Functionalized metal oxide soldering methods and UV sensor manufactured thereof

Abstract

Provided are a method of soldering a functionalized metal oxide, and an electronic device manufactured thereby, and more particularly, a method of soldering a functionalized metal oxide which is capable of growing a solder structure by a hydrothermal synthesis method using a pulsed laser, and is usable in a UV sensor, and an electronic device manufactured thereby. According to the present invention, thermal diffusion generated from a laser is limited due to the use of a pulsed laser, and thus, nanosolder having high density and a shape to be precisely adjustable may be prepared by a hydrothermal synthesis method by the pulsed laser, thereby facilitating the joining of the nanostructure, and further, the nanosolder is formed between the nanostructures, thereby being usable as a metal oxide structure having functionality.

Claims

1. A method of soldering a functionalized metal oxide comprising: forming two nanostructures on a substrate, wherein the two nanostructures are crossed with respect to one another to form an intersection point; dipping the substrate on which the nanostructures are formed in a precursor solution for hydrothermal synthesis; and irradiating at least a portion of the intersection point of the two nanostructures in a precursor solution for hydrothermal synthesis with a pulsed laser having a pulse duty ratio of 5% to 20% and a pulse width controlled in a range of 100 ns to 3000 ns to produce and grow a solder bump, so that the two nanostructures are connected to each other by the grown solder bump.

2. The method of claim 1, wherein the nanostructures have a light absorption layer for absorbing light energy of the laser, formed on at least a portion thereof.

3. The method of claim 2, wherein as the light absorption layer, different materials are used depending on a wavelength of the laser.

4. The method of claim 2, wherein the light absorption layer is one selected from the group consisting of metals and semiconductors.

5. The method of claim 1, wherein the precursor solution for hydrothermal synthesis is a mixed solution of an aqueous precursor solution and an aqueous amine compound solution.

6. The method of claim 5, wherein the aqueous precursor solution includes any one of metal precursors and semiconductor precursors.

7. The method of claim 5, wherein the amine compound is one or more selected from the group consisting of hexamethyleneamine, hexamethylenetetramine (HMT), cyclohexylamine, monoethanolamine, diethanolamine, and triethanolamine.

8. The method of claim 1, further comprising annealing the solder bump, after the forming of the solder bump.

9. The method of claim 1, wherein the substrate comprises a silicon substrate on which an oxide film having a thickness of 50 nm and a tungsten absorption layer having a thickness of 40 nm are deposited, and the pulsed laser has a peak power irradiated in a range of 5 mW/m.sup.2 to 20 mW/m.sup.2 in atmospheric pressure.

10. The method of claim 1, further comprising covering the substrate with a transparent substrate, after the dipping of the substrate on which the nanostructures are formed in a precursor solution for hydrothermal synthesis.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a photograph illustrating metal oxide nanostructures produced by a hydrothermal synthesis method by a continuous laser of the prior art.

(2) FIG. 2 is a drawing illustrating a laser lithography apparatus for carrying out the method of soldering a functionalized metal oxide according to an exemplary embodiment.

(3) FIG. 3 is a drawing illustrating a principle of the method of soldering a functionalized metal oxide according to an exemplary embodiment.

(4) FIG. 4 is a drawing illustrating nanosolder produced according to a pulse width of the method of soldering a functionalized metal oxide according to an exemplary embodiment, and a simulation result.

(5) FIG. 5 is a photograph illustrating zinc oxide solder prepared by the method of soldering a functionalized metal oxide according to an exemplary embodiment.

(6) FIG. 6 is a photograph illustrating copper oxide solder prepared by the method of soldering a functionalized metal oxide according to an exemplary embodiment.

(7) FIG. 7 is a graph illustrating volume of metal oxide solder depending on laser power and irradiating time of the method of soldering a functionalized metal oxide according to an exemplary embodiment.

(8) FIG. 8 is a drawing illustrating a principle of functionalized metal oxide solder formed by the method of soldering a functionalized metal oxide according to an exemplary embodiment.

(9) FIG. 9 is a photograph illustrating functionalized metal oxide solder prepared by the method of soldering a functionalized metal oxide according to an exemplary embodiment.

(10) FIG. 10 is a graph representing electrical properties of functionalized metal oxide solder prepared by the method of soldering a functionalized metal oxide according to an exemplary embodiment.

