KR102218158B1 - Method for forming electrochromic device of three-dimensional nanostructure and electrochromic device by the method - Google Patents

Abstract

The present invention relates to a method of forming an electrochromic device of a 3D nanostructure, and to an electrochromic device formed thereby, wherein a volume by a 3D nanostructure of a mesh structure in which a plurality of line patterns formed at a constant line width and interval are stacked crosswise. It provides a highly efficient electrochromic device with an increased to surface area ratio.

Description

Method of forming an electrochromic device of a 3D nanostructure, and an electrochromic device formed thereby

The present invention relates to a method of forming an electrochromic device of a 3D nanostructure, and to an electrochromic device formed thereby, and more particularly, to a 3D nanostructure obtained by intersecting a plurality of line patterns formed of an electrochromic material and a surface thereof. It relates to an electrochromic device including a doped film.

Electrochromic is a technology that uses the electrochemical reaction of a material, and changes the transmittance (color change) of the material by changing the oxidation number of the material through electrical energy. Such electrochromic technology is a field with high utility such as an electrochromic mirror for automobiles, a display optical shutter used for a smart window, a transparent display, a reflective display, and an electronic price tag.

For the commercialization of electrochromic technology, it is essential to develop a metal oxide-based material with excellent stability, but conventional metal oxide materials have a disadvantage in that the response speed and discoloration efficiency are lower than those of organic discoloration materials. Therefore, it is required to improve the response time and coloration efficiency of the metal oxide material.

Among the electrochromic materials of various metal oxides, nickel oxide (NiO) is one of the anodically colored materials occupying a small number and has the greatest potential in terms of commercialization.

However, nickel oxide (NiO) has a disadvantage in that it exhibits poor performance in terms of discoloration efficiency and response speed compared to other reduced coloring materials. In general, nickel oxide (NiO) is used in combination with cathodically colored materials (arranged across electrodes) to improve the performance of electrochromic devices, so when developing high-performance oxide-colored materials, the possibility of its application is possible. It is expected to be very high.

In addition, the existing color-changing material is formed by a vacuum deposition method. In order to achieve a low-cost and large-area device in terms of actual commercialization, it is essential to switch to a solution process.

Korean Patent Laid-Open Patent No. 10-2017-0101702 (published on September 6, 2017), “electrochromic device”

An object of the present invention is to provide a highly efficient electrochromic device with an increased volume-to-surface area ratio by a 3D nanostructure.

In addition, an object of the present invention is to improve discoloration efficiency and response speed by depositing a doping film on the surface of a 3D nanostructure and a 3D nanostructure having a mesh structure in which a plurality of line patterns formed with a constant line width and interval are stacked at intersections. At the time, it is intended to provide an electrochromic device exhibiting a higher transmittance.

In a method of forming an electrochromic device of a 3D nanostructure having high efficiency according to an embodiment of the present invention, the step of depositing an oxidizing color change material layer on a transparent electrode substrate, the electrochromic material on the oxidizing color change material layer Forming a 3D nanostructure by stacking a plurality of line patterns having a constant width and pitch in the form of a mesh structure and forming a 3D nanostructure. It includes the step of depositing a doped film by doping a specific element on the top.

The step of depositing the oxide color-changing material layer may include nickel oxide (NiO), tungsten oxide (WO ₃ ), molybdenum oxide (MoO ₃ ), and titanium dioxide (TiO) on the transparent electrode substrate. ₂ ) and the oxide discoloration material layer formed of a metal oxide containing any one of vanadium oxide (V ₂ O _{5) may be deposited.}

The transparent electrode substrate is formed of a transparent electrode material of any one of ITO (indium tin oxide) and FTO (tin fluorine oxide) on a substrate including any one of glass, quartz, and polymer. Can be.

The forming of the 3D nanostructure includes forming a plurality of layers in which the plurality of line patterns formed of an electrochromic material are aligned at a predetermined interval, and the plurality of line patterns constituting each layer cross each other. The three-dimensional nanostructure may be formed by being stacked in a form.

In the forming of the 3D nanostructure, the plurality of line patterns formed of an electrochromic material may be alternately stacked using a nano transfer printing technique.

