KR20080073199A - Water-soluble conjugated polymer containing metal ion and application thereof - Google Patents

Abstract

A water-soluble conjugated polymer containing metal ions is provided to show high electron and hole mobility when the polymer is applied as an organic film of an organic EL device. A water-soluble conjugated polymer containing metal ions has a structure represented by the following formula, wherein R1 and R2 are identical to or different from each other, independently of each other, a mono-substituted or multi-substituted substituent, and are hydrogen, or branched or branchless C1-12 alkyl group, C1-12 alkoxy group, or C1-12 ester group, A and B are NR'R" or SO^(3-) identical to or different from each other(wherein, R' and R" are identical to or different from each other, independently of each other, a mono-substituted or multi-substituted substituent, and are hydrogen, or branched or branchless C1-3 alkyl group), R3 and R4 are identical to or different from each other, independently of each other, a branched or branchless substituent comprising at least one oxygen atom or nitrogen atom, or a heterocycle comprising at least one oxygen atom or nitrogen atom, or crown ether, or an aromatic ring substituted with an oxygen atom or nitrogen atom, and M1 and M2 are metal ions.

Description

Water-soluble conjugated polymer containing metal ion and application about

The present invention relates to a water-soluble conjugated polymer, and more particularly, to the structure of the water-soluble conjugated polymer to which metal ions are bonded and its application.

The organic EL display device has attracted attention as a next generation display device technology because it has advantages such as low voltage driving, high luminous efficiency, wide viewing angle, and fast response speed than the liquid crystal display device. The organic EL device generally has a structure in which an organic thin film is interposed between ITO, which is a transparent electrode serving as an anode, and a cathode using a metal having a low work function. Holes and electrons injected through the anode and the cathode, respectively, recombine in the organic thin film to generate excitons, and light is emitted by energy of the excitons. The organic thin film may be made of a single material, but the organic thin film generally has a multilayer structure because of large differences in mobility between holes and electrons. The organic thin film may include, for example, a light emitting layer, a hole related layer interposed between the light emitting layer and the anode, and an electron related layer interposed between the light emitting layer and the cathode. Also, the hole related layer may include a hole injection layer and a hole transport layer, and the electron related layer may include an electron injection layer and an electron transport layer. The hole-related layer and the electron-related layer can obtain a higher efficiency by allowing the holes and electrons to effectively move to the light emitting layer.

For each layer of such an organic thin film, a single molecule or a polymer organic material suitable for its characteristics is used, and various materials have been proposed. However, existing organic materials still have problems to be improved. For example, in conventional organic EL devices, electron-related layers such as electron injection layers and electron transport layers are mainly formed by depositing monomolecular materials, but the deposition process is not only expensive expensive vacuum equipment but also thermal process. there is a problem. This is because the thermal evaporation process may damage the light emitting layer positioned under the electron related layer. In addition, the organic material used for the organic EL device should be able to exhibit high efficiency without restriction with respect to the selection of the metal electrode. Although a metal electrode having a low work function is required for a high efficiency device, there is a problem of easily oxidizing in air when a metal having a low work function is used as an electrode. Therefore, organic materials having high efficiency are required even for metal electrodes having a high work function.

In addition, the memory field continues to increase the degree of integration of currently commercialized memory, and to develop and industrialize integrated memory (nonvolatile, ultra-fast, high-density) having all the advantages of the existing memory. This memory can be used not only for computers but also for the ever-developing portable memory, smart card, system on chip (SoC). Deposition process technology plays an important role.

Current memory includes high-density dynamic random access memory (DRAM) and fast static RAM (SRAM). However, such a memory has a disadvantage in that volatile information is lost when the power is cut off. On the other hand, portable flash memory, such as a memory stick or a digital camera, is used as a portable information storage medium because it is non-volatile and does not lose information, but has a disadvantage of low speed and density compared to volatile memory. .

Memory devices using organic materials are drawing attention as next-generation memory technologies because they are easier to integrate in a multilayer structure, lower power consumption and solution processing, and lower manufacturing costs than silicon-based memory devices. . Conventional organic memory devices have a structure in which an organic material having two resistance states between upper and lower metallic electrodes is formed in a thin film form. The organic thin film may be made of a single material, but the type of organic material is very different according to the driving principle of the organic memory device, and the components of the organic thin film are not only large but also formed.