(11) FIG. 11 is a graph representing characteristics of functionalized metal oxide solder prepared by the method of soldering a functionalized metal oxide according to an exemplary embodiment, depending on an annealing step.

(12) FIG. 12 is a drawing illustrating an ultraviolet sensor manufactured by the method of soldering a functionalized metal oxide according to an exemplary embodiment.

(13) FIG. 13 is a photograph illustrating an ultraviolet sensor manufactured by the method of soldering a functionalized metal oxide according to an exemplary embodiment.

(14) FIG. 14 is a graph illustrating operation characteristics of an ultraviolet sensor manufactured by the method of soldering a functionalized metal oxide according to an exemplary embodiment.

(15) FIG. 15 is a graph illustrating characteristics of an ultraviolet sensor manufactured by the method of soldering a functionalized metal oxide according to an exemplary embodiment, depending on an ultraviolet dosage.

DETAILED DESCRIPTION OF MAIN ELEMENTS

(16) 10: Substrate 20: Nanostructure 30: Light absorption layer 40: Precursor solution for hydrothermal synthesis 50: Functionalized metal oxide solder structure (solder bump) 60: Pulsed laser

DETAILED DESCRIPTION OF EMBODIMENTS

(17) The advantages, features and aspects of the present invention will become apparent from the following description of the embodiments with reference to the accompanying drawings, which is set forth hereinafter. The present invention may, however, be embodied in different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the scope of the present invention to those skilled in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments. As used herein, the singular forms a, an and the are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms comprises and/or comprising, when used in this specification, specify the presence of stated features, integers, steps, operations, elements, and/or components, but do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, and/or groups thereof.

(18) Hereinafter, the method of soldering a functionalized metal oxide according to the present invention, and the electronic device manufactured thereby will be described in detail with reference to the accompanying drawings. Herein, the constitution and the operation of the present invention shown in the drawings, and described thereby are described as at least one Example, and the technical idea and the core constitution and operation of the present invention are not limited thereby.

(19) The terms used herein are selected as general terms which are possibly currently widely used considering their functions in the present invention, but they may be different depending on the intention of a person skilled in the art, a convention, the emergence of new technology, or the like. Further, in a certain case, there may be an optionally selected term by the applicant, and in this case, its meaning will be specifically described in the detailed description of the invention. Accordingly, it is noted that the terms used in the present invention should be defined, based on the meaning of the term, and the overall description of the present invention, not the simple designation of the term.

(20) The present invention provides a method of soldering a functionalized metal oxide including forming nanostructures on a substrate; dipping the substrate on which the nanostructures are formed in a precursor solution for hydrothermal synthesis; and irradiating the nanostructures with a pulsed laser to form a solder bump.

(21) Further, there is provided a method of soldering a functionalized metal oxide including forming two or more nanostructures on a substrate; dipping the substrate on which the nanostructures are formed in a precursor solution for hydrothermal synthesis; and irradiating any one of the nanostructures with a pulsed laser to grow a solder structure (solder bump), so that the two or more nanostructures are connected to each other.

(22) Hereinafter, the method of soldering a functionalized metal oxide according to an exemplary embodiment will be described in detail with reference to the accompanying drawings.

(23) In order to carry out the method of soldering a functionalized metal oxide according to the present invention, a laser lithography apparatus may be used, as shown in FIG. 2. The laser lithography apparatus is the apparatus capable of generating a pulsed laser, and configured to set laser power, irradiating time, a pulse width, and a focusing range. The nanostructures on a substrate may be irradiated with the pulsed laser generated in the laser lithography apparatus.

(24) FIG. 3 is a drawing illustrating a principle of the method of soldering a functionalized metal oxide according to an exemplary embodiment.

(25) Referring to FIG. 3, a substrate 10, nanostructures 20, a light absorption layer 30, and a precursor solution for hydrothermal synthesis 40 are formed sequentially in this order, and a functionalized metal oxide solder bump 50 (solder structure) may be prepared by irradiating a surface of the nanostructures dipped in the precursor solution for hydrothermal synthesis 40 with a pulsed laser 60. Herein, the pulsed laser 60 may cause a hydrothermal synthesis reaction of the precursor solution for hydrothermal synthesis.

