KR102449969B1 - Metal film type electrode, and electronic device comprising the same - Google Patents

Abstract

The present invention relates to a metal thin film-type electrode comprising a metallic glass composition having an amorphous structure and an electronic device including the same, an electrode having the form of a metallic thin film and an electronic device to which the same is applied, wherein the metallic thin film electrode comprises an amorphous metallic glass composition Including, the metallic glass composition is formed by sputtering deposition.

Description

Metal thin-film electrode and electronic device including the same

The present invention relates to a metal thin film-type electrode including a metallic glass composition having an amorphous structure and an electronic device including the same.

A commonly used metal thin film is a material that can be easily formed into a thin film through thermal evaporation, sputtering deposition, etc., and has a low coefficient of thermal expansion so that conductivity and mechanical properties are not lost even at high temperatures. In addition, since it has high conductivity and mechanical strength even in the thickness of nanometers, it has recently been widely applied as an electrode material to electronic devices such as thin-film bending sensors, strain sensors, or solar cells.

However, the conventional metal thin film has high crystallinity and consists of grains and grain boundaries. Due to these characteristics, the surface of the metal thin film is easily damaged by external attraction, and the conductivity is reduced. In addition, there is a problem in that it is vulnerable to oxygen or moisture.

Republic of Korea Patent Publication No. 10-2097805 B1

An object of the present invention is to provide a metal thin film type electrode having mechanical and chemical stability by depositing a chemically stable amorphous metal glass through a sputtering technique.

In addition, an object of the present invention is to provide an electronic device with improved efficiency and durability by applying the metal thin film electrode.

In addition, an object of the present invention is to provide a bending sensor or a strain sensor having high bendability and tensile strength, and having little damage to the surface and conductivity of a thin film even when a certain amount of strain is applied by an external force as the electronic device.

Another object of the present invention is to provide a solar cell that is stable to an external environment such as oxygen or moisture and prevents formation of an oxide film at an interface that prevents electron transfer as the electronic device.

The metal thin film type electrode according to an embodiment of the present invention is an electrode having the shape of a metal thin film, and includes a metallic glass composition having an amorphous structure, and the metallic glass composition is formed by sputtering deposition.

In the metal thin film-type electrode according to an embodiment of the present invention, the metal glass composition includes zirconium (Zr), and the zirconium (Zr) may be included in the largest amount by weight with respect to 100% by weight of the total metal glass composition. .

In the thin metal film electrode according to an embodiment of the present invention, the metallic glass composition may further include aluminum (Al), nickel (Ni), and cobalt (Co).

In the thin metal film electrode according to an embodiment of the present invention, the metallic glass composition is based on 100% by weight of the total metallic glass, zirconium (Zr): 55 to 65% by weight, aluminum (Al): 11 to 17% by weight, Nickel (Ni): 8 to 14% by weight, cobalt (Co): may include 13 to 20% by weight.

In the metal thin film-type electrode according to an embodiment of the present invention, the metal glass composition includes aluminum (Al), and the aluminum (Al) may be included in the largest amount by weight based on 100% by weight of the total metal glass composition. .

In the metal thin film-type electrode according to the embodiment of the present invention, the metallic glass composition may further include yttrium (Y), nickel (Ni), and cobalt (Co).

In the metal thin film-type electrode according to an embodiment of the present invention, the metallic glass composition comprises, with respect to 100 wt% of the total metallic glass, aluminum (Al): 80 to 90 wt%, yttrium (Y): 6 to 10 wt%, Nickel (Ni): 3 to 6% by weight, cobalt (Co): may include 1.5 to 3.5% by weight.

In the thin metal film electrode according to an embodiment of the present invention, the metal thin film electrode may have a thickness of 50 to 150 nm.

An electronic device according to an embodiment of the present invention includes the metal thin film type electrode.

In an electronic device according to an embodiment of the present invention, the electronic device is a solar cell, and includes an intermediate layer including molybdenum oxide (MoOx, 0<x≤6); photoactive layer; and an electron transport layer; Further comprising, the metal thin film electrode may be formed by sputtering deposition on an intermediate layer in which the metallic glass composition includes the molybdenum oxide (MoOx, 0<x≤6).

