KR101186816B1 - Polyimide with a carbazole brush, preparation thereof and products comprising the polymer - Google Patents

Abstract

(Ⅰ)
상기식에서, X는 -CH-, N또는 P이고;
R은 탄소수 1 내지 20의 알킬이며;
Z는 아래와 같은 군으로부터 선택되어지는 방향족 또는 지방족 유도체이다.

상기 폴리이미드의 중량평균 분자량은 5,000 내지 5,000,000, 바람직하게는 5,000 내지 500,000이다. The present invention relates to a polyimide polymer having a carbazole brush represented by Formula 1, a method for preparing the same, and a product using the same.

(Ⅰ)
Wherein X is -CH-, N or P;
R is alkyl having 1 to 20 carbon atoms;
Z is an aromatic or aliphatic derivative selected from the group below.

The weight average molecular weight of the polyimide is 5,000 to 5,000,000, preferably 5,000 to 500,000.

Description

POLYIMIDE WITH A CARBAZOLE BRUSH, PREPARATION THEREOF AND PRODUCTS COMPRISING THE POLYMER

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polymer memory device and a method for manufacturing the same, and to a novel nonvolatile memory device including a polyimide polymer having a carbazole brush that can be used in a polymer memory device as an active layer between an upper electrode and a lower electrode, and a method of manufacturing the same. It is about.

Recently, the use of digital media such as various smart cards, portable terminals, electronic money, digital cameras, game memory, MP3 players, etc. is rapidly increasing, and the amount of information to be processed and stored is also rapidly increasing. Is skyrocketing. In addition, while the technical demand for processing such a large amount of information at a high speed is increasing, a lot of researches are being conducted on the development of next generation memory devices. Next-generation memory devices must be non-volatile memory capable of ultra-large capacity, low power consumption, high-speed processing, and at the same time the recorded information does not disappear even when the power is turned off. Most of the non-volatile memory research that has been conducted so far is mainly based on silicon materials based on flash memory, but silicon-based memory devices face fundamental limitations. For example, the conventional flash memory has a limited number of write / erase times, a slow writing speed, and a miniaturization process to obtain a high density of memory capacity, thereby increasing the manufacturing cost of the memory chip and further miniaturizing the chip due to physical characteristics. You are facing limitations that you cannot do.

As the limitations of the existing flash memory technology are revealed, researches to replace the existing silicon memory devices are being actively conducted, and next-generation memories are classified according to materials constituting cells, which are basic units of semiconductors. Ferroelectric memory, ferromagnetic memory, phase change memory, nano tube memory, holographic memory, organic memory and the like. Among them, the polymer memory forms a memory layer using an organic polymer material between upper and lower electrodes, and applies a voltage thereto to implement memory characteristics using bistable stability of the resistance value of the memory layer. Cells formed at the intersections of the upper and lower electrodes provide bistable stability. That is, the polymer memory is a type of memory that can write and read data “0” and “1” by changing the resistance reversibly by the electrical signal of the polymer material between the upper and lower electrodes. Nonvolatile, which is an advantage, is expected to be a next generation memory that can overcome the problems of fairness, manufacturing cost, and integration, which have been recognized as disadvantages while implementing.

