KR20230084031A - Control of organic photodiode dark current through introduction of polar functional group - Google Patents

Abstract

The present invention relates to control of the dark current of an organic photodiode through the introduction of a polar functional group. In the organic photodiode according to the present invention, the trap density between the charge transport layer and the photoactive layer is reduced through the introduction of a polar functional group, and the inside of the active layer Due to the decrease in recombination, the dark current is lowered, and the stability is increased.

Description

Control of organic photodiode dark current through introduction of polar functional group

The present invention relates to an organic photodiode having improved characteristics by controlling the dark current of the organic photodiode through the introduction of a polar functional group.

For the past 10 years, the development of organic materials with semiconductor properties and various application studies using them have been actively conducted more than ever. The field of applied research using organic semiconductors, such as electromagnetic wave shielding films, capacitors, OLED displays, organic thin film transistors (OTFTs), solar cells, organic photodiodes, and memory devices using multiphoton absorption, continues to expand. .

A photodiode is an example of a photoelectric conversion element or photodetector capable of converting light energy into current or voltage. The photodiode has a P-N junction structure or a PIN structure. The photodiode generates free electrons and holes using the photoelectric effect. Photodiodes are widely used in CMOS image sensors and the like because of their photoelectric conversion function or photodetection function.

With the development of smart devices, image sensors including photodiodes are required to have high resolution. However, photodiodes using silicon, which are currently mainly used, are difficult to thin and have limitations in increasing absorbance. Accordingly, an organic photodiode having high light absorption and capable of controlling an absorption wavelength has been attracting attention as a material to replace silicon diodes, but existing organic photodiodes have a problem in that performance is inferior to silicon diodes. In order to solve this problem, research on the organic material layer of the organic photodiode continues.

Since the photoactive layer applied to the organic photodiode absorbs light to generate electrons and holes, there are attempts to develop it by applying a combination of an electron donor and an electron acceptor used in the photoactive layer of an organic solar cell. Dali, in the case of an organic photodiode, the problem of dark current has become an obstacle to commercialization, and efforts have been made to reduce such dark current. For example, Korean Patent Publication No. 10-2015-0026833 uses a double electron-blocking layer after an anode to reduce dark current in an organic photodiode.

On the other hand, as an attempt to develop an organic semiconductor material suitable for an organic photodiode, the present inventors have developed and registered a patent for an organic semiconductor material developed for an organic solar cell (Korean Registered Patent No. 10-2082222), some of which The present invention was completed by confirming that the material reduces the dark current when applied to a photodiode.

One object of the present invention is to provide a dark current control technology of an organic photodiode.

Another object of the present invention is to provide an organic photodiode with reduced dark current.

In order to achieve the above purpose,

In one aspect, the present invention

Provided is a photoactive layer for an organic photodiode comprising a polymer including a repeating unit represented by Chemical Formula 1 and a repeating unit represented by Chemical Formula 2.

[Formula 1]

[Formula 2]

Here, R ¹¹ , R ¹² and R ¹³ are each independently hydrogen or C1-C30 alkyl;

R ² and R ⁴ are each independently hydrogen or halogen;

Z is a sulfur element (S) or -C(R ³³ )=C(R ³⁴ )-,

R ³¹ , R ³² , R ³³ and R ³⁴ are each independently hydrogen or C1-C10 alkyl substituted with one or more hydroxy groups, but at least one is C1-C10 alkyl substituted with one or more hydroxy groups;

Each R ⁵ is independently hydrogen or C1-C30 alkyl.

In another aspect of the present invention,

An organic photodiode including the photoactive layer is provided.

In another aspect, the present invention

A photodetector or image sensor including the organic photodiode is provided.

In the organic photodiode according to the present invention, the trap density between the charge transport layer and the photoactive layer is reduced through the organic semiconductor material into which the polar functional group is introduced, and the dark current is reduced due to the decrease in recombination inside the active layer, thereby increasing stability. .

1 shows the results of measuring normalized absorbance according to wavelength for Comparative Examples and Examples according to the present invention.
Figure 2 shows the results of measuring current with respect to Comparative Examples and Examples according to the present invention.
3 shows the results of measuring energy (eV) for Comparative Examples and Examples according to the present invention.
Figure 4a shows the results of measuring current density-voltage for comparative examples and examples according to the present invention.
Figure 4b shows the results of measuring dark-JV for Comparative Examples and Examples according to the present invention.
Figure 4c shows the results of measuring EQE for Comparative Examples and Examples according to the present invention.
Figure 4d shows the results of measuring the reactivity (responsivity) with respect to the comparative examples and examples according to the present invention.
Figure 4e shows the result of measuring the detection rate of the polymer (PC ₇₁ BM blend films) with respect to Comparative Examples and Examples according to the present invention.

