KR102588434B1 - Transparent Heater for Window, and Manufacturing Method Thereof - Google Patents

Abstract

The present invention relates to a transparent heater that can be applied to windows and a method of manufacturing the same, and more specifically, to a window that has excellent thermal stability and durability, and has excellent visible and near-infrared ray transmittance and ultraviolet ray absorption, so that it is transparent and effectively blocks ultraviolet rays. It relates to a transparent heater that can be applied to and a method of manufacturing the same.

Description

Transparent heater that can be applied to windows and manufacturing method thereof {Transparent Heater for Window, and Manufacturing Method Thereof}

The present invention relates to a transparent heater that can be applied to windows and a method of manufacturing the same, and more specifically, to a window that has excellent thermal stability and durability, and has excellent visible and near-infrared ray transmittance and ultraviolet ray absorption, so that it is transparent and effectively blocks ultraviolet rays. It relates to a transparent heater that can be applied to and a method of manufacturing the same.

Energy consumption within buildings, one of the emerging issues in terms of global warming, air quality, and sustainable growth, accounts for 40% of total energy consumption. In particular, regarding energy consumption within a building, about 48% is used for heating and cooling inside the building, and about 19% is used for lighting inside the building.

In order to implement energy-efficient buildings, technologies such as windows using solar energy sources, ventilation systems using heat pumps, boilers using biomass, and hybrid heating systems combining these are being developed. Among these, windows that use solar energy sources can actively control energy compared to windows that are existing passive energy objects, so solar energy sources can be used relatively effectively.

Conventionally, in order to implement the above-described windows, they were designed with UV blocking properties and transparency in mind. However, in terms of global warming and sustainable growth, it is desirable to consider not only UV protection and transparency, but also thermal stability and durability, so research on this is urgent.

The purpose of the present invention is to provide a transparent heater that can be applied to windows and a method of manufacturing the same, which has excellent thermal stability and durability, and has excellent visible and near-infrared ray transmittance and ultraviolet ray absorption, so that it is transparent and effectively blocks ultraviolet rays.

In order to solve the above problems, the present invention provides a transparent heater that can be applied to a window, comprising: a substrate; a transparent heater portion disposed on the lower surface of the substrate; and a transparent solar cell unit disposed on the upper surface of the substrate, wherein the transparent heater unit includes: a first metal nanostructure laminated on the lower surface of the substrate; and a first metal oxide covering the first metal nanostructure, wherein the transparent solar cell unit includes: a first transparent electrode layer disposed on the upper surface of the substrate; an n-type oxide semiconductor layer disposed on the first transparent electrode layer; a p-type oxide semiconductor layer disposed on the n-type oxide semiconductor layer; and a second transparent electrode layer disposed on the upper surface of the p-type oxide semiconductor layer, wherein the second transparent electrode layer includes: a second metal nanostructure laminated on the upper surface of the p-type oxide semiconductor layer; and a second metal oxide covering the second metal nanostructure, wherein the transparent heater unit and the transparent solar cell unit are electrically connected to each other.

In the present invention, the first metal nanostructure includes one of AgNW and CuNW, and the first metal oxide includes one of ZnO, TiO ₂ , NiO, Al ₂ O ₃ , AZO, and ITO, The first metal oxide may cover the first metal nanostructure and the lower surface of the substrate.

In the present invention, the first metal nanostructure may have a diameter of 80 nm or less, and the first metal oxide may have a thickness of 20 nm or less.

In the present invention, the second metal nanostructure includes one of AgNW and CuNW, and the second metal oxide includes one of ZnO, TiO ₂ , NiO, Al ₂ O ₃ , AZO, and ITO, The second metal oxide may cover the upper surface of the second metal nanostructure and the p-type oxide semiconductor layer.

In the present invention, the second metal nanostructure may have a diameter of 40 nm or less, and the second metal oxide may have a thickness of 20 nm or less.

In the present invention, the n-type oxide semiconductor layer includes one of ZnO, TiO ₂ , WO ₃ , BiVO ₄ , and Fe ₂ O ₃ , and the p-type oxide semiconductor layer includes one of NiO, Co ₃ O ₄ , and SnS. 1, wherein the n-type oxide semiconductor layer and the p-type oxide semiconductor layer may form a p/n heterojunction structure.

In the present invention, the transparent heater may have a transmittance of 55 to 65% in the wavelength range of 550 nm.

In the present invention, the first transparent electrode layer and the transparent heater unit may be electrically connected to each other, and the transparent heater unit and the second transparent electrode layer may be electrically connected to each other.

In the present invention, the second metal nanostructure is masked by attaching Kapton tape to the upper surface of the p-type oxide semiconductor layer, and then the second metal nanostructure film is formed at a temperature range of 80 to 120 ° C. using a hot plate. It can be formed by drying.

In the present invention, the second metal oxide is applied to one surface of the second metal nanostructure with a radio frequency power of 20 to 40 W, an operating pressure of 4 to 6 mT, an Ar gas flow rate of 45 to 55 sccm, and 4 to 6 mT. It may be deposited for 5 to 15 minutes under process conditions of a rotation speed of rpm to cover the second metal nanostructure.

In order to solve the above problems, the present invention provides a method for manufacturing a transparent heater that can be applied to windows, comprising the steps of preparing a substrate; A transparent heater portion forming step of forming a transparent heater portion on the lower surface of the substrate; A transparent solar cell unit forming step of forming a transparent solar cell unit on an upper surface of the substrate, wherein the transparent heater unit forming step includes: laminating a first metal nanostructure on a lower surface of the substrate; and laminating a first metal oxide covering the first metal nanostructure, wherein the transparent solar cell unit forming step includes disposing a first transparent electrode layer on the upper surface of the substrate; disposing an n-type oxide semiconductor layer on the upper surface of the first transparent electrode layer; Disposing a p-type oxide semiconductor layer on the top surface of the n-type oxide semiconductor layer; and disposing a second transparent electrode layer on the upper surface of the p-type oxide semiconductor layer, wherein the second transparent electrode layer includes: a second metal nanostructure laminated on the upper surface of the p-type oxide semiconductor layer; and a second metal oxide covering the second metal nanostructure, wherein the transparent heater unit and the transparent solar cell unit are electrically connected to each other.

In the present invention, the first transparent electrode layer and the transparent heater unit may be electrically connected to each other, and the transparent heater unit and the second transparent electrode layer may be electrically connected to each other.

According to one embodiment of the present invention, as the ZnO/AgNW hybrid structure formed in a form where the metal oxide surrounds the metal nanostructure improves the thermal performance of the metal nanostructure, the transparent heater part can implement active heating performance and is transparent. This can have the effect of improving the PV performance of the solar cell unit.

According to one embodiment of the present invention, the performance of the transparent heater unit and the transparent solar cell unit can be improved as the ZnO/AgNW hybrid structure is applied, and as the transparent heater unit and the transparent solar cell unit are combined into one, the temperature of up to 300 ° C. It can be effective in providing a transparent heater with excellent stability and excellent durability even in a thermal environment.

