WO2024005233A1 - Hybrid photoelectrode and photoelectric device comprising same - Google Patents

Abstract

An aspect of the present invention relates to a hybrid photoelectrode comprising photosystem 1. Specifically, the present invention relates to a hybrid photoelectrode and a photoelectric device comprising same, the hybrid photoelectrode comprising: a transparent electrode; a first layer comprising a transition metal oxide formed on the transparent electrode; a second layer comprising photosystem 1 formed on the first layer; and a third layer comprising a metal oxide thin film formed on the second layer, wherein excellent stability can be realized while at the same time securing the excellent quantum efficiency characteristics of photosystem 1.

Description

Hybrid photoelectrode and photoelectric device containing the same

The present invention relates to a hybrid photoelectrode including photosystem 1 and an optoelectronic device including the same.

Photosystem 1 is one of the electron transport systems composed of several protein complexes that perform the main photochemical reactions of photosynthesis, and is characterized by a high transfer efficiency of photoelectrons generated by sunlight, up to 97%. In addition, Photosystem 1 can be extracted from plants or algae, and is attracting attention as a next-generation material for solar energy conversion due to its easy accessibility and high internal quantum efficiency.

In particular, technologies are being developed to use photosystem 1 as a photoelectrode material by fixing it on an electrode. However, in order to stably fix photosystem 1 to the electrode surface, a separate chemical functional group is introduced or a bonding material is used, but this has limitations in practicality due to the complicated manufacturing method, and photosystem 1 is damaged or deformed during the manufacturing process, deteriorating electrode performance. There is a problem of deterioration. In addition, photoelectrodes made from photosystem 1 have limitations in terms of low stability due to damage to photosystem 1 from the effects of reactive oxygen species or aerobic electrolytes that may occur during the reaction.

In other words, it is necessary to develop a new technology that can maintain the excellent quantum efficiency characteristics of photosystem 1 and simultaneously satisfy the performance and stability of the electrode by effectively fixing it to the electrode and protecting it from external conditions.

The purpose of the present invention is to provide a hybrid photoelectrode that can realize excellent stability while securing the excellent quantum efficiency characteristics of photosystem 1 and a photoelectric device containing the same.

For the above-described purposes, one aspect of the present invention includes a transparent electrode; a first layer including a transition metal oxide formed on the transparent electrode; a second layer including photosystem 1 formed on the first layer; and a third layer including a metal oxide thin film formed on the second layer.

The thickness of the third layer may be 5 to 50 nm.

The metal oxide thin film may be an atomic layer thin film formed by atomic layer deposition (ALD).

The metal oxide thin film may include one or two or more selected from aluminum oxide, silicon oxide, titanium oxide, and zinc oxide.

The transition metal oxide may be selected from titanium dioxide (TiO ₂ ), zinc oxide (ZnO), and tin dioxide (SnO ₂ ).

In addition, one aspect of the present invention is the hybrid photoelectrode; A counter electrode of the photoelectrode; and an electrolyte.

The photocurrent density (Jsc) of the photoelectric device according to one aspect may be 10 μA/cm ² to 30 μA/cm ² .

The photoelectric device according to one aspect may have a value according to Equation 1 below of 0.3 or more.

[Equation 1]

I ₆₀₀ /I ₀

(I ₀ is the initial photocurrent density,

I ₆₀₀ is the photocurrent density when measurement was continued for 600 seconds through chronoamperometry analysis.)

The photoelectric device according to one aspect may have a value according to Equation 2 below of 0.1 or more.

[Equation 2]

I ₈₀₀₀ /I ₀

(I ₀ is the initial photocurrent density,

I ₈₀₀₀ is the photocurrent density when measurement was continued for 8000 seconds through chronoamperometry analysis.)

Additionally, one aspect of the present invention provides a biosensor including the hybrid photoelectrode.

Additionally, one aspect of the present invention provides a solar cell including the hybrid photoelectrode.

