KR20150088951A - Self-assembled brush block copolymers with fluorocarbon for memory device, preparation thereof and products comprising the polymer - Google Patents

Abstract

The present invention relates to polyether polymers having properties of a digital memory and a manufacturing method thereof and, more specifically, to polyether brush polymer materials in which compounds having properties of a digital memory are formed at the end of a brush, to synthesis thereof, and to a non-volatile memory device manufactured by using the polymers as an activating layer between an upper electrode and a lower electrode. One or more functional groups are formed at the end of at least some of the brush, and are chosen among the represented chemical formula (1).

Description

FIELD OF THE INVENTION [0001] The present invention relates to a non-volatile memory self-assembling brush block copolymer having fluorocarbon incorporated therein, a method for producing the self-assembling brush block copolymer, and a memory device using the self-

The present invention relates to a non-volatile memory self-assembling brush block copolymer to which fluorocarbon having a digital memory characteristic is introduced, a process for producing the same, and a non-volatile memory block manufactured by using the inventive block copolymer as an active layer between an upper electrode and a lower electrode And a memory device.

Recently, as the use of digital media such as various smart cards, portable terminals, electronic money, digital cameras, game memory, and MP3 players is rapidly increasing, the amount of information to be processed and stored is rapidly increasing, . In addition, there is a growing demand for high-speed processing of such large-capacity information, and a lot of research is being conducted on the development of a next-generation memory device. The next generation memory device must be a nonvolatile memory capable of high capacity, low power consumption, high speed processing, and the recorded information is not lost even if the information is turned off. Most of the non-volatile memories studied so far are mainly based on silicon-based flash memory, but silicon-based memory devices are faced with fundamental limitations. For example, the conventional flash memory has a limited number of write / erase operations, a slow write speed, and a high integration memory capacity

The fabrication cost of the memory chip is increased due to the miniaturization process, and the chip is no longer miniaturized because of its physical characteristics.

As the limit of conventional flash memory technology is revealed, researches for replacing existing silicon memory devices are being actively carried out. Next-generation memories are classified according to materials constituting cells, which are basic units of semiconductor, A ferroelectric memory, a ferromagnetic memory, a phase change memory, a nanotube memory, a holographic memory, and an organic memory.

Among these, polymer memory is able to overcome the fundamental limitation that conventional metal-oxide-semiconductor based non-volatile inorganic memory devices have difficulty in stacking and storage capacity because of lack of flexibility and mobility. For example, it is possible to easily form a thin film by a method such as spin coating, inkjet printing or the like, thereby simplifying the manufacturing process of a memory device, making it possible to manufacture a memory device at a low cost, and forming a plurality of organic thin film layers by various methods such as glass, It can be formed on a substrate and the storage density can be increased indefinitely.

In the polymer memory, a memory layer is formed by using an organic polymer material between the upper and lower electrodes, and a voltage is applied to the memory layer, thereby realizing the memory characteristic by using the bistability of the resistance value of the memory layer. The cell formed at the intersection of the upper electrode and the lower electrode provides bistability.

That is, the polymer memory is a memory in which the resistance is reversibly changed due to the electrical signal of the polymer material existing between the upper and lower electrodes, and data '0' and '1' are written and read. Such a polymer memory is expected to be a next-generation memory that can overcome the problems of fairness, manufacturing cost, and integration that have been recognized as disadvantages while implementing nonvolatile memory which is an advantage of conventional flash memory.

As an example of the organic and polymer memory, U.S. Patent Publication No. 2004-27849 proposes an organic memory device in which metal nanoclusters are applied between organic active layers, and Japanese Patent Application No. 62-95882 discloses a charge transger ) Compound, CuTCNQ (7,7,8,8-tetracyano-p-quinodimethane). However, since the organic active layer of the memory device is formed by using the device vacuum deposition, the manufacturing process is complicated, and it is difficult to uniformly form the metal nano clusters in the device, the yield is very low, and the manufacturing cost is increased . On the other hand, in the polymer non-volatile memory device, examples of the compound used as the active layer include a polythiophene-based, polyacetylene-based, and poly vinylcarbazole-based polymer compound into which an alkyl group is introduced (MP Groves, CF Carvalho, and RH Prager, Materials Science and Engineering C, 3 (3), 2004) And Y.-S. Lai, C.-H., Tu and D. -L. Kwong, Applied Physics Letters, 87, 122101-122103 (2005)). In the case of the polythiophene-based polymer, there is a disadvantage that the voltage value indicating on / off state is high, unstable in the air, and the on / off ratio is not constant. Polyacetylene has a possibility as a memory element, It is known as the polymer that is most likely to be oxidized in the air among the bonded polymers. In addition, the polyvinylcarbazole-based polymer has been reported to exhibit excellent switching characteristics and has been actively studied (Y.-S. Lai, C. -H., Tu and D. -L. Kwong , Applied Physics Letters, 87, 122101-122103 (2005)). Polyaniline has also been used as a memory element material, but has a problem of low solubility in an organic solvent (RJ Tseng, J. Huang, J. Ouyang, RB Kaner, and Y. Yang, Nano Letters, 5, 1077 -1080 (2005)).