According to one embodiment of the present invention, due to a special structure in which the transparent heater unit and the transparent solar cell unit are combined into one, the transparent heater generates heat up to a temperature range of 27 to 29 ° C within 10 minutes under an AM 1.5G light source corresponding to sunlight. It can be effective.

According to one embodiment of the present invention, the n-type oxide semiconductor layer and the p-type oxide semiconductor layer form an n-ZnO/p-NiO heterojunction structure to improve the transmittance, power conversion efficiency, and thermal stability of the transparent solar cell part. It can be effective.

According to one embodiment of the present invention, by applying a transparent heater to a window to implement an active energy control window, it is possible to achieve the effect of allowing the building to utilize solar energy more effectively.

According to one embodiment of the present invention, as a transparent heater is applied to a window, the energy consumption required for lighting and heating control within the building is reduced due to the transparent heater's excellent transmission characteristics for visible and near-infrared rays and excellent absorption characteristics for ultraviolet rays. It can have the effect of reducing .

Figure 1 schematically shows the layered structure of a transparent heater according to an embodiment of the present invention.
Figure 2 schematically shows an embodiment of a transparent heater according to an embodiment of the present invention.
Figure 3 shows details on the thermal properties of the first metal nanostructure and the second metal nanostructure according to an embodiment of the present invention.
Figure 4 schematically shows a transparent heater unit according to an embodiment of the present invention.
Figure 5 shows details on the thermal characteristics of the transparent heater unit according to an embodiment of the present invention.
Figure 6 schematically shows a transparent solar cell unit according to an embodiment of the present invention.
Figure 7 shows details on the optical characteristics of a transparent solar cell unit according to an embodiment of the present invention.
Figure 8 shows details on the optical and electrical characteristics of a transparent heater according to an embodiment of the present invention.
Figure 9 illustrates electrical characteristics of a transparent heater in a thermal environment according to an embodiment of the present invention.
Figure 10 shows details on an active energy control window to which a transparent heater is applied according to an embodiment of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS Various embodiments and/or aspects are now disclosed with reference to the drawings. In the following description, for purposes of explanation, numerous specific details are set forth to facilitate a general understanding of one or more aspects. However, it will also be appreciated by those skilled in the art that this aspect(s) may be practiced without these specific details. The following description and accompanying drawings set forth in detail certain example aspects of one or more aspects. However, these aspects are illustrative and some of the various methods in the principles of the various aspects may be utilized, and the written description is intended to encompass all such aspects and their equivalents.

Additionally, various aspects and features may be presented by a system that may include multiple devices, components and/or modules, etc. It is also understood that various systems may include additional devices, components and/or modules, etc. and/or may not include all of the devices, components, modules, etc. discussed in connection with the drawings. It must be understood and recognized.

As used herein, “embodiments,” “examples,” “aspects,” “examples,” etc. may not be construed to mean that any aspect or design described is better or advantageous over other aspects or designs. .

Additionally, the terms "comprise" and/or "comprising" mean that the feature and/or element is present, but exclude the presence or addition of one or more other features, elements and/or groups thereof. It should be understood as not doing so.

Additionally, terms including ordinal numbers, such as first, second, etc., may be used to describe various components, but the components are not limited by the terms. The above terms are used only for the purpose of distinguishing one component from another. For example, a first component may be named a second component, and similarly, the second component may also be named a first component without departing from the scope of the present invention. The term and/or includes any of a plurality of related stated items or a combination of a plurality of related stated items.

In addition, in the embodiments of the present invention, unless otherwise defined, all terms used herein, including technical or scientific terms, are generally understood by those skilled in the art to which the present invention pertains. It has the same meaning as becoming. Terms defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related technology, and unless clearly defined in the embodiments of the present invention, have an ideal or excessively formal meaning. It is not interpreted as

Figure 1 schematically shows the layered structure of a transparent heater 1 according to an embodiment of the present invention.

A transparent heater (1) that can be applied to a window according to an embodiment of the present invention, comprising: a substrate (200); A transparent heater unit 300 disposed on the lower surface of the substrate 200; and a transparent solar cell unit 100 disposed on the upper surface of the substrate 200, wherein the transparent heater unit 300 includes a first metal nanostructure 310 laminated on the lower surface of the substrate 200. ; and a first metal oxide 320 covering the first metal nanostructure 310, wherein the transparent solar cell unit 100 includes a first transparent electrode layer 110 disposed on the upper surface of the substrate 200. ); an n-type oxide semiconductor layer 120 disposed on the upper surface of the first transparent electrode layer 110; a p-type oxide semiconductor layer 130 disposed on the n-type oxide semiconductor layer 120; and a second transparent electrode layer 140 disposed on the upper surface of the p-type oxide semiconductor layer 130, wherein the second transparent electrode layer 140 is laminated on the upper surface of the p-type oxide semiconductor layer 130. a second metal nanostructure (141); and a second metal oxide 142 covering the second metal nanostructure 141.

As shown in FIG. 1, the transparent heater 1 may include a structure in which the transparent heater unit 300 and the transparent solar cell unit 100 are each disposed on both sides of the substrate 200. there is.

More specifically, the transparent heater 1 has the transparent heater unit 300 disposed on the lower surface of the substrate 200 to form the first metal nanostructure 310 and the first metal oxide 320. They are stacked sequentially, and the transparent solar cell unit 100 is disposed on the upper surface of the substrate 200, including the first transparent electrode layer 110, the n-type oxide semiconductor layer 120, and the p-type oxide semiconductor layer 130. ), and the second transparent electrode layer 140 including the second metal nanostructure 141 and the second metal oxide 142 may be sequentially stacked.

The substrate 200 may be made of a transparent material, and a portion of sunlight passing through the solar cell unit disposed on the upper surface may be incident on the substrate 200.

In one embodiment of the present invention, the substrate 200 may include a glass substrate. However, the substrate 200 is not limited to this and may include any material that can transmit light.

As described above, the transparent heater unit 300 may include the first metal nanostructure 310 and the first metal oxide 320.

The first metal nanostructure 310 according to an embodiment of the present invention includes metal nanowires or metal nanopatterning, and the first metal oxide 320 includes ZnO, TiO ₂ , NiO, Al ₂ O ₃ , It includes one of AZO and ITO, and the first metal oxide may cover the first metal nanostructure and the lower surface of the substrate. Preferably, the first metal nanostructure 310 may include metal nanowires.

In one embodiment of the present invention, the first metal nanostructure 310 may include one of AgNW and CuNW. Preferably, the first metal nanostructure 310 may include AgNW, and the first metal oxide 320 may include ZnO. AgNW is a transparent electrode material that has excellent transmittance, thermal conductivity, electrical conductivity, and plasmonic effect. The plasmonic effect of AgNW can control photothermal heat through resonance of surface plasmon particles. In addition, ZnO is easy to handle at room temperature, is an eco-friendly material, has relatively high transmittance in the visible and infrared wavelength regions, and has the characteristics of being easily connected to photoelectric devices.

In addition, while metal nanostructures generally have advantageous properties for optoelectronic applications, they are vulnerable to thermal stress. For this reason, metal nanostructures are not used alone, but are used in the form of hybrid structures containing oxides, conductive oxides, conductive polymers, and two-dimensional materials.

