol is detected.

In the present specification, “sensing” means that the density of conductive electrons on the surface of the organic semiconductor layer is changed by the interaction of the surface of the organic semiconductor layer and the gas of the gas sensor.

In one embodiment of the present specification, the gas sensor may have a sensitivity to ammonia (NH ₃ ) of 1 ppm or more compared to air. Specifically, the gas sensor may have a sensitivity to ammonia (NH ₃ ) of 1 ppm or more and 90% or less compared to air.

In the present specification, “sensitivity is 1 ppm or more compared to air” may mean that it is detectable when 1 ppm or more is present in the air. For example, “sensitivity to ammonia is 1 ppm or more compared to air” may mean that even if only 1 ppm of ammonia is present in the air, it can be sensed.

In the present specification, 1% is 10,000 ppm.

In one embodiment of the present specification, the gas sensor may have a sensitivity to ethylene (C ₂ H ₄ ) of 1 ppm or more compared to air. Specifically, the gas sensor may have a sensitivity to ethylene (C ₂ H ₄ ) of 1 ppm or more and 90% or less compared to air.

In one embodiment of the present specification, the gas sensor may have a sensitivity to ethanol of greater than 0% and less than 20% of air.

In one embodiment of the present specification, the gas sensor may have a sensitivity to formaldehyde (HCHO) of 1 ppm or more compared to air. Specifically, the gas sensor may have a sensitivity to formaldehyde (HCHO) of 1 ppm or more and 90% or less compared to air.

In one embodiment of the present specification, the gas sensor may have a sensitivity to hydrofluoric acid (HF) of 1 ppm or more compared to air. Specifically, the gas sensor may have a sensitivity to hydrofluoric acid (HF) of 1 ppm or more and 90% or less of air.

In one embodiment of the present specification, the gas sensor may have a sensitivity to nitrogen oxide (NOx) of 1 ppm or more compared to air. Specifically, in the gas sensor, the gas sensor may have a sensitivity to nitrogen oxide (NOx) of 1 ppm or more and 90% or less compared to air.

In one embodiment of the present specification, the gas sensor may have a sensitivity to sulfur oxide (SOx) of 1 ppm or more compared to air. Specifically, in the gas sensor, the gas sensor may have a sensitivity to sulfur oxide (SOx) of 1 ppm or more and 90% or less compared to air.

In the present specification, the organic transistor may be a top contact structure among bottom gate structures. Specifically, the gate electrode 20 and the insulating layer 30 are sequentially formed on the substrate 10, and then the organic semiconductor layer 60 is formed on the insulating layer 30, and finally, the organic semiconductor layer ( A source electrode 40 and a drain electrode 50 may be formed on 60. 1 shows the structure of the organic transistor according to this.

In the present specification, the organic transistor may be a bottom contact structure of a bottom gate structure. Specifically, the gate electrode 20 and the insulating layer 30 are sequentially formed on the substrate 10, and then the source electrode 40 and the drain electrode 50 are formed on the insulating layer 30, and finally The organic semiconductor layer 60 may be formed on the source electrode 40 and the drain electrode 50. 2 and 3 show the organic transistor structure accordingly.

In the present specification, the organic transistor may have a top gate structure. Specifically, the source electrode 40 and the drain electrode 50 are first formed on the substrate 10, and then the organic semiconductor layer 60, the insulating layer 30 and the gate electrode 20 may be sequentially formed. have. Figure 4 shows the structure of the organic transistor according to this.

In the present specification, the substrate 10 may be formed of a transparent substrate such as glass, a silicon substrate, or plastic. The plastic substrate material includes polyethersulfone (PES), polyacrylate (PAR), polyetherimide (PET), polyethyelenen naphthalate (PEN), polyethylene terephthalide (PET, polyethyeleneterephthalate (PPS), polyphenylene sulfide (PPS), polyallylate, polyimide, polycarbonate (PC), cellulose triacetate (TAC), cellulose acetate propionate (CAP) ). Preferably, a transparent substrate such as glass capable of UV transmission is used.

