Patent Application
20200006670
The present invention relates to a chiral organic ligand, chiral complex supramolecular body, and an organic electronic device including the same. More particularly, the present invention relates to a chiral organic ligand, chiral complex supramolecular body, and an organic electronic device including the same, wherein a metal is coordinated with a chiral organic ligand to prepare a chiral complex supramolecular body, thereby securing supramolecular chirality, and being applicable as various chirality-based sensors for detecting a chiral element.
Most of amino acids, sugars, enzymes, and the like which are present in nature have chirality, and accordingly, a medicine may be also manufactured in the form of an enantiomer having chirality. One of paired enantiomers is used as a medicine, but the other one may have a potential side effects, and thus, a technique to separate and detect the enantiomers is greatly spotlighted.
The present invention has been made in an effort to provide a chiral complex supramolecular body having supramolecular chirality and a manufacturing method thereof, by preparing an organic ligand having chirality and coordinating the organic ligand with a metal.
In addition, the present invention has been made in an effort to provide an organic electronic device which can detect various elements (light, chemical gas, and the like) with high performance, by manufacturing an organic electronic device including the chiral complex supramolecular body, and a manufacturing method thereof.
An exemplary embodiment of the present invention provides a chiral organic ligand which is any one selected from the group consisting of organic ligands represented by the following Chemical Formula 1 and Chemical Formula 2:
wherein
X1 and X2 are independently of each other
R1, R3, R5, and R7 are independently of one another any one selected from the group consisting of a carboxy group, a hydroxyl group, an amino group, a sulfhydryl group, and a phosphate; and R2, R4, R6, and R8 are independently of one another any one selected from the group consisting of C1 to C5 alkyl groups and C1 to C5 aryl groups.
R1, R3, R5, and R7 may be independently of one another any one selected from the group consisting of a carboxy group, a hydroxyl group, and an amino group; and R2, R4, R6, and R8 may be independently of one another any one selected from the group consisting of C1 to C3 alkyl groups and C1 to C3 aryl groups.
R1, R3, R5, and R7 may be a carboxy group, and R2, R4, R6, and R8 may be a methyl group.
Another embodiment of the present invention provides a chiral complex supramolecular body including: a chiral organic ligand which is any one selected from the group consisting of organic ligands represented by the following Chemical Formula 1 and Chemical Formula 2; and a metal ion coordinated with the organic ligand, wherein the metal ion coordinated with the organic ligand is any one selected from the group consisting of zinc, copper, nickel, cadmium, iron, chromium, cobalt, calcium, magnesium, manganese, silver, and gold:
wherein
X1 and X2 are independently of each other
R1, R3, R5, and R7 are independently of one another any one selected from the group consisting of a carboxy group, a hydroxyl group, an amino group, a sulfhydryl group, and a phosphate; and R2, R4, R6, and R8 are independently of one another any one selected from the group consisting of C1 to C5 alkyl groups and C1 to C5 aryl groups.
A single crystal of the chiral complex supramolecular body may have a ribbon shape.
Another embodiment of the present invention provides an organic electronic device including a substrate; an electrode disposed on the substrate; and an active layer including a chiral complex supramolecular body, disposed on the electrode, wherein the chiral complex supramolecular body includes: a chiral organic ligand which is any one selected from the group consisting of organic ligands represented by the following Chemical Formula 1 and Chemical Formula 2; and a metal ion coordinated with the organic ligand, and the metal ion is any one selected from the group consisting of zinc, copper, nickel, cadmium, iron, chromium, cobalt, calcium, magnesium, manganese, silver, and gold:
wherein
X1 and X2 are independently of each other
R1, R3, R5, and R7 are independently of one another any one selected from the group consisting of a carboxy group, a hydroxyl group, an amino group, a sulfhydryl group, and a phosphate; and R2, R4, R6, and R8 are independently of one another any one selected from the group consisting of C1 to C5 alkyl groups and C1 to C5 aryl groups.
The electrode may include a first electrode and a second electrode, and the active layer may be disposed to cross the first electrode and second electrode.
A surface modified layer disposed between the substrate and the active layer may be further included, the surface modified layer may include a self-assembled monolayer (SAM), and the self-assembled monolayer (SAM) may be formed by surface-treating the substrate with any one selected from the group consisting of n-octadecyltrimethoxysilane, n-octadecyltrichlorosilane, n-octyltrichlorosilane, n-octylphosphate, and n-octadecylphosphate.
The organic electronic device may be one selected from the group consisting of an organic sensor, an organic transistor, an organic light emitting diode, and an organic solar cell.
The organic electronic device may be an organic sensor, and the organic sensor may detect one or more selected from the group consisting of light, chemical gas, and a medicine.
As a concentration of the light, the chemical gas, or the medicine is increased, the organic sensor may have decreased luminescence intensity by photoluminescence (PL).
The luminescence by photoluminescence (PL) may be fluorescence.