In the present invention, the first metal oxide 320 is formed to entirely cover the first metal nanostructure 310. Alternatively, the first metal oxide 320 according to an embodiment of the present invention may cover the lower surface of the first metal nanostructure 310 and the substrate 200.

In one embodiment of the present invention, the first metal nanostructure 310 is formed by applying the first metal nanostructure ink to the lower surface of the substrate 200 using a spin coater under process conditions of a rotation speed of 1500 to 2500 rpm. It can be formed by spin coating.

In addition, in one embodiment of the present invention, the first metal oxide 320 is applied to one surface of the first metal nanostructure 310 using magnetron sputtering, with a radio frequency power of 50 to 150 W and 4 to 6 mT. It may be deposited under process conditions of an operating pressure and an Ar gas flow rate of 45 to 55 sccm to cover the first metal nanostructure 310.

At this time, the first metal nanostructure 310 according to an embodiment of the present invention may have a diameter of 80 nm or less, and the first metal oxide 320 may have a thickness of 20 nm or less. Preferably, the first metal nanostructure 310 may have a diameter of 60 nm or less, and the first metal oxide 320 may have a thickness of 15 nm or less. More preferably, the first metal nanostructure 310 may have a diameter of 40 nm or less, and the first metal oxide 320 may have a thickness of 12.5 nm or less.

That is, the transparent heater unit 300 may include a hybrid structure in which the first metal oxide 320 surrounds the first metal nanostructure 310. Accordingly, the thermal performance of the first metal nanostructure 310 is improved, and the transparent heater unit 300 can implement active heating performance.

Preferably, in one embodiment of the present invention, as the ZnO/AgNW hybrid structure in which the metal oxide surrounds the metal nanostructure improves the thermal performance of the metal nanostructure, the transparent heater unit 300 provides active heating. It can be effective in realizing performance.

Meanwhile, as described above, the transparent solar cell unit 100 includes the first transparent electrode layer 110, the n-type oxide semiconductor layer 120, the p-type oxide semiconductor layer 130, and the second transparent electrode layer 110. It may include the second transparent electrode layer 140 including the metal nanostructure 141 and the second metal oxide 142.

The first transparent electrode layer 110 is a transparent conductive oxide (TCO) film and can be conductive while transmitting a portion of sunlight.

In one embodiment of the present invention, the first transparent electrode layer 110 may include FTO. However, the first transparent electrode layer 110 is not limited to this and may include any material that transmits light and has conductivity.

In addition, the n-type oxide semiconductor layer 120 according to an embodiment of the present invention includes one of ZnO, TiO ₂ , WO ₃ , BiVO ₄ , and Fe ₂ O ₃ , and the p-type oxide semiconductor layer 130 ) may include one of NiO, Co ₃ O ₄ , and SnS.

Preferably, the n-type oxide semiconductor may include ZnO, and the p-type oxide semiconductor may include NiO.

At this time, the n-type oxide semiconductor layer 120 and the p-type oxide semiconductor layer 130 according to an embodiment of the present invention may form a p/n heterojunction structure. Preferably, the n-type oxide semiconductor layer 120 and the p-type oxide semiconductor layer 130 may form an n-ZnO/p-NiO heterojunction structure. The p/n heterojunction structure of the n-type oxide semiconductor and the p-type oxide semiconductor can improve transmittance, power conversion efficiency, and thermal stability.

Preferably, the n-type oxide semiconductor layer 120 and the p-type oxide semiconductor layer 130 form an n-ZnO/p-NiO heterojunction structure to increase the transmittance and power conversion of the transparent solar cell unit 100. It can have the effect of improving efficiency and thermal stability.

Additionally, the second transparent electrode layer 140 may include the second metal nanostructure 141 and the second metal oxide 142, as described above.

The second metal nanostructure 141 according to an embodiment of the present invention includes metal nanowires or metal nanopatterning, and the second metal oxide 142 includes ZnO, TiO ₂ , NiO, Al ₂ O ₃ , It includes one of AZO and ITO, and the second metal oxide 142 may cover the upper surface of the second metal nanostructure 141 and the p-type oxide semiconductor layer 130. Preferably, the second metal nanostructure 141 may include metal nanowires.

In one embodiment of the present invention, the second metal nanostructure 141 may include one of AgNW and CuNW. Preferably, the first metal nanostructure 310 may include AgNW, and the first metal oxide 320 may include ZnO.

In one embodiment of the present invention, the second metal nanostructure 141 is masked by attaching Kapton tape to the upper surface of the p-type oxide semiconductor layer 130, and then heated at 80 to 120 ° C. using a hot plate. It can be formed by drying the second metal nanostructure within a temperature range.

In addition, in one embodiment of the present invention, the second metal oxide 142 is applied to one surface of the second metal nanostructure 141 with a radio frequency power of 20 to 40 W, an operating pressure of 4 to 6 mT, and 45 mT. It may be deposited for 5 to 15 minutes under process conditions of an Ar gas flow rate of 55 sccm and a rotation speed of 4 to 6 rpm to cover the second metal nanostructure 141.

At this time, the second metal nanostructure 141 may have a diameter of 40 nm or less, and the second metal oxide 142 may have a thickness of 20 nm or less. Preferably, the second metal nanostructure 141 may have a diameter of 30 nm or less, and the second metal oxide 142 may have a thickness of 15 nm or less. More preferably, the second metal nanostructure 141 may have a diameter of 20 nm or less, and the second metal oxide 142 may have a thickness of 10 nm or less.

That is, the second transparent electrode layer 140 may be formed in a structure corresponding to the transparent heater unit 300, but the diameter of the nanowire and the thickness of the oxide are preferably different from each other.

In this way, the transparent solar cell unit 100 includes the second transparent electrode layer 140 including a hybrid structure in which the second metal oxide 142 is formed to surround the second metal nanostructure 141. can do. By the hybrid structure, the thermal performance of the second metal nanostructure 141 is improved, thereby improving the performance of the transparent solar cell unit 100.

Preferably, the ZnO/AgNW hybrid structure in which the metal oxide surrounds the metal nanostructure improves the thermal performance of the metal nanostructure, thereby improving the PV performance of the transparent solar cell unit 100. It can be performed.

Meanwhile, the transparent heater unit 300 and the transparent solar cell unit 100 according to an embodiment of the present invention are electrically connected to each other. More specifically, the first transparent electrode layer 110 and the transparent heater unit 300 are electrically connected to each other, and the transparent heater unit 300 and the second transparent electrode layer 140 are electrically connected to each other. It is done.

In this case, a portion of the sunlight transmitted through the second transparent electrode layer 140 and the p-type oxide semiconductor layer 130 into the interior of the transparent heater 1 is excited in the n-type oxide semiconductor layer 120. After the photoelectrons move to the first transparent electrode layer 110, they can move to the transparent heater unit 300, which is electrically connected to the first transparent electrode layer 110, and is electrically connected to the transparent heater unit 300. By moving to the second transparent electrode layer 140, electricity can flow throughout the transparent heater 1.

