Organic electronic multi-sensor using ionic electrolyte, and method for producing same
10570251 ยท 2020-02-25
Assignee
Inventors
Cpc classification
C08L65/00
CHEMISTRY; METALLURGY
H10K10/488
ELECTRICITY
C08G61/126
CHEMISTRY; METALLURGY
C08G2261/3243
CHEMISTRY; METALLURGY
G01N27/27
PHYSICS
C08L65/00
CHEMISTRY; METALLURGY
C08G2261/3241
CHEMISTRY; METALLURGY
C08G2261/3223
CHEMISTRY; METALLURGY
H10K85/113
ELECTRICITY
Y02E10/549
GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
International classification
C08G61/12
CHEMISTRY; METALLURGY
G01N27/27
PHYSICS
G01N27/414
PHYSICS
Abstract
Provided are: an organic electronic multi-sensor wherein an ionic electrolyte and an organic semiconductor polymer are fused to form a double layer and have a mesh shape; and a method for producing same. The organic electronic multi-sensor provides different, complementary ion and charge transfer pathways depending on the volume ratio of the ionic electrolyte and thus is capable of distinguishing the electrical resistance properties of volatile organic compounds having a wide range of polarities. In addition, the organic electronic multi-sensor senses light of respective wavelengths on the basis of optical signals, converts temperatures to electrical signals according to thermal signals, and thus can sense each environment change.
Claims
1. An organic electronic multi-sensor comprising: a substrate; a composite layer formed on the substrate and including an ionic electrolyte and an organic semiconductor polymer; and a source electrode layer and a drain electrode layer formed on both sides of the composite layer and electrically connected to the composite layer, wherein the ionic electrolyte is dissolved in a non-polar solvent and contains a plurality of alkyl groups, the ionic electrolyte is doped with the organic semiconductor polymer by electrostatic attraction of the ionic electrolyte, and the composite layer adsorbs or desorbs gas molecules according to a chemical signal by fusing the ionic electrolyte with the organic semiconductor polymer, detects light per wavelength according to an optical signal, or detects an environmental change by converting a temperature into an electrical signal according to a thermal signal.
2. The organic electronic multi-sensor of claim 1, wherein the substrate includes a polyethylene terephthalate (PET) substrate having a flexible property.
3. The organic electronic multi-sensor of claim 1, wherein a precursor of the ionic electrolyte includes 1-methylimidazole, 1-alkyl-3alkyl-imidazolium, n-dialkyl-pyrrolidinium, 1,2-dialkyl-pyrazolum, n-alkyl-thiazolium, n-alkyl-pyridinium, n-diakyl-piperidinium, tetraalkyl-ammomium, tetraalkyl-phosphonium, or trialkyl-sulfonium.
4. The organic electronic multi-sensor of claim 1, wherein the ionic electrolyte contains an alkyl group with carbon numbers 1 to 12.
5. The organic electronic multi-sensor of claim 1, wherein the ionic electrolyte is either solid or liquid.
6. The organic electronic multi-sensor of claim 1, wherein the ionic electrolyte includes an anionic material selected from among PF6, NTf2, BR1R2R3R4, BF4, OTf2, N(CN)2, CH3CO2, CF3CO2NO3, Br, Cl, and I.
7. The organic electronic multi-sensor of claim 1, wherein the organic semiconductor polymer includes a polymer, in which a double bond and a single bond are alternated, selected from among thiophene, fused thiophene, carbazole, benzodithiozole, diketopyrrolopyrrole, and indacenodithiophene.
8. The organic electronic multi-sensor of claim 1, wherein the composite layer is fused with a volume ratio of 1:1, 1:2, 1:3, 1:5, 1:7, or 1:10 by increasing the volume ratio of the ionic electrolyte with respect to the organic semiconductor polymer.
9. The organic electronic multi-sensor of claim 1, wherein the ionic electrolyte and the organic semiconductor polymer of the composite layer simultaneously have different ion and charge transfer systems or have complementary ion and charge transfer systems.
10. The organic electronic multi-sensor of claim 1, wherein the composite layer is formed with a double layer by fusing the ionic electrolyte with the organic semiconductor polymer and has a mesh shape.