The medicine may include naproxen, and as a concentration of the naproxen is increased, luminescence intensity by photoluminescence (PL) may be decreased.
The medicine may include valinol, and as a concentration of the valinol is increased, luminescence intensity by photoluminescence (PL) may be decreased.
The chemical gas may include an amine compound, alcohol, and a polar solvent.
The amine compound may include at least one of hydrazine, trimethylamine (TEA), and phenylethylamine (PEA).
The chiral complex supramolecular body may have the same crystal structure before and after exposure to the chemical gas.
Yet another embodiment of the present invention provides a manufacturing method of an organic electronic device, including: (a) providing a substrate;
(b) forming an electrode on the substrate; and (c) forming an active layer including a chiral complex supramolecular body on the electrode, wherein the chiral complex supramolecular body includes: a chiral organic ligand which is any one selected from the group consisting of organic ligands represented by the following Chemical Formula 1 and Chemical Formula 2; and a metal ion coordinated with the organic ligand, wherein the metal ion is any one selected from the group consisting of zinc, copper, nickel, cadmium, iron, chromium, cobalt, calcium, magnesium, manganese, silver, and gold:
wherein
X1 and X2 are independently of each other
R1, R3, R5, and R7 are independently of one another any one selected from the group consisting of a carboxy group, a hydroxyl group, an amino group, a sulfhydryl group, and a phosphate; and R2, R4, R6, and R8 are independently of one another any one selected from the group consisting of C1 to C5 alkyl groups and C1 to C5 aryl groups.
After step (a), (a′) oxidation-treating one surface of the substrate to manufacture the substrate including a hydroxyl group (—OH) on the one surface may be further included.
After step (a′), (a″) forming a self-assembled monolayer (SAM) on one surface of the substrate may be further included, and the self-assembled monolayer (SAM) may be formed by, after oxidization-treating the one surface, treating the surface with any one selected from the group consisting of n-octadecyltrimethoxysilane, n-octadecyltrichlorosilane, n-octyltrichlorosilane, n-octylphosphate, and n-octadecylphosphate.
By coordinating a chiral organic ligand with a metal to prepare a chiral complex supramolecular body, the chiral organic ligand, the chiral complex supramolecular body, and a manufacturing method thereof according to an exemplary embodiment may secure supramolecular chirality, and minimize misarranged orientation which is disadvantageous in charge transfer, thereby greatly improving photosensitivity and electrical characteristics. In addition, a production process of a device is very simple, and may be easily applied even on a plastic substrate, thereby improving an integrated device and downsizing.
The organic electronic device and a manufacturing method thereof according to an exemplary embodiment may manufacture an organic electronic device including the chiral complex supramolecular body, thereby being applied as various chirality-based sensor devices which may detects various chiral elements (light, chemical gas, and the like) with high performance.
Hereinafter, various exemplary embodiments of the present invention will be described in detail so that a person with ordinary skill in the art to which the present invention pertains can easily carry out the present invention, referring to accompanying drawings. The present invention may be implemented in various different forms, and is not limited to exemplary embodiments described herein.
For clearly describing the present invention, parts unrelated to description are omitted, and the same reference numeral indicates the same or like constituent element throughout the specification.
In addition, since the size and the thickness of each component shown in the drawings are optionally represented for convenience of description, the present invention is not necessarily limited to those shown in the drawing. In the drawings, the thickness is expanded for clearly expressing various layers and regions. Also in the drawing, the thicknesses of some layers and regions are exaggerated for convenience of description.
In addition, when an element such as a layer, film, region or a plate is referred to as being “over” or “on” another element, the element may be “directly on” another element, and also there may be an intervening element between the two elements. In contrast, when an element is referred to as being “directly on” another element, there are no intervening elements present.
In addition, being “over” or “on” a reference element is understood to be “on” or “under” the reference element, but is not understood to be necessarily “on” or “over” in an opposite direction of gravity.
In addition, throughout the specification, a part “comprising” an element is understood to further include the stated element, not to exclude any other element, unless explicitly described to the contrary.
In addition, throughout the specification, referring to “on a plane” means when an object is viewed from above, and referring to “on a section” means when a section of a vertically cut object is viewed from the side. An alkyl group may be a saturated alkyl group having no double bond or triple bond. An alkyl group may be an unsaturated alkyl group having at least one double bond or triple bond.
Whether the alkyl group is saturated or unsaturated, the alkyl group may be branched, linear, or cyclic.
The alkyl group may be a C1 to C30 alkyl group. More specifically, the alkyl group may be a C1 to C20 alkyl group, a C1 to C10 alkyl group, or a C1 to C6 alkyl group. For example, a C1 to C4 alkyl group has 1 to 4 carbon atoms on an alkyl chain, that is, the C1 to C4 alkyl group represents that an alkyl chain is selected from the group consisting of methyl, ethyl, propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, and t-butyl.
Specifically for example, the alkyl group refers to a methyl group, an ethyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, an ethenyl group, a propenyl group, a butenyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, or the like.