 Organic materials used as organic memory devices may vary in type depending on the driving principle of the memory devices, may use a single organic material, or may have a complex form of a mixture of other materials such as metallic nanoparticles.

Organic memory devices generally implement memory characteristics by using organic materials dissolved in organic solvents or by forming a monolayer by thermal evaporation using expensive vacuum equipment. However, organic molecules dissolved in organic solvents or monomolecules that form thin films by thermal evaporation methods are unstable in the air, and in order to accurately measure their properties, a closed glove box in a nitrogen atmosphere is required as well as silicon. The structure is difficult to secure compatibility with the device.

The first object of the present invention for solving the above problems is to provide a water-soluble conjugated polymer in which metal ions are bonded.

It is a second object of the present invention to provide an organic EL device utilizing the above-described improved water soluble conjugated polymer.

It is a third object of the present invention to provide a nonvolatile organic memory device utilizing the above-described improved water soluble conjugated polymer.

In order to achieve the first object of the present invention described above, the water-soluble conjugated polymer in which the metal ions are bonded according to an aspect of the present invention is represented by the following general formula,

[General Formula]

In this case, R ₁ and R ₂ in the general formula may be selected the same or different from each other, and as a mono- or polysubstituted substituent independently of each other, hydrogen, a branched or branched alkyl group of 1 to 12 carbon atoms, carbon number An alkoxy group of 1 to 12 or an ester group of 1 to 12 carbon atoms; A and B are NR′R ″ or SO ^{3 −} , which may be selected identically or differently from each other, and R ′ and R ″ may be selected identically or differently from each other, and are mono- or polysubstituted substituents independently of one another. As an alkyl group having 1 to 3 carbon atoms with or without branches; R ₃ and R ₄ may be selected identically or differently from each other and independently of each other have a branched or non-branched substituent including at least one oxygen or nitrogen element, or a hetero containing at least one oxygen or nitrogen element Ring, or crown ether, or an aromatic ring substituted with an oxygen or nitrogen element; M ₁ and M ₂ is characterized in that the metal ion.

In addition, the metal ions represented by M ₁ and M ₂ are independently a metal cation having the same or different oxidation number, bonded to at least one oxygen or nitrogen element of R ₃ and R ₄ .

In addition, a and b are independently from each other 1 to 100, wherein n is characterized in that 1 to 10000.

The organic EL device according to the second object of the present invention is characterized by including in the organic thin film a water-soluble conjugated polymer to which the above-described improved metal ions are bonded.

Here, a water-soluble conjugated polymer in which metal ions are bonded may be used as the light emitting layer. In addition, a water-soluble conjugated polymer in which metal ions are bonded may be used as an electron-related layer including an electron injection layer and an electron transfer layer. In addition, a water-soluble conjugated polymer in which metal ions are bonded may be used as a hole related layer including a hole injection layer and a hole transport layer.

In the nonvolatile organic memory device according to the third object of the present invention, an upper electrode is formed by forming a lower electrode on a substrate, spin-coating a water-soluble conjugated polymer represented by the chemical formula above, and thermally depositing using a shadow mask. It includes a step.

The present invention as described above proposes a novel water-soluble conjugated polymer structure to which new metal ions are bound. The water-soluble conjugated polymer in which such metal ions are bonded has various advantages when used as an organic material in an organic EL device. For example, the water-soluble conjugated polymer to which the metal ion of the present invention is bonded has high efficiency of electron and hole movement by itself. This makes it possible to expect high efficiency even when a metal having a high work function is applied, and therefore a metal having a high work function that is stable in air can be employed as the electrode. In addition, most conventional electron injection materials solve all the problems associated with using single molecules. For example, the formation of monomolecules requires the use of expensive equipment, which is expensive equipment, and the light emitting layer may be damaged by the thermal process. However, the water-soluble conjugated polymer of the present invention can be formed by a simple and low temperature process by spin coding.