Despite the development of these products, however, there is a continuing need for new polymers that can be used as active layers in nonvolatile memory devices.

A problem to be solved by the present invention is to provide a novel block copolymer which can be used as an active layer in a nonvolatile memory device.

Another object of the present invention is to provide a novel block copolymer which can be used as an active layer in a nonvolatile memory device.

Another object of the present invention is to provide a novel nonvolatile memory device using a block copolymer polymer as an active layer. Another object of the present invention is to provide a method for manufacturing a nonvolatile memory device using a block copolymer brush polymer as an active layer.

In order to solve the above problems, the present invention provides a polyether brush polymer, wherein at least one brush terminal has at least one functional group selected from the group of hole transporting materials represented by the following formula (1) 1 to 20.

In the preferred embodiment of the present invention, the functional group for hole transport formed at the brush terminal of the polyether brush polymer may be represented by the following chemical formula (2), and n is an integer of 1 to 20.

In the present invention, the polyether brush polymer means a polymer in which a functional group is introduced into a polyether polymer main chain through various linkers.

In the present invention, the polyether brush polymer may form a functional group of the above formula (1) or (2) at 1-99% of the end of the brush, and at least some of the other brush terminals may have a Functional groups may be formed,

(3)

(3)

End of the other brush is _{-H, -CH 3, -COOH, -CHO} , -OH, -NH 2, -C 6 H 6, - (C 6 H 6) 2 and N _3, and select at least one from the group consisting of Functional groups may be formed.

In the practice of the present invention, the polyether brush polymer is composed of a block copolymer having a main chain, and the functional groups represented by the formulas (1) and (3) may be selectively formed at the end of a brush formed in a predetermined block have.

In the present invention, specifically, the polyether brush polymer is represented by the following chemical formula (4).

In the above formula, ρ and σ represent repeating units of carbon including R ₁ , R ₂ , R ₃ and R ₄ , and independently of each other, are values of 1 to 20;

R ₁ , R ₂ , R ₃ , R _{4 ,} Y _{1 , and} Y ₂ are each independently hydrogen or an alkyl group having 1 to 20 carbon atoms;

m and n represent the content (mol%) of the polyether unit, 0 <m? 100, 0? n <100 and m + n = 100;

Z ₁ and Z ₂ are linkers connecting the functional group at the terminal and the polyether backbone, and are -CH ₂ ORO-, -CH ₂ OROCO-, -CH ₂ ORCOO-, -CH ₂ OCORO-, -CH ₂ ORNHCO-, _{CH 2 OROCO (CH 2) 2} OCO-, -CH 2 ORCO-, -CH 2 OROCO (CH 2) 2 OCOR-, -CH 2 OCO (C 6 H 6) 2 RO-, -CH 2 OCO (C 6 _{H 6) 2 ROCO-, -CH 2} OCO (C 6 H 6) 2 RCOO-, -CH 2 OCO (C 6 H 6) 2 RNHCO-, -CH 2 OCO (C 6 H 6) 2 ROCO (CH 2 _{) 2 OCO-, -CH 2 OCO (} C 6 H 6) 2 ROCO (CH 2) 2 OCORO-, -CH 2 OCORO (C 6 H 6) 2 -, -CH 2 OCOROCO (C 6 H 6) 2 - _{, -CH 2 OCORCOO (C 6 H} 6) 2 -, -CH 2 OCORNHCO (C 6 H 6) 2, -CH 2 OCORO (C 6 H 6) 2 ORO-, -CH 2 OCORO (C 6 H 6) _{2 ORCO-, -CH 2 OCORO (C} 6 H 6) 2 ORCOO-, -CH 2 OCOROCO (C 6 H 6) 2 ORO-, -CH 2 OCOROCO (C 6 H 6) 2 ORCO-, -CH 2 OCOROCO (C ₆ H ₆ ) ₂ ORCOO-, -CH ₂ OCORCOO (C ₆ H ₆ ) ₂ ORO-, -CH ₂ OCORCOO (C ₆ H ₆ ) ₂ ORCO-, -CH ₂ OCORCOO (C ₆ H ₆ ) ₂ ORCOO -, -CH ₂ SRO-, -CH ₂ SROCO-, -CH ₂ SRCO-, -CH ₂ SRO-, -CH ₂ SRNHCO-, -CH ₂ SROCO (CH ₂ ) ₂ OCO-, -CH ₂ SRCO-, -CH ₂ SROCO (CH ₂ ) ₂ OCOR-, -CH ₂ SO ₂ RO-, -CH ₂ SO ₂ ROCO-, -CH ₂ SO ₂ RCOO-, -CH ₂ SO ₂ RNHCO-, -CH ₂ SO ₂ ROCO (CH ₂ ) ₂ OCO-, -CH ₂ SO ₂ ROCO (CH ₂ ) ₂ OCOR-, -CH ₂ SO ₂ RCO _{-, -CH 2 ORSRO-, -CH 2} ORSROCO-, -CH 2 ORSROCOR-, -CH 2 ORSRCOO-, -CH 2 ORSRNHCO-, -CH 2 ORSROCO (CH 2) 2 OCO-, -CH 2 ORSROCO (CH ₂ ) ₂ OCOR-, wherein R is selected from hydrogen or an alkyl group having 1 to 20 carbon atoms,

P is a functional group at least partially or fully selected from the above-mentioned formula (1)

X is at least part or all of the above formula (3). Wherein P and X is _{-H, -CH 3, -COOH, -CHO} , -OH, -NH 2, -C 6 H 6, - may be selected from _{(C 6 H 6) 2,} N 3, the group consisting of .