A method of manufacturing a hybrid photoelectrode according to one aspect includes (a) forming a first layer including a transition metal oxide on one surface of a transparent electrode; (b) forming a second layer containing photosystem 1 by applying a photosystem 1 dispersion solution on the first layer and drying it; and (c) forming a third layer by depositing a metal oxide thin film on the second layer by atomic layer deposition (ALD).

The photosystem 1 dispersion solution includes the steps of extracting juice from plant leaves; Removing impurities from the juice, centrifuging to remove the supernatant, and obtaining precipitated solids; dispersing the solid in a buffer solution, centrifuging, and sonicating the solid redispersion solution to obtain a chloroplast dispersion buffer solution; And heat-treating the solution of the chloroplast dispersion buffer and the surfactant solution and then centrifuging the mixture to remove precipitates and obtain a solution in which photosystem 1 is dispersed.

The atomic layer deposition method of step (c) may be performed using a metal precursor represented by the following formula (1).

[Formula 1]

M(A) _a (B) _b

(In Formula 1 above,

M is one of the group 4 to group 14 metal elements;

A and B are each independently -R ¹ , -OR ² , -N(R ³ )(R ⁴ ), a halogen element or

ego;

R ¹ to R ⁶ are each independently (C1-C7)alkyl;

a+b is the ionic value of M, and a and b are each integers from 0 to the ionic value of M.)

The hybrid photoelectrode according to one aspect can maintain the excellent quantum efficiency characteristics of photosystem 1 and simultaneously satisfy the performance and stability of the electrode by effectively fixing photosystem 1 to the electrode and protecting it from external conditions.

Additionally, the hybrid photoelectrode according to one aspect can be manufactured through a simple process, which may be advantageous for commercialization.

Figure 1 shows the average photocurrent density of photoelectrodes manufactured in Examples and Comparative Examples.

Figure 2 shows the results of measuring the photocurrent density of the photoelectrodes manufactured in Examples and Comparative Examples for 600 seconds through chronoamperometry analysis.

Figure 3 shows the results of measuring the photocurrent density of the photoelectrodes manufactured in Examples and Comparative Examples for 8000 seconds through chronoamperometry analysis.

Figure 4 shows the results of surface XPS analysis of (a) TiO ₂ and the photoelectrode prepared in Comparative Example 1 (b) before use and (c) after use.

Figure 5 shows the results of surface XPS analysis before and after use of the photoelectrodes prepared in Examples 1 to 3.

Figure 6 shows the results of XPS analysis before and after use of the photoelectrode prepared in Comparative Example 1.

Figure 7 shows the results of surface XPS analysis before and after use of the photoelectrodes prepared in Examples 1 to 3.

Unless otherwise defined herein, all technical and scientific terms have the same meaning as commonly understood by a person skilled in the art to which the present invention pertains. The terminology used in the description herein is merely to effectively describe particular embodiments and is not intended to limit the invention.

As used herein, the singular forms “a,” “an,” and “the” are intended to include the plural forms as well, unless the context clearly dictates otherwise.

In addition, the numerical range used in this specification includes the lower limit and upper limit and all values within the range, increments logically derived from the shape and width of the defined range, all double-defined values, and the upper limit of the numerical range defined in different forms. and all possible combinations of the lower bounds. Unless otherwise specified herein, values outside the numerical range that may occur due to experimental error or rounding of values are also included in the defined numerical range.

The term “comprises” in this specification is an open description with the same meaning as expressions such as “comprises,” “contains,” “has,” or “features,” and includes elements that are not additionally listed; Does not exclude materials or processes.

The term "photosystem 1" in the present name refers to the functional and structural unit of protein complexes related to photosynthesis that together perform the main photochemical reactions of photosynthesis. During the photosynthetic process, photoelectrons are collected from sunlight in the light collection complex. and causes an electron transfer reaction along the path of a complex of pigments and other cofactors with an elaborate arrangement.