In addition, when the water-soluble conjugated polymer conjugated with metal ions according to the present invention is used as a nonvolatile organic memory device, a single water-soluble conjugated polymer conjugated with metal ions to the organic layer using spin coating on a p-type high concentration silicon substrate is used. By forming a film, it is possible to implement a nonvolatile organic memory device having compatibility with existing silicon devices and having a stable high resistance state and low resistance state in the air. In addition, since the organic layer can be formed using spin coating without using an expensive vacuum equipment, not only can the manufacturing cost be lowered, but the manufacturing process is simple, the reproducibility is good, and the productivity can be increased.

It should be noted that the following examples are merely for illustrative purposes and do not limit the scope of the present invention.

The water-soluble conjugated polymer to which the metal ion of the present invention is bound according to the first object of the present invention is represented by the following general formula,

[General Formula]

In this case, R ₁ and R ₂ in the general formula may be selected the same or different from each other, and as a mono- or polysubstituted substituent independently of each other, hydrogen, a branched or branched alkyl group of 1 to 12 carbon atoms, carbon number An alkoxy group of 1 to 12 or an ester group of 1 to 12 carbon atoms; A and B are NR′R ″ or SO ^{3 −} , which may be selected identically or differently from each other, and R ′ and R ″ may be selected identically or differently from each other, and are mono- or polysubstituted substituents independently of one another. As an alkyl group having 1 to 3 carbon atoms with or without branches; R ₃ and R ₄ may be selected identically or differently from each other and independently of each other have a branched or non-branched substituent including at least one oxygen or nitrogen element, or a hetero containing at least one oxygen or nitrogen element Ring, or crown ether, or an aromatic ring substituted with an oxygen or nitrogen element; M ₁ and M ₂ is characterized in that the metal ion.

In addition, the metal ions represented by M ₁ and M ₂ are independently a metal cation having the same or different oxidation number, bonded to at least one oxygen or nitrogen element of R ₃ and R ₄ .

In addition, a and b are independently from each other 1 to 100, wherein n is characterized in that 1 to 10000.

The organic EL device according to another object of the present invention is characterized in that the organic thin film includes a water-soluble conjugated polymer to which the above-described improved metal ions are bonded.

Here, a water-soluble conjugated polymer in which metal ions are bonded may be used as the light emitting layer. In addition, a water-soluble conjugated polymer in which metal ions are bonded may be used as an electron-related layer including an electron injection layer and an electron transfer layer. In addition, a water-soluble conjugated polymer in which metal ions are bonded may be used as a hole related layer including a hole injection layer and a hole transport layer.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. The following examples are intended to illustrate, the present invention is not limited thereto.

Metal ions Combined  receptivity Conjugate  Preparation of Polymer

(Example 1)

As shown in [Scheme 1], a poly [() compound represented by Chemical Formula [3] by polymerization of the pullulene monomers of Chemical Formula [1] and Chemical Formula [2] using Suzuki Coupling reaction 9,9-bis (6-bromohexyl)-pulloene) -alt- (9,9-bis (2- (2-methoxyethoxy) ethyl) -fluorene)] (Poly [(9, 9-bis (6-bromohexyl) -fluorene) -alt- (9,9-bis (2- (2-methoxyethoxy) ethyl) -fluorene]) is produced, specifically, the monomer represented by the formula [1]. Phosphorus 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9,9- (6-dibromohexyl) -fluorene ( 2,7-bis (4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl) -9,9- (6-dibromohexyl) -fluorene) 0.7 g (1 mmol) and chemical formula [2 ] 2,7-dibromo-9,9-bis (2- (2-methoxyethoxy) ethyl) -pulluene (2,7-dibromo-9,9-bis (2-) 0.5 g (1 mmol) of (2-methoxyethoxy) ethyl) -fluorene) was dissolved in 60 mL of tetrahydrofuran (THF) solvent and maintained in a nitrogen atmosphere. 20 mL of ₂ M potassium carbonate solution (2 M K ₂ CO ₃ ) is added dropwise, after which the palladium catalyst (Pd (PPh) ₃ ) is added and stirred for 3 days at 120 ° C. The temperature is then lowered to room temperature. The precipitated reaction solution is slowly added dropwise to the methanol solution to catch precipitation, and the precipitated compound of formula [3] is dried in a vacuum oven.