The weight average molecular weight of the brush polymer compound is 5,000 to 5,000,000, preferably 5,000 to 500,000. In a preferred embodiment of the present invention, the repeating unit of each block of the brush polymer may be 10 to 1,000.

Representative examples of the self-assembled copolymer polymer of Formula 1 according to the present invention include poly (3 - ((6 - ((7- (9H-carbazole-

yl) heptanoyl) oxy) hexyl) thio) propyl glycidyl ether) _40- b-poly (glycidyl-

((3,3,4,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-heptadecafluorodecyl) oxy) 12-oxododecanoate) ₄₀ Hereinafter abbreviated as PGCHHTP ₄₀ - b - PGHFO ₄₀ ) where 20 and 40 each represent a repeating unit.

(5)

(5)

In one aspect, the present invention provides a process for preparing a polyether block copolymer of formula (4), comprising the steps of: preparing a polyether block copolymer represented by the following formula (6)

Wherein R ₁ , R ₂ , R ₃ , R ₄ , Y _{1 ,} Y ₂ , m and n are as defined in formula (1);

Reacting the functional group B attached to the side chain in the polyether block copolymer with a compound represented by the following formula (7)

X-B '(7)

Herein, X- is as defined in the above formula (1), and B and B 'are residues constituting the linker Z ₂ of the above formula (4) by, for example, an ester reaction by mutual reaction;

The functional group A attached to the side chain in the polyether block copolymer is represented by the following formula (8)

With a compound to be represented,

HO-A '(8)

Herein, A and A 'are residues constituting the linker Z ₁ of the above formula (4) by the reaction between them, for example, by the addition reaction of a double bond; And

Reacting the -OH functional group with the formula (9), wherein R is alkyl of 1-20 carbon atoms.

(9)

(9)

In a preferred embodiment of the present invention, wherein the B is -ROH, preferably -CH ₂ OH, the XB 'can be represented by the formula (10), wherein R is alkyl of 1 to 20 carbon atoms.

(10)

(10)

In a preferred embodiment of the present invention, A is a compound represented by -CH ₂ OCH-C = CH ₂ as a functional group, an allyl group is an example formed at the terminal, the P-A 'is to represent a compound of formula (11) , Wherein R is 1-20 carbon atoms.

SH-R-OH (11)

In a preferred embodiment of the present invention, the compound of formula (6) may be represented by the following formula (12), wherein R is independently alkyl of 1-20 carbon atoms.

In the practice of the present invention, the compound of formula (6) is a compound of formula (13)

Wherein X ₁ and X ₃ are independently selected from the group consisting of -R-, -O-, -COO-, -NH-, -S-, -SOO-, -R-, -20, X ₂ and X ₄ are protecting groups independently selected from (13)

May be prepared by selectively removing some protecting groups.

In the practice of the present invention, the polyether block copolymer compound of the above formula (13) can be prepared by sequentially block-copolymerizing the compounds represented by the following formula (15).

Here, X _a is X ₁ or X ₃ , X _b is X ₂ or X ₄ , and n is an integer of 1-8, which is opened under a phosphine catalyst.

In another aspect, the present invention provides an organic memory device using the compound of Formula 1. An organic memory device according to 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 formed into a film shape having a thickness of 5 to 100 nm or less formed of the above-mentioned polyether block copolymer polymer.

According to another aspect of the present invention, there is provided a method of manufacturing a thin film transistor, comprising: forming an active layer of Formula 3 on a lower electrode formed on a substrate; Nanostructuring the active layer; And forming an upper electrode to be in contact with the active layer.

In the practice of the present invention, the nanostructuring can be performed by solvent annealing of the active layer, and the nanostructure is also changed according to the volume ratio of each block in the block copolymer constituting the active layer. When the voltage is applied to both ends of the electrode of the memory device after the organic memory is manufactured, electrons and holes are introduced into the active layer through the electrode, and the current flows through the filament formed inside the active layer, Lt; / RTI &gt; When a voltage is applied to such a memory device, the resistance value of the active layer exhibits bistability and exhibits a memory characteristic. The nanostructures formed by the volume ratio of each block of the active layer polymer affect the memory characteristics.

An organic memory device using the polyether brush polymer as an active layer according to the present invention and a method of manufacturing the same are provided. In addition, a new polyether brush polymer that can be used as an active layer of an organic memory device and a method of manufacturing the same are provided.

