KR20210023473A - A photoelectrode having through vias and a method of manufacturing the same - Google Patents

Abstract

The technology disclosed in the present specification provides a photoelectrode having an electrically connecting via hole capable of transferring charge carriers generated in the photoelectrode to a counter electrode with a small resistance loss. According to an embodiment of the technology disclosed herein, the photoelectrode having the through-via includes: a first substrate; a transparent conductive film formed on the first substrate; a photoreactive film formed on the transparent conductive film; a through-via installed in a through-hole passing through the first substrate; and a conductive layer formed on the opposite surface of the first substrate on which the through-via is formed.

Description

A photoelectrode having through vias and a method of manufacturing the same}

The present invention relates to a photoelectrode having a through-via and a method for manufacturing the same, and more particularly, to a photoelectrode having a through-via capable of transferring a charge carrier generated from the photoelectrode to a counter electrode with minimal loss, and a method of manufacturing the same. will be.

In recent years, due to environmental problems such as global warming and fine dust, efforts to convert from fossil fuel-based energy to solar energy and wind power-based renewable energy are continuing. In order to compensate for the intermittentness, which is a shortcoming of renewable energy such as solar and wind power, a method of converting and storing electric energy generated from renewable energy into hydrogen generated by electrolysis of water has been proposed. Research on photoelectrochemical water decomposition as an efficient method of electrolysis of water is actively being conducted. In the case of photoelectrochemical water decomposition, electrons and holes are generated in the photoelectrode when light having a band gap energy or more is irradiated onto the photoelectrode to which a semiconductor material is applied. The generated electrons and holes move to the electrolyte by external electromotive force and contribute to the production of hydrogen or oxygen through water decomposition.

When the photoelectrode is used as the photoanode electrode, electrons generated from the photoanode electrode move to the conductive film in the photoanode electrode, are collected from the conductive film by external electromotive force, and transferred to the photocathode electrode, which is a counter electrode. The electrons transferred to the photocathode electrode are used for water-decomposition hydrogen production.

In this case, the efficiency of water decomposition can be improved by reducing the resistance loss that occurs in the process of transferring electrons generated from the photoanode electrode to the photocathode electrode.

In the prior art, a photoelectrode used for photoelectrochemical water decomposition is formed by depositing a transparent conductive film such as FTO or ITO on a glass substrate, and coating a light-absorbing semiconductor material thereon.

In the prior art, a conductive film such as FTO or ITO used for a photoelectrode is transparent compared to metal, so it has a good advantage to transmit light, but has a disadvantage of relatively high resistance loss due to high electrical resistivity compared to metal.

When a photoelectrode is manufactured in a large area to increase the amount of water decomposition, the path of electrons becomes longer, and resistance loss increases when current is generated due to a high electrical resistivity, so the efficiency of the photoelectrode decreases. As described above, the high electrical resistivity of the transparent conductive film is an obstacle to the large-area photoelectrode.

Therefore, in order to increase the area of the photoelectrode, it is necessary to develop a photoelectrode capable of reducing resistance loss when transferring charge carriers of electrons or holes generated by the photoelectrode to the opposite photoelectrode.

One of the objects of the present invention is to provide a photoelectrode having a through-via capable of transferring a charge carrier generated from the photoelectrode to a counter electrode with minimal loss, and having a through-via according to the technical idea of the technology disclosed in the present specification. The technical problem to be achieved by the photoelectrode and its manufacturing method is not limited to the problem for solving the above-mentioned problem, and another problem that is not mentioned will be clearly understood by those skilled in the art from the following description.

In order to achieve the above-described exemplary problem, an embodiment of the technology disclosed in the present specification provides a photoelectrode having a through via. The photoelectrode having such a through via may include a first substrate; A transparent conductive film formed on the first substrate; A photoreactive film formed on the transparent conductive film; A through via installed in a through hole passing through the first substrate; And a conductive film formed on the opposite surface of the first substrate on which the through via is formed.

