Method for manufacturing aluminum electrode using solution process

Abstract

The present invention provides a method for manufacturing an aluminum electrode using a solution process and an aluminum electrode manufactured thereby. The manufacturing method includes the steps of: manufacturing an aluminum precursor solution for the solution processing using AlH.sub.3 as a basic material before forming aluminum; coating the aluminum precursor solution on a substrate through the solution process and drying the aluminum precursor solution; and forming a low work function aluminum electrode through a low-temperature baking process at the temperature of at most 150 C. The method for manufacturing the aluminum electrode according to the present invention improves a thermal defect of the electrode due to a high-temperature baking process, prevents excessive loss of raw materials, and can manufacture aluminum electrodes of various sizes with area ranging from small to large at relatively low costs and by a simple process under atmospheric pressure.

Claims

1. A method for manufacturing an aluminum electrode using a solution process, the method comprising: manufacturing a solution containing an aluminum precursor (Step A); coating a first substrate formed of one of an inorganic material and an organic material non-reactive with the solution containing an aluminum precursor, with the solution containing an aluminum precursor (Step B); heating a second substrate formed of one of an organic material and an inorganic material, where an aluminum thin film electrode is to be formed, at a temperature of 80 to 150 C. (Step C); and after Step C, heating a coated layer through the heated second substrate, by contacting the coated layer on the first substrate with the second substrate heated in Step C, and removing the first substrate (Step D), wherein the aluminum electrode is formed on the surface of the second substrate, wherein a solvent used in Step A has a boiling point of at most 150 C., and wherein the aluminum precursor in Step A comprises AlH.sub.3.

2. The method of claim 1, wherein the coating in Step B is performed by one selected from the group consisting of spin coating, dip coating, spray coating, inkjet printing, roll coating, drop casting, and doctor blade coating.

3. The method of claim 1, wherein Step A is performed mixing AlCl.sub.3 with LiAlH.sub.4 at a mole ratio of 1:3.

4. The method of claim 1, wherein the first substrate in Step B comprises a fiber medium.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) The above and/or other aspects of what is described herein will be more apparent by describing certain exemplary embodiments with reference to the accompanying drawings, in which:

(2) FIG. 1 is a view illustrating a process of manufacturing an aluminum precursor solution;

(3) FIG. 2 is a view illustrating a process of forming an aluminum electrode on an inorganic material surface according to an embodiment of the present invention;

(4) FIG. 3 is a view illustrating a process of forming an aluminum electrode on one of an organic material surface and an inorganic material surface according to another embodiment of the present invention;

(5) FIG. 4 illustrates pictures of aluminum electrodes manufactured in Embodiment 1, Embodiment 2, and Embodiment 3;

(6) FIG. 5 illustrates graphs illustrating results of X-ray diffraction (XRD) of the aluminum electrodes shown in FIG. 4;

(7) FIG. 6 illustrates scanning electron microscope (SEM) pictures of the aluminum electrodes; and

(8) FIG. 7 illustrates graphs illustrating resistivity of the aluminum electrodes in different positions.

DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS

(9) Hereinafter, the present invention will be described in detail.

(10) According to an embodiment of the present invention, there is provided a method for manufacturing an aluminum electrode using a solution process, the method including: manufacturing an aluminum precursor solution (Step 1); coating a substrate with the precursor solution (Step 2); and thermally treating the coated substrate at a low temperature of 80 to 150 (Step 3).

(11) Hereinafter, steps of the present embodiment will be described in detail.

(12) Step 1 is a process of manufacturing an aluminum precursor solution. The aluminum precursor solution is allowed to form an aluminum electrode using a solution process. The aluminum precursor solution may be manufactured blending aluminum chloride AlCl.sub.3 with lithium aluminum hydride LiAlH.sub.4 at a mole ratio of 1:3. The aluminum precursor solution is manufactured through a reaction as following Reaction Formula 1
AlCl.sub.3+3LiAlH.sub.4.fwdarw.4AlH.sub.3+3LiCl<Reaction Formula 1>

(13) As shown in the Reaction Formula 1, AlCl.sub.3 is mixed with LiAlH.sub.4 at a mole ratio of 1:3, thereby generating AlH3 and LiCl.