In the present specification, the gate electrode 20 may be in the form of a pattern, but is not limited thereto. The gate electrode 20 includes gold (Au), nickel (Ni), copper (Cu), silver (Ag), aluminum (Al), aluminum alloy (Al-alloy), molybdenum (Mo), and molybdenum alloy (Moalloy) It can be formed by any one selected from.

In the present specification, the gate electrode 20 is formed by using a method selected from photolithography, offset printing, silkscreen printing, inkjet printing, thermal evaporation, and shadow mask. It may, but is not limited to this.

The gate electrode 20 may have a thickness of 10 nm to 300 nm, and preferably 10 nm to 50 nm.

In the present specification, the insulating layer 30 is composed of a single film or a multilayer film of an organic insulating film or an inorganic insulating film, or an organic-inorganic hybrid film. As the inorganic insulating film, any one or a plurality of silicon oxide films, silicon nitride films, Al ₂ O ₃ , Ta ₂ O ₅ , BST, and PZT may be used. Examples of the organic insulating layer include CYTOP ^TM , polymethylmethacrylate (PMMA, polymethylmethacrylate), polystyrene (PS, polystyrene), phenolic polymer, acrylic polymer, imide polymer such as polyimide, aryl ether polymer, amide polymer, Any one or a plurality of fluorine-based polymers, p-xylene-based polymers, vinyl alcohol-based polymers, and parylene may be used, but is not limited thereto.

In the present specification, the insulating layer 30 may be formed through a solution process, and may be generally applied in a large area through spin coating, bar coating, slit die coating, doctor blade, or the like. Preferably, an insulating layer may be formed through spin coating, but is not limited thereto. When the insulating layer is formed, heat treatment may be performed at 100 ° C to 150 ° C for 30 minutes or more to completely evaporate the used solvent.

In the present specification, the source electrode 40 and the drain electrode 50 may be made of a conductive material, for example, carbon, aluminum, vanadium, chromium, copper, zinc, silver, gold, magnesium, calcium, sodium, potassium , Titanium, indium, yttrium, lithium, gadolinium, tin, lead, neodymium, platinum, nickel, similar metals and alloys thereof; p- or n-doped silicon; Zinc oxide, indium oxide, indium tin oxide (ITO), indium zinc oxide, simple tin oxide and tin oxide indium-based complex compounds; A mixture of an oxide and a metal such as ZnO: Al, SnO ₂ : Sb; Poly (3-methylthiophene), poly [3,4- (ethylene-1,2-dioxy) thiophene] (poly [3,4- (ethylene-1,2- dioxy) thiophene]), polypyrrole, and polyaniline, and conductive polymers such as polyaniline, but is not limited thereto.

In the present specification, the organic semiconductor layer 60 may be formed through a solution process. In this case, the organic semiconductor layer 60 may be applied in a large area through spin coating, bar coating, slit die coating, doctor blade, inkjet coating, etc., but is not limited thereto.

In the present specification, when the source electrode 40 and the drain electrode 50 are formed on the organic semiconductor layer 60, the source electrode 40 and the drain electrode 50 are subjected to a photo-etching process or a shadow mask process. It can be formed using, but is not limited to, it can be formed by other methods known in the art. At this time, the distance between the source electrode 40 and the drain electrode 50 has a channel length of 2 µm to several hundred µm, and the channel width is about 10 to 1000 times the channel length. The source electrode 40 and the drain electrode 50 are usually made of gold and nickel, but other electrodes such as silver, copper, and molybdenum may be used.

Hereinafter, examples will be described in detail to specifically describe the present specification. However, the embodiments according to the present specification may be modified in various other forms, and the scope of the present specification is not interpreted to be limited to the embodiments described below. The embodiments of the present specification are provided to more fully describe the present specification to those skilled in the art.