As an example of organic and polymer memories, US Patent Publication No. 2004-27849 proposes an organic memory device in which metal nanoclusters are applied between organic active layers, and Japanese Patent Laid-Open No. 62-95882 discloses an organic metal complex charge transfer. An organic memory device using CuTCNQ (7,7,8,8-tetracyano-p-quinodimethane) compound is disclosed. However, since the organic active layer of the memory device is formed using the device vacuum deposition, the manufacturing process is complicated, it is difficult to uniformly form metal nanoclusters in the device, and the yield is very low, and the manufacturing costs are increased. . In the non-volatile memory device using a polymer, the compound used as the active layer may be a polythiophene-based, polyacetylene-based, polyvinylcarbazole-based high molecular compound in which an alkyl group is introduced, or the like. (HS Majumdar, A. Bolognesi, and AJ Pal, Synthetic metal 140, 203-206 (2004)); MP Groves, CF Carvalho, and RH Prager, Materials Science and Engineering C, 3 (3), 181-183 (1995); and Y.-S. Lai, C.-H., Tu and D.-L. Kwong, Applied Physics Letters, 87, 122101-122103 (2005). In the case of polythiophene-based polymers, there are disadvantages in that the voltage value indicating the on / off state is high and instability in air, and the on / off ratio is not constant.Polyacetylene is generally conjugated, although it may be a memory device. Since the polymer is known to be the most easily oxidized in the air, it is difficult to realize a device. In addition, polyvinylcarbazole-based polymers have been reported to exhibit excellent switching properties and are currently being actively studied (Y. -S. Lai, C. -H., Tu and D. -L. Kwong , Applied Physics Letters, 87, 122101-122103 (2005). In addition, although polyaniline has been used as a memory device material, there is a problem of low solubility in organic solvents (RJ Tseng, J. Huang, J. Ouyang, RB Kaner, and Y. Yang, Nano Letters, 5, 1077). -1080 (2005)].

Accordingly, the object of the present invention is to overcome the above-mentioned conventional technical problems, to simplify the manufacturing process, to exhibit a current-voltage switching phenomenon, low operating voltage and current, large on / off ratio, and long-term recorded information. To provide an organic nonvolatile memory device is preserved.

Another problem to be solved by the present invention is to provide a new polymer compound for a nonvolatile memory device that can solve the above-mentioned conventional problems.

Another problem to be solved by the present invention is to provide a method for manufacturing a new polymer compound for a nonvolatile memory device that can solve the above-mentioned conventional problems.

In order to solve the above problems, there is provided a polyimide polymer compound having a carbazole brush represented by the formula (1).

(Ⅰ)

(Ⅰ)

Wherein X is -CH-, N or P;

R is alkyl having 1 to 20 carbon atoms;

Z is aromatic or aliphatic derivatives selected from the group

Wherein n is a positive integer and the weight average molecular weight of the polyimide is 5,000 to 5,000,000, preferably 5,000 to 500,000.

In an aspect, the present invention provides a polyimide polymer having a carbazole brush of Formula (I), and a dianhydride compound of Formula (II)

(Ⅱ)

(Ⅱ)

Diamine Compound of Formula 3

(Ⅲ)

(Ⅲ)

Reacting to produce a polyimide polymer, characterized in that

Wherein X is -CH-, N or P; R is alkyl having 1 to 20 carbon atoms; Z is the following group:

Aromatic or aliphatic derivatives selected from.

In one embodiment of the present invention, the compound of formula 3 is characterized in that obtained by hydrolyzing a diimide compound, such as the formula (4) under a hydrazine monohydrate catalyst,

(Ⅳ)

(Ⅳ)

The compound of Chemical Formula 4 may be obtained by performing Mitsunobu reaction of Chemical Formula 5 and Chemical Formula 6 in the presence of triphenylphosphine and diisopropyl azodicarboxylate.

(Ⅴ)

(Ⅴ)

(Ⅵ)

(Ⅵ)

The compound of Chemical Formula 5 may be obtained by reacting Chemical Formula 7 and phthalic hydride under an isoquinoline catalyst.

(Ⅶ)

(Ⅶ)

The present invention provides, in one aspect, an organic memory device having an active layer containing a polyimide polymer represented by the following general formula (1) and a polyamide polymer represented by the following general formula (1) as an active layer of a semiconductor device.

(Ⅰ)

(Ⅰ)

Wherein X is -CH-, N or P;

R is alkyl having 1 to 20 carbon atoms;

Z is an aromatic or aliphatic derivative selected from the group below.