One aspect of the present invention relates to a hybrid photoelectrode comprising photosystem 1. Photosystem 1 is attracting attention as a next-generation material for solar energy conversion due to its easy accessibility and high internal quantum efficiency, but the manufacturing method is complicated to stably fix photosystem 1 to the electrode surface, which limits its practicality. There is a problem that photosystem 1 is damaged or deformed in the process, deteriorating electrode performance. In addition, photoelectrodes made from photosystem 1 have limitations in terms of low stability due to damage to photosystem 1 from the effects of reactive oxygen species or aerobic electrolytes that may occur during the reaction.

One aspect of the present invention is intended to solve the above problems, and provides a hybrid photoelectrode that can secure long-term stability of the photoelectrode while maintaining the excellent quantum efficiency characteristics of photosystem 1.

Specifically, the hybrid photoelectrode according to one aspect of the present invention includes a transparent electrode; a first layer including a transition metal oxide formed on the transparent electrode; a second layer including photosystem 1 formed on the first layer; and a third layer including a metal oxide thin film formed on the second layer.

The hybrid photoelectrode according to one aspect has the structural combination described above, and thus can simultaneously secure the performance and stability of the electrode. As an example, the metal oxide thin film (third layer) can effectively fix photosystem 1 on the transparent electrode without deteriorating the excellent quantum efficiency characteristics of photosystem 1 and protect it from external stimuli, thereby improving the stability of the electrode. You can. Additionally, the photoelectric efficiency of the hybrid photoelectrode according to one aspect can be further improved.

However, if a compound such as chlorophyll is used instead of photosystem 1 as the second layer material, not only cannot the high internal electronic efficiency of photosystem 1 be applied, but also when the third layer, a metal oxide thin film layer, is deposited, the chlorophyll Electrode performance may be significantly reduced by completely blocking contact for charge transfer with the electrolyte.

The transparent electrode is not particularly limited as long as it is a material having conductivity and transparency, but non-limiting examples include indium tin oxide (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 selected from the group consisting of alloys containing these.

The first layer formed on the transparent electrode may be a porous transition metal oxide layer. Specifically, the transition metal oxide may be selected from titanium dioxide (TiO ₂ ), zinc oxide (ZnO), and tin dioxide (SnO ₂ ). It is not limited to this.

Additionally, the metal oxide thin film of the third layer may be an atomic layer thin film formed by atomic layer deposition (ALD).

The thickness of the third layer may vary depending on the number of depositions according to the atomic layer deposition method and is not greatly limited, but may be, for example, 5 to 50 nm, specifically 5 to 30 nm, and more specifically 5 to 20 nm. It may be nm.

When the above thickness range is satisfied, the first layer of the photosystem can be stably protected and at the same time, the photoelectric efficiency of the hybrid photoelectrode according to one embodiment can be further improved.

The metal oxide thin film may include one or two or more selected from aluminum oxide, silicon oxide, titanium oxide, and zinc oxide, and may specifically be titanium oxide, and more specifically, titanium dioxide (TiO ₂ ). .

For example, the photocurrent density (Jsc) of the hybrid photoelectrode according to one aspect may be 10 μA/cm ² to 30 μA/cm ² based on the thickness of the metal oxide thin film layer of 5 to 20 nm, and specifically 10 μA. /cm ² to 25 μA/cm ² .

At the same time, the hybrid photoelectrode according to one aspect may have a value according to Equation 1 below of 0.3 or more, or 0.4 or more, or 0.5 or more, or 0.6 or more.

[Equation 1]

I ₆₀₀ /I ₀

(I ₀ is the initial photocurrent density, and I ₆₀₀ is the photocurrent density when measurement was continued for 600 seconds through chronoamperometry analysis.)

At the same time, the hybrid photoelectrode according to one aspect may have a value according to Equation 2 below of 0.05 or more, or 0.15 or more, or 0.20 or more.

[Equation 2]

I ₈₀₀₀ /I ₀

(I ₀ is the initial photocurrent density, and I ₈₀₀₀ is the photocurrent density when measurement was continued for 8000 seconds through chronoamperometry analysis.)