The plurality of line patterns is a metal including any one of nickel oxide (NiO), tungsten oxide (WO ₃ ), molybdenum oxide (MoO ₃ ), titanium dioxide (TiO ₂ ), and vanadium oxide (V ₂ O _{5 ).} It is formed of an oxide electrochromic material, and may be formed to a thickness of 50 nm or less.

In the step of depositing the doped layer, the doped layer having a thickness of 50 nm or less may be deposited on the top of the 3D nanostructure by doping an electrochromic material with the specific element.

The step of depositing the doped layer may be performed by using a method including dip-coating, spin-coating, vacuum deposition, or a combination thereof.

The specific element used for the doping may be a metal including any one of copper (Cu), aluminum (Al), lithium (Li), and cobalt (Co).

In the electrochromic device of a 3D nanostructure exhibiting high efficiency according to an embodiment of the present invention, a transparent electrode substrate, an oxidized color-changing material layer deposited on the transparent electrode substrate, and an electrochromic material on the oxidized color-changing material layer. It is formed, and includes a 3D nanostructure including a plurality of line patterns representing a constant line width and pitch, and a doped film deposited by doping a specific element on the top of the 3D nanostructure. .

The 3D nanostructure is formed of a plurality of layers in which the plurality of line patterns formed of an electrochromic material are arranged at regular intervals, and the plurality of line patterns constituting each layer are stacked in a form that crosses each other. It may have been.

An electrolyte may be filled in a predetermined interval between the plurality of line patterns.

According to an embodiment of the present invention, by providing a high-efficiency electrochromic device in which the volume-to-surface area ratio is increased by the 3D nanostructure, the area in which the electrochemical reaction occurs due to the increase in the surface area is also increased, so that the coloring and decolorization response speed is increased. Improved, and the discoloration efficiency of the electrochromic device may be improved.

In addition, according to an embodiment of the present invention, discoloration efficiency by depositing a doping film on the surface of a 3D nanostructure and a 3D nanostructure of a mesh structure in which a plurality of line patterns formed with line widths and intervals capable of interacting with visible light are stacked crosswise. And response speed can be improved.

In addition, according to an embodiment of the present invention, since the 3D nanostructure is deposited on the transparent electrode substrate to efficiently cause a toilet discoloration reaction, the transmittance increases during decolorization and decreases during coloring, so that the conventional bulk electrochromism The color contrast (change in transmittance) compared to the material can be increased.

1 is a flowchart illustrating a method of forming an electrochromic device of a 3D nanostructure according to an embodiment of the present invention.
2 is a schematic diagram illustrating a process of forming an electrochromic device of a 3D nanostructure according to an embodiment of the present invention.
3 is a schematic diagram of an electrochromic device of a 3D nanostructure according to an embodiment of the present invention.
4 shows an image of an electrochromic device of a 3D nanostructure subjected to nano-transfer printing according to an embodiment of the present invention, observed with a scanning electron microscope.
5A and 5B illustrate images and graphs of experimental results of an electrochromic device of a 3D nanostructure formed by being divided into 2, 4 and 6 transfer times according to an embodiment of the present invention.
6A and 6B are images and graphs of experimental results of an electrochromic device of a 3D nanostructure subjected to an electrochromic test according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited or limited by the embodiments. In addition, the same reference numerals shown in each drawing denote the same member.

In addition, terms used in the present specification are terms used to properly express preferred embodiments of the present invention, which may vary depending on the intention of viewers or operators, or customs in the field to which the present invention belongs. Accordingly, definitions of these terms should be made based on the contents throughout the present specification.

The present invention relates to a method of forming an electrochromic device of a 3D nanostructure by transferring a line pattern of tens to hundreds of nanometers, applicable to various metal oxide electrochromic material fields, onto a substrate. It is a manufacturing process that not only improves the performance of the material, but also eliminates the use of high-resolution lithography technology, and increases the competitiveness of the substrate in process convenience and productivity.

In addition, the present invention is a convenient process for forming a material having a required performance because the size, direction, thickness, etc. of the line pattern can be easily adjusted through a change in a manufacturing process or a template.

Hereinafter, a method of forming an electrochromic device of a 3D nanostructure according to the present invention and an electrochromic device formed thereby will be described in detail with reference to the accompanying drawings.