Wherein n is a positive integer and the weight average molecular weight of the polyimide is 5,000 to 5,000,000, preferably 5,000 to 500,000.

The organic memory device of the present invention includes a first electrode, an active layer formed on the first electrode, and a second electrode formed on the active layer. The active layer of the organic memory device of the present invention is composed of a film form within a thickness of 10 to 100nm formed of a polyimide polymer. The manufacturing method of the present invention for achieving the above object comprises the steps of forming an active layer on the lower electrode formed on the substrate; And forming an upper electrode in contact with the active layer.

In the present invention, the organic memory device includes an active layer capable of moving electrons and holes between the lower electrode and the upper electrode. The active layer is made of a polyimide polymer, and when a voltage is applied to both ends of an electrode of a memory device after fabricating an organic memory, electrons and holes are introduced into the active layer through the electrode, and current is carried through a filament formed inside the active layer. .

In the organic memory device according to the present invention, an active layer is sandwiched between a first electrode and a second electrode. When a voltage is applied to the memory device, the resistance value of the active layer exhibits bistable stability, thereby showing memory characteristics. In addition, such a memory characteristic is due to the characteristics of the organic material, and even when the power is turned off, the characteristic is maintained as it is, showing the characteristics as a nonvolatile memory device.

As described above, the polyimide polymer compound having the carbazole brush of the formula (1) of the present invention is well known as a thermally stable material. The synthesis of basic polymers that can introduce various functional groups that can have a switching effect on these polyimide polymer compounds has the effect of increasing the thermal stability of the active layer of the polymer which plays the most important role in the nonvolatile memory device and realizing various memory characteristics. This high performance polymer active layer is expected to be useful in nonvolatile memory devices.

1 is a schematic cross-sectional view of a polymer memory device according to an embodiment of the present invention.
2 is a graph showing a current change according to the voltage of the polymer memory device manufactured in Example 1. FIG.

Hereinafter, the present invention will be described with reference to the following synthesis examples and examples, but the present invention is not limited only to the following synthesis examples and examples.

≪ Synthesis Example 1 &

3,3'-dihydroxy-4,4 '-(diphthalimido) biphenyl

3,3'-dihydroxy-4,4'-biphenyl (5.0 g, 0.023 mol), phthalic anhydride (8.2 g, 0.055 mol), and isoquinoline (0.13 g, 0.001 mol) Dissolve in methyl-2-pyrrolidinone. The reaction solution is stirred at 170 ° C. for 2 hours and cooled to room temperature. The solution is precipitated in methanol to give the product. Yield: 96%. ¹ HNMR (300 MHz, DMDO- d ₆ ) .δ (ppm): 10.10 (s, 2H, -OH), 7.99-7.89 (m, 8H, Ar-H), 7.38-7.35 (d, 2H, Ar-H ), 7.20-7.16 (m, 4H, Ar-H).

≪ Synthesis Example 2 &

3,3'-bis [9-carbazole (ethyloxy)]-4,4 '-(diphthalimido) biphenyl

3,3'-Dihydroxy-4,4 '-(diphthalimido) biphenyl (2.38 g, 5 mmol) is dissolved in 80 mL of 1-methyl-2-pyrrolidinone in a nitrogen atmosphere. After addition of dry triphenyphosphine (5.24 g, 20 mmol) is added, then the temperature is lowered to 0 ° C. and isopropyl azodicarboxylate (4.04 mL, 20 mmol) is added. The reaction solution is raised to room temperature and 9H-carbazole-9-ethanol (2.54 g, 12 mmol) dissolved in 10 mL of 1-methyl-2-pyrrolidinone is added. After 24 hours of reaction at room temperature, the product was precipitated in methanol. Yield: 78%. ¹ HNMR (300 MHz, DMDO- d ₆ ) .δ (ppm): 8.00-7.90 (m, 12H, Ar-H), 7.42-7.28 (m, 10H, Ar-H), 7.00-6.95 (t, 4H, Ar-H), 6.86-6.81 (t, 4H, Ar-H). 4.66-4.35 (m, 8H, CH ₂ ).