In one embodiment, the photoelectrode having the through via may be for an anode.

In an embodiment, the through via may completely fill the through hole or may only partially fill the through hole.

Another embodiment of the present invention provides a method of manufacturing a photoelectrode having a through via. A method of manufacturing a photoelectrode having such a through via includes: manufacturing a through hole in a first substrate; Forming a transparent conductive film on the first substrate in which the through hole is formed; Forming a photoreactive film on the first substrate on which the transparent conductive film is formed; Filling a through hole formed in the first substrate with a low-resistance metal to form a through via; It may include forming a conductive film on the opposite surface of the first substrate on which the through via is formed.

According to an embodiment of the technology disclosed in the present specification, a photoelectrode having an electrical connection via hole capable of transferring a charge carrier generated from the photoelectrode to a counter electrode with a small resistance loss may be provided.

And, when the solar cell is connected to the photoelectrode according to the embodiment of the technology disclosed in the present specification, electrons or holes are moved to the electrolyte by the electromotive force of the solar cell even without external electromotive force, so that no external power is required, spontaneous hydrogen production. This becomes possible.

In addition, when the second electrode of the photoelectrode according to an embodiment of the present disclosure is used as an electrode of a solar cell, electrical loss can be reduced and efficiency of spontaneous hydrogen production can be increased.

On the other hand, the effects that can be achieved by the photoelectrode having a through-via according to an embodiment of the technology disclosed in the present specification are not limited to those mentioned above, and other effects not mentioned are to a person skilled in the art from the following description. It can be clearly understood.

In order to more fully understand the drawings cited in this specification, a brief description of each drawing is provided.
1 is a schematic cross-sectional view of a photoelectrode having a through-via according to an embodiment of the disclosed technology.
2 is a schematic cross-sectional view of a photoelectrode having a through via according to another embodiment of the technology disclosed in the present specification.
3 is a cross-sectional view schematically illustrating a photoelectrode having a through-via connected to a dye-sensitized solar cell (DSSC) according to another embodiment of the disclosed technology.
4 is a schematic cross-sectional view of a photoelectrode having a through-via connected to a dye-sensitized solar cell (DSSC) according to another embodiment of the disclosed technology.
5 is a schematic cross-sectional view of a photoelectrode having a through-via connected to a dye-sensitized solar cell (DSSC) according to another embodiment of the disclosed technology.
6 is a flowchart of a method of manufacturing a photoelectrode having a through via according to an embodiment of the technology disclosed in the present specification.
7 is a schematic process diagram illustrating a method of manufacturing a photoelectrode having a through-via according to an embodiment of the disclosed technology.

Since the technology disclosed in the present specification can make various changes and have various embodiments, specific embodiments are illustrated in the drawings, and will be described in detail through detailed description. However, this is not intended to limit the technology disclosed in this specification to a specific embodiment, and the technology disclosed in this specification is understood to include all changes, equivalents, or substitutes included in the spirit and scope of the technology disclosed in this specification. It should be.

In describing the technology disclosed in the present specification, when it is determined that a detailed description of a related known technology may unnecessarily obscure the subject matter of the technology disclosed in the present specification, the detailed description thereof will be omitted.

In the present specification, when a part is said to be "connected" with another part, this includes not only the case of being "directly connected", but also the case of being "electrically connected" with another element interposed therebetween. do.

In the present specification, when a member is said to be positioned "on" another member, this includes not only the case where the member is in contact with the other member, but also the case where another member exists between the two members.

In the disclosure of the present specification, when a part "includes" a certain component, it means that other components may be further included rather than excluding other components unless otherwise specified.

The terms "about", "substantially", etc. of the degree used in the present specification are used at or close to the numerical value when manufacturing and material tolerances specific to the stated meaning are presented, and the understanding of the present application To assist, accurate or absolute numerical values are used to prevent unreasonable use of the stated disclosure by unscrupulous infringers.