Hereinafter, a chiral organic ligand according to an exemplary embodiment will be described, using Chemical Formulae 1, 2, and 3 to 10.
The present invention provides a chiral organic ligand which is any one selected from the group consisting of organic ligands represented by Chemical Formula 1 and Chemical Formula 2:
Chirality is a term indicating asymmetry, meaning that an object is not superposed onto the mirror image thereof. Chemical Formula 1 is a (S) type organic ligand, and Chemical Formula 2 is a (R) type organic ligand. A (S)/(R) nomenclature is a method of classifying enantiomers, and (S) and (R) types are determined, after substituents bonded to a chiral center are prioritized according to certain rules (e.g., Cahn-Ingold-Prelog priority rules). Specifically, when the chiral center is rotated, a substituent having a lowest priority is positioned farthest from a viewer to be hidden by the chiral center. Thereafter, when the priority of remaining three substituents is decreased in a clockwise direction, the compound is determined as a (R) type, and when decreased in a counterclockwise direction, the compound is determined as a (S) type.
Thick wedge and dotted wedge forms of side chains to which substituents of R1 and R3 of Chemical Formula 1 and substituents of R5 and R7 of Chemical Formula 2 are connected represent (S) and (R) type organic ligands, respectively. As such, each of the chiral organic ligand according to an exemplary embodiment has (S) or (R) chiral side chains, as in Chemical Formulae 1 and 2, thereby having point chirality in which the enantiomers are not superimposed on each other, based on one point in the molecule.
Specifically, X1 and X2 in Chemical Formulae 1 and 2 are independently
of each other
R1 and R3 are independently of each other any one selected from the group consisting of a carboxy group, a hydroxyl group, an amino group, a sulfhydryl group, and a phosphate. R5 and R7 are independently of each other any one selected from the group consisting of a carboxy group, a hydroxyl group, an amino group, a sulfhydryl group, and a phosphate.
R2 and R4 are independently of each other any one selected from the group consisting of C1 to C5 alkyl groups and C1 to C5 aryl groups. R6 and R8 are independently of each other any one selected from the group consisting of C1 to C5 alkyl groups and C1 to C5 aryl groups.
As an example, R1, R3, R5, and R7 may be independently of one another any one selected from the group consisting of a carboxy group, a hydroxyl group, and an amino group, R2, R4, R6, and R8 may be independently of one another any one selected from the group consisting of C1 to C3 alkyl groups and C1 to C3 aryl groups.
Particularly, R1, R3, R5, and R7 may be a carboxy group, and R2, R4, R6, and R8 may be a methyl group.
Taken together, a specific example of the chiral organic ligand according to an exemplary embodiment may include compounds represented by the following Chemical Formulae 3 to 10:
Hereinafter, the chiral complex supramolecular body according to an exemplary embodiment will be described, using
First, referring to
When X1 of Chemical Formula 1 is
the chiral complex supramolecular body according to an exemplary embodiment of
Here, referring to
Referring to
When X1 is
the chiral complex supramolecular body according to an exemplary embodiment of
Here, referring to
Referring to
When X1 of Chemical Formula 1 is
the chiral complex supramolecular body according to an exemplary embodiment of
In the supramolecular body of
Here, referring to
The chiral complex supramolecular body according to an exemplary embodiment is formed by coordinating a chiral organic ligand which is any one selected from the group consisting of organic ligands represented by Chemical Formula 1 and Chemical Formula 2 with a metal ion. Here, the metal ion may be any one selected from the group consisting of zinc (Zn), copper (Cu), nickel (Ni), cadmium (Cd), iron (Fe), chromium (Cr), cobalt (Co), calcium (Ca), magnesium (Mg), manganese (Mn), silver (Ag), and gold (Au). In addition, the chiral complex supramolecular body may have a ribbon shape.
Hereinafter, the present invention will be described in more detail, through Examples. However, the Examples are only for illustration, and the scope of the present invention is not limited thereto.
A preparation method of the chiral organic ligand according to an exemplary embodiment will be described (Example 1).
First, a preparation method of a (S) type chiral organic ligand will be described (Example 1-1).
0.005 mol of (S)-1,4,5,8-naphthalenetetracarboxylic dianhydride and 0.01 mol of alanine are sufficiently dissolved in 600 mL of pyridine, and reacted while refluxing the reactants at 115° C. for 12 hours.
When the volume of the solution is down to about 10 mL during the reflux process, hydrogen chloride (100 mL HCl in 300 mL water) is added, separated by a filter, and washed using water, thereby preparing a naphthalene diimide (NDI) ligand of the following Chemical Formula 11 having chirality:
The NMR data of the (S) type chiral organic ligand prepared according to Example 1-1 is as follows.