11. A method of producing an organic electronic multi-sensor which includes a substrate, a composite layer formed on the substrate and including an ionic electrolyte and an organic semiconductor polymer, and a source electrode layer and a drain electrode layer formed on both sides of the composite layer and electrically connected to the composite layer, wherein the ionic electrolyte is dissolved in a non-polar solvent and contains a plurality of alkyl groups, the ionic electrolyte is doped with the organic semiconductor polymer by electrostatic attraction of the ionic electrolyte, and the composite layer adsorbs or desorbs gas molecules according to a chemical signal by fusing the ionic electrolyte with the organic semiconductor polymer, detects light per wavelength according to an optical signal, or detects an environmental change by converting a temperature into an electrical signal according to a thermal signal, the method comprising: preparing a precursor of the ionic electrolyte; introducing a functional group into the precursor so as to allow the precursor to be soluble in the non-polar solvent; preparing the ionic electrolyte by chemically bonding the precursor in which the functional group is introduced to an anionic salt; and forming the composite layer by fusing the prepared ionic electrolyte with the organic semiconductor polymer.
12. The method of claim 11, wherein, in the preparing of the precursor, the precursor of the ionic electrolyte includes 1-methylimidazole, 1-alkyl-3alkyl-imidazolium, n-dialkyl-pyrrolidinium, 1,2-dialkyl-pyrazolum, n-alkyl-thiazolium, n-alkyl-pyridinium, n-diakyl-piperidinium, tetraalkyl-ammomium, tetraalkyl-phosphonium, or trialkyl-sulfonium.
13. The method of claim 11, wherein, in the preparing the ionic electrolyte, the anionic salt includes an anionic material selected from among PF6, NTf2, BR1R2R3R4, BF4, OTf2, N(CN)2, CH3CO2, CF3CO2NO3, Br, Cl, and I.
14. The method of claim 11, wherein, in the preparing of the ionic, the prepared ionic electrolyte is in a solid or liquid state.
15. The method of claim 11, wherein, in the forming of the composite layer, the composite layer is fused with a volume ratio of 1:1, 1:2, 1:3, 1:5, 1:7, or 1:10 by increasing the volume ratio of the ionic electrolyte with respect to the organic semiconductor polymer.
16. The method of claim 11, wherein, in the forming of the composite layer, the ionic electrolyte and the organic semiconductor are fused to form a double layer, and the double layer has a mesh shape.
17. The method of claim 11, wherein the ionic electrolyte is either solid or liquid.
Description
DESCRIPTION OF DRAWINGS
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DETAILED DESCRIPTION
(12) Hereinafter, exemplary embodiments of the present inventive concept will be described in detail with reference to the accompanying drawings.
(13) The exemplary embodiments of the present inventive concept may be modified in various other forms, and the scope of the present inventive concept is not limited to the exemplary embodiments described below. Further, these embodiments are provided to more fully describe the present inventive concept to those skilled in the art. Therefore, shapes and sizes of components in the drawings may be exaggerated for clarity, and components denoted by the same reference numerals in the drawings are the same components.
(14) Embodiment
(15)
(16) Referring to
(17) A substrate 10 is formed. The substrate 10 may be any one selected from among a sapphire (Al.sub.2O.sub.3) substrate, a ZnO substrate, a Si substrate, a GaAs substrate, a SiC substrate, an InP substrate, and a GaN substrate, but the present inventive concept is not limited thereto. However, according to the present inventive concept, an organic electrolyte/semiconductor composite layer 30 which is an active layer may be formed by a simplified solution process such that the substrate 10 may include polyethylene terephthalate (PET) which is a flexible element. The substrate 10 may employ a material as long as it can be used as a flexible substrate in addition to PET.
(18) The composite layer 30 including an ionic electrolyte 20 and an organic semiconductor polymer 25 is formed on the substrate 10. The composite layer 30 is formed by fusing the ionic electrolyte 20 with the organic semiconductor polymer 25. The ionic electrolyte 20 and the organic semiconductor polymer 25 are composed of layers having mutually complementary ions and charge transfer characteristics through electrostatic attraction. In this case, the ionic electrolyte 20 may be disposed on or below the organic semiconductor polymer 25. For example, the ionic electrolyte 20 may be disposed on a lower surface of the organic semiconductor polymer 25 or on an upper surface thereof.