As used in the present specification, the term "step (to)" or "step of" does not mean "step for".

In the present specification disclosure, the term "combination of these" included in the expression of the Makushi format refers to one or more mixtures or combinations selected from the group consisting of components described in the expression of the Makushi format, and the component It means to include one or more selected from the group consisting of.

1 is a schematic cross-sectional view of a photoelectrode having a through-via according to an embodiment of the disclosed technology.

In order to achieve the above-described exemplary problem, an embodiment of the technology disclosed in the present specification provides a photoelectrode 100 having a through via.

As shown in FIG. 1, the photoelectrode 100 having a through via is formed on the first substrate 110, the transparent conductive film 120 formed on the first substrate 110, and the transparent conductive film 120. The formed photoreactive film 130, the through-via 150 installed in the through-hole 140 passing through the first substrate 110, and the through-via 150 are formed on the opposite side of the first substrate 110 The formed conductive layer 160 may be included.

The first substrate 110 may include glass or a transparent polymer, and may be a conductive glass substrate, a conductive plastic substrate, a conductive metal substrate, a semiconductor substrate or a non-conductor substrate.

The first substrate 110 may include, for example, an oxide substrate such as a _{SiO 2} substrate, an ITO substrate, a SnO ₂ substrate, a TiO ₂ substrate, and an Al ₂ O _{3 substrate;} In the group consisting of Cu, Ni, Fe, Pt, Al, Co, Ru, Pd, Cr, Mn, Au, Ag, Mo, Rh, Ta, Ti, W, U, V, Zr, Ir, and combinations thereof Selected metal substrate, or polyethylene terephthalate (PET), polyethylene sulfone (PES), polymethyl methacrylate (PMMA), polyimide, polyethylene naphthalate (Polyehylene Naphthalate; PEN), a flexible substrate such as polycarbonate (PC), or a glass substrate.

A transparent conductive film 120 may be formed on one surface of the first substrate 110.

The transparent conductive film 120 may be formed of a conductive material having high conductivity and transmittance.

Such a transparent conductive film is, for example, an indium-tin-oxide film (ITO: Indium Tin Oxide); Indium Zinc Oxide (IZO); Fluorine-doped Tin Oxide (FTO); Silver (Ag), copper (Cu), aluminum (Al), magnesium (Mg), gold (Au), platinum (Pt), tungsten (W), molybdenum (Mo), titanium (Ti), nickel (Ni) or It may be formed in the form of a metal mesh selected from the group consisting of alloys including these, but is not limited thereto.

The thickness of the transparent conductive film 120 may be preferably formed to about 10 nm to 10 μm.

The transparent conductive film 120 on the first substrate 110 may be adhered to the photoreactive film 130.

The photoreactive layer 130 to which sunlight is incident may absorb light to form a charge carrier. Charge carriers generated in the photoreactive layer 130 are collected in the transparent conductive layer 120.

The photoreactive film 130 is WO ₃ ; BVO; ZnO; Fe _x O _y , Cu _x O _y (where x, y are integers between 1 and 10); Alternatively _{, it may be formed of TiO 2} , but is not limited thereto.

The thickness of the photoreactive film 130 may be preferably formed to be approximately 10 nm to 10 μm.

A through hole 140 penetrating through the substrate is formed in the first substrate 110, and a through via 150 is formed in the through hole 140. A plurality of through-holes 140 may be formed, and as shown in FIG. 2, the through-via 150 may completely or partially fill the through-hole 140.

The through via 150 collects electric charges transferred to the transparent conductive layer 120.

The diameter of the through-hole 140 is larger than the diameter of the through-via 150, and the diameter of the through-hole 140 may be approximately 5um to 250um. In addition, a pitch between two adjacent through-holes among the plurality of through-holes in the horizontal direction may preferably be approximately 10 μm to 500 μm.