Manufacturing example  1. Preparation of Compound 1

To the flask, 20 mL of chlorobenzene, compound 1-a (0.7 g, 0.5204 mmol) and compound A (0.2202 g, 0.5204 mmol) were added and stirred. At this time, compound 1-a is Yun-Xiang Xu et al, Adv. Mater. It was prepared and added in the same manner as in the synthesis method described in 2012, 24, 6356-6361. Then, 10 mg of tris (dibenzylideneacetone) dipalladium (0), (Pd ₂ (dba) ₃ )) and tri- (o-tolyl) phosphine (tri- (o -tolyl) phosphine) 28mg was added and stirred at 140 ° C for 48 hours. Subsequently, 0.5 mL of tri-butyltin-thiophene was added and stirred for 4 hours, followed by bromo-thiophene and stirred for 24 hours. After the mixture was cooled to room temperature, poured into methanol, the solid was filtered, soxhlet extraction was performed with acetone, hexane, and methylene chloride, and then the methylene chloride portion was precipitated again in methanol to filter the solid. (Yield: 60%, number average molecular weight: 39,500 g / mol, PDI: 1.36)

5 is a diagram showing an NMR spectrum of compound 1-a.

6 is a diagram showing an MS spectrum of Compound 1-a.

7 is a diagram showing the UV spectrum of Compound 1.

8 is a diagram showing the CV spectrum of Compound 1.

Manufacturing example  2. Preparation of compound 2

To the flask, 16 mL of chlorobenzene, compound 1-a (0.5 g, 0.3717 mmol) and compound B (0.2391 g, 0.3717 mmol) were added and stirred. Then, 10 mg of tris (dibenzylideneacetone) dipalladium (0), (Pd ₂ (dba) ₃ )) and tri- (o-tolyl) phosphine (tri- (o -tolyl) phosphine) 28 mg was added and stirred at 140 ° C for 48 hours. Subsequently, 0.5 mL of tri-butyltin-thiophene was added and stirred for 4 hours, then bromo-thiophene was added and stirred for 24 hours. After the mixture was cooled to room temperature, poured into methanol, the solid was filtered, soxhlet extraction was performed on acetone, hexane, methylene chloride, chloroform and chlorobenzene, and then the chlorobenzene portion was precipitated again in methanol to filter the solid. (Yield: 57%, number average molecular weight: 29,000 g / mol, PDI: 1.12)

Manufacturing example  3. Preparation of compound 3

To the flask was added 18 mL of chlorobenzene, compound 1-a (0.45 g, 0.3345 mmol) and compound C (0.3034 g, 0.3345 mmol) and stirred. Then, 10 mg of tris (dibenzylideneacetone) dipalladium (0), (Pd ₂ (dba) ₃ )) and tri- (o-tolyl) phosphine (tri- (o -tolyl) phosphine) 28mg was added and stirred at 140 ° C for 48 hours. Subsequently, 0.5 mL of tri-butyltin-thiophene was added and stirred for 4 hours, then bromo-thiophene was added and stirred for 24 hours. After the mixture was cooled to room temperature, poured into methanol, the solid was filtered, soxhlet extraction was performed with acetone, hexane, and methylene chloride, and then the methylene chloride portion was precipitated again in methanol to filter the solid. (Yield: 72%, number average molecular weight: 43,200 g / mol, PDI: 1.26)

9 is a view showing the UV spectrum of Compound 3.

In FIG. 9, (a) is UV data in a solution state of Compound 3, and (b) is UV data obtained by measuring Compound 3 in a film state.

10 is a diagram showing the CV spectrum of compound 3.