Next, poly [(9,9-bis (6-bromohexyl)-pulloene) -alt- (9,9-bis (2- (2-methoxy) which is a compound represented by the dry chemical formula [3] Methoxy) ethyl) -fluorene)] is dissolved in 30 mL of tetrahydrofuran (THF) solvent. Then 5 ml of trimethylamine solution is added dropwise. If precipitation occurs with stirring, water is added dropwise to dissolve. The reactant was distilled under vacuum to give [E] solution of poly [(9,9-bis (6-bromoethyl) -fluorene) -alt- (9,9-bis (2). -(2-methoxyethoxy) ethyl) -fluorene)] dibromide (Poly [(9,9-bis (6-bromohexyl) -fluorene) -alt- (9,9-bis (2- (2- methoxyethoxy) ethyl) -fluorene)] dibromide) precipitates.

Figure 2 is a graph showing the structure and peaks of the compound of formula [4] synthesized by [Scheme 1] of the present invention confirmed by 1H-NMR. Poly [(9,9-bis (6-bromoethyl) -fluorene) -alt- (9,9-bis (2- (2-methoxyethoxy) which is a compound represented by the formula [4] in FIG. The production and structure of ethyl) -fluorene)] dibromide can be confirmed.

Poly [(9,9-bis (6-bromoethyl) -fluorene) -alt- (9,9-bis (2- (2) which is a compound represented by the formula [4] obtained in the above [Scheme 1]. -Methoxyethoxy) ethyl) -fluorene)] dibromide is dissolved in a mixed solution of methyl alcohol and water, and then an aqueous sodium chloride solution is added. After mixing for 4 hours dialysis is used to filter out unbound sodium chloride. The remaining solution was then lyophilized to give sodium-poly [(9,9-bis (6-bromohexyl) -fluorene) -alt- (9,9-bis (2- (2-methoxyethoxy) ethyl) -fluorene)] dibromide (Poly [(9,9-bis (6-bromohexyl) -fluorene) -alt- (9,9-bis (2- (2-methoxyethoxy ) ethyl) -fluorene)] dibromide).

Example 2

In the same manner as in Scheme 2, poly [(9,9-bis (6-bromoethyl) -fluorene) -alt- (9,9), which is a compound represented by Chemical Formula [4] obtained in Scheme 1 above. An aqueous solution of calcium chloride is added to bis (2- (2-methoxyethoxy) ethyl) -fluorene)] dibromide. After 4 hours of mixing dialysis is used to filter out unbound calcium chloride. The remaining solution was then freeze-dried to calculate calcium-poly [(9,9-bis (6-bromohexyl) -fluorene) -alt- (9,9), a compound represented by the formula [6] to which calcium ions were bound. -Bis (2- (2-methoxyethoxy) ethyl) -fluorene)] dibromide (calcium-poly [(9,9-bis (6-bromohexyl) -fluorene) -alt- (9,9-bis (2- (2-methoxyethoxy) ethyl) -fluorene)] dibromide) was obtained.

Figure 3a is a graph showing the XPS test results of the water-soluble conjugated polymer of Example 1 according to the present invention, Figure 3b is a graph showing the XPS test results of the water-soluble conjugated polymer of Example 2 according to the present invention. 3A and 3B, the metal cations are bound to the oxygen element of the synthesized water-soluble polymer by measuring binding energy using XPS (X-ray Photoelectron Spectroscopy).

3A and 3B, through the X-ray Phtoelectron Spectroscopy (XPS) experiment, by confirming the binding energy of the formula [5] and [6], in the compound represented by the formula [4] in each It was confirmed that the oxygen element and sodium ions (Na ⁺ ) or calcium ions (Ca ⁺ ) are bonded.

The present invention is also apparent that the metal ions used in Examples 1 and 2 above are not limited to calcium or sodium. Therefore, any metal complex may be added as long as it can be bonded with a cation in [Scheme 2] and [Scheme 3].

Metal ions Combined  receptivity Conjugate  Application of polymer

(Example 3)

In the present Example, the water-soluble conjugated polymer which the metal ion of this invention couple | bonded was used as the electron injection layer of organic electroluminescent element, and the improvement of the efficiency of this organic electroluminescent element was measured.