The through-via 150 installed in the through-hole 140 is formed by filling the through-hole 140 formed in the first substrate 110 with a low-resistance metal. The low-resistance metal is, for example, aluminum (Al), platinum (Pt), palladium (Pd), silver (Ag), magnesium (Mg), gold (Au), nickel (Ni), neodymium (Nd), iridium. It may be at least one selected from the group including (Ir), chromium (Cr), lithium (Li), calcium (Ca), molybdenum (Mo), titanium (Ti), tungsten (W), and copper (Cu).

Meanwhile, the conductive layer 160 is formed on a surface opposite to the first substrate 110 on which the through via 150 is formed. The conductive layer 160 functions to collect electrons collected in the through via 150.

Such a conductive film is, for example, an indium-tin-oxide film (ITO: Indium Tin Oxide); Indium Zinc Oxide (IZO); Fluorine-doped Tin Oxide (FTO); Silver (Ag), copper (Cu), aluminum (Al), magnesium (Mg), gold (Au), platinum (Pt), tungsten (W), molybdenum (Mo), titanium (Ti), nickel (Ni) or Although it is preferable to form a low-resistance conductive material such as an alloy containing these, it is not necessarily limited thereto.

The thickness of the conductive layer 160 may be preferably formed to be approximately 10 nm to 10 μm.

In one embodiment, the photoelectrode 100 having the through via may be for an anode. When sunlight is incident, the photoreactive layer 130 absorbs the light to form a charge carrier, and the charge carrier generated by the photoreactive layer 130 is the transparent conductive layer 120 and the through via 150 It may be collected in the conductive layer 160 and transferred to the counter electrode. Therefore, there is an advantage in that the charge carrier generated from the photoelectrode can be transferred to the counter electrode with a small resistance loss.

3 to 5 are cross-sectional views schematically illustrating a photoelectrode having a through-via connected to a dye-sensitized solar cell (DSSC) according to another embodiment of the disclosed technology.

As shown in FIGS. 3 to 5, a dye-sensitized solar cell (DSSC) 200 may be connected to the photoelectrode 100 having a through via. A photoelectrode having a through-via connected to a dye-sensitized solar cell has the advantage that the electromotive force of the solar cell moves electrons or holes to the electrolyte without external electromotive force, enabling spontaneous hydrogen production without external power. .

In one embodiment, the dye-sensitized solar cell 200 connected to the photoelectrode 100 may include a second substrate 210, a solar cell electrode 300, and an electrolyte 400.

The second substrate 210 may be formed by depositing a transparent electrode such as a transparent conductive film on a transparent substrate such as a glass substrate or a transparent polymer substrate.

FTO or a metal electrode may be applied to the opposite side of the second substrate 210. The applied metal is, for example, aluminum (Al), platinum (Pt), palladium (Pd), silver (Ag), magnesium (Mg), gold (Au), nickel (Ni), neodymium (Nd), iridium ( It may be at least one selected from Ir), chromium (Cr), lithium (Li), calcium (Ca), molybdenum (Mo), titanium (Ti), tungsten (W), and copper (Cu).

The electrolyte 400 used in the dye-sensitized solar cell is not particularly limited as long as it receives electrons from the counter electrode by oxidation or reduction in the dye-sensitized solar cell and transfers it to the dye, but more preferably An iodine-based oxidation and reduction electrolyte of can be used, and a solution in which iodine is dissolved in acetonitrile can be used.

In one embodiment, the photoelectrode 100 on the front side and the solar cell electrode 300 on the rear side are electrically connected through the edge of the second substrate 210. Electrons or holes formed in the photoelectrode 100 move to the edge of the second substrate 210 and move to the solar cell electrode 300.

When the second electrode of the photoelectrode according to an embodiment of the present disclosure is used as a solar cell electrode, electrical loss can be reduced and efficiency of spontaneous hydrogen production can be increased.