Manufacturing example  4. Preparation of compound 4

(1) Preparation of compound 4-c

Compound 4-a (13.0 g, 43.3 mmol) and potassium carbonate (K ₂ CO ₃ , 24.0 g) were added to 250 ml of dimethylformamide (DMF), and the mixture was melted by adding temperature to 145 ° C. To this solution, 2-ethylhexyl bromide (2-ethylhexylbromide, 38.6 g, 200 mmol) was added at once using a syringe. Thereafter, the mixture was stirred at 145 ° C for 15 hours or more, cooled to room temperature, poured into 500 ml or more of cold water, stirred, washed several times with water and alcohol, and filtered. After drying it, a compound 4b in the form of a dark purple solid powder was obtained through a silica column (eluent; Hexane: Methylene chloride = 1: 10). (Yield: 87.4%)

11 is a diagram showing an NMR spectrum of compound 4-b.

600 ml of chloroform (chloroform, CF) with compound 4-b (5.0 g, 9.52 mmol) and n-bromosuccinimide (N-bromosuccinimide, NBS, 1.60 g, 9.99 mmol) light at room temperature It was stirred. After confirming the reaction by thin-layer chromatography, a dark purple solid powder compound 4-c was obtained through a silica column (eluent; Hexane: Methylene chloride = 3: 7). (Yield 59.7%)

12 is a diagram showing an NMR spectrum of compound 4-c.

13 is a diagram showing an MS spectrum of compound 4-c.

(2) Preparation of compound 4-h

After dissolving compound 4-d (6.0 g, 31.2 mmol) in 50 ml chloroform (CF): 50 ml trifluoro acetic acid (TFA), sodium perboratemonohydrate, NaBO ₃ H ₂ O, 7.39 g, 72.8mmol) and stirred at room temperature for 1 hour. It was poured into water and extracted with chloroform. The solvent was removed under reduced pressure to obtain a white solid compound 4-e as a silica column (eluent: Hx / MC = 1/1). (Yield 35%)

Compound 4-e (2.4 g, 11.4 mmol) was dissolved in 60 ml of tetrahydrofuran (THF) under nitrogen conditions. 25.4 ml of 3,7-dimethyloctylmagnesium bromide (BrMgC ₁₀ H ₂₁ , 1M solution in diethyl ether) was slowly injected at -25 ° C. The mixture was stirred for 10 hours while raising the temperature to room temperature, and the reaction was stopped while 50 ml of water was added. Extracted with ethyl acetate (EA) and the residual water was removed using magnesium sulfate (MgSO ₄ ). The liquid yellow compound 4f was obtained through a silica column. (Yield 93%)

Compound 4-f (4.5 g, 12.0 mmol) was dissolved in 100 ml toluene under nitrogen conditions. 300 mg sodium p-toluenesulfonic acid monohydrate (p-TSA) was added and reacted at 120 ° C. for 3 hours. The reaction solution was added to water and toluene was added for extraction. It was dried over magnesium sulfate (MgSO ₄ ) and then the solvent was removed under reduced pressure. Silica column (eluent: Hx) gave 4-g of the compound in the form of a yellow liquid. (Yield: 95%)

Compound 4-g (0.58 g, 1.2 mmol) was dissolved in 20 ml tetrahydrofuran (THF) under nitrogen conditions. After slowly adding n-butyllithium (1.7ml, 1.6M solution in hexane) at 78 ° C, the mixture was stirred for 30 minutes and then stirred at room temperature for 2 hours. At 78 ° C., 0.92 ml of tributyltin chloride solution was added. After heating it, the mixture was stirred for 10 hours at room temperature, poured into water, and extracted with hexane. The solvent was removed under reduced pressure to obtain compound 4-h in the form of a brown liquid with a silica column (eluent: Hx, 10% triethylamine). (Yield: 97%)

14 is a diagram showing an NMR spectrum of compound 4-h.