In the electronic device according to an embodiment of the present invention, the thickness of the intermediate layer including the molybdenum oxide (MoOx, 0<x≤6) may be 5nm to 20nm.

The electronic device according to an embodiment of the present invention is a bending sensor or a strain sensor, and a film including a polymer polymer; and the metal thin film electrode is sputtered ( Sputtering) may be formed by deposition.

In the electronic device according to an embodiment of the present invention, the high-molecular polymer is a polyimide polymer, and the film including the polyimide polymer may have a thickness of 100 μm to 200 μm.

A method of manufacturing a solar cell as an electronic device according to an embodiment of the present invention comprises the steps of preparing a substrate; forming an electron transport layer by coating a ZnO precursor solution on the substrate and then performing heat treatment; forming a photoactive layer by coating a solution of PBDTTT-EFT and PC70BM on the electron transport layer; forming an intermediate layer by thermally depositing molybdenum oxide (MoOx, 0<x≤6) on the photoactive layer; and forming the metal thin film-type electrode by sputtering and depositing a metallic glass composition on the thermally deposited intermediate layer.

A method for manufacturing a bending sensor or a strain sensor as an electronic device according to an embodiment of the present invention comprises the steps of: preparing a film including a polyimide polymer; and forming the metal thin film electrode by sputtering and depositing a metallic glass composition on the film including the polyimide polymer.

The present invention provides a metal thin film type electrode having excellent mechanical and chemical stability.

In addition, it provides an electronic device with improved efficiency and durability by applying the metal thin film electrode.

In addition, as the electronic device, it has high bendability and tensile strength, and provides a bending sensor or a deformation sensor with little damage to the thin film surface and conductivity even when a certain amount of strain is applied by an external force.

In addition, as the electronic device, there is provided a solar cell that is stable in an external environment such as oxygen or moisture and prevents formation of an oxide film at an interface that prevents electron transfer.

1 is a comparison of mechanical and chemical properties of metal thin films according to (a, b) Comparative Examples and (c, d) Examples of the present invention.
FIG. 2 shows the structures of (a) a bending sensor, and (b) an organic solar cell according to an embodiment of the present invention.
3 illustrates a process for manufacturing an organic solar cell according to an embodiment of the present invention.
4 is a graph comparing diffraction patterns of metal thin films according to Examples and Comparative Examples of the present invention by X-ray diffraction (XRD).
5 (a) and (b) are graphs showing the UPS spectrum of the metal thin film electrode according to an embodiment of the present invention.
6 is a strain-resistance change rate of a metal thin film according to (a) a comparative example of the present invention, (b) a metal thin film bending test according to an embodiment, and (c) a comparative example and an embodiment of the present invention. It is a graph showing the comparison graph, and (d) 100 times bending test results of the metal thin film according to Example.
7 is a graph comparing (a) JV curve curve, (b) EQE spectra, and (c) durability of organic solar cells to which a metal thin film is applied according to Comparative Examples and Examples of the present invention.
FIG. 8 shows SEM images after bending test of a metal thin film according to (a) Comparative Example and (b) Example of the present invention.
9 is a photograph showing changes in stability and sheet resistance according to (a, c) Comparative Examples and (b, d) Examples of the present invention.
10 is a photograph of an organic solar cell metal thin film electrode according to (a) Comparative Example and (b) Example of the present invention after time elapses in air.
11 shows a method for measuring the strain by bending of the present invention.

Hereinafter, the present invention will be described in more detail through examples. These examples are only for illustrating the present invention and should not be construed as limiting the scope of the present invention by these examples.

As used herein, an expression such as "comprising" is understood as an open-ended term that includes the possibility of including other embodiments, unless specifically stated otherwise in the phrase or sentence in which the expression is included. should be

As used herein, “preferred” and “preferably” refer to embodiments of the invention that may provide certain advantages under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Additionally, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the invention.

The metal thin film electrode according to an embodiment of the present invention is an electrode having a metal thin film shape, and has characteristics of a metal having high electrical conductivity, low coefficient of thermal expansion, and high mechanical strength. By using thin-film metal as an electrode in electronic devices such as transistors, photovoltaic cells, electrochemical devices, and sensors, light, portable, and flexible electronic devices with high conductivity even at a thin nano-micrometer scale are manufactured. can do.