By the above-described electrical connection structure, the transparent solar cell unit 100 can supply the produced electrical energy and power to the transparent heater unit 300, and the transparent heater unit 300 can supply the electrical energy and power. The transparent heater 1 can be operated by controlling the temperature by the photothermal effect.

In one embodiment of the present invention, the transparent heater 1 can generate heat up to a temperature range of 20 to 30° C. within 10 minutes under an AM 1.5G light source. Preferably, the transparent heater 1 can generate heat up to a temperature range of 27 to 29° C. within 10 minutes under an AM 1.5G light source. More preferably, the transparent heater 1 can generate heat up to a temperature of 28.5° C. within 10 minutes under an AM 1.5G light source.

Preferably, due to a special structure in which the transparent heater unit 300 and the transparent solar cell unit 100 are combined into one, the transparent heater 1 operates within 10 minutes under an AM 1.5G light source corresponding to sunlight. It can exert the effect of generating heat up to a temperature range of 29°C.

In addition, preferably, as the ZnO/AgNW hybrid structure is applied, the performance of the transparent heater unit 300 and the transparent solar cell unit 100 can be improved, and the transparent heater unit 300 and the transparent solar cell unit 100 can be improved. As the battery unit 100 is combined into one, it is possible to provide the transparent heater 1 with excellent stability and excellent durability even in a thermal environment of up to 300 ° C.

Figure 2 schematically shows an embodiment of the transparent heater 1 according to an embodiment of the present invention.

Figure 2(a) shows the AM 1.5G light source (the spectral AM1.5 solar spectral irradiance), which accounts for a spectral power density of 1000 W/m ² . The AM 1.5G light source has a power density of 93.9 W/m ² in the ultraviolet wavelength range (280 to 400 nm) and a power density of 496 W/m ² in the visible wavelength range (400 to 800 nm), It can have a power density of 353 W/m ² in the near-infrared wavelength range (800 to 1400 nm).

In general, in the case of buildings, it is desirable to block the ultraviolet wavelength range as it can cause a wide range of harmful effects such as skin cancer, photosensitivity disorders, eye-related diseases, viral infections due to immunosuppression, biomaterial degradation, and mutated plant physiological functions. On the other hand, it is preferable that the visible light wavelength region is transmitted for the sunlight of people inside the building and the photosynthesis of plants inside the building, and the near-infrared wavelength region is also preferably transmitted for the heating inside the building.

In one embodiment of the present invention, the transparent heater 1 is applied to a window to implement an active energy control window, thereby blocking ultraviolet rays and transmitting visible and near-infrared rays into the building interior. In this case, heating inside the building by solar radiation can also be implemented.

Figure 2(b) schematically shows the transparent heater 1. As shown in FIG. 2(b), the transparent heater 1 can maintain daylight by blocking the ultraviolet wavelength range and transmitting the visible ray wavelength range to the inside, ensure thermal safety, and have a Power can be directly produced in the field by the transparent solar cell unit 100 disposed.

Preferably, the transparent heater can be applied to a window to implement an active energy control window, thereby enabling the building to utilize solar energy more effectively.

Figure 3 shows details on the thermal characteristics of the first metal nanostructure 310 and the second metal nanostructure 141 according to an embodiment of the present invention.

As mentioned above, metal nanostructures have characteristics that make them vulnerable to thermal stress. In contrast, in the present invention, an AgNW network sample is used as shown in FIG. 3 to confirm the heat absorption characteristics of AgNW included in the first metal nanostructure 310 and the second metal nanostructure 141. An experiment was performed. The AgNW network sample corresponds to a sample in which a plurality of AgNWs are stacked together to form one network.

Figure 3(a) shows the AgNW network sample while maintaining a steady state (250°C) after applying heat using a lamp from room temperature to 250°C with an intermediate bias of 0.5V applied to the AgNW network sample. The behavior is schematically shown.

As shown in FIG. 3(a), the current flow through the AgNW network sample is 66.3 mA at room temperature, while the network welding and Joule heating phenomenon of the AgNW network sample occur during the temperature increase process. Due to heating, the current flow decreased to 59 mA. In addition, while maintaining the steady state, the current flow continued to drop to 50 mA due to the Rayleigh instability phenomenon, which is activated at a temperature that changes the composition of the AgNW network sample. If this steady state continues, the AgNW network sample may decompose into nanospheres at a temperature much lower than the bulk melting temperature due to capillary action.

However, in terms of current flow, the current flow within the AgNW network sample can rapidly decrease within a few seconds, and when the AgNW network sample is decomposed into nanosphere-shaped aggregates, it can be electrically insulated.

Figure 3(b) schematically shows the shape of the AgNW network sample. As shown in Figure 3(b), as the AgNW network sample absorbs heat, network welding phenomenon, Joule heating phenomenon (D1), Rayleigh instability phenomenon (D2), network loss phenomenon (D3), and aggregation phenomenon ( It may change compositionally due to D4).

As mentioned above, AgNW shows characteristics of being vulnerable to thermal stress. For this reason, when the metal nanostructure containing AgNW is applied alone to the transparent heater unit 300 and the second transparent electrode layer 140 provided in the transparent solar cell unit 100, the transparent The characteristics of the heater unit 300 and the transparent solar cell unit 100 may become unstable, and as a result, the electrical conductivity of the transparent heater 1 may become unstable.

Figure 4 schematically shows the transparent heater unit 300 according to an embodiment of the present invention.

As shown in FIG. 4(a), the transparent heater unit 300 according to an embodiment of the present invention includes AgNW as the first metal nanostructure 310, and the first metal nanostructure 310 ) may include ZnO as the first metal oxide 320 covering the .

Figure 4(b) schematically shows a cross section of the transparent heater unit 300. As shown in FIG. 4(b), the first metal oxide 320 containing ZnO has a thickness of 20 nm or less, preferably 15 nm or less, and more preferably 12.5 nm or less. You can.

FIG. 4(c) schematically shows the results of HAADF imaging (high-angle annular dark-field imaging) and elemental mapping of a portion of the transparent heater unit 300. As shown in FIG. 4(c), the transparent heater unit 300 according to an embodiment of the present invention includes AgNW having a diameter of 35 to 45 nm and a nanocrystalline ZnO shell having a thickness with excellent uniformity. It may include a ZnO/AgNW hybrid structure. Preferably, the transparent heater unit 300 may include AgNW with a diameter of 40 nm.

FIG. 4(d) schematically shows an energy-dispersive X-ray spectrum of a portion of the transparent heater unit 300. As shown in FIG. 4(d), the Ag element, Zn element, and O element constituting the transparent heater unit 300 may contain atomic percentages of 36.97%, 29.4%, and 33.62%, respectively.

Due to this hybrid structure of the first metal nanostructure 310 and the first metal oxide 320, the transparent heater unit 300 can have excellent active heating performance.

Figure 5 shows details about the thermal characteristics of the transparent heater unit 300 according to an embodiment of the present invention.

As shown in FIG. 5(a), the transparent heater unit 300 generated a temperature difference of 100°C or less (△T = T _final -T _initial ) under an operating voltage of 3 V, and the increased temperature was 4. It can be stabilized within minutes. Meanwhile, the transparent heater unit 300 may generate ΔT exceeding 300° C. under an operating voltage of 7 V, and the time for the elevated temperature to stabilize may be relatively fast compared to an operating voltage of 3 V.