Hereinafter, the present invention will be described in detail.

Meanwhile, the embodiments of the present invention may be modified in various forms, and the scope of the present invention is not limited to the embodiments described below. In addition, the embodiments of the present invention are provided to more completely explain the present invention to those skilled in the art.

Furthermore, "include" a certain component throughout the specification means that other components may be further included without excluding other components unless otherwise stated.

In this specification, “alkyl” means a monovalent radical as a substituent containing all structural isomers of straight or branched chain as a completely saturated hydrocarbon. When C1-C30 alkyl, it means that the number of carbon atoms constituting the hydrocarbon ranges from 1 to 30.

In the present specification, "halogen" is an element belonging to group 7 on the periodic table of elements, and refers to a monovalent radical as a substituent containing all of fluoro, chloro, bromo, and iodo.

The present invention describes a polymer included in a photoactive layer for an organic photodiode provided in one aspect.

The polymer includes a repeating unit represented by Formula 1 and a repeating unit represented by Formula 2.

[Formula 1]

[Formula 2]

Here, R ¹¹ , R ¹² and R ¹³ are each independently hydrogen or C1-C30 alkyl;

R ² and R ⁴ are each independently hydrogen or halogen;

Z is a sulfur element (S) or -C(R ³³ )=C(R ³⁴ )-,

R ³¹ , R ³² , R ³³ and R ³⁴ are each independently hydrogen or C1-C10 alkyl substituted with one or more hydroxy groups, but at least one is C1-C10 alkyl substituted with one or more hydroxy groups;

Each R ⁵ is independently hydrogen or C1-C30 alkyl.

In another embodiment,

R ¹¹ are each independently C1-C30 alkyl;

R ¹² and R ¹³ are each hydrogen;

R ² and R ⁴ are each independently halogen;

Z is a sulfur element (S) or -C(R ³³ )=C(R ³⁴ )-,

R ³¹ and R ³⁴ are each independently C1-C10 alkyl substituted with one or more hydroxyl groups;

R ³² and R ³³ are each hydrogen;

R ⁵ is hydrogen.

In another embodiment,

R ¹¹ are each independently C4-C30 alkyl;

R ¹² and R ¹³ are each hydrogen;

R ² and R ⁴ are each independently fluoro, chloro and bromo;

Z is a sulfur element (S) or -C(R ³³ )=C(R ³⁴ )-,

R ³¹ and R ³⁴ are each independently C1-C6alkyl substituted with 1 to 2 hydroxyl groups;

R ³² and R ³³ are each hydrogen;

R ⁵ is hydrogen.

In another embodiment,

R ¹¹ are each independently C8-C24 alkyl;

R ¹² and R ¹³ are each hydrogen;

R ² and R ⁴ are each fluoro;

Z is a sulfur element (S) or -C(R ³³ )=C(R ³⁴ )-,

R ³¹ and R ³⁴ are each independently C1-C4alkyl substituted with 1 hydroxyl group;

R ³² and R ³³ are each hydrogen;

R ⁵ is hydrogen.

In another embodiment,

R ¹¹ are each independently C14-C18 alkyl;

R ¹² and R ¹³ are each hydrogen;

R ² and R ⁴ are each fluoro;

Z is a sulfur element (S) or -C(R ³³ )=C(R ³⁴ )-,

R ³¹ and R ³³ are each independently C1-C4alkyl substituted with 1 hydroxyl group;

R ³² and R ³³ are each hydrogen;

R ⁵ is hydrogen.

In another embodiment,

R ¹¹ are each independently C14-C18 alkyl;

R ¹² and R ¹³ are each hydrogen;

R ² and R ⁴ are each fluoro;

Z is a sulfur element (S) or -C(R ³³ )=C(R ³⁴ )-,

R ³¹ and R ³³ are each independently C1-C4alkyl substituted with 1 hydroxyl group;

R ³² and R ³³ are each hydrogen;

R ⁵ is hydrogen.

In another embodiment,

The polymer may be a polymer represented by Formula 3 or Formula 4 below.