1H NMR (Me2SO-d6, 500 MHz): δ 8.69 (s, 4H, naphthalene ring) 5.59 (q, 2H, J 6.5 Hz) 1.57 (d, 3H, J7 Hz). 13C NMR (Me2SO-d6, 500 MHz): d 171.2 (two equivalent carbonyls of carboxylic acid) 162.1 (four equivalent carbonyls), 131.1, 126.2 (aromatic carbons), 49.2 (chiral carbon), 14.5 (methylene carbon).
Next, a preparation method of the (R) type chiral organic ligand will be described (Example 1-2).
The naphthalene diimide (NDI) ligand of the following Chemical Formula 12 is prepared in the same manner as in Example 1-1, except that (R)-1,4,5,8-naphthalenetetracarboxylic dianhydride is used instead of (S)-1,4,5,8-naphthalenetetracarboxylic dianhydride:
The NMR data of the (R) type chiral organic ligand prepared according to Example 1-2 is as follows.
1H NMR (Me2SO-d6, 500 MHz): δ 8.69 (s, 4H, naphthalene ring) 5.59 (q, 2H, J 6.5 Hz) 1.57 (d, 3H, J7 Hz). 13C NMR (Me2SO-d6, 500 MHz): d 171.2 (two equivalent carbonyls of carboxylic acid) 162.1 (four equivalent carbonyls), 131.1, 126.2 (aromatic carbons), 49.2 (chiral carbon), 14.5 (methylene carbon).
Hereinafter, the preparation method of a chiral complex supramolecular body according to an exemplary embodiment will be described (Example 2).
First, a preparation method of a (S) type chiral complex supramolecular body will be described (Example 2-1).
0.1 mmol of the (S) type chiral organic ligand prepared according to Example 1-1 and 0.1 mmol of zinc iodide (ZnI2) powder are dissolved in 3 mL of N,N-dimethylmethanamide (DMF) to prepare a solution which is placed in a Teflon tube, and then placed again in a stainless-steel tube which is then sealed. The stainless-steel tube is heated in an oven at 120° C. for 72 hours to proceed with the reaction to produce a crystal, which is filtered and washed with N,N-dimethylmethanamide (DMF) several times, thereby preparing a (S) type chiral complex supramolecular body having a ribbon shape. The (S) type chiral complex supramolecular body is dissolved in ethanol for manufacturing a device. (yield=29%)
The elemental analysis data of the (S) type chiral complex supramolecular body prepared according to Example 2-1 is as follows.
Anal. Calcd. for C26H26ZnN4O10 (%): C, 50.38, H, 4.23, N, 9.04; found (%): C, 50.13, H, 4.10, N, 8.70.
Next, a preparation method of a (R) type chiral complex supramolecular body will be described (Example 2-2).
A (R) type chiral complex supramolecular body having a ribbon shape is prepared in the same manner as in Example 2-1, except that 0.1 mmol of the (R) type chiral organic ligand prepared according to Example 1-2 is used instead of 0.1 mmol of the (S) type chiral organic ligand prepared according to Example 1-1. (yield=27%)
The elemental analysis data of the (R) type chiral complex supramolecular body prepared according to Example 2-2 is as follows.
Anal. Calcd. for C26H26ZnN4O10 (%): C, 50.38, H, 4.23, N, 9.04; found (%): C, 50.07, H, 4.11, N, 8.72.
Next, a preparation method of a racemic chiral complex supramolecular body will be described (Example 2-3).
A racemic type chiral complex supramolecular body having a ribbon shape is prepared in the same manner as in Example 2-1, except that 0.05 mmol of the (S) type chiral organic ligand prepared according to Example 1-1 and 0.05 mmol of the (R) type chiral organic ligand prepared according to Example 1-2 are used instead of 0.1 mmol of the (S) type chiral organic ligand prepared according to Example 1-1. (yield=21%)
The elemental analysis data of the racemic type chiral complex supramolecular body prepared according to Example 2-3 is as follows.
Anal. Calcd. for C26H26ZnN4O10 (%): C, 50.38, H, 4.23, N, 9.04; found (%): C, 50.05, H, 4.22, N, 8.93.
Hereinafter, a manufacturing method of an organic electronic device having the chiral complex supramolecular body according to an exemplary embodiment as an active layer according will be described (Example 3).
First, a manufacturing method of an organic electronic device including a (S) type chiral complex supramolecular body active layer will be described (Example 3-1).
A n-type doped silicon wafer is prepared as a substrate. The silicon wafer has a 300 nm silicon oxide thin film formed thereon, and this is used as a gate dielectric material of a transistor (capacitance=11.5 nF/cm2). The surface of the silicon oxide thin film is treated with a piranha solution (a mixed solution of 70 vol % H2SO4 and 30 vol % H2O2), and n-octadecyltrimethoxysilane (OTS) is spin coated to form a self-assembled monolayer (SAM). The wafer was placed in a desiccator saturated with ammonia water for a day to remove residual n-octadecyltrimethoxysilane (OTS), and washed using toluene, acetone, or isopropyl alcohol.
