KR100252782B1 - Conductive polymer thin film manufacturing method and device thereof - Google Patents

Abstract

PURPOSE: A method for preparing a conductive polymer thin film and its apparatus are provided, to form a conductive polymer thin film of the emeraldin-salt state on a substrate directly, thereby to lower the cost and to improve the production yield. CONSTITUTION: The apparatus comprises a main valve(101), a cryostat(104), a water baffle(105), a diffusion pump(106), a molecular sieve(107), a rotary pump(108), an ion gauge(115), first and second roughing valves(116,118), and a backing valve(117) for maintaining a main chamber(101) to be vacuum; the first thermal bath(109) which is set below the main chamber and vaporizes aniline monomer and ammonium sulfate; the first molecular flow controller(111) and a thermocouple gauge(113) which control the amount of vapor of aniline monomer and ammonium sulfate generated from the first thermal bath; the second thermal bath(110) which is set in the opposite side of the first thermal bath and vaporizes HCl salt; the second molecular flow controller(112) and a pH meter(114) which are set over the second thermal bath and control the amount of HCl vapor and the pH; a substrate holder(102) which holds a substrate where a conductive polymer thin film is formed; and a vent valve which ventilates the inside of the main chamber.

Description

Conductive polymer thin film manufacturing method and manufacturing apparatus

1 is a structural diagram showing an oxidation process of polyaniline, which is an example of a polymer used in the present invention.

2 is a diagram showing the structural formula of a sample used in the present invention.

3 is a view showing a vacuum system for producing a polymer thin film of the emerald salt in accordance with the present invention.

* Explanation of symbols for main parts of the drawings

1: Polyaniline Molecular Structure in Emerald Base State

2: Molecular structure of polyaniline in the emerald salt state

3: molecular structure of the monomer aniline

4: sulfated ammonium 5: 1 mol hydrochloric acid

101: main chamber 102: substrate holder

103: main valve 104: cryostat

105: mole regulator 106: diffusion pump

107 molecular sieve 108 rotary pump

109: first temperature control container 110: second temperature control container

111: first molecular flow controller 112: second molecular flow controller

113: thermocouple gauge 114: pH meter

115: ion gauge 116: first roughing valve

117: check valve 118: second roughing valve

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a liquid crystal alignment film from a conductive polymer, and more particularly, to a manufacturing apparatus and a method for manufacturing a conductive polymer thin film for forming a conductive polymer in an emeraldine salt state directly on a substrate.

In general, the liquid crystal alignment layer uses a conductive polymer in the emeraldine salt state having high electrical conductivity.

The conductive polymer in the emeraldine salt state is prepared by doping the polymer in the emeraldine base state with an acid.

An example of a method of preparing polyaniline in an emeraldine-based state, which is one of the polymers, will be described as follows. First, 20 ml (0.22 mol) of aniline and (NH ₄ ) ₂ S ₂ O ₈ (ammonium sulfate) 11.5 g (0.05 mol) was reacted with 500 ml of 1 M hydrochloric acid (HCl) cooled to 0 ° C. for 90 minutes. At this time, the reaction color is dark green and coppery luster appears on the surface of the solution over time. After 90 minutes, the reaction precipitate was filtered using a filter paper, and the pieces of the filter paper were filtered again and stirred in a 500 mL 1M hydrochloric acid solution for 15 hours with a magnetic stir and then filtered in a funnel connected to a water inhaler. . The filtration is washed with 2 L of 1 M hydrochloric acid until the filtrate is completely colorless and thus gives about 6 g of 50% protonated polyaniline. The 50% protonated fragment of emeraldine hydrochloride is insoluble in organic solvents, making it nearly impossible to process. Therefore, the fragment of the emeraldine hydrochloride was again immersed in 500mL, 0.1M NH ₄ OH solution and stirred with a magnetic picket for 15 hours, and the acidity was maintained at 9. After 15 hours, the resultant was washed with 1 L of 0.1 M NH ₄ OH and filtered, and the obtained pieces were placed in a drying tube connected with a vacuum line and dried under ultra-vacuum (10 ⁻³ torr) for 48 hours. The dried powder is agitated for 20 minutes in a mortar to make it uniform, thereby obtaining polyaniline in an emeraldine base state, and the polyaniline in an emeraldine base state is dissolved in an organic solvent, thereby allowing a processing process.