That is, the hybrid photoelectrode according to one aspect can have excellent photocurrent density and long-term stability.

Additionally, one aspect of the present invention provides an optoelectronic device including the hybrid photoelectrode. For example, the photoelectric device may include a hybrid photoelectrode according to one aspect; A counter electrode of the hybrid photoelectrode; and an electrolyte.

The photoelectric device may be applied to, for example, solar cells, biosensors, etc.

Hereinafter, a method for manufacturing a hybrid photoelectrode according to one aspect will be described.

A method of manufacturing a hybrid photoelectrode according to one aspect is

(a) forming a first layer containing a transition metal oxide on one surface of a transparent electrode;

(b) forming a second layer containing photosystem 1 by applying a photosystem 1 dispersion solution on the first layer and drying it; and

(c) forming a third layer by depositing a metal oxide thin film on the second layer using atomic layer deposition (ALD).

Detailed descriptions of the transparent electrode, transition metal oxide, and metal oxide thin film are the same as described above and are therefore omitted.

Specifically, step (a) may involve forming a first layer by applying a dispersion solution containing a transition metal and heat treating it. The application method includes, for example, spin coating, dip coating, roll coating, screen coating, spray coating, and spin casting. ), flow coating, screen printing, ink jet, or drop casting may be used, but are not limited thereto.

In addition, the heat treatment in step (a) may be performed at 100 ℃ to 200 ℃ for 30 minutes to 2 hours, or at 200 ℃ to 300 ℃ for 1 hour to 2 hours, or at 400 ℃ to 600 ℃ for 1 hour to 3 hours. Stepwise heat treatment may be performed using one or a combination of two or more temperature conditions selected from these.

The photosystem 1 dispersion solution in step (b) includes the steps of extracting juice from the leaves of the plant; Removing impurities from the juice, centrifuging to remove the supernatant, and obtaining precipitated solids; After dispersing the solid in a buffer solution and centrifuging, sonicating the redispersion solution of the solid to obtain a chloroplast dispersion buffer solution: heat-treating and centrifuging a mixture of the chloroplast dispersion buffer solution and the surfactant solution. It may be prepared including the step of removing the precipitate and obtaining a solution in which photosystem 1 is dispersed.

The type of plant is not greatly limited, but for example, spinach can be used among fruits and vegetables.

Additionally, in step (b), the concentration of the photosystem 1 dispersion solution may be 400 μg chlorophyll/mL to 600 μg chlorophyll/mL, and the application method may be, for example, spin coating or dip coating. , roll coating, screen coating, spray coating, spin casting, flow coating, screen printing, ink jet or drop. Casting (drop casting), etc. may be used, but are not limited to this.

Additionally, in step (b), drying may be performed at normal temperature, and reduced pressure conditions may be used if necessary. Here, room temperature may be the temperature without artificial temperature control. For example, the room temperature may be 20°C to 40°C, or 20°C to 30°C, or 23 to 26°C.

In step (c), the atomic layer deposition method may be performed using a metal precursor represented by the following formula (1).

[Formula 1]

M(A) _a (B) _b

(In Formula 1 above,

M is one of the group 4 to group 14 metal elements;

A and B are each independently -R ¹ , -OR ² , -N(R ³ )(R ⁴ ), a halogen element or

ego;

R ¹ to R ⁶ are each independently (C1-C7)alkyl;

a+b is the ionic value of M, and a and b are each integers from 0 to the ionic value of M.)

For example, M may be titanium (Ti), tin (Sn), zinc (Zn), aluminum (Al), silicon (Si), indium (In), or tantalum (Ta), but is not limited thereto.

Specifically, M may be titanium, A and B may be the same as each other and -N(R ³ )(R ⁴ ), and R ³ and R ⁴ may be the same as each other and may be (C1-C3)alkyl. .