(26) In the method of soldering a functionalized metal oxide according to the present invention, when the precursor solution for hydrothermal synthesis received thermal energy through laser irradiation, an amine compound reacts with a water molecule contained in an aqueous solution to generate ammonia, and the ammonia reacts with the water molecule to form an ammonium ion and a hydroxyl ion. The hydroxyl ion may react with a metal or a semiconductor ion contained in a metal precursor or a semiconductor precursor solution to prepare a metal oxide or a semiconductor oxide, but this is not necessarily followed.

(27) In the method of soldering a functionalized metal oxide according to the present invention, the metal precursor contained in the precursor solution for hydrothermal synthesis may be a zinc precursor, and it is preferred that the zinc precursor is one or more compounds selected from the group consisting of zinc chloride (ZnCl.sub.2), zinc sulfate (ZnSO.sub.4), zinc acetate (Zn(CH.sub.3CO.sub.2).sub.2), zinc citrate (Zn.sub.3[O.sub.2CCH.sub.2C(OH)(CO.sub.2)CH.sub.2CO.sub.2].sub.2), zinc nitrate (Zn(NO.sub.3).sub.2), zinc nitrate hexahydrate (Zn(NO.sub.3).sub.2.6H.sub.2O), and zinc acetate dihydrate (Zn(OOCCH.sub.3).sub.2.2H.sub.2O), which are used for supplying zinc ions in the hydrothermal synthesis.

(28) Further, the metal precursor contained in the precursor solution for hydrothermal synthesis may be a copper precursor, and it is preferred that the copper precursor is one or more compounds selected from the group consisting of copper sulfate (CuSO.sub.4), copper(I) chloride (CuCl), copper (II) chloride (CuCl.sub.2), copper nitrate (Cu(NO.sub.3).sub.2), copper acetate (CH.sub.3COOCu), copper carbonate (CuCO.sub.3), copper cyanide (Cu(CN).sub.2), and copper iodide (CuI), which are used for supplying copper ions in the hydrothermal synthesis.

(29) Though the copper precursor or the zinc precursor may be used as above, the present invention is not necessarily limited thereto, and all kinds of metal precursors or semiconductor precursors may be used, as well as the copper precursor or the zinc precursor.

(30) In the method of soldering a functionalized metal oxide according to the present invention, it is preferred that the amine compound may be one or more selected from the group consisting of hexamethyleneamine (HMA), hexamethylenetetramine (HMTA), cyclohexylamine, monoethanolamine, diethanolamine, and triethanolamine, which are used for supplying hydroxyl ions in the hydrothermal synthesis.

(31) In the method of soldering a functionalized metal oxide according to the present invention, it is preferred to further include covering the substrate with a transparent substrate, after dipping the substrate on which the nanostructures are formed in the precursor solution for hydrothermal synthesis. This may be carried out for preventing the applied precursor solution for hydrothermal synthesis from evaporating.

(32) In the method of soldering a functionalized metal oxide according to the present invention, it is preferred to further include depositing one selected from the group consisting of gold, platinum, silver, copper, aluminum, tin, nickel, chromium, cobalt, tungsten, iron, and semiconductors on at least a portion of the nanostructures, before connecting the two or more nanostructures to each other, by irradiating any one of the nanostructures with a pulsed laser to grow a solder structure (solder bump). This is the step for coating a material for absorbing the laser before forming nanostructures on a substrate, and coating the material on the substrate is advantageous in obtaining sufficient temperature for growing metal oxide solder with small laser power. The light absorption layer may be formed differently depending on the wavelength of the laser, thereby increasing light absorption efficiency. As the light absorption layer, semiconductors as well as metals may be used, and also any materials having many free electrons may be used.

(33) In the method of soldering a functionalized metal oxide according to the present invention, annealing the solder structure (solder bump) may be further carried out, after forming the solder structure (solder bump). This may be a treatment method for heating materials to the temperature enough to diffuse them, then slowly cooling them to be in a stable state as it is shown in an equilibrium state. In case of the materials representing change of state with change of temperature, they may be slowly cooled down for sufficient time, to be in a stable equilibrium state shown in a phase diagram, thereby growing the solder structure (solder bump) having better quality.