1 is a schematic cross-sectional view of a polymer memory device according to an embodiment of the present invention.
In the case of Example 1, 1 is an Al electrode, 2 is a polymer active layer, 3 is an Al electrode, and 4 is SiO ₂ / Si.
FIG. 2 is a graph showing a current change according to a voltage of a polymer (PGCHHTP ₄₀ - b - PGHFO ₄₀ ) having a volume ratio of 1: 1 between polymer blocks of an active layer having a thickness of 10 nm of the polymer memory device prepared in Example 1.
FIG. 3 is a graph showing the relationship between polymer blocks having a volume ratio of 1: 1 (PGCHHTP ₄₀ ) using a grazing incidence X-ray scattering (GIXS) apparatus for analyzing a polymer thin film structure using a 9A beamline of a Pohang radiation accelerator - b -PGHFO ₄₀ ), which is a two-dimensional image.
(a) shows the results of Grazing Incidence Small Angle X-ray Scattering (GISAXS)
(b) shows the results of Grazing Incidence Wide Angle X-ray Scattering (GISAXS)

Hereinafter, the present invention will be described in detail with reference to examples. It should be noted that the following examples are not intended to limit the invention but to illustrate the invention.

&Lt; Synthesis Example 1 &

Each of the other blocks by volume (AGE / EEGE = 60/20, 40/40 , 20/60) having a polyether block copolymer, poly (allyl glycidyl ether glycidyl ether- -ethoxyethyl b) (b-PAGE-PEEGE the anionic polymerization method All polymerizations are carried out in a glovebox under controlled conditions of humidity and oxygen under argon gas.The synthesis of block copolymers with a block volume ratio of AGE / EEGE = 40/40 is representative. (3.42 mmol) of phenylpropyl alcohol, 130.0 mL of toluene, and 3.42 mL (3.42 mmol) of t-Bu-P4 phosphine catalyst are added to a round bottom flask equipped with a stirrer, ), And the mixture was stirred at room temperature for 20 hours. Then, 6.63 mL (44.5 mmol) of ethoxyethyl glycidyl ether was added thereto, and the mixture was stirred at room temperature for 20 hours. g) was added to terminate the reaction. . D. gives mukyeo as tetrahydrofuran is after 8 hours and dried to the polyether block copolymer under vacuum to 40 ° C then purified using an alumina column, and the shot and the solvent was prepared _{(PAGE 40 b -PEEGE 40) Yield} : 70 ^{% 1 H NMR (300 MHz,} CDCl 3, δ (ppm)):. 7.21-7.29 (m, 5H, aromatic protons from initiator), 5.88 (m, 40H, -OCH 2 C H C (H a) H b ), 5.25 (d, 40H, -OCH 2 CHC (H a) H b), 5.15 (d, 40H, -OCH 2 CHC (H a) H b), 4.69 (q, 65H, -OC H (CH 3 _{) O- EEGE), 4.0 (d} , 80H, -O CH 2 CHC (H a) H b), 3.43-3.69 (m, -OC H 2 C H- C H 2 groups in main chain, -OC H2 CH _{3 - EEGE, Ph-CH 2} CH 2 C H 2 O), 2.68 (t, 2H, Ph-C H 2 CH 2 CH 2 O), 1.87 (m, 2H, Ph-CH 2 C H 2 CH 2 O ), 1.29 (d, 195H, -OCH (C H 3) O- EEGE), 1.20 (t, 195H, -OCH 2 C H 3 - EEGE); ^{13 C NMR (75 MHz, CDCl} 3, δ: 15.3, 19.8, 31.2, 32.3, 60.7, 64.8, 69.8, 70.0, 70.6, 72.2, 78.9, 99.7, 116.7, 125.7, 128.3, 128.4, 134.9, 141.9; IR ( ^{film, / (cm -1))} : 3100 (w), 2978 (s), 2930-2870 (s), 1650 (w), 1455 (m), 1380, 1340, 1300, 1270 (m), 1135- 1060 (s), 1000 (m), 930 (m), 877 (m).

&Lt; Synthesis Example 2 &

1.80 g of the polyether block copolymer compound obtained in Synthesis Example 1 (ethoxyethyl glycidyl ether = 6.90 mmol) was dissolved in tetrahydrofuran, and 6.90 mmol of hydrochloric acid was added thereto, followed by stirring at room temperature for 5 hours. Subsequently, sodium bicarbonate is added to the solution to neutralize the solution, and then the solvent is blown under a high pressure. The compound thus obtained was dissolved in chloroform, and the insoluble material was filtered off. The chloroform was then blown off and dried under vacuum at 40 ° C for 8 hours to obtain the desired compound (PAGE ₄₀ - b- PG ₆₅ ). Yield: 87%. ^{1 H NMR (300 MHz, DMSO-} d 6, δ (ppm)): 7.16-7.29 (m, 5H, aromatic protons from initiator), 5.88 (m, 40H, -OCH 2 C H C (H a) H b ), 5.25 (d, 40H, -OCH 2 CHC (H a) H b), 5.15 (d, 40H, -OCH 2 CHC (H a) H b), 4.50 (br, 65H, - (CH 2) O H ), 4.00 (d, 80H, -OC H ₂ CHC (H _a ) H _b ), 3.43-3.69 (m, -OC H ₂ C H - , C H ₂ groups directly bonded to the main chain, _{2 CH 2 C H 2 O)} , 2.68 (t, 2H, Ph-C H 2 CH 2 CH 2 O), 1.80 (m, 2H, Ph-CH 2 C H 2 CH 2 O).