The metal thin film electrode includes a metallic glass composition having an amorphous structure. Metallic glass having an amorphous structure is a solid metal having disordered atomic states and no crystalline structure, and has the properties of metals described above. Since the crystalline metal thin film lacks flexibility and elasticity, there is a problem in that the performance of the electronic device is deteriorated under external stress. In addition, there is a problem in that oxidation and electrical conductivity are lowered because chemical stability to oxygen and moisture is low. For example, when an aluminum (Al) or silver (Ag) electrode is used as an electrode of an organic solar cell or a perovskite solar cell, the electrode has low stability against oxygen and moisture, and thus the organic layer from the electrode ions move and form an insulating metal oxide layer to impede the movement of electrons. This is because cracks are formed at the grain boundaries of the crystalline metal, and the grain boundaries act as chemically active sites where chemical reactions are initiated. However, metallic glass has greater elasticity and toughness than crystalline metals, and has excellent stability against chemical reactions. According to the present invention, a mechanically and chemically stable electronic device can be manufactured by applying a metallic glass having these characteristics to an electronic device as a thin-film electrode.

1 is a comparison of mechanical and chemical properties of a crystalline metal thin film (a, b) and a metallic glass thin film (c, d). The metallic glass thin film can be used as an electrode of an electronic device because it has excellent mechanical properties with excellent flexibility and chemical properties with excellent resistance to oxidation.

The metal thin film electrode is formed by sputtering deposition of the metal glass composition. It should be possible to prevent the metallic glass alloy from crystallizing during the manufacturing process, and a manufacturing process with a fast quenching rate is required. The metallic glass can be applied as an electrode by sputtering deposition, and can form a thin electrode thin film on a desired substrate such as an oxide layer or a polymer in an electronic device. Since the cooling rate of the sputtered deposited atoms is very fast, the deposited layer can maintain an amorphous phase. In particular, since it is difficult to form an amorphous electrode in the case of a metallic glass composition to be described later, deposition of the metallic glass composition by sputtering deposition is necessarily required to form a metal thin film type electrode.

In the metal thin film type electrode according to the embodiment of the present invention, the metallic glass composition may include zirconium (Zr). In addition, the zirconium (Zr) may be included in the largest percentage by weight based on 100% by weight of the total metal glass composition. In addition, the metallic glass composition may further include aluminum (Al), nickel (Ni), and cobalt (Co). In addition, other unavoidable impurities may be further included in addition to the above elements.

The zirconium (Zr) may be 55 to 65% by weight, more preferably 57 to 63% by weight, more preferably 59 to 61% by weight based on 100% by weight of the total metallic glass. If the content is out of the range, it is out of the optimization range of bendability and tensile strength, and when a certain amount of strain is applied by an external force, the thin film surface and conductivity may be damaged, and there may be a problem in forming amorphous metal.

The aluminum (Al) may be in an amount of 11 to 17 wt%, more preferably 13 to 15 wt%, based on 100 wt% of the total metallic glass. If the content is out of the range, it is out of the optimization range of bendability and tensile strength, and when a certain amount of strain is applied by an external force, the thin film surface and conductivity may be damaged, and there may be a problem in forming amorphous metal.

The nickel (Ni) may be in an amount of 8 to 14% by weight or 10 to 12% by weight based on 100% by weight of the entire metallic glass. When the content is out of the above range, it is vulnerable to an external environment such as oxygen or moisture, an oxide film at the interface that prevents electron transfer may be formed, and there may be a problem in forming amorphous metal.

The cobalt (Co) may be 13 to 20% by weight, more preferably 15 to 18% by weight, more preferably 16 to 17% by weight based on 100% by weight of the total metallic glass. When the content is out of the above range, it is vulnerable to external environments such as oxygen or moisture, an oxide film at the interface that prevents electron transfer may be formed, and there may be a problem in forming amorphous metal.