1 is a flowchart illustrating a method of forming an electrochromic device of a 3D nanostructure according to an embodiment of the present invention, and FIG. 2 is a flowchart illustrating a process of forming an electrochromic device of a 3D nanostructure according to an embodiment of the present invention. It is shown schematically.

Referring to FIGS. 1 and 2, in step 110, an oxidized color change material layer 220 is deposited on the transparent electrode substrate 210.

As shown in FIG. 2(a), in step 110, an oxidized color-changing material layer 220 may be deposited on the entire surface of a transparent electrode substrate 210. In this case, in the present invention, the oxidized discoloration material layer 220 formed of nickel oxide (NiO) has been described, but the oxidization discoloration material layer 220 is not limited thereto, and nickel oxide (NiO), tungsten oxide (WO _{3 ).} ), molybdenum oxide (MoO ₃ ), titanium dioxide (TiO ₂ ), and vanadium oxide (V ₂ O ₅ ). It may be a layer formed of an electrochromic material of a metal oxide.

Further, in the present invention, the oxidized discoloration material layer 220 and a line pattern 230 are formed by using the same metal oxide. For example, the oxide discoloration material layer 220 is among nickel oxide (NiO), tungsten oxide (WO ₃ ), molybdenum oxide (MoO ₃ ), titanium dioxide (TiO ₂ ), and vanadium oxide (V ₂ O ₅ ). When formed of nickel oxide (NiO), the line pattern 230 may also be formed of the same nickel oxide (NiO).

The transparent electrode substrate 210 is a transparent electrode material of any one of ITO (indium tin oxide) and FTO (tin fluorine oxide) on a substrate including any one of glass, quartz, and polymer It may be formed of.

In the present invention, when electrochromic reaction proceeds in the future, oxidation discoloration of nickel oxide (NiO) on the transparent electrode substrate 210 to prevent an electrochemical reaction between the transparent electrode of the substrate and the electrolyte (260 in FIG. 3) It is characterized in that the material layer 220 is formed in a bulk form.

In step 120, a plurality of line patterns 230 that are formed of an electrochromic material on the oxidized color change material layer 220 and have a constant line width and pitch are formed in the form of a mesh structure. The three-dimensional nanostructure 250 is formed by stacking at an intersection.

As shown in FIGS. 2(b) to 2(d), in step 120, a plurality of line patterns 230 formed of an electrochromic material form a plurality of layers arranged at regular intervals, A plurality of line patterns 230 constituting each layer may be stacked to cross each other to form a 3D nanostructure 250.

In step 120, a plurality of line patterns 230 formed of an electrochromic material may be alternately stacked using a nano transfer printing technique.

For example, in step 120, a plurality of line patterns 230 formed using a silicon master template having a constant line pattern on the oxidized color changing material layer 220 formed of a bulk material of metal oxide are transferred by a nano-transfer printing technique. can do.

More specifically, the process of transferring the plurality of line patterns 230 by nano-transfer printing is described, the present invention spin-coating a 4wt% solution of Poly(methylmethacrylate) (PMMA) (100kg/mol) on the silicon master template Then, after bonding it with a commercial polyimide (PI) tape, it is removed and the line pattern is duplicated. Thereafter, the present invention forms a metal oxide nanowire on the replicated line pattern by diagonally depositing the PPMA replica pattern at a predetermined angle using an E-beam evaporator. The fabricated metal oxide nanowires are transferred to an arbitrary substrate after being exposed to a solvent vapor in which acetone and haptane are mixed in a 1:1 volume ratio. Thereafter, in step 120, the 3D nanostructure 250 based on the metal oxide nanowire (or a plurality of line patterns, 230) is fabricated by repeating the lamination several times with the angle of the nano-transfer printing different from the previous transfer process. .

At this time, each of the plurality of line patterns 230 is nickel oxide (NiO), tungsten oxide (WO ₃ ), molybdenum oxide (MoO ₃ ), titanium dioxide (TiO ₂ ), and vanadium oxide (V ₂ O ₅ ). It is formed of an electrochromic material of a metal oxide including any one of, and the thickness of the metal oxide deposition may be 50 nm or less. Likewise, in the present invention, each of the plurality of line patterns 230 is formed of an electrochromic material of the same metal oxide as the oxidized discoloration material layer 220.