&Lt; Synthesis Example 3 &

Add 2 g (8.7 mmol) of dodecanedioic acid, 2 g (10.4 mmol) of EDC and 0.64 g (5.2 mmol) of DMAP in a 100 mL round bottom flask and dissolve in 30 mL of chloroform. The heptadecafluorodecane alcohol is dissolved in 30 ml of chloroform, slowly added, and stirred at 35 ° C for 24 hours. After cooling the solution to room temperature, it is extracted with chloroform, washed with water, and then water is removed using MGSO ₄ . After removing the solvent by using reduced pressure heating, the product is purified by recrystallization using chloroform and hexane to obtain heptadecafluorodecyloxy-12-oxododecane-oic acid compound. Yield: 2.58 g (44%). ^{1 H NMR (δ (ppm)} , 300 MHz, DMSO): δ12.0 (s, 1H), 4.3 (t, 2H), 2.65 (t, 2H), 2.3 (t, 2H), 2.15 (t, 2H ), 1.5 (m, 4H), 1.2 (m, 12H).

&Lt; Synthesis Example 4 &

0.15 g (PG = 0. 81 mmol) of the polyether block copolymer compound PAGE ₄₀ -b-PG ₄₀ obtained in Synthesis Example 2 was dissolved in 20 mL of chloroform, to which 0.66 g (0.97 mmol) of the compound obtained in Synthesis Example 3, 0.37 g (1.9 mmol) of EDC and 0.12 g (0.97 mmol) of DMAP were added thereto, followed by stirring at 35 ° C for 24 hours. After removing the solvent by using pressure heating, it is dissolved in chloroform and precipitated many times in methanol. After several submergence purification, the desired compound PAGE ₄₀ - b - PGHFO ₄₀ is obtained. _{PAGE 40 - b -PGHFO 40, Yield} : 72.0%, 1 H NMR (300 MHz, CDCl 3, δ (ppm)): 5.88 (m, 40H, -OCH 2 CHC (H a) H b), 5.1-5.3 _{(m, 80H, -OCH 2 CHC} (H a) H b), -OCH 2 CHC (H a) H b), 4.35 (m, 80H, -COOCH 2 CH 2 CF 2 -), 4.05-4.3 (br _{, 80H, -OCH 2 CHC (H} a) H b), 3.89-4.0 (br, 80H, -OCH 2 CHC (H a) H b), 3.43-3.70 (m, -OCH 2 CH-, CH 2 - AGE groups directly bonded to the main chain , Ph-CH 2 -CH 2 CH 2 O), 2.68 (t, 2H, Ph-CH 2 CH 2 CH 2 O), 2.45 (br, 74H, -COOCH 2 CH 2 CF _{2 CF 2 -), 2.28 (} br, 160H, -COOCH 2 (CH 2) 8 CH 2 COO -), 1.87 (m, 2H, Ph-CH 2 CH 2 CH 2 O), 1.6 (br, 160H, - CH ₂ (CH ₂ ) ₆ CH ₂ -), 1.25 (br, 480H, - (CH ₂ ) ₆ -).

&Lt; Synthesis Example 5 &

To a 50 mL shrinkage flask, add 0.25 g of the compound obtained in Synthesis Example 4, PAGE ₄₀ - b - PGHFO ₄₀ (AGE = 0.68 mmol), and dissolve in 7 mL of chloroform and dimethylformamide mixed solvent (volume ratio 1:10). To this, 0.084 g (0.51 mmol) of AIBN and 0.74 ml (5.5 mmol) of 6-mercapto-1-hexanol are added and the solvent oxygen and moisture are removed through decaching. This solution is stirred at 75 ° C for 24 hours. After cooling down to room temperature, some solvent is removed through a leaching process and precipitation is carried out in a mixed solvent of water and methanol. After dissolution in chloroform and subsequent purification by precipitation with diethyl ether several times, the target compound PGPSHOH ₄₀ -b-PGHFO ₄₀ can be obtained. Tield: 71%. ^{1 H NMR (300 MHz, CDCl} 3, δ (ppm)): 4.35 (m, 2H, -COOCH 2 CH 2 CF 2 -), 4.05-4.3 (br, 4H, -OCH 2 CHC (H a) H b ), 3.43-3.70 (m, -OCH ₂ CH-, CH _{2 -GPGHOH} group directly bonded to the main chain, Ph-CH ₂ -CH ₂ CH ₂ O, -CH ₂ CH ₂ OH, -OCH ₂ CH ₂ CH _{2 S-), 2.68 (t,} 2H, Ph-CH 2 CH 2 CH 2 O), 2.4-2.5 (br, 6H, -CH 2 CH 2 SCH 2, -COOCH 2 CH 2 CF 2 -), 2.28 ( _{br, 4H, -COOCH 2 (CH} 2) 8 CH 2 COO-), 1.87 (br, 4H, Ph-CH 2 CH 2 CH 2 O, -OCH 2 CH 2 CH 2 S-), 1.59-1.63 (br _{, 8H, -CH 2 (CH 2} ) 6 CH 2 -, --SCH 2 CH 2 (CH 2) 3, -CH 2 CH 2 OH), 1.25-1.4 (br, 28H, - (CH 2) 6 - , -S (CH ₂ ) ₂ (CH ₂ ) ₂ (CH ₂ ) ₂ OH).