In the metal thin film type electrode according to the embodiment of the present invention, the metal glass composition may include aluminum (Al). In addition, the aluminum (Al) may be included in the largest amount by weight based on 100% by weight of the total metal glass composition. In addition, the metallic glass composition may further include yttrium (Y), nickel (Ni), and cobalt (Co). In addition, other unavoidable impurities may be further included in addition to the above elements.

The aluminum (Al) may be 80 to 90% by weight, more preferably 82 to 88% by weight, more preferably 84 to 86% by weight based on 100% by weight of the total metal glass. If the content is out of the range, it is out of the optimization range of bendability and tensile strength, and when a certain amount of strain is applied by an external force, the thin film surface and conductivity may be damaged, and there may be a problem in forming amorphous metal.

The yttrium (Y) may be 6 to 10% by weight, more preferably 7 to 9% by weight based on 100% by weight of the total metallic glass. If the content is out of the above range, there may be problems in strength and thermal durability, and there may be problems in forming amorphous metals.

The nickel (Ni) may be 3 to 6% by weight, 4 to 5% by weight based on 100% by weight of the entire metallic glass. When the content is out of the above range, it is vulnerable to external environments such as oxygen or moisture, an oxide film at the interface that prevents electron transfer may be formed, and there may be a problem in forming amorphous metal.

The cobalt (Co) may be in an amount of 1.5 to 3.5 wt%, more preferably 2 to 3 wt%, based on 100 wt% of the total metallic glass. When the content is out of the above range, it is vulnerable to external environments such as oxygen or moisture, an oxide film at the interface that prevents electron transfer may be formed, and there may be a problem in forming amorphous metal.

In the thin metal film electrode according to the embodiment of the present invention, the metal thin film electrode may be 50 to 150 nm, more preferably 70 to 130 nm, more preferably 90 to 110 nm. The metal thin film electrode may be adjusted to have the thickness by a sputtering process. In addition, since the metal thin film electrode of the above thickness range is applied to the electrode device, it is possible to manufacture a light, portable and flexible electronic device.

An electronic device according to an embodiment of the present invention includes the metal thin film type electrode. The electronic device includes a transistor, a photovoltaic cell, an electrochemical device, and a sensor. However, if the metal thin film type electrode can be applied, it is not particularly limited thereto.

2 shows a structure in which a metallic glass thin film is applied to a bending sensor (a) and an organic solar cell (b) as an embodiment.

As an embodiment, the electronic device may be a solar cell. In particular, when a metal thin film electrode including an aluminum-based metallic glass composition is applied to an organic solar cell, it may have high chemical stability without deterioration of battery performance.

The solar cell may further include an intermediate layer, a photoactive layer, or an electron transport layer. Each layer is a layer conventional in a solar cell, and there is no particular limitation thereto.

More preferably, the solar cell may include an intermediate layer including molybdenum oxide (MoOx, 0<x≤6).

The metal thin film-type electrode may be formed by sputtering and depositing a metallic glass composition on the intermediate layer including the molybdenum oxide (MoOx, 0<x≤6). The molybdenum oxide (MoOx, 0<x≤6) layer may shield the organic layer from damage caused by sputter deposition of the metallic glass composition.

In addition, the thickness of the intermediate layer including the molybdenum oxide (MoOx, 0<x≤6) may be 5 nm to 20 nm, more preferably 7 to 15 nm, more preferably 9 to 12 nm. Damage applied to the intermediate layer including molybdenum oxide (MoOx, 0<x≤6) during sputter deposition of the metallic glass within the thickness range may be prevented. Therefore, the thickness of the intermediate layer including the molybdenum oxide (MoOx, 0<x≤6) should be thicker than the thickness used in the case of a conventional Ag electrode.

A method of manufacturing a solar cell as an electronic device according to an embodiment of the present invention includes preparing a substrate. In one embodiment, the substrate may be an ITO substrate. Preparing the substrate may include ultrasonicating the substrate. Also, the method may include hydrophilizing the substrate.

In addition, the method of manufacturing a solar cell of the present invention may include coating a ZnO precursor solution on the substrate and then heat-treating it to form an electron transport layer. The method of coating the ZnO precursor solution may be coated by a coating method such as spin coating, slit coating, dip coating, spray coating, doctor blade, or bar coating, but is not particularly limited thereto. However, more preferably, it may be deposited by spin coating.