Figure 5(b) schematically shows the performance of the transparent heater 1 in terms of power and ΔT. As shown in Figure 5(b), the performance of the transparent heater 1 in terms of power and △T can realize △T of 100 ℃ under 4.5 W power, and △ of 310 ℃ under 21.7 W power. T can be implemented.

Figure 5(c) schematically shows the results of an ice-making experiment after placing ice on the upper surface of the transparent heater unit 300. It can be confirmed that the ice placed on the upper surface of the transparent heater unit 300 was de-icing after applying voltage to the transparent heater unit 300.

That is, the transparent heater unit 300 according to an embodiment of the present invention can implement excellent thermal performance while having a high transmittance.

Figure 6 schematically shows the transparent solar cell unit 100 according to an embodiment of the present invention.

Figure 6(a) schematically shows the transparent solar cell unit 100. As shown in FIG. 6(a), in one embodiment of the present invention, the substrate 200 includes a glass substrate, the first transparent electrode layer 110 includes FTO, and the n-type oxide semiconductor. The layer 120 includes ZnO, the p-type oxide semiconductor layer 130 includes NiO, and the second transparent electrode layer 140 includes AgNW as the second metal nanostructure 141, and the second metal nanostructure 141. The second metal oxide 142 covering the metal nanostructure 141 may include ZnO.

At this time, as described above, the n-type oxide semiconductor layer 120 and the p-type oxide semiconductor layer 130 may form a p/n heterojunction structure, and the n-type oxide semiconductor layer 120 and the p-type oxide semiconductor layer 130 may form a p/n heterojunction structure. The p-type oxide semiconductor layer 130 may be formed by large-area sputtering at room temperature.

Figure 6(b) schematically shows a cross-sectional TEM image of the transparent solar cell unit 100. As shown in FIG. 6(b), the p/n heterojunction structure of the n-type oxide semiconductor layer 120 and the p-type oxide semiconductor layer 130 is conformal and may be intact. At this time, ZnO serves to absorb light, and NiO can serve as a heterojunction partner.

Additionally, as shown in FIG. 6(b), it can be seen that the two second metal nanostructures 141 are stacked on the upper surface of the p-type oxide semiconductor layer 130. This can be seen more clearly in Figure 6(c), which enlarges the upper area of the transparent solar cell unit 100.

As shown in FIG. 6(c), the second metal nanostructure 141 is piled on the upper surface of the p-type oxide semiconductor layer 130, and the second metal oxide 142 is the second metal nanostructure. It may be formed to cover the structure 141. At this time, the second metal nanostructure 141 may have a diameter of 40 nm or less, and the second metal oxide 142 may have a thickness of 20 nm or less. Preferably, the second metal nanostructure 141 may have a diameter of 30 nm or less, and the second metal oxide 142 may have a thickness of 15 nm or less. More preferably, the second metal nanostructure 141 may have a diameter of 20 nm or less, and the second metal oxide 142 may have a thickness of 10 nm or less.

Figure 7 shows details about the optical characteristics of the transparent solar cell unit 100 according to an embodiment of the present invention.

Figure 7(a) schematically shows the optical spectrum of the transparent solar cell unit 100 according to an embodiment of the present invention and comparative examples.

In Figure 7(a), the green line represents the optical spectrum of the transparent solar cell unit 100 according to an embodiment of the present invention, and the red line represents the transparent solar cell unit (second transparent electrode layer (second transparent electrode layer)), which is one of the comparative examples. 140) represents the optical spectrum of the second metal nanostructure 141 containing AgNW only), and the black line represents the photopic response of the human eye, which is the remaining one of the above comparative examples. At this time, the transparent solar cell unit 100 may include a second metal nanostructure 141 containing AgNW and a second metal oxide 142 containing ZnO as the second transparent electrode layer 140.

As shown in FIG. 7(a), in the visible light wavelength range (400 to 800 nm) and the near-infrared wavelength range (800 to 1400 nm), the transparent solar cell unit 100 (green) of the present invention has 62.2% It shows a transmittance of , and the transparent solar cell unit 100 (red) of the comparative example can show a transmittance of 51.1%.

Additionally, the photopic response (black) of the human eye may have a peak value at a wavelength of 550 nm, which is the wavelength for color-neutral perception, building integration, and daylight ( corresponds to a wavelength suitable for daylighting. At this time, the transparent solar cell unit 100 (green) of the present invention exhibits a transmittance of 65.5% at the wavelength of 550 nm, while the transparent solar cell unit (red) of the comparative example exhibits a transmittance of 59% at the wavelength of 550 nm. It can represent the transmittance of .

Figure 7(b) schematically shows the absorption spectrum of the transparent solar cell unit 100 according to an embodiment of the present invention and the transparent solar cell unit of the comparative example. As shown in FIG. 7(b), both transparent solar cell units 100 can exhibit excellent absorption characteristics in the ultraviolet wavelength range.

Figure 7(c) shows a photograph of the transparent solar cell unit 100 according to an embodiment of the present invention and the transparent solar cell unit of a comparative example. As shown in FIG. 7(c), both of the two transparent solar cell units 100 can be confirmed to function as transparent windows suitable for application as window devices for building integration.

That is, as shown in FIGS. 7(a) to 7(c), the transparent solar cell unit 100 according to an embodiment of the present invention is the comparative example in which only the second metal nanostructure 141 is applied. Compared to the transparent solar cell part, it exhibits relatively excellent transmittance in the visible and near-infrared wavelength regions, while in the ultraviolet wavelength region, it can effectively absorb ultraviolet rays and exhibit excellent ultraviolet ray blocking function. This corresponds to the result of optical matching to reduce the reflectance of the second transparent electrode layer 140 and the reduction of scattering in the cross section.

Preferably, the transparent solar cell unit 100 according to an embodiment of the present invention may have excellent transmission characteristics for visible rays and near-infrared rays and excellent absorption characteristics for ultraviolet rays.

Figure 8 shows the optical and electrical characteristics of the transparent heater 1 according to an embodiment of the present invention.

As shown in FIG. 8(a), the transparent heater 1 according to an embodiment of the present invention has a first metal nanostructure 310 including AgNW and ZnO on the lower side centered on the substrate 200. A transparent heater unit 300 containing a first metal oxide 320 is disposed, and on the upper side, a first transparent electrode layer 110 containing FTO, an n-type oxide semiconductor layer 120 containing ZnO, and NiO A p-type oxide semiconductor layer 130 containing a second metal nanostructure 141 containing AgNW and a second transparent electrode layer 140 containing a second metal oxide 142 containing ZnO. A transparent solar cell unit 100 may be disposed.

Figure 8(b) schematically shows the transmittance spectrum of the transparent heater 1. In Figure 8(b), the red line represents the transmittance spectrum of the transparent heater 1 according to an embodiment of the present invention, and the black line represents only the transparent solar cell unit 100 according to an embodiment of the present invention. Shows the transmittance spectrum.