An ethanol solution in which the (S) type chiral complex supramolecular body of Example 2-1 is dispersed is coated on a substrate, and dried in a vacuum oven at 60° C. for a day to remove residual ethanol, thereby preparing an active layer. Next, a gold electrode is patterned on the active layer using heat deposition and a shadow mask, thereby manufacturing an organic sensor device.
Next, a manufacturing method of an organic electronic device including the (R) type chiral complex supramolecular body active layer will be described (Example 3-2).
An organic sensor device is manufactured in the same manner as in Example 3-1, except that an ethanol solution in which the (R) type chiral complex supramolecular body of Example 2-2 is dispersed is used, instead of the ethanol solution in which the (S) type chiral complex supramolecular body of Example 2-1 is dispersed.
Next, a manufacturing method of an organic electronic device including the racemic type chiral complex supramolecular body active layer will be described (Example 3-3).
An organic sensor device is manufactured in the same manner as in Example 3-1, except that an ethanol solution in which the racemic type chiral complex supramolecular body of Example 2-3 is dispersed is used, instead of the ethanol solution in which the (S) type chiral complex supramolecular body of Example 2-1 is dispersed.
The chiral complex supramolecular body according to the above-described exemplary embodiment may be used in an active layer of an organic electronic device, which will be described below.
Hereinafter, an organic electronic device according to an exemplary embodiment will be described, using
Referring to
An substrate 10 may include materials such as glass, metal or plastic, and has a thickness d1 of about 250 μm to about 300 μm. However, the material and thickness of the substrate 10 are not limited thereto.
On the substrate 10, a gate insulation film 20 is disposed. The gate insulation film 20 may include materials such as silicon nitride (SiNx), silicon oxide (SiOx), and aluminum oxide (AlxOy). The gate insulation film 20 may have a thickness d2 of about 250 nm to about 350 nm. Between the substrate 10 and the gate insulation film 20, a gate electrode (not shown) is disposed, and the gate insulation film 20 may serve as the gate dielectric material.
On the gate insulation film 20, a surface modified layer 30 may be disposed. The surface modified layer 30 may include a self-assembled monolayer (SAM) formed by surface-treating the substrate 10 with any one selected from the group consisting of n-octadecyltrimethoxysilane (OTS), n-octadecyltrichlorosilane, n-octyltrichlorosilane, n-octylphosphate, and n-octadecylphosphate. Particularly, the surface modified layer 30 may be a self-assembled monolayer (SAM) in which the substrate 10 is surface-treated with n-octadecyltrimethoxysilane (OTS).
On the surface modified layer 30, an electrode 40 including gold (Au) or chromium (Cr) is disposed. The electrode 40 includes a first electrode 41 and a second electrode 42, and one of the first electrode 41 and the second electrode 42 may be a source electrode and the other one may be a drain electrode, depending on the direction in which voltage or current is applied.
Here, the first electrode 41 and the second electrode 42 may be formed, so that a portion of the gate insulation film 20 is exposed by an etching process using a pattern mask, after the surface modified layer 30 and a material layer forming the electrode 40 are sequentially laminated on the gate insulation film 20. A portion of the exposed gate insulation film 20 may be brought into contact with the active layer 50. According to an exemplary embodiment, the surface modified layer 30, the first electrode 41, and the second electrode 42 may be formed without an etching process.
The surface modified layer 30 may have a thickness (not shown) of about 5 nm or less, and the electrode 40 may have a thickness (not shown) of about 40 nm. Therefore, the total thickness d4 of the surface modified layer 30 and the electrode 40 may be about 45 nm or less.
On the gate insulation film 20, the surface modified layer 30, and the electrode 40, an active layer 50 may be disposed. The active layer 50 includes a chiral complex supramolecular body formed by coordinating a chiral organic ligand which is any one selected from the group consisting of organic ligands represented by Chemical Formula 1 and Chemical Formula 2 with a metal ion which is any one selected from the group consisting of zinc (Zn), copper (Cu), nickel (Ni), cadmium (Cd), iron (Fe), chromium (Cr), cobalt (Co), calcium (Ca), magnesium (Mg), manganese (Mn), silver (Ag), and gold (Au).
The active layer 50 includes the chiral complex supramolecular body according to an exemplary embodiment, thereby securing supramolecular chirality in which the entire active layer 50 has chirality. The chirality refers to asymmetry in which a chemical structure is not superposed onto the mirror image thereof, as described above, and most of amino acids, sugars, enzymes, and the like which exist in nature have chirality. Medicines may be also prepared as an enantiomer having chirality. Here, since one of the compounds in an enantiomer relationship may be used as a medicine, and the other one may have a potential side effect, there is a need for a technique to separate and detect the two compounds.
Meanwhile, circular polarization is light having chirality in a polarization state, and has a polarization form different from linear polarization. A technique to separate and detect materials having a circular polarization characteristic and a linear polarization characteristic is likely to be utilized in optical communication technology and polarization imaging. Particularly, in the case of the optical communication technology, the circular polarization may transfer new information of a polarization form, in addition to a wavelength band or intensity which is basic information of electromagnetic waves. Therefore, possibility to be applied to optical communication technology which is encrypted or has enhanced security may be high.