In addition, the method of manufacturing the solar cell of the present invention may include forming a photoactive layer on the electron transport layer. The photoactive layer may include an organic material, a quantum dot, or a material having a perovskite structure, but is not particularly limited thereto. As an embodiment, a photoactive layer may be formed by coating a solution of PBDTTT-EFT and PC70BM. The coating method is not limited, but more preferably, it may be deposited by spin coating.

In addition, the method of manufacturing a solar cell of the present invention may include thermally depositing molybdenum oxide (MoOx, 0<x≤6) on the photoactive layer to form an intermediate layer. The molybdenum oxide (MoOx, 0<x≤6) layer can shield the organic layer from damage caused by sputtering deposition of the metallic glass composition, and make the sputtering deposition of the metallic glass composition more stable.

In addition, the method for manufacturing a solar cell of the present invention includes the step of forming the metal thin film-type electrode by sputtering and depositing a metallic glass composition on the thermally deposited intermediate layer.

3 illustrates a process for manufacturing an organic solar cell as an embodiment.

Also, as an embodiment, the electronic device may be a bending sensor or a deformation sensor.

In particular, when a metal thin film electrode including a zirconium-based metallic glass composition is applied to a bending sensor or a strain sensor, the ability to detect deformation may be improved.

In addition, in the case of polycrystalline metal thin films, grain boundaries have elastic limits and cause plastic deformation and crack formation. Therefore, the metallic glass thin film of the present invention in which grain boundaries do not exist has a high elastic limit.

In one embodiment, the bending sensor or the deformation sensor may further include a film including a polymer polymer. The polymer is not particularly limited, but more preferably a polyimide polymer. The metal thin film-type electrode may be formed by sputtering and depositing a metal glass composition on a film including the polymer polymer.

In addition, the thickness of the film including the polyimide polymer may be 100 to 200 μm, more preferably 120 to 180 μm, more preferably 130 to 160 μm. Within the above thickness range, the metallic glass composition may be stably sputter deposited.

The method of manufacturing a bending sensor or a strain sensor as an electronic device according to an embodiment of the present invention may include preparing a film including a polyimide polymer.

Also, the method may include sputtering and depositing a metal glass composition on the film including the polyimide polymer to form the metal thin film electrode.

<Analysis method>

The atomic structure of the metal thin film was analyzed by New D8-Advance (Brucker-AXS) X-ray diffraction analysis.

The work function of the metal thin film was calculated from ultraviolet photoelectron spectroscopy (UPS) spectrum measurement results using a Thermo VG Scientific (sigma probe).

The resistance response was analyzed by collecting electrical signals after measurement using a homemade bend tester with a Keithley 2400 source meter.

The equivalent strain due to bending was calculated by measuring the distance between the two ends of the polyimide film as shown in FIG. 11 and substituting it in Equation 1 below.

[Equation 1]

(In Equation 1, ε is the strain, t is the thickness of the substrate, and R is the bending radius)

The SEM image of the metal thin film was SE-analyzed with a Hitachi S-3400N.

The sheet resistance of the metal thin film was measured with a Loresta-GP MCP-T610 (Mitsubishi Chemical) with a 4-point probe.

To evaluate the performance and stability of organic solar cells, current density-voltage characteristics were measured with ZIVE SP1 under simulated sunlight of 1 sun (100 mW/cm ² , Air Mass 1.5 G).

The external quantum efficiency (EQE) of the organic solar cell was measured with a monogromator (Dongwoo Optron Co., Ltd, MonoRa-500i, Korea) after power calibration (Abet Technologies, Inc., LS150, USA).