(34) In the method of soldering a functionalized metal oxide according to the present invention, the pulsed laser may be irradiated at a pulse duty ratio of 5% to 20%, and a pulse width controlled in a range of 100 ns to 3000 ns. The pulse duty ratio is a ratio of the time for laser irradiation in one cycle. If the pulse ratio is less than 5%, the time for laser irradiation will be too short so that sufficient energy for hydrothermal synthesis is not applied, which causes the growth of the solder structure (solder bump) to be too slow. If the pulse ratio is above 20%, the time for cooling will be too short so that the solder structure (solder bump) has lower density, and the shape of the solder structure (solder bump) will not be precisely adjusted, while the precursor solution for hydrothermal synthesis will be heated to above its boiling point, thereby generating bubbles therein which causes lower density, and difficulty in precisely adjusting the shape of the nanostructures.

(35) The pulse width is the time for laser irradiation in one cycle. If the laser is irradiated with the pulse width of less than 100 ns, the time for laser irradiation will be too short so that sufficient energy for hydrothermal synthesis is not applied, which causes the growth of the solder structure (solder bump) to be too slow. If the pulse width is above 3000 ns, the precursor solution for hydrothermal synthesis will be heated to above its boiling point, thereby generating bubbles therein, which causes lower density, and it will be difficult to precisely adjust the shape of the solder structure (solder bump). Referring to FIG. 4, if the pulse width is 400 ns, it was observed that growing was well done. However, if the pulse width is 4000 ns or 40000 ns, it is appreciated that there are generated a number of spaces within the solder structure (solder bump), thereby forming the solder structure (solder bump) having lower density.

(36) Further, in the present invention, the pulsed laser may preferably have peak power in a range of 5 mW/m.sup.2 to 20 mW/m.sup.2, in case where an oxide film having a thickness of 50 nm, and a tungsten absorption layer having a thickness of 40 nm are deposited on a silicon substrate under a normal pressure. FIG. 5 is a photograph illustrating zinc oxide solder prepared by the method of soldering a functionalized metal oxide according to an exemplary embodiment, and FIG. 6 is a photograph illustrating copper oxide solder prepared by the method of soldering a functionalized metal oxide according to an exemplary embodiment.

(37) Referring to FIG. 5, in case of irradiation with a laser having power at 23.5 mW, and in case of irradiation with a laser having power at 31.7 mW, change of the zinc oxide solder with time was observed. It is appreciated that in case of irradiation with a laser having power at 23.5 mW, the solder grows at a relatively slow rate, but the zinc oxide solder having high density was prepared, and in case of irradiation with a laser having power at 31.7 mW, zinc oxide solder in a crater shape was initially formed, but after some time passed, the crater part was filled, so that the zinc oxide solder having a relatively large diameter and high density was prepared.

(38) Further, referring to FIG. 6, in case of irradiation with a laser having power at 23.5 mW, and in case of irradiation with a laser having power at 31.7 mW, change of the copper oxide solder with time was observed. It is appreciated that in case of irradiation with a laser having power at 23.5 mW, the solder grows at a relatively slow rate, but the copper oxide solder having high density was formed, and in case of irradiation with a laser having power at 31.7 mW, the solder grows at a relatively fast rate, but had rather low density.

(39) FIG. 7 is a graph illustrating volume of metal oxide solder depending on laser power and irradiating time of the method of soldering a functionalized metal oxide according to an exemplary embodiment.

(40) Referring to FIG. 7, in case of a laser having power at 15.4 mW, the metal oxide solder grows at a rate too slow, so that the time required for the preparation process is increased, and in case of a laser having power at 55.9 mW, the metal oxide solder grows at a fast rate, but the prepared metal oxide solder has low density. Thus, the power of the laser may be controlled in a range of 15.4 mW to 55.9 mW, more preferably in a range of 20 mW to 40 mW.

(41) FIG. 8 is a drawing illustrating a principle of functionalized metal oxide solder formed by the method of soldering a functionalized metal oxide according to an exemplary embodiment.

(42) Referring to FIG. 8, two nanostructures 100a and 100b are formed to be crossed to each other, and the nanostructures 100a and 100b are dipped in a precursor solution for hydrothermal synthesis. At least a portion of the intersecting points of the nanostructures 100a and 100b was irradiated with a pulsed laser 600 to grow a metal oxide solder structure 500. The metal oxide solder structure 500 may connect the two nanostructures 100a and 100b to each other by growing.

(43) FIG. 9 is a photograph illustrating functionalized metal oxide solder prepared by the method of soldering a functionalized metal oxide according to an exemplary embodiment.