Since complex optical equipment such as a linear polarizing plate and a phase retardation plate is required for detecting circular polarization having left and right directionalities, there is a problem in that downsizing or integration of sensing equipment is difficult. In order to solve the problem, a study on an electronic device detecting circular polarization light was conducted, however, the wavelength band of detected light is limited to wavelengths in an ultraviolet region of about 360 nm and an infrared region of about 1200 nm or more, and there is a problem in that a photosensitive characteristic and electrical properties are poor.
Accordingly, circular polarization in a visible light region having high usage in real life is not selectively detected, and light sensing capability is very poor, and consequently, there is a problem in that application and use as an actual electronic device are difficult.
Thus, the organic electronic device according to an exemplary embodiment includes an active layer 50 including a chiral complex supramolecular body. The entire of an organic electronic device system may secure chirality by a supramolecular body in which a chiral organic ligand and a metal ion are coordinated with each other. Misarranged orientation which is disadvantageous in charge transfer is minimized, thereby providing an organic electronic device having greatly improved photosensitivity and electrical characteristics. In addition, since a manufacturing method of the organic electronic device according to an exemplary embodiment is very simple, and easily applicable even on a plastic substrate 10, the organic electronic device is advantageous for integrated devices and downsizing. The manufacturing method of the organic electronic device according to an exemplary embodiment will be described later.
Particularly, the organic electronic device according to an exemplary embodiment may be utilized as various chirality sensors which detect various elements having chirality such as light and chemical gas with high performance.
The active layer 50 may have a thickness d3 of about 200 nm to about 1000 nm, referring to
According to an exemplary embodiment, the electrode 40 may be disposed on the active layer 50. However, when the electronic device is manufactured so that the active layer 50 is disposed on the electrode 40 as in the above Example, simplification of the manufacturing process such as reducing manufacturing time may be promoted, and relatively high safety may be secured.
Hereinafter, the manufacturing method of the organic electronic device including the chiral complex supramolecular body according to
First, (a) substrate 10 is provided.
After step (a), (a′) one surface of the substrate 10 is oxidation-treated to manufacture a substrate 10 including a hydroxyl group (—OH) on the one surface. The surface including a hydroxyl group (—OH) may be a gate insulation film 20.
After step (a′), (a″) a self-assembled monolayer (SAM) may be formed on the surface of the substrate 10 which is oxidation-treated. The self-assembled monolayer (SAM) may be formed by treating the oxidation-treated surface of the substrate 10 with any one selected from the group consisting of n-octadecyltrimethoxysilane (OTS), n-octadecyltrichlorosilane, n-octyltrichlorosilane, n-octylphosphate, and n-octadecylphosphate, particularly, n-octadecyltrimethoxysilane (OTS).
The self-assembled monolayer (SAM) may be a surface modified layer 30.
Next, (b) an electrode 40 including gold or chromium is formed on the substrate 10. The electrode 40 may form a first electrode 41 and a second electrode 42 together with the surface modified layer 30 formed in step (a″).
Next, (c) an active layer 50 is formed on the first electrode 41 and second electrode 42 to manufacture the organic electronic device.
The active layer 50 includes a chiral complex supramolecular body formed by coordinating a chiral organic ligand which is any one selected from the group consisting of organic ligands represented by Chemical Formula 1 and Chemical Formula 2 with a metal ion which is any one selected from the group consisting of zinc, copper, nickel, cadmium, iron, chromium, cobalt, calcium, magnesium, manganese, silver, and gold.
Step (c) may include (c-1) manufacturing a chiral complex supramolecular body having a ribbon shape by coordinating the chiral organic ligand with the metal, and (c-2) forming the active layer 50 including the chiral complex supramolecular body on the substrate 10.
According to an exemplary embodiment, the active layer 50 may be first formed on the substrate 10, and the electrode 40 including the first electrode 41 and the second electrode 42 may be formed thereon.
Hereinafter, specific shapes of the chiral complex supramolecular body and the organic electronic device according to an exemplary embodiment will be described, using
Referring to
Referring to
The chiral complex supramolecular body formed on the electrode 40 becomes the active layer 50 of the organic electronic device, and may serve to detect various elements having chirality. The active layer 50 may be disposed to cross the first electrode 41 and the second electrode 42 with the gate insulation film 20 including silicon oxide and the like interposed therebetween.
The organic electronic device according to an exemplary embodiment may be one or more selected from the group consisting of organic transistors, organic light emitting diodes, and organic solar cells, as well as organic sensors, as described above.
When the organic electronic device is the organic sensor, the organic sensor may detect one or more selected from the group consisting of light, chemical gas, alcohol, hydrazine (N2H4), and medicines. The chemical gas may include an amine solution including a nitrogen element such as aniline, trimethylamine (TEA), and phenylethylamine (PEA), a polar solvent, and the like.