On the indium tin oxide (ITO) which is a transparent electrode substrate, PEDOT: PSS, which is a hole injection layer, is spin-coated for 30 seconds at a speed of 4000 rpm and dried. Poly [2-methoxy, 5- (2'-ethyl-hexyloxy) -1,4-phenylenevinylene] as a light emitting layer on PEDOT: PSS (MEH-PPV: poly [2-methoxy, 5- (2 '-ethyl-hexyloxy) -1,4-phenylenevinylene] (MEH-PPV)) was dissolved in 0.8 wt% of chlorobenzene and spin-coated at 2000 rpm for 30 seconds to dry. 0.5 wt% of the compound represented by Chemical Formula [5] and Chemical Formula [6] to be used as the electron injection layer was dissolved in methyl alcohol (CH 3 OH), followed by spin coating at a speed of 3000 rpm and drying. Silver, which is a metal for the cathode, is formed at a low rate of 0.1 mW / s in a high vacuum state of 10 to 6 Torr atmosphere through a thermal deposition method.

5A to 5D are graphs showing the results of comparative measurements of a device using the water-soluble conjugated polymer of the metal ion of the present invention as an electron injection layer in an organic EL device and a device without an electron injection layer. 5A to 5D, when the water-soluble conjugated polymer in which the metal ion of the present invention is bound is used as the electron injection layer of the organic EL device (Examples 1 and 2), otherwise (denoted as 'without EIL' in the drawing). Compared to this, electron density, brightness, external quantum efficiency, and power efficiency are greatly improved.

When the water-soluble conjugated polymer in which the metal cation is bonded is used as the electron injection layer, the efficiency is improved by the effects described below. First, each of the metal by the electrostatic force due to the voltage applied from outside the cation Na ^+, or Ca ⁺ is moved toward the negative electrode and the negative ions (Br ^-), when was used a water-soluble polymer binding the metal cation to an electron injection layer Moves toward the anode. At this time, since the metal cations collected in the cathode by moving in the direction of the cathode in the electron injection layer are in a state in which electrons are insufficient, for example, electrons are easily received from a cathode made of silver and injected into the light emitting layer. Therefore, silver used as a negative electrode has a large work function but high efficiency, and thus a stable negative electrode is obtained in air. In other words, if the conjugated polymer of the metal ion of the present invention is applied to the electron injection layer, the efficiency of the organic EL device is increased even when silver having a large work function is used as the cathode. Of course, since a large work function of silver was used as the cathode, a more stable state is obtained even in the air. Secondly, in the electron injection layer, each moved metal cation and anion (Br ⁻ ) move in the direction of each cathode and anode, and induced dipole monent due to the space charge effect is induced. Occurs. As a result, the open circuit voltage increases. The increased open circuit voltage causes the reduction of the energy barrier of the silver cathode and the electron injection layer, thereby facilitating electron injection.

As a result of the measurement using the organic EL device measuring equipment, a water-soluble conjugated polymer having a metal cation bound thereto (a polymer of formula [5] and a formula [6]) when a silver having a large work function but stable in air was used as a cathode When used as an electron injection layer, it shows current density even at low voltage. It shows that current flows well even under low voltage. Luminance begins to glow at a low voltage of 3.5V and maximum brightness of over 4000 cdm ^-2 . 5C and 5D show the dramatic increase in the external quantum efficiency and the power efficiency, respectively. This is because when the low work function of barium (Ba) reported in the journal (Chem. Mater, 2004, 16, 708.) is used as the cathode, and has a high work function as in the present invention and is stable in air ( It can be seen that the same efficiency can be seen by comparing the case where the water-soluble conjugated polymer in which the metal cation is bonded as the electron injection layer while using the Ag) cathode.

Thus, the water-soluble conjugated polymer in which the metal ion of the present invention assists the movement of electrons and holes includes not only the above-described electron injection layer but also an electron-related layer including an emission layer, an electron transfer layer, and a hole injection layer and a hole transfer layer. Of course, it can be applied to the hole-related layer.

(Example 4)

In this embodiment, the water-soluble conjugated polymer in which the metal ions of the present invention are bonded was used in a nonvolatile organic memory device having an array structure, and electrical characteristics were evaluated.