≪ Synthesis Example 3 &

3,3'-bis [9-carbazole (ethyloxy) biphenyl] -4,4'-diamine

3,3'-bis [9-carbazole (ethyloxy)]-4,4 '-(diphthalimido) biphenyl (5.17 g, 6 mmol) was dissolved in 100 mL of dimethylacetamide and 80 ° C. Raise to. Hydrazine monohydrate (18 g) is added slowly. After stirring for 2 hours, the temperature is lowered to room temperature. The reaction solution was precipitated in water to obtain a product. Recrystallization was carried out with a mixed solution of dimethylacetamide / methanol. Yield: 64%. ¹ HNMR (300 MHz, DMDO- d ₆ ) .δ (ppm): 8.14-8.12 (d, 4H, Ar-H), 7.74-7.72 (d, 4H, Ar-H), 7.46-7.41 (t, 4H, Ar-H), 7.21-7.16 (t, 4H, Ar-H). 6.78 (s, 2 H, Ar-H). 6.73-6.72 (d, 2H, Ar-H). 6.71-6.70 (d, 2H, Ar-H). 6.44-6.42 (d, 2H, Ar-H). 4.86-4.82 (t, 4H, CH ₂ ). 4.35-4.31 (t, 4H, CH ₂ ). 4.17 (s, 4H, NH ₂ ).

≪ Synthesis Example 4 &

Poly {3,3 '-[9-carbazole (ethyloxy)] biphenylene pyromellitimide} (PMDA-HAB-CBZ)

3,3'-bis [9-carbazole (ethyloxy) biphenyl] -4,4'-diamine (0.1204 g, 0.2 mmol) and pyromellitic acid dihydrate (0.0436 g, 0.2 mmol) in a 20 mL flask ) Was dissolved in 1.8 mL of 1-methyl-2-pyrrolidinone. The reaction mixture was then stirred at rt for 12 h. As the reaction proceeded gradually, the viscosity of the reaction mixture gradually increased to obtain polyamic acid. The polyamic acid solution was filtered and then applied to the glass substrate and dried at 80 ° C. for 1 hour. Subsequently, the glass substrate was heat-treated under nitrogen gas atmosphere at 150 ° C. for 1 hour, at 200 ° C. for 1 hour, and at 250 ° C. for 1 hour to obtain poly {3,3 ′-[9-carbazole (ethyloxy)] biphenylene. Pyromellitimide}. IR (film, cm- ¹ ): 3150-3020 (aromatic CH stretch), 2980-2850 (aliphatic CH stretch), 1779, 1724, 1380 (C = O imide I and CNC imide II). 1228 (COC stretch in alkyl aryl ether)

≪ Synthesis Example 5 &

Poly {3,3 '-[9-carbazole (ethyloxy)] biphenylene-4,4'-biphenyltetracarboxyimide} (BPDA-HAB-CBZ)

Same as in Synthesis Example 4, except that 3,3 ', 4,4'-biphenyltetracarboxylic acid dihydrate (0.0588g, 0.2mmol) was used instead of pyromellitic acid dihydrate (0.0436g, 0.2mmol) According to the method, the corresponding polyamic acid was obtained. And poly {3,3 '-[9-carbazole (ethyloxy)] biphenylene-4,4'-biphenyl tetracarboxylic imide} was obtained from this polyamic acid according to the same method as in Synthesis example 4. IR (film, cm ^-1 ): 3150-3020 (aromatic CH stretch), 2980-2830 (aliphatic C-Hstretch), 1778,1724,1386 (C = O imideI and CNC imideII), 1228 (COC stretchinalkylarylether)

≪ Synthesis Example 6 &

Poly {3,3 '-[9-carbazole (ethyloxy)] biphenylene-4,4'-oxydiphthalimide} (Oe-HAB-CBZ)