(19) The ionic electrolyte 20 may be a solid or a liquid, may be dissolved in a non-polar solvent, and may contain a plurality of alkyl groups. For example, the ionic electrolyte 20 may contain an alkyl group with carbon numbers 1 to 12.
(20) The ionic electrolyte 20 may be doped with the organic semiconductor polymer 25 by electrostatic attraction. The organic semiconductor polymer 25 may include a material, which alternately contains a double bond and a single bond and has anions, such as PF.sub.6, NTf.sub.2, BR.sub.1R.sub.2R.sub.3R.sub.4, BF.sub.4, OTf.sub.2, N(CN).sub.2, CH.sub.3CO.sub.2, CF.sub.3CO.sub.2NO.sub.3, Br, Cl, or I.
(21) The composite layer 30 may be a layer which has a new signal transfer system by fusing the ionic electrolyte 20 with the organic semiconductor polymer 25. For example, the composite layer 30 may be fused by increasing a volume ratio of the ionic electrolyte 20 to the organic semiconductor polymer 25 to 1:1, 1:2, 1:3, 1:5, 1:7, or 1:10.
(22) The ionic electrolyte 20 and the organic semiconductor polymer 25 of the composite layer 30 may simultaneously have different ion and charge transfer systems or may have complementary ion and charge transfer systems.
(23) The composite layer 30 may adsorb or desorb gas molecules according to a chemical signal by fusing the ionic electrolyte 20 with the organic semiconductor polymer 25, detect light per wavelength according to an optical signal, and detect an environmental change by converting a temperature into an electrical signal according to a thermal signal. In particular, in the composite layer 30, the ionic electrolyte 20 may be doped with and fused with the organic semiconductor polymer 25 by the electrostatic attraction of the ionic electrolyte 20 to form ion and charge transfer pathways. More specifically, when gas molecules are adsorbed or desorbed on the composite layer 30, electrical resistance of the composite layer 30 may be increased or decreased according to polar and non-polar characteristics. For example, the ionic electrolyte 20 and the organic semiconductor polymer 25 of the composite layer 30 are complementarily fused in ion and charge transfer systems such that the composite layer 30 may efficiently convert a chemical signal into an electrical signal to detect a gas while gas molecules are absorbed or desorbed. Further, due to a photoelectric characteristic, the organic semiconductor polymer 25 of the composite layer 30 may be electrically doped by absorbing light per wavelength such that the composite layer 30 may detect a specific optical signal through the through complementary ion and charge transfer pathways by efficiently converting the specific optical signal into an electrical signal. Alternatively, a structure of the ionic electrolyte 20 of the composite layer 30 may be easily changed due to a temperature and thus an electrical characteristic of the ionic electrolyte 20 is varied such that the composite layer 30 may detect a variation in temperature through the complementary ion and charge transfer pathways by converting the variation in temperature into an electrical signal.
(24) A source electrode layer 40 and a drain electrode layer 50 may be connected to the composite layer 30 and formed on both sides of the composite layer 30. Each of the source electrode layer 40 and the drain electrode layer 50 may be formed of an indium tin oxide (ITO) or Au, but the present inventive concept is not limited thereto. Further, the composite layer 30 is electrically connected to the source electrode layer 40 and the drain electrode layer 50 such that a current 60 may flow.
(25) Hereinafter, a method of producing an organic electronic multi-sensor will be described.
(26) Firstly, a precursor of the ionic electrolyte 20 may be prepared.
(27) The precursor of the ionic electrolyte 20 may be any one of Formula 1.