As shown in FIG. 8(b), the transparent heater 1 (red) can have a transmittance of 55 to 65% in the wavelength range of 550 nm with a neutral color viewpoint. Preferably, the transparent heater 1 may have a transmittance of 58 to 60% in a wavelength range of 550 nm with a neutral color viewpoint. More preferably, the transparent heater 1 may have a transmittance of 59.1% in a wavelength range of 550 nm with a neutral color viewpoint.

That is, the transparent heater 1 according to an embodiment of the present invention can exhibit a relatively broadband transmittance in the visible light region.

Figure 8(c) schematically shows the current-voltage (I-V) characteristics showing the PV (photovoltaic) performance of the transparent heater 1 under an AM 1.5G light source. In Figure 8(c), the blue line represents the characteristics of the transparent heater 1 according to an embodiment of the present invention, and the red line represents the second transparent heater including only the second metal nanostructure 141 including AgNW. The characteristics of the transparent heater 1, which is a comparative example to which the electrode layer 140 is applied, are shown.

As shown in FIG. 8(c), the transparent solar cell part (red) of the comparative example transparent heater has an open-circuit voltage (V _OC ) of 0.485 V and a short-circuit current density of 0.422 mA/cm ² (short-circuit current density; J _SC ), a fill factor (FF) of 32.2%, and a power conversion efficiency (PCE) of 0.065%.

On the other hand, the transparent solar cell unit 100 (blue) of the transparent heater 1 according to an embodiment of the present invention has an open-circuit voltage (V _OC ) of 0.573 V, 0.445 mA/cm. It can exhibit a short-circuit current density (J _SC ) of ² , a fill factor (FF) of 45.4%, and a power conversion efficiency (PCE) of 0.115%. This corresponds to the results of the effects of improving the conductive properties of the metal nanostructure, reducing carrier scattering, reducing hole recombination on the upper surface by passivation, and reducing trapping of gas molecules.

In other words, the PV performance of the transparent solar cell unit 100 is improved by the second transparent electrode layer 140 formed as the metal oxide surrounds the metal nanostructure, thereby ensuring the operational stability of the transparent heater 1. can be demonstrated.

Figure 9 shows electrical characteristics of the transparent heater 1 in a thermal environment according to an embodiment of the present invention.

Figures 9(a) to 9(c) schematically show the I-V characteristics and shape of a transparent heater, which is a comparative example, to which a second transparent electrode layer containing only a second metal nanostructure containing AgNW was applied.

At this time, after attaching a thermocouple to the transparent heater of the comparative example, without heating (before heating) and applying a preset bias, the steady-state temperature is controlled to a temperature range of 50 to 300 ℃ and maintained for 5 minutes. The characteristics and shape were confirmed after being air-cooled at room temperature (after heating).

As shown in Figure 9(a), it can be seen that the performance of the transparent heater, which is the comparative example, deteriorates due to the heat-absorbing effect. More specifically, J _SC increased from 0.42 to 0.473 mA/cm ² in the temperature range of 50 to 250 ℃, while V _OC slightly improved and then gradually decreased from 0.485 V to 0.38 V.

This may correspond to a result generated as the second metal nanostructure absorbs heat, and depending on the heating temperature range, network formation (50 to 150 ℃), Rayleigh instability (200 to 250 ℃), and filter network loss (loss of percolating network (250 to 300 °C), and agglomeration of the upper electrode (300 °C) may occur sequentially. This can also be confirmed in Figures 9(b) and 9(c). As shown in FIGS. 9(b) and 9(c), the network of the second metal nanostructure may be damaged as it absorbs heat.

Meanwhile, Figures 9(d) to 9(f) show a second transparent electrode layer 140 containing a second metal nanostructure 141 containing AgNW and a second metal oxide 142 containing ZnO. The I-V characteristics and shape of the transparent heater 1 according to an embodiment of the present invention are schematically shown.

At this time, the transparent heater 1 is, after attaching a thermocouple, to correspond to the transparent heater of the comparative example, without heating (before heating) and applying a preset bias to maintain a steady-state temperature of 50 to 300 ° C. It was maintained for 5 minutes while controlling the temperature range, and then air-cooled at room temperature (after heating) to check the characteristics and shape.

As shown in Figure 9(d), it can be seen that the performance of the transparent heater 1 according to an embodiment of the present invention is improved due to the heat-absorbing effect. More specifically, J _SC and FF show values of 0.454 mA/cm ² and 45.2%, respectively, and V _OC can be confirmed to have decreased from 570 V to 0.512 V in the temperature range of 50 to 250°C.

This can also be confirmed in Figures 9(e) and 9(f). As shown in FIGS. 9(e) and 9(f), the second transparent electrode layer 140 including the second metal nanostructure 141 and the second metal oxide 142 absorbs heat. It can be integrated by doing this.

Figure 9(g) shows a graph of PCE and V _OC versus temperature of the transparent heater of the comparative example and the transparent heater (1) of the present invention under thermal stress.

As shown in FIG. 9(g), in one embodiment of the present invention, the performance of the transparent heater unit 300 and the transparent solar cell unit 100 can be improved as the ZnO/AgNW hybrid structure is applied. There is an effect of providing the transparent heater 1 with excellent stability and excellent durability even in a thermal environment of up to 300 ° C by combining the transparent heater unit 300 and the transparent solar cell unit 100 into one. can be demonstrated.

Figure 10 shows details about an active energy control window to which the transparent heater 1 is applied according to an embodiment of the present invention.

As described above, the transparent heater 1 can be applied to a window. In this case, the transparent heater 1 can implement an active energy control window and provide heating, anti-fogging, and ice-making functions for the exterior surface of the building. Figure 10(a) schematically shows such an active energy control window.

Figure 10(b) schematically shows a photograph of an active energy control window to which the transparent heater 1 is applied under a light source of AM 1.5G. At this time, a thermocouple is attached to obtain temperature difference (△T) performance under the light source.

AgNW, a metal nanostructure that can be applied to the transparent heater 1, may have excellent PT (Photothermal) effect. For example, △T = 15 ℃ was obtained at a laser excitation wavelength of 532 nm, and △T = 30 ℃ could be obtained with dipole resonance. Due to the PT effect of AgNW, light and material interact with each other to create a nanoscale heater with local and remote heating functions. More specifically, the interaction between light and material can generate a surface plasmon effect in AgNWs, which can have effects such as PT conversion, local enhancement of the electric field, and generation and injection of hot carriers.

Figure 10(c) schematically shows the design of an active energy control window to which the transparent heater 1 is applied. As shown in FIG. 10(c), the active energy control window to which the transparent heater 1 is applied can generate energy by coupling the transparent solar cell unit 100, causing joule heating, deterioration, and Integrated thermal performance can be achieved through various thermal processes such as Peltier.

In order to track the ΔT value of the active energy control window to which the transparent heater 1 is applied, the transparent solar cell unit ( 100) was placed and a light source of AM 1.5G was irradiated. The lower part of Figure 10(d) schematically shows the ΔT value recorded on the thermocouple for 10 minutes, through which it can be seen that the ΔT value gradually increases to 15.8°C inside the box.