<Example 1-1> Preparation of Zr-MG thin film (Zr-based metallic glass thin film)

A Zr ₆₀ Al ₁₅ Ni ₁₀ Co ₁₅ composition was prepared as a sputter target, and a metal glass thin film was prepared through DC sputter deposition. A Zr ₆₀ Al ₁₅ Ni ₁₀ Co ₁₅ metallic glass sputtering target was prepared by powder metallurgy treatment using a Zr ₆₀ Al ₁₅ Ni ₁₀ Co ₁₅ composition metallic glass powder. First, a Zr ₆₀ Al ₁₅ Ni ₁₀ Co ₁₅ composition master alloy having a designed atomic composition is prepared through a vacuum furnace, and then, a metallic glass alloy powder is prepared by an argon gas atomizer. The powder is then sintered under 60 kg/mm ² pressure to produce a reinforced billet. The sintering process was carried out at 1173 K. Finally, a 6 inch disc type target is produced through cutting and grinding. DC sputter deposition is performed by injecting Ar gas at a partial pressure of 5 to 200 mTorr in a high vacuum of 10 ^-4 to 10 ^-6 Torr, applying a deposition power of 50 to 1000 mW, and depositing for 1 to 3600 seconds to form a thin film. to form

<Example 1-2> Preparation of Al-MG thin film (Al-based metallic glass thin film)

Al ₈₅ Ni ₅ Y ₈ Co ₂ A composition was prepared as a sputter target, and a metal glass thin film was prepared through DC sputter deposition. An Al ₈₅ Ni ₅ Y ₈ Co ₂ metallic glass sputtering target was prepared by powder metallurgy treatment using an Al ₈₅ Ni ₅ Y ₈ Co ₂ composition metallic glass powder. First, an Al ₈₅ Ni ₅ Y ₈ Co ₂ composition master alloy having an atomic composition is prepared through a vacuum furnace, and then, a metallic glass alloy powder is prepared by an argon gas atomizer. The powder is then sintered under 60 kg/mm ² pressure to produce a reinforced billet. The sintering process was carried out at 723 K. Finally, a 6 inch disc type target is produced through cutting and grinding. DC sputter deposition is performed by injecting Ar gas at a partial pressure of 5 to 200 mTorr in a high vacuum of 10 ^-4 to 10 ^-6 Torr, applying a deposition power of 50 to 1000 mW, and depositing for 1 to 3600 seconds to form a thin film. to form

<Comparative Example 1> Al thin film

An Al sputter target was purchased, and a crystalline Al thin film was manufactured through DC sputter deposition. DC sputter deposition is performed by injecting Ar gas at a partial pressure of 5 to 200 mTorr in a high vacuum of 10 ^-4 to 10 ^-6 Torr, applying a deposition power of 50 to 1000 mW, and depositing for 1 to 3600 seconds to form a thin film. to form

<Example 2> Preparation of organic solar cell to which Al-MG thin film electrode is applied

The ITO substrate was cleaned by ultrasonication in deionized water (DI), acetone, and isopropyl alcohol for 20 minutes.

Next, 0.25 g of Zinc acetate dihydrate (Zn(CH ₃ COO) ₂ ·2H ₂ O 99.5%, Aldrich) and 69 μl of ethanolamine (Aldrich) were dissolved in 5 ml of 2-methoxyethanol (Aldrich) to prepare a ZnO precursor solution. did. Thereafter, the ZnO precursor solution was spin-coated on an ITO substrate in a glove box filled with argon, and then annealed at 220° C. for 1 hour to form a ZnO electron transport layer of 35 nm.

Next, a polyethyleneimine (PEI) layer was spin-coated on the ZnO electron transport layer outside the glove box at a speed of 5000 rpm for 40 seconds.

Next, polythieno[3,4-b]-thiophene-co-benzodithiophene(PTB7) and [6,6]-phenyl C ₇₀ butyric acid methyl ester (PC ₇₀ BM) (1: 1.5, w/w) were mixed with chlorobenzene and 1,8-diiodooctane (97: 3, v/v), and then spin-coated the solution on the PEI layer to form a photoactive layer.

Next, a 5 nm molybdenum oxide (MoOx) layer was deposited on the photoactive layer by thermal evaporation to form an intermediate layer having a thickness of 10 nm.

Al 85 Ni 5 Y 8 Co 2 A metal glass having a composition of Al ₈₅ Ni ₅ Y ₈ Co ₂ was sputtered and deposited on the MoOx intermediate layer as a sputter target to form an Al-MG electrode having a thickness of 100 nm.

<Comparative Example 2> Preparation of organic solar cell to which Ag crystalline metal thin film electrode is applied

An organic solar cell was manufactured by the same process as in Example 2, except that the molybdenum oxide (MoOx) layer was formed to a thickness of 5 nm and Ag was deposited on the MoOx intermediate layer by thermal evaporation to form an Ag electrode.