Specifically, step (c) includes introducing the electrode obtained in step (b) into the reaction chamber; Supplying raw material gas containing a metal precursor represented by Formula 1 to a reaction chamber; purging the reaction chamber using an inert gas; Supplying a reaction gas to the reaction chamber; And the unit process including the step of purging the reaction chamber using an inert gas may be repeated one or more times.

The inert gas may be used without particular limitation as long as it is commonly known, but may be, for example, argon (Ar), nitrogen (N ₂ ), or helium (He).

The reaction gas may be any one selected from water vapor (H ₂ O), air, oxygen (O ₂ ), and ozone (O ₃ ), and may specifically be water vapor, but is not limited thereto.

Hereinafter, the above-described implementation example will be described in more detail through examples. However, the following examples are for illustrative purposes only and do not limit the scope of rights.

[Production Example 1] Photosystem 1 dispersion solution preparation

Photosystem 1, which has photoactivity, was extracted from spinach (Spinacia oleracea) after separation into protein structures through mechanical grinding and chemical grinding using a surfactant. Specifically, the stems and leaves of thoroughly washed spinach (300 g) were separated, and only the leaves were obtained and squeezed through a juicer. Large pieces of crushed juice were removed using gauze, divided into 30 mL portions, and centrifuged (10,000 xg, 4°C, 5 minutes) to remove additional impurities. After centrifugation supernatant was removed, it was dispersed in 30 mL neutral buffer solution (50 mM sodium phosphate buffer & 10 mM NaCl, pH 7.0), and broken chloroplast pieces were obtained by additional centrifugation, and ultrasound was applied for 1 minute. Broken chloroplast dispersion buffer solution and surfactant solution (50 mM Tris-HCl & 3% Triton . As is known, photosystem 2 is easily denatured by heat. Accordingly, photosystem 2 can be removed by removing the precipitate by centrifugation after heat treatment at 45°C. To remove the surfactant present in the solution obtained by centrifugation, the solution was dialyzed against a buffer solution (Tris buffered saline, pH 7.6) for 12 hours using a 50 kDa MWCO (Molecular weight cut off) membrane to obtain a dispersion in which photosystem 1 was dispersed. did.

[Example 1] Manufacturing of hybrid photoelectrode

First layer formation

FTO, a transparent electrode, was cleaned of impurities using ultrasonic pulverization in a solvent in the following order: acetone-ethanol-non-ionized water, then dried, and the surface was modified by pretreatment using a UV ozone cleaner. After masking the pretreated FTO to _1cm The obtained TiO ₂ paste film was heat treated at 100°C for 1 hour and 500°C for 2 hours to remove the solvent in the paste and prepare an electrode with a TiO ₂ film formed thereon.

Second layer formation

After pre-treating the electrode on which the TiO ₂ film obtained above was formed with a UV ozone cleaner, 50 μL of the photosystem 1 dispersion solution with a concentration of 470 μg chlorophyll/mL was applied on the TiO ₂ film by drop casting. did. Afterwards, the solvent of the photosystem 1 dispersion solution was removed through vacuum drying at room temperature, and an electrode with a “TiO ₂ /photosystem 1” structure on which only photosystem 1 was deposited was manufactured.

Third layer formation

Afterwards, a TiO ₂ primary layer thin film was formed on the photosystem 1 layer using atomic layer deposition (ALD). Specifically, a P type Si(100) wafer with a diameter of 100 mm was used for TiO ₂ thin film deposition at low temperature. Traveling type ALD equipment was used for thin film deposition. Tetrakis(dimethylamino)titanium (IV) (TDMAT) was used as a precursor for thin film formation, H ₂ O was used as a reaction gas for oxidation, and Ar was used as a purging gas. A hybrid photoelectrode with a “TiO ₂ /photosystem 1/TiO ₂ thin film” structure in which a 5 nm thick TiO ₂ thin film layer was formed by repeating 110 cycles of deposition at a substrate temperature of 200°C was manufactured.

[Example 2]

In the third layer forming step, the same procedure as Example 1 was performed, except that the TiO ₂ thin film layer was formed to a thickness of 10 nm.