[Formula 3]

[Formula 4]

x is a number greater than 0 and less than 1, and in some embodiments, x is 0.03, 0.05, or 0.1.

The weight average molecular weight of the polymer according to the present invention may be 1,000 to 1,000,000 g/mol, 10,000 to 400,000 g/mol, or 10,000 to 200,000 g/mol.

In the polymer of the present invention,

The mole ratio of the repeating unit according to Chemical Formula 1 and the repeating unit according to Chemical Formula 2 may be as follows.

greater than 0 and less than 1, greater than 0 and less than 0.5, greater than 0 and less than 0.3, greater than 0.01 and less than 0.3, greater than 0.01 and less than 0.2, greater than 0.01 and less than 0.15, greater than 0.03 It can be large and smaller than 0.10.

The polymer may be a polymer in which repeating units of Formulas 1 and 2 are alternately or randomly included.

The polymer may function as an electron acceptor in the photoactive layer, and may be included in the photoactive layer together with an electron donor.

The polymer according to the present invention can function as a photoactive layer by forming a film by a solution process of dissolving in an organic solvent and then applying it to a substrate. At this time, the electron donor can be dissolved or dispersed together during the solution process. Specifically, a film may be formed by applying and coating by any one method selected from R2R, spin coating, slot die coating, inkjet printing, screen printing, doctor blade method, etc., but is not limited thereto.

In the present invention, the electron donor included in the photoactive layer is not particularly limited, but may be a fullerene, a fullerene derivative, or a non-fullerene derivative. As a specific example, PCBM (phenyl CXX butyric acid methyl ester; where XX is carbon number) may be included. , and may include PC60BM, PC61BM, PC71BM, ITIC, IDTBR, Y6, and the like.

Another aspect of the present invention provides a photodiode including the photoactive layer, and the photodiode may be composed of two or more electrodes and a photoactive layer between the electrodes. The photodiode may further include an electron transport layer and/or a hole transport layer on both sides of the photoactive layer.

The organic photodiode of the present invention

transparent electrode; The photoactive layer in the present invention laminated on the transparent electrode; and

an electrode on the photoactive layer; It may have a structure.

preparing a transparent electrode;

Laminating the photoactive layer of the present invention on a transparent electrode; and

An organic photodiode may be manufactured by stacking an electrode on the photoactive layer.

The organic photodiode according to the present invention further includes PC71BM in a photoactive layer, and may have a D ^* (Specific detectivity) value of 1x10 ¹¹ Jones or higher. In another embodiment, the D ^* may be 5x10 ¹¹ Jones or more, 7x10 ¹¹ Jones or more, 1x10 ¹² Jones or more, or 1x10 ¹³ Jones or more.

In another aspect of the present invention, the photodiode may be included in a photodetector or an image sensor.

Hereinafter, the present invention will be described in detail through preparation examples and experimental examples.

However, the preparation examples and experimental examples to be described below are only to specifically illustrate the present invention in one aspect, but the present invention is not limited thereto.

< manufacturing example > Synthesis of organic semiconductor compounds

The organic semiconductor compound according to the present invention represented by Formula 3 or Formula 4 below was synthesized as described in Korean Patent Registration No. 10-20822221 (Example 3 and Example 4). In the present specification, preparation examples 1 to 6 are shown in Table 1.

[Formula 3]

[Formula 4]

On the other hand, for comparison, the compound of Comparative Example 2 described in the same Republic of Korea Patent Registration No. 10-20822221 was prepared as Comparative Preparation Example 1.

Formula 3 formula 4 Comparative Preparation Example 1 (x=0; PffBT4T-T3) Preparation Example 1 (x=0.03; PffBT4T-T3-3TMO) Preparation Example 4 (x=0.03; PffBT4T-T3-3P2MO) Preparation Example 2 (x=0.05; PffBT4T-T3-5TMO) Preparation Example 5 (x=0.05; PffBT4T-T3-5P2MO) Preparation Example 3 (x=0.10; PffBT4T-T3-3TMO) Preparation Example 6 (x=0.10; PffBT4T-T3-10P2MO)

Meanwhile, the analogs of Example 1 and Example 2 and the polymer of Example 6 described in Korean Patent Registration No. 10-20822221 were additionally synthesized to confirm the effect of controlling the dark current, respectively, in Comparative Preparation Examples 2 to 10. did In this process, comparative preparation examples were prepared by varying the value of x in Formulas 5 to 7 below.