<Example 3> Preparation of bending sensor to which Zr-MG thin film electrode is applied

The Zr ₆₀ Al ₁₅ Ni ₁₀ Co ₁₅ composition was sputter-deposited to a thickness of 100 nm on a polyimide (PI) film having a thickness of 150 μm as a sputtering target.

<Comparative Example 3> Manufacture of bending sensor to which Al crystalline metal thin film electrode is applied

An Al thin film was sputter deposited to a thickness of 100 nm on a polyimide (PI) film having a thickness of 150 μm.

<Experimental Example 1>

4 is a graph showing the diffraction patterns of the metal thin films according to Example 1-1, Example 1-2, and Comparative Example 1 by X-ray diffraction analysis (XRD). According to the analysis result, it can be confirmed that the metal thin films according to Examples 1-1 and 1-2 were formed in a completely amorphous structure. On the other hand, it can be confirmed that the metal thin film according to Comparative Example 1 has a crystalline structure.

Table 1 below shows the results of analyzing the composition ratios of the Zr-MG thin films and Al-MG thin films prepared in Examples 1-1 and 1-2 through energy dispersive X-ray spectroscopy (EDS). to be.

According to Table 1, it can be confirmed that the actual atomic composition of the manufactured metal thin film was maintained at the same atomic composition as that of the metallic glass composition serving as the sputtering target.

5 is a UPS spectrum measurement result of the metal thin film according to Examples 1-1 and 1-2. The work function of the metallic glass thin film was calculated by Equation 2 below by inducing secondary electron blocking in the UPS spectrum.

[Equation 2]

(In Equation 2, hv is the He(I) irradiation energy of 21.22eV, and E _cutoff is the secondary cutoff level derived from the UPS spectrum.)

E _cutoffs of Examples 1-1 and 1-2 were 15.50 eV and 16.83 eV, respectively, and the calculated work function and sheet resistance values are shown in Table 2 below.

<Experimental Example 2>

6 shows the amount of resistance change according to the bending deformation of the metal thin film according to and Comparative Examples (a) and Example 1 (b). According to the graph, the metal thin film according to Example 1 shows a stable reaction and degree of change with respect to the deformation applied by bending. The resistance increases as the amount of deformation applied increases. According to FIG. 6( c ), in the metal thin film according to Example 1, the amount of change in resistance is constantly increased according to the amount of deformation, and the R-square value is a value close to 1. However, in the metal thin film according to Comparative Example 1, it can be seen that the amount of change in resistance does not constantly increase even when the amount of deformation increases, and the amount of change in resistance is constant throughout the deformation range. According to Figure 6(d), it can be confirmed that the metal thin film according to Example 1-1 did not lose the deformation detection ability even after 100 bending tests.

<Experimental Example 3>

The measured values of FIG. 7 are shown in Table 3 below. According to FIG. 7( c ), since the organic solar cell according to Comparative Example 2 is poor with respect to air and moisture, the performance degradation is accelerated after 500 hours. On the other hand, it can be seen that the organic solar cell according to Preparation Example 1 does not significantly decrease the efficiency even after 4500 hours.

<Experimental Example 4>

FIG. 8 shows SEM images after applying a bending strain of 0.7% for 100 times to the metal thin film according to (a) Comparative Example 1 and (b) Example 1-1. As a result of the above analysis, it can be confirmed that cracks are randomly formed in the metal thin film according to Comparative Example 1, and the conductive path is not completely recovered even after the deformation is released. On the other hand, the metal thin film according to Example 1-1 was hardly damaged, and it can be confirmed that this is consistent with the relationship between the resistance change rate of FIG. 6(c) described above.

9 is a photograph showing the state of the metal thin film according to Example 1-1 and Comparative Example 1 after being placed under 85° C./85% humidity for 12 hours in order to compare the oxidation properties of the metal thin film. According to this, it can be confirmed that the metal thin film according to Comparative Example 1 is severely decomposed by the atmosphere and moisture, but it can be confirmed that the metal thin film according to Example 1-1 is stably maintained.