(3) Preparation of compound 4-i

300 ml of tetrahydrofuran (THF) was added compound 4-h (2.0 g, 1.8996 mmol), compound 4-c and tetrakis (triphenylphosphine) palladium (0) (Pd (PPh ₃ ) ₄ , 0.13 g). After adding and dissolving, the mixture was reacted at 100 ° C for 20 hours. Then, this solution was poured into water, extracted twice with methylenechloride, washed twice with water, and residual water was removed with magnesium sulfate. The remaining solution was removed under reduced pressure, and a brown solid compound 4-i was obtained through a silica column (eluent: hexane / MC = 10: 2). (Yield: 78%)

15 is a diagram showing an NMR spectrum of compound 4-i.

16 is a diagram showing the HPLC spectrum of compound 4-i.

(4) Preparation of compound 4-j

After dissolving compound 4-i (0.720 g, 0.4736 mmol) in 100 ml of chloroform (CF), N-bromosuccinimide (NBS) (0.17 g, 0.9613 mmol) was added and stirred. Thereafter, the mixture was extracted with distilled water and ethyl acetate (EA), and the organic layer was removed with anhydrous sodium sulfate, and then the solid impurities were removed by filtration under reduced pressure. Separated by column chromatography (eluent: MC / Hx = 10: 5) to obtain a fine powder compound 4-j. (Yield 50.4%)

17 is a diagram showing an MS spectrum of compound 4-j.

18 is a diagram showing the UV spectrum of compound 4-j.

19 is a diagram showing the CV spectrum of compound 4-j.

(5) Preparation of compound 4

To the flask, 10 mL of chlorobenzene, compound 1-a (0.1442 g, 0.1073 mmol) and compound 4-j (180 mg, 0.1073 mmol) were added and stirred. Thereafter, 5 mg of tris (dibenzylideneacetone) dipalladium (0), (Pd ₂ (dba) ₃ )) and tri- (o-tolyl) phosphine (tri- (o -tolyl) phosphine) 12 mg was added and stirred at 140 ° C for 48 hours. Then 4-bromo-trifluoromethylbenzene was added and stirred for 24 hours. After the mixture was cooled to room temperature, poured into methanol, the solid was filtered, soxhlet extraction was performed with acetone, hexane, and methylene chloride, and then the methylene chloride portion was precipitated again in methanol to filter the solid. (Yield: 71%, number average molecular weight: 28,400 g / mol, PDI: 1.46)

Example  One.

Diluted water (DI water), acetone (acetone), isopropyl alcohol (IPA) in the order of 10 minutes each washed on a Si / SiO ₂ wafer substrate by dissolving compound 1 in 1,2-dichlorobenzene and spin-coating 30 ° C at 200 ℃ Heat treated for a minute. Thereafter, Au was formed as a source electrode and a drain electrode to a thickness of 13 nm, respectively, using thermal lamination to prepare an organic transistor.

20 is a diagram showing the performance measurement results of the organic transistor prepared in Example 1.

Example  2.

An organic transistor was manufactured in the same manner as in Example 1, except that Compound 2 was used instead of Compound 1 in the preparation method of Example 1.

21 is a diagram showing the performance measurement results of the organic transistor prepared in Example 2.

Example  3.

An organic transistor was prepared in the same manner as in Example 1, except that Compound 3 was used instead of Compound 1 in the preparation method of Example 1.

22 is a diagram showing the performance measurement results of the organic transistor prepared in Example 3.

Example  4.

An organic transistor was prepared in the same manner as in Example 1, except that Compound 4 was used instead of Compound 1 in the preparation method of Example 1.

23 is a diagram showing the performance measurement results of the organic transistor prepared in Example 4.

Table 1 shows the properties of the organic transistors according to Examples 1 to 4.

band gap
(eV) Average hole mobility
(cm ² / Vs) Threshold voltage
(V) On / Off Example 1 1.90 0.03 -30 4x10 ⁶ Example 2 1.88 0.008 -31 1x10 ⁶ Example 3 1.45 0.02 -11 3x10 ³ Example 4 1.52 0.004 -14 1x10 ⁴

Example  5.