That is, the transparent heater 1 according to an embodiment of the present invention can effectively transfer energy and charge by the plasmon effect of AgNW as the ZnO/AgNW structure is applied, and can be applied to windows to implement active energy control windows. You can.

Figure 10(e) shows PT+PV performance and PT performance of the active energy control window to which the transparent heater 1 according to an embodiment of the present invention is applied, based on values measured by a thermocouple for 10 minutes. The T value is schematically shown. As shown in FIG. 10(e), the active energy control window to which the transparent heater (1) is applied has △T of 27.9°C, while the window to which the general transparent heater (1) without the ZnO/AgNW structure is applied has ΔT of 27.9°C. It can be confirmed that △T is 23.2 ℃. Figure 10(f) is shown as a bar chart to quantify this.

That is, the transparent heater 1 according to an embodiment of the present invention can improve sunlight, UV blocking, field power production, and safety when applied to a window to implement an active energy control window.

Preferably, the transparent heater 1 can be applied to a window to implement an active energy control window, thereby enabling the building to utilize solar energy more effectively. In addition, as the transparent heater (1) is applied to the window, the energy required for lighting and heating control within the building is reduced due to the excellent transmission characteristics of the transparent heater (1) for visible and near-infrared rays and the excellent absorption characteristics for ultraviolet rays. It can have the effect of reducing consumption.

Below, a method of manufacturing the transparent heater 1 according to an embodiment of the present invention will be described.

A method of manufacturing a transparent heater (1) that can be applied to a window according to an embodiment of the present invention, comprising: preparing a substrate (200); A transparent heater unit 300 forming step of forming a transparent heater unit 300 on the lower surface of the substrate 200; It may include a transparent solar cell unit 100 forming step of forming the transparent solar cell unit 100 on the upper surface of the substrate 200.

In the substrate 200 preparation step, in one embodiment of the present invention, the substrate 200 can be cleaned in an ultrasonic cleaner using acetone, methanol, and distilled water for 5 to 15 minutes, respectively, and then dried in a nitrogen atmosphere. there is. Preferably, the substrate 200 can be cleaned for 8 to 12 minutes, and more preferably, the substrate 200 can be cleaned for 10 minutes.

In one embodiment of the present invention, the substrate 200 may include a glass substrate coated with FTO on one side.

The forming step of the transparent heater unit 300 includes laminating a first metal nanostructure 310 on the lower surface of the substrate 200; and laminating a first metal oxide 320 covering the first metal nanostructure 310.

In the step of laminating the first metal nanostructure 310, in one embodiment of the present invention, the first metal is applied to the lower surface of the substrate 200 using a spin coater under process conditions of a rotation speed of 1500 to 2500 rpm. The first metal nanostructure 310 can be formed by spin coating nanostructure ink. At this time, the first metal nanostructure 310 may include metal nanowires or metal nanopatterning, and preferably, the first metal nanostructure 310 may include metal nanowires. In one embodiment of the present invention, the first metal nanostructure 310 includes one of AgNW and CuNW, and preferably, the first metal nanostructure 310 may include AgNW.

In addition, in the step of laminating the first metal oxide 320, in one embodiment of the present invention, 50 to 150 W of radio frequency power is applied to one surface of the first metal nanostructure 310 using magnetron sputtering, The first metal oxide 320 can be formed to cover the first metal nanostructure 310 by depositing under process conditions of an operating pressure of 4 to 6 mT and an Ar gas flow rate of 45 to 55 sccm. At this time, the first metal oxide 320 includes one of ZnO, TiO ₂ , NiO, Al ₂ O ₃ , AZO, and ITO, and preferably, the first metal oxide 320 includes ZnO. You can.

The forming step of the transparent solar cell unit 100 includes disposing a first transparent electrode layer 110 on the upper surface of the substrate 200; Disposing an n-type oxide semiconductor layer 120 on the upper surface of the first transparent electrode layer 110; Disposing a p-type oxide semiconductor layer 130 on the n-type oxide semiconductor layer 120; and disposing a second transparent electrode layer 140 on the upper surface of the p-type oxide semiconductor layer 130.

In the step of disposing the n-type oxide semiconductor layer 120 and the step of disposing the p-type oxide semiconductor layer 130, in one embodiment of the present invention, magnetron sputtering is used to change the sputtering power related to the thin film growth rate. Except that, each of the n-type oxide semiconductor layer 120 and the p-type oxide semiconductor layer 130 can be formed under corresponding conditions.

The n-type oxide semiconductor layer 120 can be formed with a sputtering power of 250 to 350 W, realizing a growth rate of 6 to 7 nm/min, and preferably, 300 W to realize a growth rate of 6.66 nm/min. It can be formed with a sputtering power of W. At this time, the n-type oxide semiconductor layer 120 includes one of ZnO, TiO ₂ , WO ₃ , BiVO ₄ , and Fe ₂ O ₃ , and preferably, the n-type oxide semiconductor layer 120 includes ZnO. It can be included.

In addition, the p-type oxide semiconductor layer 130 can be formed with an Ar/O ₂ gas flow rate of 15/1 to 25/10 sccm and a sputtering power of 40 to 60 W to achieve a growth rate of 2 nm/min. , Preferably, it can be formed with an Ar/O ₂ gas flow rate of 20/5 sccm and a sputtering power of 50 W to realize a growth rate of 2 nm/min. At this time, the p-type oxide semiconductor layer 130 includes one of NiO, Co ₃ O ₄ , and SnS. Preferably, the p-type oxide semiconductor layer 130 may include NiO.

It is preferable that the n-type oxide semiconductor layer 120 and the p-type oxide semiconductor layer 130 according to an embodiment of the present invention form a p/n heterojunction structure.

In the step of disposing the second transparent electrode layer 140, the second transparent electrode layer 140 includes a second metal nanostructure 141 laminated on the upper surface of the p-type oxide semiconductor layer 130; and a second metal oxide 142 covering the second metal nanostructure 141.

The second metal nanostructure 141 is masked by attaching Kapton tape to the upper surface of the p-type oxide semiconductor layer 130, and then the second metal nanostructure is formed at a temperature range of 80 to 120° C. using a hot plate. It can be formed by drying. At this time, the second metal nanostructure 141 may include metal nanowires or metal nanopatterning. Preferably, the second metal nanostructure 141 may include metal nanowires. In one embodiment of the present invention, the second metal nanostructure 141 includes one of AgNW and CuNW, and preferably, the second metal nanostructure 141 may include AgNW.

The second metal oxide 142 is applied to one surface of the second metal nanostructure 141 by applying radio frequency power of 20 to 40 W, operating pressure of 4 to 6 mT, Ar gas flow rate of 45 to 55 sccm, and 4 It may be deposited for 5 to 15 minutes under process conditions of a rotation speed of 6 rpm to cover the second metal nanostructure 141. At this time, the second metal oxide 142 includes one of ZnO, TiO ₂ , NiO, Al ₂ O ₃ , AZO, and ITO. Preferably, the second metal oxide 142 includes ZnO. You can.