(28) ##STR00001##
(29) Formula 1 may include N, P, or S, and R, R.sub.1, R.sub.2, R.sub.3, and R.sub.4 may each include an alkyl group. In particular, the precursor of the ionic electrolyte 20 may be one selected from among 1-methylimidazole, 1-alkyl-3alkyl-imidazolium, n-dialkyl-pyrrolidinium, 1,2-dialkyl-pyrazolum, n-alkyl-thiazolium, n-alkyl-pyridinium, n-diakyl-piperidinium, tetraalkyl-ammomium, tetraalkyl-phosphonium, and trialkyl-sulfonium.
(30) Secondarily, a functional group is introduced so as to dissolve the precursor of the ionic electrolyte 20 in the non-polar solvent. The functional group introduced into the precursor of the ionic electrolyte 20 may be an alkyl group with carbon numbers 1 to 12. However, even when a functional group is further introduced, it is preferable that the ionic electrolyte 20 is in a solid or liquid state.
(31) Thirdly, the ionic electrolyte 20 into which the functional group is introduced is chemically combined with an anionic salt to produce the ionic electrolyte 20. In particular, the ionic electrolyte 20 may be doped with the anionic salt. The salt may be an anionic material including one selected from among PF.sub.6, NTf.sub.2, BR.sub.1R.sub.2R.sub.3R.sub.4, BF.sub.4, OTf.sub.2, N(CN).sub.2, CH.sub.3CO.sub.2, CF.sub.3CO.sub.2NO.sub.3, Br, Cl, and I.
(32) As described above, the functional group is further introduced into the ionic electrolyte 20 and the ionic electrolyte 20 is doped with the anionic salt such that the ionic electrolyte 20 may be fused with the organic semiconductor polymer 25. For example, a volume ratio of the ionic electrolyte 20 to the organic semiconductor polymer 25 may be increased and fused with the organic semiconductor polymer 25 with the volume ratios of 1:1, 1:2, 1:3, 1:5, 1:7, and 1:10.
(33) The organic semiconductor polymer 25 may be a polymer, in which a double bond and a single bond are alternated, selected from among thiophene, fused thiophene, carbazole, benzodithiozole, diketopyrrolopyrrole, and indacenodithiophene, but the present inventive concept is not limited thereto. However, for an electrostatic interact with the ionic electrolyte, it is preferable that the organic semiconductor polymer 25 is made of a polymer and a monomer, each having an alternating electron donor-acceptor system. For example, the organic semiconductor polymer 25 may be DT-PDPP2T-TT.
(34) As described above, the ionic electrolyte 20 and the organic semiconductor polymer 25 may be fused with each other to be formed as a double layer on the composite layer, and the double layer may have a mesh shape. Further, when the ionic electrolyte 20 and the organic semiconductor polymer 25 are fused, the mesh shape of the composite layer 30 may be varied according to the volume ratio of the ionic electrolyte 20 contained in the composite layer 30. For example, when the ionic electrolyte 20 and the organic semiconductor polymer 25 are fused and the volume ratio of the ionic electrolyte 20 is increased, an inner diameter between meshes of the double layer of the composite layer 30 may be increased.
(35) A signal mechanism of the composite layer 30 will be described below.
(36) A charge transfer pathway 100 and an ion transfer pathway 300 may be disposed by electrostatic attraction 200. For example, the charge transfer pathway 100 may be constituted with the organic semiconductor polymer 25, and the ion transfer pathway 300 may be constituted with the ionic electrolyte 20. The charge transfer pathway 100 and the ion transfer pathway 300 may have a mesh shape by the electrostatic attraction 200.
(37) Further, owing to electrostatic forces between anions and cations of the ionic electrolyte 20 in the composite layer 30 formed on the substrate 10, the organic semiconductor polymer 25 may be electrochemically doped to increase or decrease electrical resistance through complementary ion and charge transfer pathways. As described above, the composite layer 30 adsorbs or desorbs gas molecules to decrease or increase resistance such that the organic electronic multi-sensor may detect a variation for the gas molecules.
(38) Hereinafter, exemplary examples will be described in order to facilitate understanding of the present inventive concept. It should be noted, however, that the following exemplary examples are only for aiding in understanding of the present inventive concept, and the present inventive concept is not limited by the following examples.