Distilled water (DI water), acetone (acetone), and isopropyl alcohol (IPA) were used for 10 minutes each, followed by photolithography on a glass substrate, and 13nm Au / 3nm Ni as a source electrode and a drain electrode through a thermal deposition process. Formed. The length of the channel between the formed source electrode and the drain electrode was 10 μm, and the width was 1 mm. The substrate on which the electrodes were formed was washed with di water, acetone, and isopropyl alcohol (IPA) for 10 minutes each, and then dried. Compound 1 dissolved in 1,2-dichlorobenzene solvent was spin-coated on the dried substrate and dried at a temperature of 200 ° C. After that, polymethyl methacrylate (PMMA) was dissolved in methoxyethylene at a concentration of 80 mg / mL as an insulating layer, spin-coated on the compound 1 film, and dried at 80 ° C for 2 hours. Thereafter, aluminum was thermally deposited to a thickness of 50 nm as a gate electrode to prepare an organic transistor.

Example  6.

An organic transistor was prepared in the same manner as in Example 5, except that the compound 1 dissolved in the 1,2-dichlorobenzene solvent was spin-coated and heat-treated at 250 ° C in the preparation method of Example 5.

Example  7.

An organic transistor was prepared in the same manner as in Example 5, except that the compound 1 dissolved in the 1,2-dichlorobenzene solvent was spin-coated in Example 5, and then heat-treated at 300 ° C.

Example  8.

Distilled water (DI water), acetone (acetone), and isopropyl alcohol (IPA) were used for 10 minutes each, followed by photolithography on a glass substrate, and 13nm Au / 3nm Ni as a source electrode and a drain electrode through a thermal deposition process. Formed. The length of the channel between the formed source electrode and the drain electrode was 10 μm, and the width was 1 mm. The substrate on which the electrodes were formed was washed with di water, acetone, and isopropyl alcohol (IPA) for 10 minutes each, and then dried. Compound 2 dissolved in 1,2-dichlorobenzene solvent was spin-coated on the dried substrate and dried at a temperature of 200 ° C. After that, polymethyl methacrylate (PMMA) was dissolved in methoxyethylene at a concentration of 80 mg / mL as an insulating layer, spin-coated on the compound 2 film, and dried at 80 ° C for 2 hours. Thereafter, aluminum was thermally deposited to a thickness of 50 nm as a gate electrode to prepare an organic transistor.

Example  9.

An organic transistor was prepared in the same manner as in Example 8, except that the compound 2 dissolved in the 1,2-dichlorobenzene solvent was spin-coated after heat treatment at 250 ° C in the preparation method of Example 8.

Example  10.

An organic transistor was prepared in the same manner as in Example 8, except that the compound 2 dissolved in the 1,2-dichlorobenzene solvent was spin-coated in Example 8, and then heat-treated at 300 ° C.

Example  11.

Distilled water (DI water), acetone (acetone), and isopropyl alcohol (IPA) were used for 10 minutes each, followed by photolithography on a glass substrate, and 13nm Au / 3nm Ni as a source electrode and a drain electrode through a thermal deposition process. Formed. The length of the channel between the formed source electrode and the drain electrode was 10 μm, and the width was 1 mm. The substrate on which the electrodes were formed was washed with di water, acetone, and isopropyl alcohol (IPA) for 10 minutes each, and then dried. Compound 3 dissolved in 1,2-dichlorobenzene solvent was spin-coated on the dried substrate and dried at a temperature of 200 ° C. After that, polymethyl methacrylate (PMMA) was dissolved in methoxyethylene at a concentration of 80 mg / mL as an insulating layer, spin-coated on the compound 3 film, and dried at 80 ° C for 2 hours. Thereafter, aluminum was thermally deposited to a thickness of 50 nm as a gate electrode to prepare an organic transistor.

Example  12.

In the production method of Example 11, an organic transistor was prepared in the same manner as in Example 11, except that the compound 3 dissolved in the 1,2-dichlorobenzene solvent was spin-coated and then heat-treated at 250 ° C.

Example  13.