Referring to FIG. 6, an organic memory device is formed on a substrate 110, and includes an upper electrode 150 and a lower electrode 135, and an organic layer 140 is formed therebetween. The upper electrode 150 and the lower electrode 135 are formed to have a structure intersecting in the form of (+), and a cell formed at a point intersecting with (+) provides bistable characteristics.

The substrate 110 is electrically insulating and may be made of a transparent material. Preferably it may be glass, silicone, or a transparent plastic film.

By forming a single film between the lower electrode 130 and the upper electrode 150, the water-soluble conjugated polymer 140 having the above-described characteristics ensures compatibility with the silicon device of the lower electrode 130, and has a stable high resistance state in the air. And a nonvolatile organic memory device having a low resistance state can be implemented.

 7A to 7E illustrate cross-sectional views of a method of manufacturing a nonvolatile organic memory device according to an embodiment of the present invention.

7A to 7E, the manufacturing of a nonvolatile organic memory device having an array structure through a water-soluble conjugated polymer according to the present invention may include forming silicon oxide 120 on a substrate 110 (FIG. 7A), lower portion. Forming an electrode 130 (FIG. 7B), etching the lower electrode 130 (FIG. 7C), spin coating the water-soluble conjugated polymer 140 (FIG. 7D), and forming an upper electrode having an array structure (FIG. 7B). 150) may be formed (FIG. 7E).

Forming the silicon oxide 120 on the substrate 110 (FIG. 7A) and forming the lower electrode 130 (FIG. 7B) may be performed by lowering a polycrystalline high concentration p-type silicon thin film on the silicon substrate 110. Forming the electrode 130.

The etching of the lower electrode 130 (FIG. 7C) is performed by performing a pattern on the array structure and etching to selectively remove unnecessary portions so that a thin p-type silicon thin film deposited on the entire silicon substrate is formed into an array structure. Step.

Spin coating the water-soluble conjugated polymer 140 (FIG. 7D) spins the water-soluble conjugated polymer 140 at a speed of 2000 rpm for 30 seconds to apply the water-soluble conjugated polymer 140 to the upper portion of the lower electrode 135 formed of an array structure. Coating and drying.

Finally, forming the upper electrode 150 having an array structure (FIG. 7E) is performed to measure current-voltage of a nonvolatile memory device manufactured through the above process, and the upper electrode 150 spins. In the high vacuum state of 10 ^-6 Torr, a shadow mask was applied at a low rate of 0.1 Å / s by thermal evaporation of silver of a metal on the water-soluble conjugated polymer thin film 140 subjected to the coating step. It was used to form an array structure intersected with the lower electrode 135 in the form (+).

8 illustrates electrical characteristics of an organic memory device using a water-soluble conjugated polymer according to an embodiment of the present invention.

Referring to FIG. 8, when the voltage is increased from 0 V to 6 V, the organic memory device which is initially in a high resistance state may have a threshold voltage due to an induced dipole moment due to a space charge effect. In the vicinity of the threshold voltage (3 V), the current rapidly increases to a low resistance state. The low resistance state thus formed is changed to the initial high resistance state when the voltage is reduced from 6 V to -3 V, resulting in two characteristic high resistance states and low resistance states as the voltage changes. This is a memory characteristic that represents two states, “1” (ON) and “0” (OFF).

9 illustrates memory retention of an organic memory device using a water-soluble conjugated polymer according to an embodiment of the present invention.

Referring to FIG. 9, the memory retention phenomenon is a result of stability when a high resistance state or a low resistance state is formed, and each state of ON and OFF is set for a predetermined time. It is maintained above. As a result, it can be seen that the characteristics required for the memory element are excellent.

Although described above with reference to a preferred embodiment of the present invention, those skilled in the art will be variously modified and changed within the scope of the invention without departing from the spirit and scope of the invention described in the claims below I can understand that you can.

1 is a general formula of a water-soluble conjugated polymer conjugated with metal ions according to the present invention.

Figure 2 is a graph showing the structure and peaks of the compound of formula [4] synthesized by [Scheme 1] of the present invention confirmed by 1H-NMR.

Figure 3a is a graph showing the XPS experimental results of the water-soluble conjugated polymer of Example 1 according to the present invention.