[Formula 5]

[Formula 6]

[Formula 7

Formula 5 formula 6 Formula 7 Comparative Preparation Example 2 (x=0.03; PffBT4T-T3-3TO) Comparative Preparation Example 5 (X=0.03; PffBT4T-T3-3PTO) Comparative Preparation Example 8 (x=0.03; PffBT4T-T3-3PTO-F) Comparative Preparation Example 3 (x=0.05; PffBT4T-T3-5TO) Comparative Preparation Example 6 (X=0.05; PffBT4T-T3-5PTO) Comparative Preparation Example 9 (x=0.05; PffBT4T-T3-5PTO-F) Comparative Preparation Example 4 (x=0.10; PffBT4T-T3-10TO) Comparative Preparation Example 7 (X=0.10; PffBT4T-T3-10PTO) Comparative Preparation Example 10 (x=0.1; PffBT4T-T3-10PTO-F)

< Example 1 to 6> photodiode produce

According to the general process below, photodiodes using the polymers of Preparation Examples 1 to 6 and Comparative Preparation Examples 1 to 10 were manufactured, and Examples 1 to 6 and Comparative Examples 1 to 10 were obtained.

<General Photodiode Production>

An organic substrate coated with ITO (Indium Tin Oxide), a transparent electrode (first electrode), is immersed in deionized water containing a cleaning solution, washed in an ultrasonic cleaner for 15 minutes, and washed three times each with deionized water, acetone, and IPA. After that, it was dried in an oven at 130° C. for 5 hours. After washing the ITO glass substrate as described above, UV/ozone treatment was performed for 15 minutes, and ZnO·NPs having a thickness of 30 nm were spin-coated on the ITO substrate. Then, the substrate coated with ZnO NPs was heat treated at 100° C. for 10 minutes on a hot plate.

A 0.4 wt% poly(ethyleneimine)-ethoxylated (PEIE) solution was applied on the ZnO NPs layer by spin coating to a thickness of 3 nm.

Then, the device was transferred to a glove box filled with argon to apply the photoactive layer. The photoactive layer contains 3% (volume ratio) of diphenyl ether (DPE) at a weight ratio of 1:2 between the polymer prepared in Preparation Examples and Comparative Preparation Examples of the present invention described in Table 2 below and PC71BM (EM index). It was prepared by dissolving it in a xylene solvent and then filtering through a 0.45 μm (PTFE) syringe filter, and applying it on the PEIE layer to a thickness of 200 nm through a spin coating method (the process temperature is in the table below). 2 and Table 3). An organic photodiode was completed by depositing the obtained device structure on the photoactive layer in a thermal evaporator under a vacuum of 3 X 10 ^-6 torr, MoO ₃ having a thickness of 10 nm, and Ag electrode having a thickness of 100 nm as an uppermost electrode.

< Experimental example 1> Optical Characterization

Optical properties were analyzed for Comparative Example 1, Example 2, and Example 5 according to the present invention, and the results are shown in FIGS. 1 to 3.

< Experimental example 2> Analysis of dark current characteristics

Dark current characteristics were analyzed for Comparative Example 1 and Examples 1 to 6 according to the present invention, and the results are shown in FIGS. 4A to 4E and Table 3 below. Figure 4a shows current density-voltage, Figure 4b shows dark-JV, Figure 4c shows EQE, Figure 4d shows responsivity, and Figure 4e shows the detection rate of the polymer (PC ₇₁ BM blend films). .

Polymer Thickness [nm] Voc [V] Jsc [mA/cm ² ] FF [%] PCE [%] J _D @ -2V
[A/cm ² ] EQEmax
@λ [nm] Responsivity/R [A/W]

]Detectivity/
D* [Jones or cm

] comparative example
One 210 0.77 17.90
(17.52*) 66 9.29 7.27×10 ^-4 77.5%
@ 620 nm 0.3875 2.54×10 ¹⁰ Example 1 200 0.77 18.39 (18.73*) 69 9.87 1.42×10 ^-6 81.5%
@ 640 nm 0.4206 6.24×10 ¹¹ Example 2 210 0.78 18.41 (17.75*) 69 10.06 3.52×10 ^-7 78.7%
@ 620 nm 0.3935 1.17×10 ¹² Example 3 210 0.77 18.45 (17.78*) 66 9.48 4.81×10 ^-5 79.0%
@ 620 nm 0.3950 1.00×10 ¹¹ Example 4 200 0.77 17.11 (16.68*) 72 9.66 1.80×10 ^-9 77.1%
@ 560 nm 0.3481 1.45×10 ¹³ Example 5 200 0.77 16.61 (17.08*) 72 9.52 2.01×10 ^-9 77.1%
@ 640nm 0.3979 1.56×10 ¹³ Example 6 200 0.78 19.03 (18.48*) 70 10.47 2.24×10 ^-9 81.7%
@ 620 nm 0.4085 1.52×10 ¹³