As shown in FIG. 2, a plurality of line patterns 230 are arranged at a certain interval to form a layer, and each of the plurality of line patterns 230 has a line width and spacing of less than 1 μm. It may have a size that can cause interaction with visible light in a form formed with a (pitch) and a depth less than 100 nm.

In addition, each of the plurality of layers in which the plurality of line patterns 230 are arranged at a predetermined interval are intersectedly stacked in a vertical direction. At this time, the angle of nano transfer printing to transfer the plurality of line patterns 230 is determined by the line pattern transferred in the process of transferring the previous layer so that the line pattern can be stacked and stacked in a vertical direction. It is characterized in that the angle of conduct is not parallel.

In step 130, a doped layer 240 is deposited by doping a specific element on the top of the 3D nanostructure 250.

As shown in FIG. 2(e), in step 130, a thin doped film 240 of 50 nm or less may be deposited on the top of the 3D nanostructure 250 by doping an electrochromic material with a specific element.

In the present invention, after adjusting the transfer angle and the number of transfers of nano-transfer printing to form the 3D nanostructure 250, and the shape and size of the line pattern 230, doping with a specific element to improve the implantation ability of ions The doped layer 240 of one metal oxide may be formed to a thickness of 50 nm or less.

For example, step 130 uses a method including dip-coating, spin-coating, and vacuum deposition, or a combination of a specific element on top of the nanostructure 250. Doping may be performed to deposit the doped layer 240. In this case, the specific element used for doping may be a metal including any one of copper (Cu), aluminum (Al), lithium (Li), and cobalt (Co).

3 is a schematic diagram of an electrochromic device of a 3D nanostructure according to an embodiment of the present invention.

Referring to FIG. 3, the electrochromic device 200 includes a transparent electrode substrate 210, an oxidized color change material layer 220, a 3D nanostructure 250 including a plurality of line pattern layers 231 and 232, and doping. It includes a membrane 240.

The transparent electrode substrate 210 is a transparent electrode material of any one of ITO (indium tin oxide) and FTO (tin fluorine oxide) on a substrate including any one of glass, quartz, and polymer It may be formed of.

The oxide discoloration material layer 220 is a layer formed of nickel oxide (NiO), and is entirely deposited on the transparent electrode substrate 210. In this case, the oxidized discoloration material layer 220 may be formed to have the same size as the substrate 210, and the thickness is not limited.

In addition, the plurality of line patterns 230 forming the oxide-chromic material layer 220 and the 3D nanostructure 250 are nickel oxide (NiO), tungsten oxide (WO ₃ ), molybdenum oxide (MoO ₃ ) , Titanium dioxide (TiO ₂ ) and vanadium oxide (V ₂ O ₅ ) may be formed of an electrochromic material of the same metal oxide.

The 3D nanostructure 250 is formed by stacking a plurality of line pattern layers 231 and 232 in which a plurality of line patterns 230 are formed. In this case, the plurality of line patterns 230 are formed of an electrochromic material on the oxidized color change material layer 220 and may be formed with a constant line width and pitch.

The 3D nanostructure 250 is formed of a plurality of layers 231 and 232 in which a plurality of line patterns 230 formed of an electrochromic material are arranged at regular intervals, and a plurality of lines constituting each layer The patterns 230 may be stacked to cross each other. For example, if the line pattern layer 231 of the first layer is vertically aligned with a plurality of line patterns 230 at regular intervals, the line pattern layer 232 of the second layer is a plurality of line patterns 230 ) Are arranged horizontally at regular intervals, so that the line pattern layer 231 of the first layer and the line pattern layer 232 of the second layer are stacked in an intersecting manner.

Referring to FIG. 3, an electrolyte 260 may be filled at a predetermined interval between a plurality of line patterns 230. For example, the line patterns 230 of each layer forming the 3D nanostructure 250 are arranged and arranged at regular intervals, and the electrolyte 260 is disposed between the plurality of line patterns 230 at regular intervals. Can be formed.

The doped layer 240 is deposited by doping a specific element on the top of the 3D nanostructure 250.

Referring to FIG. 3, a doped layer 240 is deposited on top of a plurality of line patterns 230 positioned at the top of the 3D nanostructure 250, and a plurality of line patterns 230 constituting the top layer It can also be deposited on regular intervals between.

4 shows an image of an electrochromic device of a 3D nanostructure subjected to nano-transfer printing according to an embodiment of the present invention, observed with a scanning electron microscope.