As shown in FIG. 7, a method of manufacturing a photoelectrode having a through via (S100) according to an embodiment of the technology disclosed in the present specification includes a first step (S110) of manufacturing a through hole in a first substrate, the through A second step (S120) of forming a transparent conductive film on the first substrate with a hole formed thereon (S120), a third step (S130) of forming a photoreactive film on the first substrate on which the transparent conductive film is formed, A fourth step (S140) of forming a through-via by filling a resistive metal, and a fifth step (S150) of forming a conductive film on the opposite surface of the first substrate on which the through-via is formed. Explain about it.

The first step (S110)

Referring to FIG. 7, in a first step (S110) of manufacturing a through hole in the first substrate, the through hole 140 passes through the first substrate 110 and a hole is made.

The through hole passing through the first substrate 110 is manufactured by stamping, mechanical drilling, laser drilling, powder blasting, water jetting, or any other method suitable for manufacturing the through hole 140 in the first substrate 110 Can be.

The second step (S120)

As a second step (S120) of forming a transparent conductive film on a first substrate having a through hole, a semiconductor material is applied to the first substrate 110 in which the through hole is formed, as exemplarily shown in FIG. 7.

The transparent conductive film 120 formed on the first substrate 110 is a dry process such as sputtering and evaporation, dip coating, spin coating, roll coating, It may be formed using a wet process such as spray coating or a direct patterning process such as screen printing or inkjet printing, but is not limited thereto.

The third step (S130)

As a third step (S130) of forming a photoreactive film on the first substrate on which the transparent conductive film is formed, as exemplarily shown in FIG. 7, the photoreactive film 130 is formed on the first substrate 110 on which the through hole is formed. To form.

The photoreactive film 130 formed on the transparent conductive film 120 is a dry process such as sputtering and evaporation, dip coating, spin coating, roll coating, It may be formed using a wet process such as spray coating or a direct patterning process such as screen printing or inkjet printing, but is not limited thereto.

The fourth step (S140)

As a fourth step (S140) of forming a through via by filling the through hole formed in the first substrate with a low-resistance metal, as illustrated in FIG. 7, the through hole passing through the first substrate 110 ( A through-via 150 is formed by plating a low-resistance metal in 140).

The through-via 150 installed in the through-hole 140 is formed by filling the through-hole 140 formed in the first substrate 110 with a low-resistance metal. The through via 150 may completely fill the through hole 140 or may only partially fill the through hole 140.

The method of filling the low-resistance metal may be filled by any suitable process, for example, an electroplating method, an electroless plating method, an immersion plating method, a physical vapor deposition method, a chemical vapor deposition method, a plasma vapor deposition method, or a metal spray method. I can.

The fifth step (S150)

As a fifth step (S150) of forming a conductive film on the opposite side of the first substrate on which the through via is formed, as exemplarily shown in FIG. 7, the conductive film 160 is formed on one side of the first substrate 110. Is formed.

The conductive film 160 formed on the opposite side of the first substrate 110 on which the through via 150 is formed is a dry process such as sputtering and evaporation, dip coating, and spin coating. ), Wet process such as Roll coating, Spray coating, or direct patterning process such as Screen Printing and Inkjet Printing, laser lithography, transfer process, It may be formed by using a lift-off process or the like, but is not limited thereto.

Hereinafter, embodiments will be described in detail to aid in understanding the technology disclosed in the present specification. However, the following examples are merely illustrative of the content of the technology disclosed in the present specification, and the scope of the technology disclosed in the present specification is not limited to the following examples. Embodiments of the technology disclosed in the present specification are provided to more completely describe the present invention to those of ordinary skill in the art.

Example 1: Manufacture of photoelectrode having through via

As a substrate for a photoelectrode, a glass substrate (Corning, material: glass thickness of 2.2cm) was prepared. Subsequently, through-holes having a diameter of 25 mm were prepared in the glass substrate by laser processing at intervals of 100 mm. Then, after FTO was applied to the glass substrate (using a sputtering method), the substrate was heat-treated at 500° C. for 30 minutes to form a transparent conductive film (thickness: 700 nm). Subsequently, _{after coating WO 3} (using a sputtering method), the substrate was heat-treated at 500° C. for 120 minutes to form a photoreactive film (thickness: 30 nm). Then, a through via was formed by electroplating copper in the through hole formed in the glass substrate.