(14) A solvent used in Step 1 may have a boiling point of 150 C. or less. To use an aluminum precursor solution as a material of a cathode of environmental energy devices such as organic solar cell and OLEDs, it is required to form an aluminum electrode through a low-temperature baking process at the temperature of at most 150 in which organic material substrates such as electron injection layers, on which the aluminum electrode is formed, are thermally safe. As the solvent, 1,3,5-trimetylbenzene and Ether organic solvent may be used, which has a suitable boiling point and thermal decomposition point depending on a temperature for generating aluminum and a temperature for forming an electrode.

(15) In Step 1, AlCl.sub.3 and LiAlH.sub.4 may be put into the solvent to be supersaturated. When putting AlCl.sub.3 and LiAlH.sub.4 as a base material to be supersaturated, an equilibrium moves right in the Reaction Formula 1, thereby generating a larger amount of AlH.sub.3. Accordingly, to more easily and quickly form an aluminum electrode, it is required to put AlCl.sub.3 and LiAlH.sub.4 into the solvent to be supersaturated. A selected solvent is put thereinto and stirred and reacted for one hour at room temperature to a temperature of 100 C., thereby manufacturing an aluminum precursor solution. In this case, the reaction may be performed under an argon atmosphere to prevent aluminum from being oxidized.

(16) With respect to Step 1, when using dibutyl ether as a solvent, for example, a solution whose reaction is completed includes a solution H.sub.3AlO(C.sub.4H.sub.9).sub.2 containing AlH.sub.3 and precipitate LiCl. When filtering the same, there is obtained H.sub.3AlO(C.sub.4H.sub.9).sub.2, which is an aluminum precursor solution.

(17) Step 2 is a process of coating a substrate with the precursor solution. The substrate may be coated with the aluminum precursor solution using one of spin coating, dip coating, spray coating, inkjet printing, roll coating, drop casting, and doctor blade coating. However, a method for coating a substrate with an aluminum precursor solution is not limited thereto. After the coating is completed, the substrate is dried at room temperature. Step 2 may also be performed under an argon atmosphere in order to prevent aluminum from being oxidized.

(18) Step 3 is a process of thermally treating the coated substrate at a low temperature of 80 to 150. The substrate coated and dried in Step 2 is put on a device capable of thermally treating such as a hot plate and heated at a temperature of 80 to 150. The thermal treatment may be performed slowly increasing a heat temperature. Particularly, when the heat temperature is higher than 120 and a thermal treatment device previously heated is used, a part of an aluminum electrode layer is carbonized to be black, which requires special attention. To prevent aluminum from being oxidized, the thermal treatment in Step 3 may be performed under an argon atmosphere.

(19) A reaction during the thermal treatment at a low temperature is performed as following Reaction Formula 2.
4AlH.sub.3.fwdarw.4Al(s)+6H.sub.2(g)<Reaction Formula 2>

(20) For example, when dibutylether is used as a solvent, by gradual heating, O(C.sub.4H.sub.9).sub.2 is removed from drying H.sub.3AlO(C.sub.4H.sub.9).sub.2 layer, in which hydrogen concurrently falls off from AlH.sub.3, thereby leaving an aluminum layer. In this case, when putting the substrate where the H.sub.3AlO(C.sub.4H.sub.9).sub.2 layer is formed on, on the hot plate previously heated, the H.sub.3AlO(C.sub.4H.sub.9).sub.2 layer is evaporated before forming the aluminum layer or it is impossible to form an uniform electrode due to the carbonization of a part of an organic solvent. To form an aluminum layer, the substrate where the H.sub.3AlO(C.sub.4H.sub.9).sub.2 layer is formed on may be on a hot plate at room temperature and heated at a temperature 80 to 150 C.

(21) According to another embodiment of the present invention, there is provided a method for manufacturing an aluminum electrode using a solution process, the method including: manufacturing an aluminum precursor solution (Step A); coating a substrate formed of one of an inorganic material and an organic material non-reactive with a precursor material with the aluminum precursor solution (Step B); heating a substrate formed of one of an organic material and an inorganic material, which is to be coated, at a temperature of 80 to 150 C. (Step C); and putting and thermally treating the substrate coated in Step B on the substrate formed of one of an organic material and an inorganic material, heated in Step C, at a low temperature of 80 to 150 C. and removing the substrate formed of one of an inorganic material and an organic material non-reactive with a precursor material (Step D).

(22) Hereinafter, steps of the present embodiment will be described in detail.

(23) Step A is performed the same as Step 1.