In more detail, FIG. 4 is a three-dimensional nanostructure in which nickel oxide is stacked once and twice by a nano transfer printing technique using a template having a period of 50 nm (50-50-80) and 300 nm (300-50-80). The electrochromic element of is shown in an image magnified 50,000 times with a scanning electron microscope (SEM).

The present invention forms an electrochromic device of a 3D nanostructure by controlling the transfer angle, the number of transfers, and the shape and size of the line pattern through the nano-transfer printing technique, and a metal oxide doped with specific ions to improve the implantation ability of ions The doped film of was formed to a thickness of less than 30 nm.

Referring to FIG. 4, the first layer of the line pattern layer (1 layer) and the second layer of the line pattern layer (2 layers) forming an electrochromic device of a 3D nanostructure are deposited in a form crossing each other in a vertical direction. It can be seen that, in each of the line pattern layers, it can be seen that a plurality of line patterns are arranged at regular intervals.

5A and 5B illustrate images and graphs of experimental results of an electrochromic device of a 3D nanostructure formed by being divided into 2, 4 and 6 transfer times according to an embodiment of the present invention.

More specifically, FIG. 5A shows an image of an electrochromic device of a 3D nanostructure manufactured according to the number of transfer repetitions of the present invention, and FIG. 5B is an electrochromic image of a 3D nanostructure manufactured according to the number of transfer repetitions. It shows a graph of the experimental results of the transmittance to air for the device.

In the present invention, after forming a line pattern of nickel oxide with a silicon master template having a period of 50 nm and 300 nm, it is transferred to a flat substrate on which 100 nm of nickel oxide is deposited in a bulk form at a transfer angle of 90 degrees to electrochromize the 3D nanostructure. A device was formed, and a layer was formed by dividing the number of transfers into 2, 4 and 6 transfer times.

Referring to FIG. 5B, as a result of measuring the transmittance of the electrochromic device of the 3D nanostructure according to the number of transfers, in the case of the electrochromic device of the 3D nanostructure in which a layer is formed by the number of transfers two times, based on a wavelength of 520 nm. It can be seen that the bleaching transmittance was increased by up to 8% or more compared to the bulk nickel oxide.

That is, referring to FIG. 5, it can be seen that a similar spectrum is displayed according to the number of stacks, and it can be seen that optical characteristics are determined according to factors of the thickness and shape of the line pattern.

6A and 6B are images and graphs of experimental results of an electrochromic device of a 3D nanostructure subjected to an electrochromic test according to an embodiment of the present invention.

More specifically, FIG. 6A shows an image of an electrochromic device of a 3D nanostructure subjected to an electrochromic test after being divided by the number of transfer repetitions, and FIG. 6B is formed by dividing the number of transfer repetitions, A graph of the experimental results of the transmittance versus air for the electrochromic device of the 3D nanostructure subjected to the electrochromic test is shown.

In the present invention, the electrochromic device of the 3D nanostructure formed by the process of FIG. 5 was subjected to coloring and decolorization tests for 15 seconds at a voltage of +2 and -2V in a KOH 1M solution.

6A shows an image after bleaching and coloring of an electrochromic device of a 3D nanostructure, and referring to the left drawing of FIG. 6B, the bleaching transmittance is a three-dimensional layer formed by two transfer times. It can be seen that the electrochromic device of the nanostructure is the highest. Furthermore, it can be seen that as the number of stacks increases, the color transmittance decreases.

In addition, referring to the right drawing of FIG. 6B, it can be seen that the electrochromic element of the 3D nanostructure layered with the number of transfers of two times has the highest decolorization transmittance, and the graph gradually decreases. In addition, it can be seen that the colored transmittance is effectively reduced.

As shown in FIG. 6B, it can be seen that the color transmittance at a wavelength of 520 nm was reduced by up to 14% compared to bulk nickel oxide.

That is, in the present invention, when decolorizing the electrochromic device of the 3D nanostructure, the transmittance increases and the transmittance decreases when coloring, thereby confirming an increase in color contrast. Furthermore, it can be seen that the degree of enhancement of the transmittance is affected by the structure, width, thickness, and number of stacks of the 3D nanostructure.