Hereinafter, the characteristics of the chiral complex supramolecular body according to an exemplary embodiment will be described, using
Referring to
Referring to
The chiral complex supramolecular body (Examples 2-1 to 2-3) of
Hereinafter, referring to
Referring to
Referring to
Referring to
Hereinafter, referring to
Spectrometry using luminescence characteristics may be used for analyzing the atomic or molecular structure of a certain material. Spectrometry uses the characteristics in which when a certain material absorbs light, electron potential in the material is changed, whereby absorbance and light intensity are changed. Luminescence may be classified into fluorescence, phosphorescence, chemiluminescence, thermoluminescence, or the like, depending on the aspect. Among them, fluorescence and phosphorescence emit light in a manner that light is absorbed to transit electrons from a ground state to an unstable excited state, and when the electrons return to the ground state, heat or light at another wavelength is emitted. The fluorescence and phosphorescence is referred to as photoluminescence (PL).
The fluorescence more easily occurs than phosphorescence, and stays in the excited state for a short time so that interference between signals is small, and thus, may be advantageous for being used as an analysis method. Thus, an exemplary embodiment will be described through an experiment results measuring fluorescence intensity during photoluminescence (PL).
The fluorescence characteristics of a certain material may be affected by a molecular structure and chemical environment. As an example, the fluorescence intensity of a certain material may be affected by a quenching phenomenon. The quenching phenomenon refers to a phenomenon in which fluorescence intensity is decreased by another certain compound present in a certain material.
Hereinafter, the sensing characteristic of the chiral complex supramolecular body according to an exemplary embodiment for the amine compound, in particular, hydrazine (N2H4) will be described by the photoluminescence (PL) quenching phenomenon.
Referring to
Referring to
Referring to
As such, it is confirmed that the chiral complex supramolecular body according to an exemplary embodiment has a quenching degree in proportion to the concentration of hydrazine, effectively senses the concentration of hydrazine, and allows hydrazine to be selectively distinguished by the photoluminescence (PL) quenching phenomenon.
Hereinafter, referring to
Referring to
As compared with the Comparative Example, the luminescence intensity for the material to which an amine compound is added is rapidly decreased by the above-described quenching phenomenon. Specifically, a quenching degree is increased in the order of hydrazine, trimethylamine (TEA), and phenylethylamine (PEA). Particularly, in the case of hydrazine, luminescence intensity is close to 0, and thus, it is found that the chiral complex supramolecular body according to an exemplary embodiment most sensitively senses hydrazine among the amine compounds. The material to which trimethylamine (TEA) or phenylethylamine (PEA) is added is quenched to a similar degree, and trimethylamine (TEA) is a little more quenched than phenylethylamine (PEA).
As such, when various amine compounds are added at a constant concentration (1M in the present Example), the chiral complex supramolecular body according to an exemplary embodiment has sensing ability which is excellent in the order of hydrazine, trimethylamine (TEA), and phenylethylamine (PEA).
In addition, the wavelength region to be quenched may be in a range of about 420 nm to about 600 nm, that is, a visible light region, and in particular in a range of about 450 nm to about 550 nm.
As seen from
Hereinafter, the sensing characteristics for a medicine of the organic electronic device according to an exemplary embodiment will be described by photoluminescence (PL) characteristics, using
Referring to
The Comparative Example is a material to which naproxen is not added, and it is confirmed that fluorescence intensity is greatly decreased due to the above-described quenching phenomenon, for the material to which naproxen is added, as compared with the Comparative Example. It is confirmed from the quenching phenomenon that an exemplary embodiment detects naproxen.
Referring to
According to
Referring to
e.e=(R−S)/(R+S)×100 [Equation 1]
wherein R is a content ratio of (R) type naproxen, and S is a content ratio of (S) type naproxen. For example, when the object to be sensed contains only (S) type naproxen, R=0, and the relative mixing ratio (e.e) is −100, and when the mixing ratio of (R) type and (S) type naproxen (R:S) is 1:3, the value is −50, and when (R) type and (S) type naproxen are contained identically, R=S=1, and thus, the value is 0.
According to
Specifically, as a relative mixing ratio (e.e) of naproxen is increased, that is, the content of (R) type naproxen is increased, the quenching degree is increased, and a change in fluorescence intensity is increased, whereby naproxene may be effectively sensed.
Hereinafter, the sensing characteristics for another medicine of the chiral complex supramolecular body according to an exemplary embodiment will be described, using
In the present Example, description will be provided for valinol as an example of the medicine. Valinol (2-amino-3-methyl-1-butanol) is an organic compound having chirality. Valinol is also a chiral target compound having chirality like the above-described naproxen, and may include (S) type or (R) type. Valinol may be used as an intermediate material for synthesizing a medicine having chirality.