In the production method of Example 11, an organic transistor was prepared in the same manner as in Example 11, except that the compound 3 dissolved in the 1,2-dichlorobenzene solvent was spin-coated and then heat-treated at 300 ° C.

Example  14.

Distilled water (DI water), acetone (acetone), and isopropyl alcohol (IPA) were used for 10 minutes each, followed by photolithography using a photolithography to 13nm Au / 3nm Ni as a source electrode and a drain electrode through a thermal deposition process. Formed. The length of the channel between the formed source electrode and the drain electrode was 10 μm, and the width was 1 mm. The substrate on which the electrodes were formed was washed with di water, acetone, and isopropyl alcohol (IPA) for 10 minutes each, and then dried. Compound 4 dissolved in 1,2-dichlorobenzene solvent was spin-coated on the dried substrate and dried at a temperature of 200 ° C. After that, polymethyl methacrylate (PMMA) was dissolved in methoxyethylene at a concentration of 80 mg / mL as an insulating layer, spin-coated on the compound 4 film, and dried at 80 ° C. for 2 hours. Thereafter, aluminum was thermally deposited to a thickness of 50 nm as a gate electrode to prepare an organic transistor.

Example  15.

An organic transistor was prepared in the same manner as in Example 14, except that the compound 4 dissolved in the 1,2-dichlorobenzene solvent was spin-coated and then heat-treated at 250 ° C.

Example  16.

Among the preparation methods of Example 14, an organic transistor was prepared in the same manner as in Example 14, except that the compound 4 dissolved in the 1,2-dichlorobenzene solvent was spin coated and then heat-treated at 300 ° C.

Table 2 shows the properties of the organic transistors prepared in Examples 5 to 16.

compound Heat treatment temperature band gap
(eV) Average hole mobility
(cm ² / Vs) threshold voltage
(V) On / Off Example 5 Compound 1 200 ℃ 1.9 0.03 -30 4x10 ⁵ Example 6 Compound 1 250 ℃ 0.04 -34 1x10 ⁴ Example 7 Compound 1 300 ℃ 0.08 -41 3x10 ⁵ Example 8 Compound 2 200 ℃ 1.88 0.008 -31 1x10 ⁵ Example 9 Compound 2 250 ℃ 0.01 -18 1x10 ⁴ Example 10 Compound 2 300 ℃ 0.005 -15 3x10 ⁵ Example 11 Compound 3 200 ℃ 1.44 0.02 -11 3x10 ³ Example 12 Compound 3 250 ℃ 0.03 -11 2x10 ³ Example 13 Compound 3 300 ℃ 0.03 -10 1x10 ³ Example 14 Compound 4 200 ℃ 1.52 0.001 -37 4x10 ⁵ Example 15 Compound 4 250 ℃ 0.004 -14 2x10 ³ Example 16 Compound 4 300 ℃ 0.004 -28 2x10 ²

In Tables 1 and 2, the higher the on / off value, the better the organic transistor is driven without malfunction, and the lower the threshold voltage, the lower the driving voltage.

It can be seen from Tables 1 and 2 that other compounds in one embodiment of the present specification can be used as the charge transfer layer of the organic transistor.

Example  17.

A 50 nm aluminum gate electrode was deposited through thermal evaporation on a flexible polyethylene naphthalate (PEN) substrate washed with distilled water (DI water), acetone, and isopropyl alcohol (IPA) for 10 minutes each. Thereafter, the polyimide dissolved in cyclohexanone at 80 mg / ml as an insulating layer was spin-coated, dried at 90 ° C. for 2 minutes, crosslinked under 365 nm UV for 10 minutes, and then heat treated at 90 ° C. for 10 minutes. Then, the compound 1 was dissolved in 1,2-dichlorobenzene on the insulating layer and spin-coated. Finally, an organic transistor-based gas sensor was manufactured by forming Au as a source electrode and a drain electrode to a thickness of 13 nm using thermal lamination.