Figure 3b is a graph showing the XPS experimental results of the water-soluble conjugated polymer of Example 2 according to the present invention.

4 is a schematic diagram of the structure and energy barrier of an organic EL device using a water-soluble conjugated polymer in which a metal ion of the present invention is bonded as an electron injection layer.

5A to 5D are graphs showing the results of comparative measurements of a device using a metal-ion-bonded water-soluble conjugated polymer of the present invention as an electron injection layer in an organic EL device and a device without an electron injection layer.

6 is a perspective view of a nonvolatile organic memory device having an array structure according to an embodiment of the present invention.

7A to 7E illustrate cross-sectional views of a method of manufacturing a nonvolatile organic memory device according to an embodiment of the present invention.

8 illustrates electrical characteristics of an organic memory device using a water-soluble conjugated polymer according to an embodiment of the present invention.

9 illustrates memory retention of an organic memory device using a water-soluble conjugated polymer according to an embodiment of the present invention.

<Explanation of symbols for the main parts of the drawings>

110 substrate 120 silicon oxide film

130: lower electrode 135: etched lower electrode

140: organic layer 150: upper electrode

Claims (12)

A water-soluble conjugated polymer in which metal ions are represented by the following general formulas. [General Formula]

R ₁ and R ₂ in the general formula may be selected the same or different from each other, a mono- or polysubstituted substituent independently of each other, hydrogen, or an alkyl group having 1 to 12 carbon atoms with or without branch, carbon number 1 An alkoxy group of ˜12 or an ester group of 1 to 12 carbon atoms, A and B are NR′R ″ or SO ^{3 −} , which may be selected identically or differently from each other, and R ′ and R ″ are the same or different from each other; A mono- or polysubstituted substituent which is independently selected from each other, hydrogen or a branched or unsubstituted alkyl group having 1 to 3 carbon atoms, R ₃ and R ₄ may be selected the same or different from each other and are independent of each other A branched or branched substituent containing at least one oxygen or nitrogen element, or a heterocyclic ring, or crown ether, or oxygen containing at least one oxygen or nitrogen element Bovine or a nitrogen element is a substituted aromatic ring, M ₁ and M ₂ is the water-soluble conjugated polymer is a metal ion, it characterized in that the binding metal ions. The method of claim 1, The metal ions represented by M ₁ and M ₂ are independently bonded to at least one oxygen or nitrogen element of R ₃ and R ₄ , and the metal ions are bonded to each other, wherein the metal ions are the same or different from each other. Water soluble conjugated polymer. The method of claim 1, Wherein a and b are each independently 1 to 100, and n is 1 to 10000, wherein the metal ions are water-soluble conjugated polymers. An organic EL device comprising the water-soluble conjugated polymer in which the metal ions in claim 1 are bonded to the organic thin film. The method of claim 4, wherein An organic EL device characterized in that the water-soluble conjugated polymer in which the metal ion is bonded as a light emitting layer. The method of claim 4, wherein An organic EL device using the water-soluble conjugated polymer in which the metal ion is bonded as an electron-related layer including an electron injection layer and an electron transfer layer. The method of claim 4, wherein An organic EL device using the water-soluble conjugated polymer in which the metal ion is bonded as a hole related layer including a hole injection layer and a hole transport layer. A nonvolatile organic memory device comprising a water-soluble conjugated polymer in which the metal ions of claim 1 are bonded between a lower electrode and an upper electrode. Forming a lower electrode on the substrate; Spin coating a water-soluble conjugated polymer represented by the chemical formula of claim 1; And A method of fabricating a nonvolatile organic memory device comprising forming an upper electrode through thermal deposition using a shadow mask. 10. The method of claim 9, wherein the lower electrode and the upper electrode are formed in an array structure. The method of claim 9, wherein the spin coating, Method of manufacturing a nonvolatile organic memory device, characterized in that performed for 30 seconds at a speed of 2000rpm. The method of claim 9, wherein the thermal deposition using the shadow mask, A method of manufacturing a nonvolatile organic memory device, characterized in that it is carried out at a rate of 0.1 Å / s in a vacuum state of 10 ^-6 Torr.

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