Referring to
It is confirmed that in each test example of
Here, in each test example, a variation width of the quenching degree (I0/I) depending on the concentration of valinol is different. A variation width of the quenching degree (I0/I) depending on the increased concentration of valinol is the highest in the Experimental Example in which the (R) type chiral supramolecular body senses (S) type valinol, and the lowest in the Experimental Example in which the (S) type chiral supramolecular body senses (S) type valinol. As such, a chiral quencher, which is a medicine such as valinol in the present Example may be effectively sensed, using the fact that the quenching degree (I0/I) is different depending on a combination of the supramolecular body and a quencher having different chirality.
Meanwhile, when the concentration of valinol is constant, sensing ability of the (R) type supremolecular body (MOF) for the (S) type valinol is the best. Next, the sensing ability is excellent in the order of (R) type valinol of the (R) type supremolecular body (MOF), (R) type valinol of the (S) type supramolecular body (MOF), and (S) type valinol of the (S) type supramolecular body (MOF). This trend is significant when the concentration of valinol is about 0.2 mM or more. When the concentration of valinol is less than about 0.2 mM, sensing ability according to each Example may be almost similar.
As seen from
Hereinafter, referring to
Referring to
The organic electronic device according to an exemplary embodiment does not show change in current to non-polar chemical gas, but it is confirmed that as the polarity of the chemical gas is higher, change in current is bigger. That is, the organic electronic device according to an exemplary embodiment may sense polar chemical gas, and shows bigger change in electrical conductivity to chemical gas having high polarity.
Referring to
It is confirmed that the change in conductivity (ΔG/G0) hardly appears when sensing dichloromethane and n-hexane which are non-polar gas, and has a significant value when sensing other polar gases.
Particularly, the change in conductivity (ΔG/G0) is highest in the case of aniline having highest polarity among the chemical gases of the present Example, and is high in the order of methanol and ethanol. The reaction sensitivity is about 0.1 to 1 pA/ppm in the case of anilines, which is the highest, and about 0.0001 pA/ppm in the case of methanol and ethanol, which is similar to each other. That is, sensing is more sensitive as the chemical gas has higher polarity.
Referring to
Referring to
According to
As such, the chiral complex supramolecular body according to an exemplary embodiment may have the same crystal structure as before exposure, even after being exposed to target chemical gas. That is to say, it is confirmed that an increase in electrical conductivity as seen from
Hereinafter, referring to
Referring to
Referring to
Immediately when voltage of about 0 V to 50 V is applied after the organic electronic device by Example 3-2 is exposed to trimethylamine (TEA), it is confirmed that current of about 0 pA to 10 pA flows. Particularly, when voltage of about 40 V to 50V is applied, current of about 8 pA to 10 pA flows, and the maximum current value may be about 10 pA.
When supply of trimethylamine (TEA) to the organic electronic device by Example 3-2 is stopped, and after 10 seconds, trimethylamine (TEA) is removed (degassing), the current hardly flows, as before exposure. That is, when the organic electronic device according to an exemplary embodiment is exposed to trimethylamine (TEA), sensing trimethylamine (TEA) may be confirmed by flowing current.
Referring to
When voltage of about 0 V to 50 V is applied immediately after the organic electronic device by Example 3-1 is exposed to trimethylamine (TEA), it is confirmed that current of about 0 pA to 11 pA flows. Particularly, when voltage of about 40 V to 50 V is applied, current of about 9 pA to 11 pA flows, and the maximum current value may be about 11 pA. As compared with Example 3-2 ((S) type) of
As in
As such, when the chiral complex supramolecular body according to an exemplary embodiment is exposed to trimethylamine (TEA), sensing trimethylamine (TEA) may be confirmed by flowing current, as compared with the Comparative Example, and the case of degassing.
As described above, the chiral complex supramolecular body according to an exemplary embodiment may effectively sense medicines such as naproxen and valinol which are chiral target compounds by photoluminescence (PL) analysis. The medicine having chirality is selectively detected, thereby separating the medicine from another material having a side effect in the enantiomers, so that a potential risk may be prevented.
In addition, the chiral complex supramolecular body according to an exemplary embodiment may effectively sense light, polar chemical gas, and the like, as well as various amine compounds including nitrogen, by photoluminescence (PL) analysis.
The organic electronic device according to an exemplary embodiment includes the active layer including the chiral complex supramolecular body as described above, thereby sensing various chiral polymers. The entire organic electronic device system secures chirality by the supramolecular body in which the chiral organic ligand and a metal ion are coordinated with each other, thereby being utilized as an organic sensor which detects various elements having chirality with high performance.
In addition, according to an exemplary embodiment, misarranged orientation which is disadvantageous in charge transfer is minimized, thereby providing the organic electronic device having greatly improved photosensitivity and electrical characteristics.
While this invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims.
| Number | Date | Country | Kind |
|---|---|---|---|
| 10-2018-0073789 | Jun 2018 | KR | national |
| 10-2018-0157410 | Dec 2018 | KR | national |