(24) Step B is a process of coating a substrate formed of one of an inorganic material and an organic material non-reactive with a precursor material with the aluminum precursor solution. When a surface on which an electrode is formed is formed of an organic material, and particularly formed of a material reactive with a solvent used for manufacturing a precursor solution, the substrate may react with the precursor solution and cause a defect on the substrate. Accordingly, it is important to prevent a direct contact between a precursor solution and a substrate where an electrode is to be formed on. Therefore, it is required to use a substrate formed of one of an inorganic material and an organic material non-reactive with a precursor solution. Also, Step B may be performed under an argon atmosphere in order to prevent aluminum from being oxidized.

(25) The coating in Step B may be performed using one of spin coating, dip coating, spray coating, inkjet printing, roll coating, drop casting, and doctor blade coating the aluminum precursor solution manufactured in Step A. However, a method for coating a substrate with an aluminum precursor solution is not limited thereto. After the coating is completed, the substrate is dried at room temperature.

(26) Step C is a process of heating a substrate formed of one of an organic material and inorganic material, which is to be coated, at a temperature of 80 to 150. The substrate on whose surface an electrode is to be formed is put on a thermal treatment device such as a hot plate and heated at a temperature of 80 to 150 while the surface thereof is upward. Step C may be performed under an argon atmosphere to prevent aluminum from being oxidized.

(27) Step D is a process of putting and thermally treating the substrate coated in Step B on the substrate formed of one of an organic material and an inorganic material, heated in Step C, at a low temperature of 80 to 150 and removing the substrate formed of one of an inorganic material and an organic material non-reactive with a precursor material. When a surface of the substrate coated with the precursor solution and dried is in contact with a surface of the substrate formed of one of an organic material and an inorganic material, heated in Step C, which is to be coated, a solvent is removed while thermally decomposed and hydrogen is separated from AlH.sub.3 as shown in Reaction Formula 2, thereby forming an Al layer on the substrate formed of an organic material. Since there is formed aluminum powder from a precursor solution coating layer in contact with the surface formed of an organic material, an aluminum electrode layer is formed on the substrate formed of one of an organic material and an inorganic material, opposite to the substrate formed of one of an inorganic material and an organic material non-reactive with a precursor material, which is coated with the precursor solution and dried. Step D may also be performed under an argon atmosphere in order to prevent aluminum from being oxidized.

(28) Also, Steps C and D may solve a difficulty that may occur while heating the substrate coated with an aluminum precursor solution to form an aluminum electrode in Step 3, the difficulty of forming a uniform electrode due to the evaporation of a coating layer and the carbonization of an organic solvent forming the coating layer when thermally treating the substrate at a temperature higher than 120 on a thermal treatment device previously heated.

(29) In addition, according to still another embodiment of the present invention, there is provided a method for manufacturing an aluminum electrode using a solution process, the method including: manufacturing an aluminum precursor solution (Step a); putting a fiber medium coated with the aluminum precursor solution on a first substrate (Step b); heating a second substrate for forming an electrode at a temperature of 80 to 150 C. (Step c); and putting and thermally treating the first substrate on the heated substrate at a low temperature of 80 to 150 C. and removing the first substrate and the fiber medium coated with the precursor solution (Step d).

(30) Step a is performed the same as Step 1.

(31) Step b is a process of putting a fiber medium coated with the aluminum precursor solution on a first substrate. For example, the fiber medium may be paper. Since the fiber medium may absorb a large amount of an aluminum precursor solution, different from a substrate, it is possible to form a thickness of an aluminum electrode, depending on an amount of the absorbed aluminum precursor solution. Also, since an absorption amount of the same material is the same, it is possible to form an aluminum electrode with a uniform thickness. The aluminum precursor solution is put on the first substrate and dried at room temperature. Step b may also be performed under an argon atmosphere in order to prevent aluminum from being oxidized.

(32) Step c is a process of heating a second substrate for forming an electrode at a temperature of 80 to 150 C. The substrate on whose surface an electrode is to be formed is put on a thermal treatment device such as a hot plate and heated at a temperature of 80 to 150 while the surface thereof is upward. Step c may also be performed under an argon atmosphere to prevent aluminum from being oxidized.

(33) Step d is a process of putting and thermally treating the first substrate on the heated substrate at a low temperature of 80 to 150 C. and removing the first substrate and the fiber medium coated with the precursor solution. When the first substrate where the fiber medium coated with the precursor solution is attached is in contact with the surface of the second substrate, which is to be coated, a solvent is thermally decomposed and removed, and as shown in Reaction Formula 2, hydrogen is separated from AlH.sub.3 and an Al layer is formed on the second substrate. Since aluminum powder is formed from a precursor solution coating layer in contact with the second substrate, the Al layer is formed on the second substrate opposite from the first substrate. Step d may also be performed under an argon atmosphere in order to prevent aluminum from being oxidized.