In the same manner as in Synthesis Example 4, except that 3,3 ', 4,4'-oxydiphthalic dianhydride (0.0620g, 0.2mmol) was used instead of pyromellitic acid dihydrate (0.0436g, 0.2mmol). Accordingly a corresponding polyamic acid was obtained. And poly {3,3 '-[9-carbazole (ethyloxy)] biphenylene-4,4'-oxydiphthalimide} was obtained from this polyamic acid according to the same method as in Synthesis example 4. IR (film, cm ^-1 ): 3150-3010 (aromatic CH stretch), 2980-2850 (aliphatic C-Hstretch), 1775,1724,1383 (C = O imideI and CNC imideII), 1228 (COC stretchinalkylarylether)

≪ Synthesis Example 7 &

Poly {3,3 '-[9-carbazole (ethyloxy)] biphenylene-4,4'-sulfondiphthalimide} (DSDA-HAB-CBZ)

In the same manner as in Synthesis Example 4, except that 3,3 ', 4,4'-sulfondiphthalic dianhydride (0.0714 g, 0.2 mmol) was used instead of pyromellitic acid dihydrate (0.0436 g, 0.2 mmol). Accordingly a corresponding polyamic acid was obtained. And poly {3,3 '-[9-carbazole (ethyloxy)] biphenylene-4,4'-sulfon diphthalimide} was obtained from this polyamic acid according to the same method as in Synthesis example 4. IR (film, cm ^-1 ): 3150-3000 (aromatic CH stretch), 2980-2850 (aliphatic C-Hstretch), 1779,1724,1380 (C = O imideI and CNC imideII), 1224 (COC stretchinalkylarylether)

1 is a schematic cross-sectional view of an organic memory device according to an embodiment of the present invention. Referring to FIG. 1, an Al electrode 3 having a thickness of 200 to 300 nm was formed by sputtering on the glass substrate 4.

Next, the polyamic acid prepared in Synthesis Example 4-7 was filtered through a 0.2 micro filter syringe filter, and the solution was spin-coated on the Al electrode, followed by nitrogen at 80 ° C. for about 1 hour, Heat treatment was performed at 150 ° C. for 1 hour, 200 ° C. for 1 hour, and 250 ° C. for 1 hour to form a thin film 2 having a polymer active layer having a thickness of 20 to 100 nm on the electrode. In this case, the thickness of the active layer was measured using an alpha-step profiler and an ellipsometry. The Al electrode 1 was deposited to a thickness of 1 nm to 1000 nm by using an electron beam or a thermal evaporator on the polymer active layer thus formed to complete a memory device. At this time, the thickness of the deposited electrode was controlled through a quartz crystal monitor.

[Experimental Example 1]

Characteristic test of memory device

In order to measure the electrical characteristics of the organic memory device obtained in Example 1, a probe station connected to a semiconductor analyzer was used. The switching characteristics were observed by contacting the tungsten tip of the probe station to the electrodes at both ends of the polymer active layer and measuring the change in current as the voltage was applied.

As can be seen from the graph of the voltage-current relationship of the device based on the ITO electrode of FIG. 2, the memory device having a polyimide polymer having a triphenylamine as the main chain as the active layer according to the present invention has a low current at low voltage State, off-state and then turn-on at a specific voltage (2.0-3.5 V) to maintain high current state and on-state, and stable on even after repeated bidirectional sweep The tendency to maintain state is shown. Here, the turn-on phenomenon corresponds to the 'Write' phenomenon in the memory, and this device does not erase ('Erase') once it has been 'Write' and keeps it in the ON state, that is, the 'Write' state. The write-once-read-many times (WORM) phenomenon is shown. In addition, this memory device (PMDA-HAB-CBZ) has 6.6 x 10 ^-2 A current in two resistance states (On & Off), e.g. On at 1.5 V and 2.7 x 10 in Off state. ^The on-off ratio of ^-10 A and on-off state is 10 ⁷ -10 ⁸ , which shows the characteristics of the WORM memory device which is quite stable.