&Lt; Synthesis Example 6 &

Add 3.5 g (20.9 mmol) of carbazole and 1.26 g (31.4 mmol) of NaH to a 100 mL round bottom flask and dissolve in 104 mL of dimethylformamide and stir gently at 50? For 20 min. Then, 4.07 ml (20.9 mmol) of ethyl 7-bromo-undecanoate is slowly added and the mixture is stirred at 80 ° C for 12 hours. After cooling the solution to room temperature, the reaction is terminated by using 5% aqueous solution of ammonium chloride (350 ml). After extraction with ethyl acetate and water, the organic solution is washed again with brine and then water is removed using MGSO4. The silica gel column was eluted with 1: 3 volume ratio of ethyl acetate and hexane to obtain a compound after purification. Yield: 5.42 g (80%). ^{1 H NMR (δ (ppm)} , 300 MHz, CDCl 3): δ8.1 (d, 2H), 7.4 (m, 4H), 7.2 (t, 2H), 4.28 (t, 2H), 4.1 (q, 2H), 2.25 (t, 2H), 1.85 (m, 2H), 1.58 (m, 2H) 1.37 (m, 4H) 1.2 (t, 3H).

In the second step, a solution of 5.42 g (16.8 mmol) of ethyl 7-carbazoleheptanoate dissolved in 50 ml of tetrahydrofuran is slowly added to a solution of 2.82 g (50.3 mmol) of KOH in 7.5 ml of methanol. After stirring at 35 ° C for 2 hours, the reaction mixture was cooled to room temperature and the reaction was terminated by using 500 ml of water. Add 35% hydrochloric acid solution until PH becomes 2, and precipitate occurs. Thereafter, silica gel column was eluted with 1: 2 volume ratio of ethyl acetate and hexane solution to obtain a compound. Yield: 4.46 g (90%). ^{1 H NMR (δ (ppm)} , 300 MHz, CDCl 3): δ11.0 (b, 1H), δ8.1 (d, 2H), 7.4 (m, 4H), 7.2 (t, 2H), 4.1 ( q, 2H), 2.25 (t, 2H), 1.85 (m, 2H), 1.58 (m, 2H) 1.37 (m, 4H).

&Lt; Synthesis Example 7 &

0.25 g (PGPSHOH = 0.27 mmol) of the polyether block copolymer compound PGPSOH ₄₀ - b- PGHFO ₄₀ obtained in Synthesis Example 5 was dissolved in 8 mL of chloroform, to which 0.12 g (0.41 mmol) of the compound obtained in Synthesis Example 6, 0.16 g (0.82 mmol) of EDC and 0.05 g (0.41 mmol) of DMAP are added, and the mixture is stirred at 35? For 24 hours. After removing the solvent by using pressure heating, it is dissolved in chloroform and precipitated many times in methanol. After several times of precipitation purification, the desired compound PGCHHTP ₄₀ - b - PGHFO ₄₀ is obtained. _{PGCHHTP 40 - b -PGHFO 40, Yield} : 72.0%, 1 H NMR (300 MHz, CDCl 3, δ (ppm)): δ8.1 (d, 2H), 7.4 (m, 4H), 7.2 (t, 2H ), 4.35 (m, 2H, -COOCH 2 CH 2 CF 2 -), 4.05-4.3 (br, 6H, -OCH 2 CHC (H a) H b, -CH2-carbazole, -CH2OCOCH2-), 3.43-3.70 _{(m, -OCH 2 CH-, CH} 2 - GPGPSHOH group directly bonded to the main chain, Ph-CH 2 -CH 2 CH 2 O, -OCH 2 CH 2 CH 2 S-), 2.68 (t, 2H, Ph _{-CH 2 CH 2 CH 2 O)} , 2.4-2.5 (br, 6H, -CH 2 CH 2 SCH 2, -COOCH 2 CH 2 CF 2 -), 2.2-2.28 (br, 6H, -COOCH 2 (CH 2 _{) 8 CH 2 COO-, -COOCH 2} (CH 2) 5 -carbazole), 1.83-1.87 (br, 6H, Ph-CH 2 CH 2 CH 2 O, -OCH 2 CH 2 CH 2 S -, - CH 2 CH ₂ -carbazole), 1.59-1.63 (br, 10H, -CH ₂ (CH ₂ ) ₆ CH ₂ -, -SCH ₂ CH ₂ (CH ₂ ) ₃ , -CH ₂ CH ₂ OH, -OCOCH ₂ CH ₂ ), 1.25-1.58 (br, 32H, - (CH 2) 6 -, -S (CH 2) 2 (CH 2) 2 (CH 2) 2 O-, -CH 2 CH 2 CH 2 CH 2 -carbazole) .

Embodiment of Memory Device Manufacturing Example

An insulating film SiO ₂ was formed on the silicon substrate through thermal oxidation and then an Al electrode having a thickness of 30 to 100 nm was formed thereon using an electron beam or a thermal evaporator .