(34) In addition, according to an embodiment of the present invention, there is provided an aluminum electrode manufactured using the method for manufacturing an aluminum electrode using a solution process.

(35) The aluminum electrode may be manufactured using a solution process of thermally treating through a low-temperature baking process at the temperature of at most 150 C. in a short time, thereby solving a thermal defect of an electrode, occurring due to general high-temperature baking processes. Also, it is possible to prevent excessive loss of raw material and to form an electrode under atmospheric pressure, thereby reducing a charge for manufacturing and maintaining. Also, it is possible to manufacture aluminum electrodes with various sizes from a small size to a large size. Also, the aluminum electrode has the same or higher properties as those of general organic solar cells requiring a low work function electrode and OLED cathodes.

(36) Examples of the present invention will now be described in further detail below. It would be obvious to those skilled in the art that these examples are intended to be more concretely illustrative and the scope of the present invention as set forth in the appended claims is not limited to or by the examples.

Manufacturing an Aluminum Electrode on a Glass Substrate ( )

(37) Step 1. Manufacturing an Aluminum Precursor Solution

(38) To allow the mole ratio of aluminum chloride to lithium aluminum hydride to be 1:3, 0.133 g of aluminum chloride AlCl.sub.3 and 0.114 g of lithium aluminum hydride LiAlH.sub.4 was put into a flask with three inlets and a reflux condenser and heated and stirred at a temperature of 80 C. for one hour under an argon atmosphere using 100 ml of dibutyl ether as a solvent. Compounds were LiCl and AlH.sub.3 and LiCl was filtered and removed, thereby manufacturing an aluminum precursor solution OAlH.sub.3(C.sub.4H.sub.9).sub.2 in which AlH.sub.3 was dissolved in a solvent.

(39) Step 2. Coating a Substrate with a Precursor Solution

(40) An amorphous glass substrate was coated with the aluminum precursor solution manufactured in Step 1 by dipping therein and dried.

(41) Step 3. Thermally Treatment at a Low Temperature

(42) The substrate coated and dried in Step 2 was put on a hot plate at room temperature and heated to 140 C., thereby manufacturing an aluminum electrode.

Manufacturing an Aluminum Electrode on a Glass Substrate (II)

(43) Step 1. Manufacturing an Aluminum Precursor Solution

(44) An aluminum precursor solution was manufactured by performing the same as that of Step 1 of Embodiment 1.

(45) Step 2. Coating a Substrate with the Aluminum Precursor Solution

(46) An aluminum precursor solution layer was formed on a glass substrate by performing the same as that of Step 2 of Embodiment 2.

(47) Step 3. Heating a Substrate Formed of an Inorganic Material

(48) A glass substrate where an electrode was to be formed was put on a hot plate and heated to 140 C.

(49) Step 4. Forming an Aluminum Electrode on the Substrate Formed of an Inorganic Material

(50) A surface of the substrate of Step 2, coated with the aluminum precursor solution, was put downward on the glass substrate heated in Step 3, whose top was to be coated, and heated at a temperature of 140 C. for one minute, thereby manufacturing an aluminum electrode on the glass substrate.

Manufacturing an Aluminum Electrode on a Substrate Formed of an Organic Material

(51) Step 1. Manufacturing an Aluminum Precursor Solution

(52) An aluminum precursor solution was manufactured by performing the same as that of Step 1 of Embodiment 1.

(53) Step 2. Coating a Substrate with the Aluminum Precursor Solution

(54) A glass substrate was coated with the aluminum precursor solution by dipping therein and dried.

(55) Step 3. Heating a Substrate Formed of an Organic Material

(56) A polyethylene substrate where an electrode was to be formed was put on a hot plate and heated at a temperature of 140 C.

(57) Step 4. Forming an Aluminum Electrode on the Substrate Formed of an Organic Material

(58) A surface of the substrate of Step 2, coated with the aluminum precursor solution, was put downward on the polyethylene substrate heated in Step 3, whose top was to be coated, and heated at a temperature of 140 C. for one minute, thereby manufacturing an aluminum electrode on the polyethylene substrate.