PRODUCTION EXAMPLE 1
(39) Preparation of C.sub.1C.sub.12 IMBr
(40) C.sub.1C.sub.12 IMBr is a material prepared by chemically bonding C.sub.1C.sub.12, imidazole (IM), and Br. More specifically, 1-methylimidazole (C.sub.4H.sub.6N.sub.2) having a methyl group Cl at one side thereof is a precursor. 6 g (73 mmol) of 1-methylimidazole (C.sub.4H.sub.6N.sub.2) having a methyl group Cl at one side thereof and 20 g (80.2 mmol) of 1-bromododecane (C.sub.12H.sub.25Br) are dissolved in 80 ml of toluene (C.sub.7H.sub.8). The dissolved solution is stirred and reacted in a nitrogen gas atmosphere at a temperature of 110 C. for 72 hours. After the reaction is completed, the solvent is removed by evaporating the yellow reaction mixture, 100 ml of ethyl acetate is added, and then filtering is performed such that 21.5 g of white solid ionic electrolyte C.sub.1C.sub.12 IMBr is obtained.
PRODUCTION EXAMPLE 2
(41) Preparation of C.sub.1C.sub.12 IMPF6
(42) C.sub.1C.sub.12 IMPF6 is a product of the ionic electrolyte prepared by chemically bonding PF.sub.6 to C.sub.1C.sub.12 IMBr using C.sub.1C.sub.12IMBr prepared through a chemical bonding of Production Example 1 as a precursor. More specifically, C.sub.1C.sub.12 IMBr (14.4 g and 43.4 mmol) prepared according to Production Example 2 is dissolved in 200 ml of distilled water, 21.25 g (130 mmol) of quaternary ammonium hexafluorophosphate (NH.sub.4PF.sub.6) is added, and then stirring is performed at room temperature for 72 hours. After the reaction is completed, the produced solid is filtered and dissolved in chloroform again, and then MgSO.sub.4 is added to remove moisture. Further, in order to remove the residual salt or halide starting material, dehydrated dichloromethane is dissolved and kept at a temperature of 30 C. for 24 hours. After 24 hours of storage, 16.2 g of white solid state C.sub.1C.sub.12 IMPF.sub.6 is obtained by filtering the product to remove the solvent therefrom and vacuum drying the product.
PRODUCTION EXAMPLE 3
(43) Fusion of C.sub.1C.sub.12 IMPF.sub.6 with DT-PDPP2T-TT
(44) C.sub.1C.sub.12 IMPF.sub.6 is an ionic electrolyte produced according to Production Example 2, and DT-PDPP2T-TT is an organic semiconductor polymer. The ionic electrolyte C.sub.1C.sub.12 IMPF.sub.6 and the organic semiconductor polymer DT-PDPP2T-TT are fused by increasing a volume ratio of the ionic electrolyte C.sub.1C.sub.12 IMPF.sub.6 prepared according to Production Example 2 to the organic semiconductor polymer DT-PDPP2T-TT. For example, the fusion is performed by increasing the volume ratio of the ionic electrolyte C.sub.1C.sub.12 IMPF.sub.6 with respect to the organic semiconductor polymer DT-PDPP2T-TT to 1:1, 1:2, 1:3, 1:5, 1:7, and 1:10. In this time, the ionic electrolyte C.sub.1C.sub.12 IMPF.sub.6 and the organic semiconductor polymer DT-PDPP2T-TT are chemically bonded and fused by being stirred at a temperature of 20 C. to 60 C. for 30 minutes to 2 hours.
PRODUCTION EXAMPLE 4
(45) Formation of Composite Layer
(46) A composite layer is formed of the material fused according to Production Example 3 through a solution process.
(47) A flexible substrate or a rigid substrate is prepared, and the composite layer is formed on the substrate through spin coating. Spin coating is carried out at 2500 rpm for 60 seconds.
(48)
(49) Referring to
(50)
(51) Referring to
(52) A crystal of the organic electronic multi-sensor may be formed about a (100) crystal face having an ionic electrolyte. As disclosed in the fusion ratio of 1:7 (organic semiconductor polymer 1:ionic electrolyte 7), the organic electronic multi-sensor may have a (010) crystal face, a (200) crystal face, a (300) crystal face, a (400) crystal face, or a (500) crystal face in addition to the (100) crystal face. As a content of the ionic electrolyte to the organic semiconductor polymer is increased, many diffraction points in plane with the substrate are generated. Therefore, it can be seen that a crystal structure is varied according to the fusion ratio.