The polyaniline in the emeraldine base state prepared as described above is dissolved in a solvent in a state in which a processing process is possible, and then a polyaniline thin film is prepared by various methods. Next, the polyaniline thin film of the emeraldine salt state is prepared through the doping process reacted with an acid in order to impart conductivity to the prepared polyaniline thin film of the emeraldine base state, and applied to the liquid crystal alignment layer.

The doping process will be described in more detail.

In general, the most central concept that distinguishes conductive polymers from existing insulating polymers is doping. Doping refers to an operation of converting a polymer from insulating to conductive by delocalizing π-electrons on a polymer chain to increase charge mobility.

The doping includes p- and n-type doping by chemical and electrochemical oxidation and reduction, protonic acid doping without photooxidation and reduction, photo doping and charge injection doping. This is known. In practice, however, the choice of doping method depends on the properties of the polymer (electronic structure, chemical structure, etc.).

Representative polymers exhibiting conductivity by doping as described above are polyacetylene, poly para-phenylene, polythiophene, poly para-phenylene vinyline -phenylenevinylene), polyaniline, etc., and a common feature of these polymers is that they have a conjugated structure in which a single defect and a double bond are alternately repeated in the polymer backbone. Unlike conductive polymers, it is easily converted into a material having high conductivity by protonic acid doping, and it is easy to synthesize derivatives by functional groups to rings and nitrogen positions. It has many advantages, such as having high solubility in common solvents by pre-functionalization.

The polyaniline is represented by the following general formula and is a generic term for compounds induced by control of oxidation state and substitution by nitrogen and ring position.

The average state of the polyaniline is given as a 1-y value from the fully reduced state (leucoemeraldine base: 1-y = 0) to the intermediate oxidation state (emeraldine base: 1-y = 0.5). Continuous oxidation is possible with the complete oxidation state (pernigraniline base: 1-y = 1). Among the oxidation states, the emeraldine base in an intermediate oxidation state that is stable in the air has a form in which oxidized and reduced units are alternately repeated. In addition, the emeraldine base is doped in an acidic solution to form polysemiquinone radical cation (polaron), wherein a large electrical conductivity from 10 ^-10 S / cm to 5 S / cm Indicates an increase.

FIG. 1 shows the protonation mechanism of the emeraldine base in polyaniline, a kind of conductive polymer, and has an acidic molecular structure of 2XH ² A ^-in the emeraldine base of polyaniline. Protonic Acid Doping by reacting with solution causes H and A ^- to be covalently bonded to the reduced nitrogen of the emeraldine base, and the emeraldine base to which 2XH ⁺ A ^- is bonded is itself. Polypyrimol of Emeraldind Salt (2, Emeraldind Salt), a structure in which the oxidized unit and the reduced unit of the emeraldine base are identical through an internal redox reaction and a polar separation process. Is manufactured. At this time, the electrical conductivity may be increased to about 10 ⁴ S / cm.

As described above, a method of manufacturing a conductive polymer such as a liquid crystal alignment film using a conductive polymer may include preparing an aniline monomer in an emeraldine-based polymer, and organically preparing an emeraldine-based conductive polymer in the organic solvent. A thin film manufacturing process step for preparing a thin film by dissolving in a solvent, and the step of preparing a conductive polymer thin film in the emeraldine salt state through the doping process by reacting the conductive polymer thin film of the emeraldine base state with an acid to improve electrical conductivity Through the conductive polymer thin film having a high electrical conductivity can be obtained.

However, in order to manufacture the conductive polymer thin film as described above, it has to go through three complicated processes, resulting in a decrease in yield due to an increase in manufacturing cost and complexity of the process.

Accordingly, in order to solve the above problems, the present invention manufactures a conductive polymer thin film of the emeraldine salt state directly through the aniline monomer state without the emeraldine base state by the thin film manufacturing apparatus, thereby simplifying the manufacturing process and lowering the manufacturing cost. The purpose is to increase the yield.