24 is a diagram showing the performance measurement results of the gas sensor prepared in Example 17. In FIG. 24, (a) is when the gate voltage is -5V, and (b) is when the gate voltage is -20V.

Example  18.

A gas sensor was manufactured in the same manner as in Example 17, except that Compound 2 was used instead of Compound 1 in the production method of Example 17.

25 is a view showing the performance measurement results of the gas sensor prepared in Example 18. In FIG. 25, (a) is when the gate voltage is -5V, and (b) is when the gate voltage is -20V.

Example  19.

A gas sensor was manufactured in the same manner as in Example 17, except that Compound 3 was used instead of Compound 1 in the production method of Example 17.

26 is a view showing the performance measurement results of the gas sensor prepared in Example 19. In FIG. 26, (a) is when the gate voltage is -5V, and (b) is when the gate voltage is -20V.

27 is a graph showing the gas sensor results according to Examples 17 to 19. Specifically, a graph of a gas sensor including the polymers represented by Chemical Formulas 1 to 3 in an organic semiconductor layer, the gas sensor is exposed to ammonia (NH ₃ ) after 25 minutes in air, and again after 110 minutes to air It is a measure of current change and sensitivity while giving a change that is exposed during. According to FIG. 27, it can be confirmed that when the ammonia gas was injected, the organic transistor current was lowered. Through this, it can be confirmed that the gas sensor manufactured in one embodiment of the present specification is driven by the ammonia gas sensor.

10: substrate
20: gate electrode
30: insulating layer
40: source electrode
50: drain electrode
60: organic semiconductor layer

Claims (12)

It includes a unit represented by any one of the following Formula 1-1 to Formula 1-4,
Terminal group

or

Phosphorus compound:
[Formula 1-1]

[Formula 1-2]

[Formula 1-3]

[Formula 1-4]

In the above Chemical Formulas 1-1 to 1-4,
X1 to X4 are each S,
R1 to R4 are the same as or different from each other, and each independently an aryl group substituted with an alkyl group,
X10 to X16, X10 ', X13', X14 ', X20 and X20' are the same as or different from each other, and each independently is S or NR,
R is an alkyl group,
R10 to R12, R10 ', R20 and R20' are the same as or different from each other, and each independently a hydrogen or an alkyl group,
x, x ', y and y' are each 1,
a, a ', b and b' are each 1 or 2,
n is an integer from 1 to 10,000. delete delete delete The method according to claim 1,
The compound is a compound represented by any one of the following compounds 1 to 4:
[Compound 1]

[Compound 2]

[Compound 3]

[Compound 4]

In the compounds 1 to 4, n is an integer of 1 to 10,000. The method according to claim 1,
The compound has a number average molecular weight of 5,000g / mol to 1,000,000g / mol. An organic transistor comprising a gate electrode, a source electrode, a drain electrode, an insulating layer and an organic semiconductor layer, wherein the organic semiconductor layer comprises a compound according to any one of claims 1, 5 and 6. A gas sensor comprising a gate electrode, a source electrode, a drain electrode, an insulating layer and an organic semiconductor layer, wherein the organic semiconductor layer includes a compound according to any one of claims 1, 5 and 6. The method according to claim 8,
The gas sensor is a gas sensor to detect ammonia (NH ₃ ), ethylene (C ₂ H ₄ ), formaldehyde (HCHO), hydrofluoric acid (HF), nitrogen oxides (NOx), sulfur oxides (SOx) or ethanol. The method according to claim 8,
The gas sensor is a gas sensor having a sensitivity to ammonia (NH ₃ ) of 1 ppm or more compared to air. The method according to claim 8,
The gas sensor is a gas sensor having a sensitivity to ethylene (C ₂ H ₄ ) of 1 ppm or more compared to air. The method according to claim 8,
The gas sensor is a gas sensor in which the sensitivity to ethanol is greater than 0% and less than 20% compared to air.

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