[Example 3]

In the third layer forming step, the same procedure as Example 1 was performed, except that the TiO ₂ thin film layer was formed to a thickness of 20 nm.

[Comparative Example 1]

A photoelectrode having a “TiO ₂ /photosystem 1” structure was manufactured in the same manner as in Example 1, except that the third layer forming step was not performed.

<Evaluation example>

Evaluation 1. Evaluation of photoelectrochemical properties

The hybrid photoelectrode manufactured in the above examples and comparative examples was used as a working electrode, a platinum wire (Pt wire) was used as a counter electrode, and Ag/AgCl (NaCl saturated) was used as a reference electrode, and 0.1 M potassium phosphate buffer solution (potassium phosphate) was used as a reference electrode. buffer, pH 7), 1 mM K ₃ Fe(CN) ₆ and 1 mM K ₄ Fe(CN) ₆ electrolyte, and +0.3 V bias under conditions of solar simulator (Solar simulator, Xenon lamp, HAL 320, Asahi Spectra) , Tokyo, Japan, AM 1.5G, 1 Sun output) was used as a light source to evaluate the photoelectrochemical properties. The results are shown in Table 1 and Figures 1 and 2 below.

Figure 1 shows the photocurrent density value obtained by calculating the average of the increased current density values for each region under repetitive illumination conditions. The hybrid photoelectrode of the example has a photocurrent density value that increases as a TiO ₂ thin film is deposited on the photosystem first layer. It can be seen that there is a marked improvement. In addition, as the thickness of the TiO ₂ thin film increased, the photocurrent density value increased, and the photocurrent density of Example 3, where the TiO ₂ thin film was 20 nm thick, was more than twice that of Comparative Example 1.

Table 1, Figures 2 and 3 below show the photocurrent and maintenance ratio generated when light irradiation is repeatedly continued and the measurement time is increased to 600 seconds and 8000 seconds or more through chronoamperometric analysis.

Referring to Figures 1 to 3, it can be seen that the hybrid photoelectrode according to one aspect of the present invention not only has excellent photocurrent density but also has excellent stability, enabling excellent reproducibility and reliability.

	Example 1	Example 2	Example 3	Comparative Example 1
I 0	24.94	22.33	26.81	15.00
I 600	12.06	14.91	16.68	5.56
I 8000	4.34	5.82	6.08	1.23
I 0 : Initial photocurrent density I 600 : Photocurrent density when measurement was continued for 600 seconds through chronoamperometry analysis I 8000 : Photocurrent density when measurement was continued for 8000 seconds through chronoamperometry analysis

Evaluation 2. Stability evaluation

Using X-ray photoelectron spectroscopy (XPS; was evaluated. The results are shown in Figures 4 to 6.

Figure 4 shows the results of analyzing the Ti2p signal due to TiO ₂ on the surface of the hybrid photoelectrode manufactured in Comparative Example 1. Referring to this, it was confirmed that the Ti2p signal, which was not visible before use, reappeared after use. That is, it can be seen that in the hybrid photoelectrode of Comparative Example 1, photosystem 1 is not stably fixed and thus falls off photosystem 1 after use.

Figure 5 shows the results of analyzing the Ti2p signal caused by TiO ₂ on the surface of the hybrid photoelectrode manufactured in Examples 1 to 3. It can be confirmed that surface TiO ₂ remains even after use, effectively protecting photosystem 1.

In addition, Figure 6 shows the results of analyzing the C1s signal caused by photosystem 1 protein on the surface of the hybrid photoelectrode prepared in Comparative Example 1. After use, the intensity of the C-C bond peak decreased to 1/10 level, causing photosystem 1 to fall off the electrode. You can see that it happens.

On the other hand, referring to FIG. 7, it can be seen that photosystem 1 is stably attached to the hybrid photoelectrodes manufactured in Examples 1 to 3 even after use.