In order to achieve the above object, the present invention is a main component (Main Chamber), a main valve (Main Valve), a cryostat (Cryostat), a water control device (Water Baffle), a diffusion pump (basic components) to maintain a vacuum state Diffusion Pump, Molecular Sleve, Rotary Pump, Ion Gauge, First, Roughing Valve, and Backing Valve, and Bottom of Main Chamber A first thermal bath for filling and vaporizing aniline monomer and sulfated ammonium, and aniline monomer and sulfated ammonium vapor generated in the first temperature control vessel. A first molecular flow controller and a thermocouple gauge for adjusting the amount, and a second temperature regulating vessel for filling the hydrochloride to vaporize is installed opposite the first temperature control vessel A second molecular flow controller and a pH meter installed at an upper portion of the second temperature vessel to adjust the amount and acidity of hydrochloric acid vapor generated from the second temperature controller; And a substrate holder for mounting a substrate on which a conductive polymer thin film is to be formed, and an emeraldine salted polymer thin film manufacturing apparatus including a vent valve for venting the inside of the main chamber.

In addition, as a method for producing a conductive polymer thin film in the emeraldine salt state by the manufacturing apparatus, first the aniline monomer and the ammonium sulfate ammonium is filled in a constant ratio in the first temperature control vessel of the manufacturing apparatus, the second temperature control degree vessel Filling hydrochloric acid into the main chamber, the main valve of the manufacturing apparatus using a main valve, a cryostat, a water regulator, a diffusion pump, a molecular sieve, a rotary pump, an ion gauge, first and second roughing valves, and a backing valve. Vacuuming the interior, heating a first temperature control vessel to vaporize the aniline monomer and ammonium sulfate, and controlling the amount of the mixed vapor using a first molecular flow controller and a thermocouple gauge. And heating the second temperature control vessel to vaporize the hydrochloride at the same time as the above step, and convert the generated hydrochloride vapor into the second molecular flow controller and the acidity. Adjusting the acidity and the increase amount by using a measuring device, and the mixed polymer of the aniline monomer and sulfated ammonium sulfate and the hydrochloride vapor deposited on the substrate while reacting in a vacuum chamber in the emeraldine salt state conductive polymer thin film It is characterized by manufacturing.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

2 is a view showing molecules reacting in a vaporized state in the first and second temperature control vessels 109 and 110 of the apparatus for producing an emeraldine salt in accordance with the present invention. ), Ammonium sulfate (4), and 1M hydrochloride (5) are vaporized to react inside the main chamber 101 to form an emeraldine salted conductive polymer thin film on the substrate.

Next, FIG. 3 shows an apparatus 100 for manufacturing the conductive polymer thin film in the emerald salt state according to the present invention, and includes a main chamber 101 providing conditions under which the conductive polymer thin film in the emerald salt state is formed. In addition, a main valve 103, a low temperature holding device 104, a water regulating device 105, a diffusion pump 106, a rotary pump 108, and ions, which are basic components for maintaining the vacuum in the main chamber 101 The gauge 115 is provided with first and second roughing valves 116 and 118 and a backing valve 117. In addition, a lower portion of the main chamber 101 is provided with a first temperature control vessel 109 for filling and vaporizing the aniline monomo 3 and the sulfated ammonium 4, the first temperature control vessel A first molecular flow controller 111 and a thermocouple gauge 113 for controlling the amount of aniline monomer (3) and ammonium sulfate (4) vapors generated at 109 are located above the first temperature control vessel 109. Installed in order. In addition, the second temperature control vessel 110 is provided on the opposite side of the first temperature control vessel 109 to fill the hydrochloride (5) to vaporize, the upper portion of the second temperature control vessel (110) A second molecular flow controller 112 and an acidity meter 114 for controlling the amount and acidity of the hydrochloride 5 vapor generated from the second temperature control vessel 110 are sequentially formed. In addition, a substrate holder 102 for mounting a substrate on which the conductive polymer thin film is to be formed in the main chamber 101 and a vent valve (not shown) for ventilating the inside of the main chamber 101 are formed.