(44) Referring to FIG. 9, two nanostructures spaced from each other are formed to be crossed to each other. Herein, the intersecting point of the nanostructures is irradiated with a pulsed laser to grow a metal oxide solder structure, and accordingly, two nanostructures spaced from each other are soldered. As in FIG. 9, it is appreciated that copper oxide solder and zinc oxide solder grow on two nanostructures spaced from each other, thereby connecting the two nanostructures spaced from each other to each other. FIG. 10 is a graph representing the result of measuring current depending on voltage by grounding a lower nanostructure of the two nanostructures, and applying voltage to an upper nanostructure. In can be seen from FIG. 10 that as voltage is increased, current is increased in proportion, and thus, the two nanostructures are electrically joined.

(45) FIG. 11 is a graph representing the case of annealing the functionalized metal oxide solder structure prepared by the method of soldering a functionalized metal oxide according to an exemplary embodiment 1100, and the case without annealing 1200. Referring to FIG. 11, it is appreciated that electrical conductivity is further improved by annealing the functionalized metal oxide solder prepared by the method of soldering a functionalized metal oxide according to an exemplary embodiment.

(46) Further, there is provided an electronic device manufactured by a method including forming two or more nanostructures on a substrate; dipping the substrate on which the nanostructures are formed in a precursor solution for hydrothermal synthesis; and irradiating any one of the nanostructures with a pulsed laser to grow a solder structure (solder bump), so that the two or more nanostructures are connected to each other.

(47) FIG. 12 is a drawing illustrating a principle of an ultraviolet sensor manufactured by the method of soldering a functionalized metal oxide according to an exemplary embodiment. The ultraviolet sensor manufactured by the method of soldering a functionalized metal oxide has electrical conductivity varying with ultraviolet dosage, and is illustrated in FIG. 13.

(48) Referring to FIGS. 12 and 13, the ultraviolet sensor manufactured by the method of soldering a functionalized metal oxide according to an exemplary embodiment may have a functionalized metal oxide solder 900 formed between two electrodes 700 and 800. The functionalized metal oxide solder 900 is a metal oxide having electrical conductivity varying with ultraviolet intensity, and the ultraviolet intensity with which the functionalized metal oxide solder 900 is irradiated may be determined by measuring change in the electrical conductivity.

(49) Referring to FIG. 14, in the ultraviolet sensor manufactured by the method of soldering a functionalized metal oxide according to an exemplary embodiment, current increase was confirmed in case of ultraviolet irradiation, and it can be seen whether there is ultraviolet irradiation by sensing such current change. Further, FIG. 15 illustrates the characteristics of the ultraviolet sensor manufactured by the method of soldering a functionalized metal oxide according to an exemplary embodiment, depending on the ultraviolet irradiation intensity, according to the correlation between voltage and current. It is appreciated that the electrical conductivity is low without ultraviolet irradiation, and as the ultraviolet intensity is increased to 0.33 mW/cm.sup.2, 2.31 mW/cm.sup.2 and 28.8 mW/cm.sup.2, the electrical conductivity of the ultraviolet sensor is increased.

(50) As described above, it is confirmed that metal oxide solder structure or semiconductor solder structure may be grown by the method of soldering a functionalized metal oxide according to an exemplary embodiment. This method is to irradiate the surface of nanostructures with a pulsed laser to heat the surface of the nanostructures, and to grow the metal oxide solder structure or semiconductor solder structure by a hydrothermal synthesis reaction between the heated nanostructures and a precursor solution for hydrothermal synthesis. In case where the laser is a continuous laser, thermal diffusion may excessively occur on the surface of the nanostructures so that the growing solder structure is difficult to be controlled, the uprightness of the solder structure may be lowered due to excessive heat, and the density of the solder structure may be lowered or the nanostructure may be broken due to bubbles generated in the precursor solution by heat. If the laser is a pulsed laser, the solder structure may grow locally on the surface of the nanostructures, and is possible to grow only on a desired area at a rapid rate.

(51) According to the present invention, thermal diffusion generated from a laser is limited due to the use of a pulsed laser, and thus, nanosolder having high density and a shape that may be precisely adjustable may be prepared by a hydrothermal synthesis method by the pulsed laser, and it may be grown to facilitate the joining of the nanostructures, and further, formed between the nanostructures thereby being used as a metal oxide structure having functionality.