This can also be confirmed in FIGS. 10 (a) and (b). It can be confirmed that the Al-MG metal glass thin film electrode deposited on the MoOx layer remains intact even when exposed to ambient oxygen and moisture for a long period of time compared to the Al metal thin film electrode.

According to the experimental example, it was possible to manufacture a stable and excellent electronic device using amorphous metallic glass as an electrode through the sputtering deposition process.

When applied to the bending sensor, when an external force corresponding to various strains was applied to the thin film through a bending test, the resistance change rate was directly proportional to the change rate, and it was confirmed that it has stability against mechanical stress and stability against temperature and humidity. .

When applied to an organic solar cell, it was confirmed that it had excellent durability while maintaining a chemically stable state for a long time while showing performance comparable to that of the existing crystalline metal thin film electrode device.

Claims (15)

As an electrode having the form of a metal thin film,
A metallic glass composition having an amorphous structure,
The metallic glass composition is formed by sputtering deposition,
The metallic glass composition is based on 100% by weight of the total metallic glass, zirconium (Zr): 55 to 65% by weight, aluminum (Al): 11 to 17% by weight, nickel (Ni): 8 to 14% by weight, cobalt ( Co): 13 to 20% by weight,
Metal thin-film electrode.
delete delete delete As an electrode having the form of a metal thin film,
A metallic glass composition having an amorphous structure,
The metallic glass composition is formed by sputtering deposition,
The metallic glass composition comprises aluminum (Al),
The aluminum (Al) is included in the largest percentage by weight with respect to 100% by weight of the total metallic glass,
Metal thin-film electrode.
6. The method of claim 5,
The metallic glass composition further comprises yttrium (Y), nickel (Ni), and cobalt (Co),
Metal thin-film electrode.
6. The method of claim 5,
The metallic glass composition is based on 100% by weight of the total metallic glass,
Aluminum (Al): 80 to 90% by weight, Yttrium (Y): 6 to 10% by weight, Nickel (Ni): 3 to 6% by weight, Cobalt (Co): containing 1.5 to 3.5% by weight,
Metal thin-film electrode.
6. The method of claim 1 or 5,
The metal thin-film electrode is 50 to 150 nm thick,
Metal thin-film electrode.
Comprising the metal thin film type electrode according to claim 1 or 5,
electronic device.
10. The method of claim 9,
The electronic device is a solar cell,
an intermediate layer comprising molybdenum oxide (MoOx, 0<x≤6);
photoactive layer; and
electron transport layer; further comprising,
The metal thin film electrode is formed by sputtering deposition on the intermediate layer including the metal glass composition (MoOx, 0 < x ≤ 6),
electronic device.
11. The method of claim 10,
The thickness of the intermediate layer containing the molybdenum oxide (MoOx, 0 <x≤6) is 5nm to 20nm,
electronic device.
10. The method of claim 9,
The electronic device is a bending sensor or a deformation sensor,
A film comprising a high molecular polymer; further comprising,
The metal thin film-type electrode is formed by sputtering deposition on a film including the high molecular weight metal glass composition,
electronic device.
13. The method of claim 12,
The high molecular polymer is a polyimide polymer,
The thickness of the film comprising the polyimide polymer is 100 μm to 200 μm,
electronic device.
In the method of manufacturing a solar cell as an electronic device,
preparing a substrate;
forming an electron transport layer by coating a ZnO precursor solution on the substrate and then performing heat treatment;
forming a photoactive layer by coating a solution of PBDTTT-EFT and PC ₇₀ BM on the electron transport layer;
forming an intermediate layer by thermally depositing molybdenum oxide (MoOx, 0<x≤6) on the photoactive layer; and
A method comprising: sputtering and depositing a metallic glass composition on the thermally deposited intermediate layer to form a metal thin film type electrode according to claim 1 or 5;
A method for manufacturing an electronic device.
In the method of manufacturing a bending sensor or a deformation sensor as an electronic device,
preparing a film comprising a polyimide polymer; and,
Forming a metal thin film type electrode according to claim 1 or 5 by sputtering deposition of a metallic glass composition on the film containing the polyimide polymer;
A method for manufacturing an electronic device.

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