Then, the polymer prepared in Synthesis Example 7 was dissolved in a tetrahydrofuran solvent in different mass percentages, and then filtered with a syringe filter of 0.22 microfilter to spin-coat the solution on the above Al electrode. The polymer active layer thus formed was annealed at 40 ° C for 24 hours under vacuum to form a thin film having a polymer active layer of 5 to 50 nm thick on the electrode. The thickness of the active layer was measured using an alpha-step profiler and an ellipsometer. The polymer active layer thus formed is allowed to form a nanostructure by using a vapor of a solvent. PGCHHTP ₄₀ - b - PGHFO ₄₀ , PGCHHTP ₆₀ - b - PGHFO ₂₀ , PGCHHTP ₂₀ - b - PGHFO ₆₀ For the polymers with different volume ratios, the nanostructures are formed by heat treatment at 90? For 2 hours. An Al electrode was deposited on the polymer active layer to a thickness of 20 nm to 100 nm using an electron beam or a thermal evaporator to complete a memory device. The thickness of the deposited electrode was controlled through a quartz crystal monitor.

Characterization of memory devices

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 tungsten tips of the probe station were contacted with electrodes at both ends of the polymer active layer, and the switching characteristics were measured by measuring the change of current as voltage was applied.

As can be seen from the graph of the voltage-current relationship of the device based on the Al electrode shown in FIG. 2, the memory device having the polyether block copolymer polymer according to the present invention as an active layer has a low current at low voltage, (± 1 ~ 9 V) and maintains high current state and on-state after a certain voltage (± 1 ~ 9 V) On-state. The phenomenon that turns on here corresponds to the write phenomenon in the memory phenomenon. These devices can not be erased if they are written once according to the nanostructure of the active layer, but can be kept in the ON state, that is, the Write-Once-Read-Many times (WORM) And a dynamic random access memory (DRAM) phenomenon, which is a characteristic of maintaining a write state. These memory devices are also available in two On and Off states, for example, a current of 6.9 x 10 ^-3 A in the On state at 0.5 V and 2.3 x 10 ^-10 A in the Off state, (On-off ratio) of about 10 &lt; ⁶ &gt; to about 10 &lt; ^{7 &} gt ;. That is, the most important factor determining the characteristics of the memory device is the polymer active layer. It is confirmed that the polyether block copolymer polymer active layer according to the present invention has various memory characteristics and excellent data storage ability according to the formed nanostructure I could.

As described above, the hole transporting material of the present invention and the self-assembling brush block copolymer polymer having fluorocarbon introduced at the end thereof are highly soluble in an organic solvent and thus have excellent processability and excellent mechanical properties such as thermal stability and mechanical strength. In addition, a switching phenomenon occurs at a low driving voltage due to electrical characteristics, and it is confirmed that there are two on / off current states, so that a memory device can be implemented using the same as an active layer. In addition, since the memory characteristics can be made different depending on the nanostructure of the self-assembling brush block copolymer polymer into which the hole transferring material and the fluorocarbon are introduced, the memory device having excellent performance using the above- It is expected that it will be possible to manufacture it at the production cost.

Claims (20)

And at least one functional group selected from the following formula (1) is formed on at least a part of the brush end.

The polyether brushed polymer according to claim 1, wherein the functional group of the formula (1) is represented by the following formula (2).

The polyether brush polymer according to claim 1, wherein the brush polymer is a polyether block copolymer. The polyether brush polymer according to claim 1, wherein the polyether brush polymer has a functional group of formula (1) or (2) at 1-99% of the end of the brush, and at least a part of the other brush terminal has a functional group Is formed on the surface of the polyether-bridged polymer.

(3) A polyether brush polymer represented by the following formula (4).