Claims (17)

Polyimide polymer compound represented by the formula (1):

(Ⅰ)
Wherein X is -CH-, N or P;
R is alkyl having 1 to 20 carbon atoms;
Z is an aromatic or aliphatic derivative selected from the group below.

Wherein n is a positive integer and the weight average molecular weight of the polyimide is 5,000 to 5,000,000. The polyimide polymer compound of claim 1, wherein the polyimide polymer has a weight average molecular weight of 5,000 to 500,000. Diane hydride compounds of the formula (2)

(Ⅱ)
Diamine Compound of Formula 3

(Ⅲ)
Wherein X is -CH-, N or P; R is alkyl having 1 to 20 carbon atoms; Z is an aromatic or aliphatic derivative selected from the group

Method for producing a polyimide polymer, characterized in that the reaction. The method of claim 3, wherein the compound of Formula 3 is obtained by hydrolyzing a diimide compound of Formula 4 under a hydrazine monohydrate catalyst.

(Ⅳ) The method of claim 4, wherein the compound of Formula 4 is prepared by the Mitsunobu reaction of Formula 5 and Formula 6 in the presence of triphenylphosphine and diisopropyl azodicarboxylate.

(Ⅴ)

(Ⅵ) The method of claim 5, wherein the compound of Formula 5 is obtained by reacting Formula 7 and phthalic hydride under an isoquinoline catalyst.

(Ⅶ) Diamine compound represented by the following formula (3):

(Ⅲ)
Wherein X is -CH-, N or P; and R is alkyl having 1 to 20 carbon atoms. The diimide compound represented by the following general formula (4):

(Ⅳ)
Wherein X is -CH-, N or P; and R is alkyl having 1 to 20 carbon atoms. A polymer memory device comprising an active layer consisting of a polyimide polymer of Formula 1 below.

(Ⅰ)
Wherein X is -CH-, N or P;
R is alkyl having 1 to 20 carbon atoms;
Z is an aromatic or aliphatic derivative selected from the group below.

Wherein n is a positive integer and the weight average molecular weight of the polyimide is 5,000 to 5,000,000. The memory device of claim 9, wherein the memory device forms an upper electrode on an active layer, wherein the upper electrode is gold, silver, platinum, copper, cobalt, nickel, tin, aluminum, indium tin oxide, titanium, or the like. Polymer memory device, characterized in that selected from the group consisting of a combination.
The memory device of claim 9, wherein the memory device forms a lower electrode under the active layer, and the lower electrode is gold, silver, platinum, copper, cobalt, nickel, tin, aluminum, indium tin oxide, titanium, or one thereof. Polymer memory device, characterized in that selected from the group consisting of the above combination. The polymer memory device of claim 9, wherein the polymer active layer is connected to an electrode and a diode. Forming an active layer on the lower electrode formed on the substrate;
Forming an upper electrode in contact with the active layer,
Wherein the active layer is represented by the following formula,

(Ⅰ)
Wherein X is -CH-, N or P;
R is alkyl having 1 to 20 carbon atoms;
Z is an aromatic or aliphatic derivative selected from the group below.

Wherein n is a positive integer and the weight average molecular weight of the polyimide is 5,000 to 5,000,000. The method of claim 13, further comprising applying a voltage to both ends of the memory device to introduce electrons and holes into the active layer to allow a current to flow through the filament inside the active layer. The method of claim 13, wherein the forming of the polymer active layer comprises coating a polymer solution. 16. The method of claim 15, wherein the coating is performed by one of spin coating, spray coating, electrostatic coating, dip coating, bleed coating, ink jet coating, and roll coating. A semiconductor active layer made of the polyimide polymer compound according to claim 1.

Images