Meanwhile, the transparent heater unit 300 and the transparent solar cell unit 100 according to an embodiment of the present invention are electrically connected to each other. More specifically, the first transparent electrode layer 110 and the transparent heater unit 300 are electrically connected to each other, and the transparent heater unit 300 and the second transparent electrode layer 140 are electrically connected to each other. It is done.

By the above-described electrical connection structure, the transparent solar cell unit 100 can supply the produced electrical energy and power to the transparent heater unit 300, and the transparent heater unit 300 can supply the electrical energy and power. The transparent heater 1 can be operated by controlling the temperature by the photothermal effect.

According to one embodiment of the present invention, as the ZnO/AgNW hybrid structure formed in a form where the metal oxide surrounds the metal nanostructure improves the thermal performance of the metal nanostructure, the transparent heater part can implement active heating performance and is transparent. This can have the effect of improving the PV performance of the solar cell unit.

According to one embodiment of the present invention, the performance of the transparent heater unit and the transparent solar cell unit can be improved as the ZnO/AgNW hybrid structure is applied, and as the transparent heater unit and the transparent solar cell unit are combined into one, the temperature of up to 300 ° C. It can be effective in providing a transparent heater with excellent stability and excellent durability even in a thermal environment.

According to one embodiment of the present invention, the n-type oxide semiconductor layer and the p-type oxide semiconductor layer form an n-ZnO/p-NiO heterojunction structure to improve the transmittance, power conversion efficiency, and thermal stability of the transparent solar cell part. It can be effective.

According to one embodiment of the present invention, due to a special structure in which the transparent heater unit and the transparent solar cell unit are combined into one, the transparent heater generates heat up to a temperature range of 27 to 29 ° C within 10 minutes under an AM 1.5G light source corresponding to sunlight. It can be effective.

According to one embodiment of the present invention, by applying a transparent heater to a window to implement an active energy control window, it is possible to achieve the effect of allowing the building to utilize solar energy more effectively.

According to one embodiment of the present invention, as a transparent heater is applied to a window, the energy consumption required for lighting and heating control within the building is reduced due to the transparent heater's excellent transmission characteristics for visible and near-infrared rays and excellent absorption characteristics for ultraviolet rays. It can have the effect of reducing .

As described above, although the embodiments have been described with limited examples and drawings, various modifications and variations can be made by those skilled in the art from the above description. For example, the described techniques are performed in a different order than the described method, and/or components of the described system, structure, device, circuit, etc. are combined or combined in a different form than the described method, or other components are used. Alternatively, appropriate results may be achieved even if substituted or substituted by an equivalent. Therefore, other implementations, other embodiments, and equivalents of the claims also fall within the scope of the claims described below.

Claims (12)

As a transparent heater that can be applied to windows,
Board;
a transparent heater portion disposed on the lower surface of the substrate; and
It includes a transparent solar cell unit disposed on the upper surface of the substrate,
The transparent heater part,
A first metal nanostructure laminated on the lower surface of the substrate; and
It includes a first metal oxide covering the first metal nanostructure,
The transparent solar cell unit,
a first transparent electrode layer disposed on the upper surface of the substrate;
an n-type oxide semiconductor layer disposed on the first transparent electrode layer;
a p-type oxide semiconductor layer disposed on the n-type oxide semiconductor layer; and
It includes a second transparent electrode layer disposed on the upper surface of the p-type oxide semiconductor layer,
The second transparent electrode layer,
A second metal nanostructure laminated on the upper surface of the p-type oxide semiconductor layer; and
It includes a second metal oxide covering the second metal nanostructure,
A transparent heater wherein the transparent heater unit and the transparent solar cell unit are electrically connected to each other.
In claim 1,
The first metal nanostructure includes any one of AgNW and CuNW,
The first metal oxide includes any one of ZnO, TiO ₂ , NiO, Al ₂ O ₃ , AZO, and ITO,
The first metal oxide covers the first metal nanostructure and the lower surface of the substrate.
In claim 1,
The first metal nanostructure has a diameter of 80 nm or less,
A transparent heater wherein the first metal oxide has a thickness of 20 nm or less.
In claim 1,
The second metal nanostructure includes any one of AgNW and CuNW,
The second metal oxide includes any one of ZnO, TiO ₂ , NiO, Al ₂ O ₃ , AZO, and ITO,
The second metal oxide covers the upper surface of the second metal nanostructure and the p-type oxide semiconductor layer.
In claim 1,
The second metal nanostructure has a diameter of 40 nm or less,
A transparent heater wherein the second metal oxide has a thickness of 20 nm or less.
In claim 1,
The n-type oxide semiconductor layer includes any one of ZnO, TiO ₂ , WO ₃ , BiVO ₄ , and Fe ₂ O ₃ ,
The p-type oxide semiconductor layer includes any one of NiO, Co ₃ O ₄ , and SnS,
A transparent heater wherein the n-type oxide semiconductor layer and the p-type oxide semiconductor layer form a p/n heterojunction structure.
In claim 1,
The transparent heater has a transmittance of 55 to 65% in the wavelength range of 550 nm.
In claim 1,
The first transparent electrode layer and the transparent heater unit are electrically connected to each other,
The transparent heater unit and the second transparent electrode layer are electrically connected to each other.
In claim 1,
The second metal nanostructure is,
A transparent heater formed by attaching Kapton tape to the upper surface of the p-type oxide semiconductor layer to mask it, and then drying the second metal nanostructure film at a temperature range of 80 to 120 ° C. using a hot plate.
In claim 1,
The second metal oxide is,
5 to 15 times on one side of the second metal nanostructure under the process conditions of 20 to 40 W of radio frequency power, 4 to 6 mT of operating pressure, 45 to 55 sccm of Ar gas flow rate, and 4 to 6 rpm of rotation speed. A transparent heater deposited for several minutes and formed to cover the second metal nanostructure.
A method of manufacturing a transparent heater that can be applied to windows,
A substrate preparation step of preparing a substrate;
A transparent heater portion forming step of forming a transparent heater portion on the lower surface of the substrate;
It includes a transparent solar cell unit forming step of forming a transparent solar cell unit on the upper surface of the substrate,
The transparent heater portion forming step is,
Laminating a first metal nanostructure on the lower surface of the substrate; and
Comprising: laminating a first metal oxide covering the first metal nanostructure,
The transparent solar cell unit forming step is,
disposing a first transparent electrode layer on the upper surface of the substrate;
disposing an n-type oxide semiconductor layer on the upper surface of the first transparent electrode layer;
disposing a p-type oxide semiconductor layer on the n-type oxide semiconductor layer; and
Comprising: disposing a second transparent electrode layer on the upper surface of the p-type oxide semiconductor layer,
The second transparent electrode layer,
A second metal nanostructure laminated on the upper surface of the p-type oxide semiconductor layer; and
It includes a second metal oxide covering the second metal nanostructure,
A method of manufacturing a transparent heater, wherein the transparent heater unit and the transparent solar cell unit are electrically connected to each other.
In claim 11,
The first transparent electrode layer and the transparent heater unit are electrically connected to each other,
A method of manufacturing a transparent heater, wherein the transparent heater unit and the second transparent electrode layer are electrically connected to each other.