In the above formula, ρ and σ represent repeating units of carbon including R ₁ , R ₂ , R ₃ and R ₄ , and independently of each other, are values of 1 to 20;
R ₁ , R ₂ , R ₃ , R _{4 ,} Y _{1 , and} Y ₂ are independently hydrogen or an alkyl group having 1 to 20 carbon atoms;
m and n represent the content (mol%) of the polyether unit, 0 <m? 100, 0? n <100 and m + n = 100;
Z ₁ and Z ₂ are linkers connecting the functional group at the terminal and the polyether backbone, and are -CH ₂ ORO-, -CH ₂ OROCO-, -CH ₂ ORCOO-, -CH ₂ OCORO-, -CH ₂ ORNHCO-, _{CH 2 OROCO (CH 2) 2} OCO-, -CH 2 ORCO-, -CH 2 OROCO (CH 2) 2 OCOR-, -CH 2 OCO (C 6 H 6) 2 RO-, -CH 2 OCO (C 6 _{H 6) 2 ROCO-, -CH 2} OCO (C 6 H 6) 2 RCOO-, -CH 2 OCO (C 6 H 6) 2 RNHCO-, -CH 2 OCO (C 6 H 6) 2 ROCO (CH 2 _{) 2 OCO-, -CH 2 OCO (} C 6 H 6) 2 ROCO (CH 2) 2 OCORO-, -CH 2 OCORO (C 6 H 6) 2 -, -CH 2 OCOROCO (C 6 H 6) 2 - _{, -CH 2 OCORCOO (C 6 H} 6) 2 -, -CH 2 OCORNHCO (C 6 H 6) 2, -CH 2 OCORO (C 6 H 6) 2 ORO-, -CH 2 OCORO (C 6 H 6) _{2 ORCO-, -CH 2 OCORO (C} 6 H 6) 2 ORCOO-, -CH 2 OCOROCO (C 6 H 6) 2 ORO-, -CH 2 OCOROCO (C 6 H 6) 2 ORCO-, -CH 2 OCOROCO (C ₆ H ₆ ) ₂ ORCOO-, -CH ₂ OCORCOO (C ₆ H ₆ ) ₂ ORO-, -CH ₂ OCORCOO (C ₆ H ₆ ) ₂ ORCO-, -CH ₂ OCORCOO (C ₆ H ₆ ) ₂ ORCOO -, -CH ₂ SRO-, -CH ₂ SROCO-, -CH ₂ SRCO-, -CH ₂ SRO-, -CH ₂ SRNHCO-, -CH ₂ SROCO (CH ₂ ) ₂ OCO-, -CH ₂ SRCO-, -CH ₂ SROCO (CH ₂ ) ₂ OCOR-, -CH ₂ SO ₂ RO-, -CH ₂ SO ₂ ROCO-, -CH ₂ SO ₂ RCOO-, -CH ₂ SO ₂ RNHCO-, -CH ₂ SO ₂ ROCO (CH ₂ ) ₂ OCO-, -CH ₂ SO ₂ ROCO (CH ₂ ) ₂ OCOR-, -CH ₂ SO ₂ RCO _{-, -CH 2 ORSRO-, -CH 2} ORSROCO-, -CH 2 ORSROCOR-, -CH 2 ORSRCOO-, -CH 2 ORSRNHCO-, -CH 2 ORSROCO (CH 2) 2 OCO-, -CH 2 ORSROCO (CH ₂ ) ₂ OCOR-, wherein R is selected from hydrogen or an alkyl group having 1 to 20 carbon atoms,
X is a functional group at least partially selected from the group consisting of at least one group represented by the following formula (1)
P is a derivative at least partially of the following formula (3)
The weight average molecular weight of the brush polymer compound is 5,000 to 5,000,000.

(1)

(3). The polyether brush polymer according to claim 5, wherein the functional group of the formula (1) is represented by the following formula (2).

The polyether brush polymer according to claim 5, wherein the polyether brush polymer is represented by the following formula (5).

(5)

Here, m and n represent the content (mol%) of the polyether unit, where 0 <m? 100, 0? N <100, and m + n = 100.
A polyether block copolymer represented by the following formula (6)

Wherein R ₁ , R ₂ , R ₃ , R ₄ , Y _{1 ,} Y ₂ , m and n are as defined in formula (1);
Reacting the functional group B attached to the side chain in the polyether block copolymer with a compound represented by the following formula (7)
X-B '(7)
Wherein X- is the same as defined in the above formula (1), and the residues constituting the linker Z ₂ of claim 3 by the B and B 'ester reactions;
The functional group A attached to the side chain in the polyether block copolymer is represented by the following formula (8)
With a compound to be represented,
HO-A '(8)
Herein, A and A 'are residues constituting the linker Z ₁ of claim 3 by the addition reaction of a double bond, and
Reacting the -OH functional group with a compound of formula (9) wherein R is alkyl of 1-20 carbon atoms

(9)
&Lt; / RTI &gt; 9. The method of claim 8, wherein B is -R-OH and A is -R-O-R = C, wherein each R is independently an alkyl of 1-20 carbon atoms. The method of claim 8, wherein the formula (6) is represented by the following formula (12), wherein R is an alkyl having 1 to 20 carbon atoms.

The method of claim 8, wherein X-B 'in the formula (7) is represented by the following formula (11), wherein R is an alkyl having 1 to 20 carbon atoms.

(11) The method of claim 8, wherein HO-A 'in the formula (8) is represented by the following formula (10), wherein R is 1-10 alkyl.
SH-R-OH (10) The polyether block copolymer according to claim 8, wherein the polyether block copolymer represented by formula (6) of claim 8 is a compound represented by formula (13)

Wherein R 1 is a linker independently selected from the group consisting of X ₁ and X ₃ , -RO-, -O-, -COO-, -NH-, -S-, -SOO-, -20, X ₂ and X ₄ are protecting groups independently selected from (14)

And then selectively removing some of the protecting groups. A polymer memory device having an active layer comprising a polyether brush polymer according to any one of claims 1-7. The method of claim 14, wherein the polymer memory element
A lower electrode; An organic active layer formed on the lower electrode; And an upper electrode formed on the organic electrode. 15. The polymer memory device according to claim 14, wherein the polyether brush polymer is nanostructured. Forming an active layer including a polyether brush polymer according to any one of claims 1 to 7 on a lower electrode formed on a substrate; And
And forming an upper electrode to be in contact with the active layer. 18. The method of claim 17, wherein the polyether brush polymer is a nano-structured polyether brush polymer. 19. The method of claim 18, wherein the nanostructuring is performed through solvent annealing of the active layer. 20. The method of claim 19, further comprising the step of injecting electrons and holes into the active layer by applying a voltage to both ends of the polymer memory device so that current flows through the filament in the active layer.

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