The method for producing a conductive polymer thin film using the emeraldine salted conductive polymer thin film manufacturing apparatus 100 configured as described above, first, the aniline monomer (1) in the first temperature control vessel 109 of the manufacturing apparatus 100 ( 3) and ammonium sulfate (4) is filled at a constant rate, and the hydrochloride salt (5) is filled in the second temperature control container (110). Next, the main valve 103, the cryostat 104, the water regulator 105, the diffusion pump 106, the molecular sieve 107, the rotary pump 108, the ion gauge 115 of the manufacturing apparatus 100. ), The first and second roughing valves 116 and 118, and the backing valve 117 to vacuum the inside of the main chamber 101, and then the aniline monomer 3 and ammonium sulfate (4). The first temperature control vessel 109 is heated to vaporize, and the amount of mixed vapor generated from the first temperature control vessel 109 is adjusted to the first molecular flow controller 111 and the thermocouple gauge 113. It is adjusted to be discharged to the main chamber 101. At this time, the second temperature control vessel 110 is heated to vaporize the hydrochloride (5) while simultaneously generating steam of the aniline monomer (3) and ammonium sulfate (4), and generating the generated hydrochloride (5) vapor. The second molecular flow controller 112 and the acidity meter 114 are used to adjust the acidity and the amount of steam to release hydrochloric acid vapor maintained in the 1M state into the main chamber 101. The mixed vapor of the aniline monomer 3 and the ammonium 4 discharged into the main chamber 101 and the hydrochloride (5) vapor react with each other to be deposited on a substrate to produce an emeraldine salted conductive polymer thin film.

As described above, the present invention forms the conductive polymer thin film in the emeraldine salt state directly on the substrate, thereby reducing the manufacturing cost of manufacturing the conductive polymer thin film and increasing the yield due to the simplification of the process. You can.

The manufacturing apparatus and the manufacturing method described above can be applied to the liquid crystal alignment layer using the conductive polymer and all other thin film processes. In other words, by simultaneously forming a thin film by reacting two or more materials in a vacuum state, it is also applicable to ECD (Electrochromic Display), ELD (Electroluminescent Display), and Solar Cell.

Claims (3)

Basic valves for maintaining the main chamber in a vacuum, such as the main valve, cryostat, water regulator, diffusion pump, molecular sieve, rotary pump, ion gauge, first and second roughing valves, and backing valve, A first temperature control container installed at a lower portion of the main chamber to fill and vaporize aniline monomer and sulfated ammonium; A first molecular flow controller and thermocouple gauge for controlling the amount of aniline monomer and sulfated ammonium vapor generated in the first temperature regulating vessel; A second temperature control container installed opposite the first temperature control container to fill and vaporize hydrochloride; A second molecular flow controller and an acidity meter installed on an upper portion of the second temperature controller to adjust the amount and acidity of the hydrochloride vapor generated from the second temperature controller; A substrate holder for mounting a substrate on which the conductive polymer thin film is installed in the main chamber; Apparatus for producing a conductive polymer thin film in the emeraldine salt state including a vent valve for ventilating the inside of the main chamber. Filling the first temperature control container with aniline monomer and ammonium sulfate ammonium at a constant ratio, and filling the second temperature control container with hydrochloride; Vacuuming the inside of the main chamber using a main valve, a cryostat, a water regulator, a diffusion pump, a molecular sieve, a rotary pump, an ion gauge, first and second roughing valves, and a backing valve of the manufacturing apparatus; , Heating a first temperature control vessel to vaporize the aniline monomer and the sulfated ammonium, and adjusting the amount of the mixed vapor using a first molecular flow controller and a thermocouple gauge; Heating the second temperature control vessel to vaporize the hydrochloride at the same time as the above step, and adjusting the acidity and the amount of steam using the generated hydrochloride vapor using a second molecular flow controller and an acidity meter; And a step of depositing a mixed film of the aniline monomer and ammonium sulfate ammonium and hydrochloride vapor on a substrate while reacting in a vacuum chamber. The method of claim 2, Method for producing a conductive polymer thin film in the emeraldine salt state, characterized in that the concentration of the hydrochloride is maintained at 1M.