As described above, the present invention has been described with specific details and limited embodiments, but these are provided only to facilitate a more general understanding of the present invention, and the present invention is not limited to the above embodiments, and the field to which the present invention belongs is not limited to the above embodiments. Those skilled in the art can make various modifications and variations from this description.

Accordingly, the spirit of the present invention should not be limited to the described embodiments, and the scope of the patent claims described below as well as all modifications that are equivalent or equivalent to the scope of this patent claim shall fall within the scope of the spirit of the present invention. .

Claims (14)

1. transparent electrode; a first layer including a transition metal oxide formed on the transparent electrode; a second layer including photosystem 1 formed on the first layer; and a third layer comprising a metal oxide thin film formed on the second layer.
2. According to clause 1,

   A hybrid photoelectrode wherein the third layer has a thickness of 5 to 50 nm.
3. According to clause 2,

   The metal oxide thin film is an atomic layer thin film formed by atomic layer deposition (ALD), a hybrid photoelectrode.
4. According to clause 3,

   A hybrid photoelectrode wherein the metal oxide thin film includes one or two or more selected from aluminum oxide, silicon oxide, titanium oxide, and zinc oxide.
5. According to clause 1,

   The transition metal oxide is a hybrid photoelectrode selected from titanium dioxide (TiO ₂ ), zinc oxide (ZnO), and tin dioxide (SnO ₂ ).
6. A hybrid photoelectrode according to any one selected from claims 1 to 5; A counter electrode of the photoelectrode; and an electrolyte.
7. According to clause 6,

   The photoelectric device has a photocurrent density (Jsc) of 10 μA/cm ² to 30 μA/cm ² .
8. According to clause 7,

   The photoelectric device has a value of 0.3 or more according to Equation 1 below.

   [Equation 1]

   I ₆₀₀ /I ₀

   I ₀ is the initial photocurrent density,

   I ₆₀₀ is the photocurrent density when measurement was continued for 600 seconds through chronoamperometry analysis.
9. According to clause 8,

   The photoelectric device is a photoelectric device having a value of 0.1 or more according to Equation 2 below.

   [Equation 2]

   I ₈₀₀₀ /I ₀

   I ₀ is the initial photocurrent density,

   I ₈₀₀₀ is the photocurrent density when measurement was continued for 8000 seconds through chronoamperometry analysis.
10. A biosensor comprising a hybrid photoelectrode according to any one of claims 1 to 5.
11. A solar cell comprising a hybrid photoelectrode according to any one of claims 1 to 5.
12. (a) forming a first layer containing a transition metal oxide on one surface of a transparent electrode;

    (b) forming a second layer containing photosystem 1 by applying a photosystem 1 dispersion solution on the first layer and drying it; and

    (c) forming a third layer by depositing a metal oxide thin film on the second layer by atomic layer deposition (ALD).
13. According to clause 12,

    The photosystem 1 dispersion solution is,

    Obtaining juice by squeezing the leaves of the plant;

    Removing impurities from the juice, centrifuging to remove the supernatant, and obtaining precipitated solids;

    dispersing the solid in a buffer solution, centrifuging, and sonicating the solid redispersion solution to obtain a chloroplast dispersion buffer solution; and

    A method of manufacturing a hybrid photoelectrode, which is prepared including the step of heat-treating the mixed solution of the chloroplast dispersion buffer solution and the surfactant solution and then centrifuging it to remove the precipitate and obtain a solution in which photosystem 1 is dispersed.
14. According to clause 12,

    The atomic layer deposition method of step (c) is a method of manufacturing a hybrid photoelectrode using a metal precursor represented by the following formula (1).

    [Formula 1]

    M(A) _a (B) _b

    In Formula 1,

    M is one of the group 4 to group 14 metal elements;

    A and B are each independently -R ¹ , -OR ² , -N(R ³ )(R ⁴ ), a halogen element or

    

    ego;

    R ¹ to R ⁶ are each independently (C1-C7)alkyl;

    a+b is the ionic value of M, and a and b are each integers from 0 to the ionic value of M.

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