(53)
(54)
(55) Referring to
(56)
(57) Referring to
(58) It can be confirmed that various volatile organic compounds are detected in a low voltage (0.3 V or 1 V) state at room temperature without an additional heating device. It can be confirmed that the driven organic electronic multi-sensor is excellent in adsorption performance of the volatile organic compound even at a low voltage at room temperature in comparison with a state in which driving of the organic electronic multi-sensor is stopped. It can be confirmed that resistance increases in the case of polar volatile organic compounds (acetone and butanol), and resistance decreases in the case of non-polar volatile organic compounds (toluene and, chlorobenzene). Therefore, it can be confirmed that the organic electronic multi-sensor distinguishes the polarities of the volatile organic compounds.
(59)
(60) Referring to
(61)
(62) Referring to
(63)
(64) As described above, a variation value according to the concentrations and the fusion volume ratio of IPA and acetone, which are polar solvents, refers to the adsorption performance of the organic electronic multi-sensor for IPA and acetone, which are the polar solvents, and it can be confirmed that resistance values of a Y-axis of IPA and acetone, which are polar organic compound gases, decrease. In particular, in the case of an organic electronic multi-sensor fused with 1:7 of a volume ration of the organic semiconductor polymer to the ionic electrolyte, the resistance value exhibited a most reduced value. Therefore, it can be confirmed that when IPA and acetone among polar organic compound gases are fused with a volume ratio of 1:7, the adsorption performance of the organic electronic multi-sensor is most excellent.
(65)
(66) Referring to
(67) Referring to
(68) As described above, a variation value according to the concentrations and the fusion volume of chlorobenzene and toluene which are non-polar solvents refers to the adsorption performance of the organic electronic multi-sensor for chlorobenzene and toluene which are non-polar solvents. Further, in the case of the non-polar organic compound gas, it can be confirmed that the resistance value of the Y-axis increases. As described above, through a decrease or an increase of the resistance of the organic electronic multi-sensor, the volatile organic compound may be distinguished from the polar organic compound or the non-polar organic compound.
(69) Consequently, according to a variation in volume ratio of the ionic electrolyte fused with the organic semiconductor polymer, an electrical characteristic and gas adsorption performance of the organic electronic multi-sensor may be improved.
(70) Further, the volume ratio of the ionic electrolyte to the organic semiconductor polymer is increased, and a modification is made to the shape of the organic electrolyte layer such that the characteristic of adsorption performance of the organic electronic multi-sensor for the organic compound may be controlled.
(71)
(72) Referring to
(73)
(74) Referring to
(75) As a result of the characteristic of light reaction by irradiating light in the range of various wavelengths, it can be seen that characteristics of light reaction of a single organic semiconductor polymer and the organic electrolyte were hardly observed, but in the case of composite layers fused with a ratio of 1:1, 1:5, and 1:10, very high characteristics of light reaction were exhibited. In particular, it can be seen that a characteristic of light reaction of a layer fused with a ratio of 1:1 is increased up to 10.sup.8 times for each wavelength.
(76) As a result of comparing normalized light reactivity for each wavelength, a range showing maximum light reactivity is an NIR range (700 nm to 900 nm), and this result is accurately consistent with the absorption data. However, it can be seen that, as an amount of the organic electrolyte is increased, the light reactivity is degraded. This is because a content of the organic semiconductor polymer is relatively decreased.
(77)
(78) Referring to
(79) The organic electronic multi-sensor has a two-terminal structure not requiring a gate electrode and can be driven at room temperature and a low voltage such that process stability can be increased due to not requiring an additional heating device, and a production cost of a process can also be reduced. Further, the organic electronic multi-sensor of the present inventive concept can implement a characteristic of low consumption power even on a flexible PET substrate, thereby having high economic feasibility as a next-generation wearable electronic device.