Manufacturing a Thick Aluminum Electrode

(59) Step 1. Manufacturing an Aluminum Precursor Solution

(60) An aluminum precursor solution was manufactured by performing the same as that of Step 1 of Embodiment 1.

(61) Step 2. Coating a Piece of Paper with the Aluminum Precursor Solution

(62) A piece of paper was coated with the aluminum precursor solution manufactured in Step 1, put on a first substrate formed of glass, and dried.

(63) Step 3. Heating a Substrate

(64) A second glass substrate where an electrode was to be formed was put on a hot plate and heated at a temperature of 140 C.

(65) Step 4. Forming an Aluminum Electrode on the Glass Substrate

(66) The first glass substrate where the piece of paper coated with the aluminum precursor solution and dried in Step 2 was attached to was put on the second glass substrate heated in Step 3 and heated at a temperature of 140 C. for three minutes, thereby manufacturing an aluminum electrode with a thickness of 263 nm.

Visual Observation on the Manufactured Electrode

(67) To check external properties, the aluminum electrodes manufactured in Embodiment 1, Embodiment 2, and Embodiment 3 were observed by naked eyes and a result thereof were shown in FIG. 4.

(68) Referring to FIG. 4, aluminum electrodes were manufactured on amorphous glass substrates in Embodiment 1 and Embodiment 2 and a polyethylene substrate in Embodiment 3, and as a result thereof, it was possible to know that aluminum films uniformly coated and coated metal layers had very high reflectance as a reflecting plate. Also, there was no defect such as a detachment in the aluminum electrode film manufactured on the polyethylene substrate, which had flexibility as that of the polyethylene substrate.

XRD Analysis

(69) To investigate crystallizability of aluminum, an X-ray diffraction (XRD) analysis was performed with respect to the aluminum electrodes manufactured in Embodiment 1, Embodiment 2, and Embodiment 3 and a result thereof were shown in FIG. 5.

(70) Referring to FIG. 5, it was possible to know that XRD patterns of the manufactured electrodes were identical to a face centered cubic (FCC) structure according to JSPDS card Al(04-0407). Therefore, it was possible to know that AlH3 contained in the aluminum precursor solution manufactured using the method according to the embodiments of the present invention was very effective to form an aluminum layer.

SEM Pictures Analysis

(71) To check a microstructure and thickness of aluminum layers formed on the aluminum electrodes manufactured in Embodiment 1, Embodiment 2, and Embodiment 3, a scanning electron microscope (SEM) was used and a result thereof was shown in FIG. 6.

(72) Referring to FIG. 6, there was rarely formed air hole on the surface of the aluminum layers, which has a dense structure. Also, as a result of observe the cross-section of the electrodes, it was possible to know that thicknesses of the electrodes formed on glass substrates in A (Embodiment 1) and B (Embodiment 2) and a polyethylene substrate in C (Embodiment 3) were 117 nm, 102 nm, and 70 nm, respectively. Also, referring to SEM pictures of Embodiments 1 to 3, it may be known that the manufactured aluminum electrodes are in the shape of a thin film with a dense structure. Since the density of an electrode is required to improve electrical properties thereof, the result as described above allows it to be estimated that the aluminum electrodes manufactured according to the present invention have excellent electrical properties.

Measuring Resistivity

(73) To check resistivity depending on a position thereof, the resistivity of the aluminum electrodes manufactured in Embodiment 1, Embodiment 2, and Embodiment 3 was measured using 4 point probe method and a result thereof was shown in FIG. 7.

(74) Referring to FIG. 7, respective positions where resistivity was measured and the resistivity of the respective positions were shown in graphs. The mean resistivity values of the aluminum electrodes manufactured in Embodiment 1, Embodiment 2, and Embodiment 3 in five positions were 12.52 .Math.cm, 8.49 .Math.cm, and 15.53 .Math.cm, respectively, which were relatively low. The standard deviation depending on the position of the respective electrodes were 0.46 .Math.cm, 1.74 .Math.cm, and 0.65 .Math.cm, which indicates that electrical properties of the electrodes were very excellent and uniform.

(75) The foregoing exemplary embodiments and advantages are merely exemplary and are not to be construed as limiting the present invention. The present teaching can be readily applied to other types of apparatuses. Also, the description of the exemplary embodiments of the present inventive concept is intended to be illustrative, and not to limit the scope of the claims, and many alternatives, modifications, and variations will be apparent to those skilled in the art.