Although the embodiments have been described by the limited embodiments and drawings as described above, various modifications and variations can be made from the above description to those of ordinary skill in the art. For example, the described techniques are performed in a different order from the described method, and/or components such as a system, structure, device, circuit, etc. described are combined or combined in a form different from the described method, or other components Alternatively, even if substituted or substituted by an equivalent, an appropriate result can be achieved.

Therefore, other implementations, other embodiments, and claims and equivalents fall within the scope of the claims to be described later.

200: electrochromic element
210: transparent electrode substrate
220: oxidative discoloration material layer
230: line pattern
231, 232: line pattern layer
240: doped film
250: 3D nanostructure
260: electrolyte

Claims (12)

In the method of forming an electrochromic device of a three-dimensional nanostructure exhibiting high efficiency,
Depositing a layer of an oxidized color change material on the transparent electrode substrate;
A three-dimensional nanostructure is formed by intersecting a plurality of line patterns formed of an electrochromic material on the oxidized discoloring material layer and having a constant line width and pitch in the form of a mesh structure. Forming; And
Depositing a doped film by doping a specific element on the top of the 3D nanostructure
Including,
The step of forming the 3D nanostructure is
The plurality of line patterns formed of an electrochromic material form a plurality of layers arranged at regular intervals, and the plurality of line patterns constituting each layer are stacked to cross each other to form the 3D nanostructure Method of forming an electrochromic device of a 3D nanostructure to form a. The method of claim 1,
The step of depositing the oxidized color change material layer
Nickel oxide (NiO), tungsten oxide (WO ₃ ), molybdenum oxide (MoO ₃ ), titanium dioxide (TiO ₂ ), and vanadium oxide (V ₂ O _{5) are all over the transparent electrode substrate.} A method of forming an electrochromic device of a 3D nanostructure by depositing the oxidized color changing material layer formed of an electrochromic material of a metal oxide including any one of. The method of claim 2,
The transparent electrode substrate
It is characterized in that it is formed of any one of transparent electrode material of ITO (indium tin oxide) and FTO (tin fluoride oxide) on a substrate including any one of glass, quartz, and polymer, Method of forming an electrochromic device of a 3D nanostructure. delete The method of claim 1,
The step of forming the 3D nanostructure is
A method of forming an electrochromic device of a 3D nanostructure, in which the plurality of line patterns formed of an electrochromic material are stacked at an intersection using a nano transfer printing technique. The method of claim 5,
The plurality of line patterns
As an electrochromic material of metal oxide containing any one of nickel oxide (NiO), tungsten oxide (WO ₃ ), molybdenum oxide (MoO ₃ ), titanium dioxide (TiO ₂ ) and vanadium oxide (V ₂ O ₅₎ Is formed, characterized in that formed to a thickness of 50 nm or less, 3D nanostructure electrochromic device forming method. The method of claim 1,
Depositing the doped layer comprises:
A method for forming an electrochromic device of a 3D nanostructure, in which the doped film having a thickness of 50 nm or less is deposited on an upper portion of the 3D nanostructure by doping an electrochromic material with the specific element. The method of claim 7,
Depositing the doped layer comprises:
A method of forming an electrochromic device of a 3D nanostructure, in which the doped layer is deposited using a method including dip-coating, spin-coating, vacuum deposition, or a combination thereof. The method of claim 8,
The specific element used for the doping is
Copper (Cu), aluminum (Al), lithium (Li), and a method of forming an electrochromic device of a three-dimensional nanostructure, characterized in that the metal containing any one of cobalt (Co). In the electrochromic device of a three-dimensional nanostructure showing high efficiency,
Transparent electrode substrate;
An oxide-chromic material layer deposited on the transparent electrode substrate;
A 3D nanostructure formed of an electrochromic material on the oxidized discoloring material layer and including a plurality of line patterns having a constant line width and a pitch; And
Doped film deposited by doping a specific element on the top of the 3D nanostructure
Including,
The 3D nanostructure is
The plurality of line patterns formed of an electrochromic material are formed as a plurality of layers arranged at regular intervals, and the plurality of line patterns constituting each layer are stacked in an intersecting manner. Electrochromic element. delete The method of claim 10,
Electrochromic device of a 3D nanostructure, characterized in that the electrolyte is filled in a predetermined interval between the plurality of line patterns.

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