Subsequently, after FTO was applied to the opposite side of the glass substrate (using a sputtering method), the substrate was heat-treated at 500° C. for 30 minutes to form a conductive film (thickness: 700 nm) to prepare a photoelectrode.

Example 2: Fabrication of a photoelectrode having a through-via connected to a dye-sensitized solar cell

A photoelectrode manufactured under the same conditions and processes as in Example 1 was prepared. Subsequently, a glass substrate (Corning, material: glass, thickness 2.2 cm) was prepared as a substrate for a solar cell. Subsequently, after FTO was applied to the glass substrate (using a sputtering method), the substrate was heat-treated at 500° C. for 30 minutes to prepare a solar cell electrode.

As shown in FIG. 3, the solar cell was electrically connected to the photoelectrode by arranging the conductive film of the photoelectrode to face the glass substrate of the solar cell.

In addition, as shown in FIGS. 4 and 5, the solar cell was electrically connected to the photoelectrode by disposing the conductive film of the photoelectrode and the glass substrate of the solar cell so as to face each other.

Although the present invention has been described in detail above, the scope of the rights of the technology disclosed in the present specification is not limited thereto, and various modifications and variations are possible within the scope not departing from the technical spirit of the technology disclosed in the present specification described in the claims. This will be apparent to those of ordinary skill in the art.

100: photoelectrode
110: first substrate
120: transparent conductive film
130: photoreactive film
140: through hole
150: through via
160: conductive film
200: solar cell
210: second substrate
300: solar cell electrode
400: electrolyte

Claims (10)

A first substrate;
A transparent conductive film formed on the first substrate;
A photoreactive film formed on the transparent conductive film;
A through via provided in a plurality of through holes passing through the first substrate; And
A photoelectrode having a through-via, comprising a conductive film formed on an opposite surface of the first substrate on which the through-via is formed. The method of claim 1,
The photoelectrode is for an anode, and a photoelectrode having a through via. The method of claim 1,
The through-via completely fills the through-hole, and the photoelectrode having a through-via. The method of claim 1,
The through-via is a photoelectrode having a through-via that partially fills the through-hole. The method of claim 1,
The through vias are aluminum (Al), platinum (Pt), palladium (Pd), silver (Ag), magnesium (Mg), gold (Au), nickel (Ni), neodymium (Nd), iridium (Ir), chromium (Cr), lithium (Li), calcium (Ca), molybdenum (Mo), titanium (Ti), tungsten (W), copper (Cu) consisting of one or more metals selected from or an alloy containing them, having a through via Photoelectrode. The method of claim 1,
The photoelectrode having a through via, characterized in that the diameter of the through hole is 5um to 250um. The method of claim 1,
The photoelectrode having a through-via, characterized in that the spacing of the plurality of through-holes is 10um to 500um. The photoelectrode according to any one of claims 1 to 7, wherein the photoelectrode having the through-via is configured to be connected to a dye-sensitized solar cell (DSSC). As a method of manufacturing a photoelectrode having a through via,
A first step of manufacturing a through hole in a first substrate;
A second step of forming a transparent conductive film on the first substrate in which the through hole is formed;
A third step of forming a photoreactive film on the first substrate on which the transparent conductive film is formed;
A fourth step of forming a through via by filling the through hole formed in the first substrate with a low-resistance metal; And
Including a fifth step of forming a conductive film on the opposite surface of the first substrate on which the through via is formed
A method of manufacturing a photoelectrode having a through via. The method of claim 9,
A method of manufacturing a photoelectrode having a through-via comprising connecting a solar cell electrode of a dye-sensitized solar cell (DSSC) to the conductive film.

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