Referring to Table 2, in Example 2 and Example 5, one and two OH groups were introduced, respectively, and it can be seen that the dark current is greatly reduced as the OH group is introduced. In addition, it was confirmed that the detectivity value greatly improved from 10 ¹⁰ to 10 ¹² and 10 ¹³ by reducing the dark current while maintaining EQE. In addition, a comparative experiment was conducted to see whether there was an effect of reducing the dark current in the organic photodiodes of Comparative Examples 2 to 9. performed.

The results are shown in Table 4.

Polymer Thickness [nm] J _D @ -2V
[A/cm ² ] EQEmax
@λ [nm] Responsivity/R [A/W]

)Detectivity/D* [Jones or cm

) comparative example
One 210 7.27×10 ^-4 77.5%
@ 640nm 0.3875 2.54×10 ¹⁰ Comparative Example 2 200 4.20×10 ^-4 81.5%
@ 640nm 0.403 3.50×10 ¹⁰ Comparative Example 3 210 5.24×10 ^-4 78.7%
@ 640nm 0.3413 3.2×10 ¹⁰ Comparative Example 4 210 8.01×10 ^-3 79.0%
@ 640nm 0.397 7.9×10 ⁹ Comparative Example 5 200 5.11×10 ^-4 77.1%
@ 640nm 0.413 3.3×10 ¹⁰ Comparative Example 6 200 9.2×10 ^-5 77.1%
@ 640nm 0.408 7.5×10 ¹⁰ Comparative Example 7 200 5.73×10 ^-5 81.7%
@ 640 nm 0.397 9.3×10 ¹⁰ comparative example
8 200 8.18×10 ^-3 77.1%
@ 640nm 0.387 7.7×10 ⁹ comparative example
9 200 4.37×10 ^-3
77.1%
@ 640 nm 0.423 1.1×10 ¹⁰ comparative example
10 200 9.66×10 ^-3 81.7%
@ 640 nm 0.387 7×10 ⁹

Looking at the above table, in the case of polymers of formulas 5, 6, and 7, even if -OH groups are introduced, when there is only thiophene without BT (benzothizole), a comparative example in which a polar group is not introduced due to deterioration in crystallinity and aggregation due to rotation of molecular bonds Compared to 1, it was confirmed that the dark current characteristics were not improved.

< Experimental example 3> Analysis of charge recombination properties and trap density

The charge recombination characteristics and trap density of Comparative Example 1, Example 2, and Example 5 according to the present invention were analyzed, and the results are shown in Table 4 below.

Polymer Hole Mobility
[cm ² /Vs] Hole Mobility
[cm ² /Vs] Electron Mobility
[cm ² /Vs] α β Gmanx
[#/ ^cm3.s ] P(E,T)
[%] Trap Density
[#/cm ³ ] Comparative Example 1 1.76×10 ^-4 1.34×10 ^-4 1.82×10 ^-3 0.9428 1.45 kT/q 5.89×10 ²⁷ 91.77 1.90×10 ¹⁵ Example 2 2.05×10 ^-4 2.09×10 ^-4 1.60×10 ^-3 0.9425 1.16 kT/q 5.75×10 ²⁷ 96.04 1.32×10 ¹⁵ Example 5 3.17×10 ^-4 2.16×10 ^-4 1.50×10 ^-3 0.9333 1.03 kT/q 5.36×10 ²⁷ 95.75 1.10×10 ¹⁵

Referring to Table 5, it can be seen that the charge β value decreases from 1.45 to 1.03 and the charge recombination decreases as the polar functional group is introduced. In addition, as the charge trap density between the electron transport layer and the photoactive layer decreased from 1.9 to 1.1, it was confirmed that charge recombination inside the photoactive layer and decrease in trap density at the interface caused the dark current to decrease.

< Experimental example 4> photostability analyze

For Comparative Example 1 and Examples 1 to 6 according to the present invention, light stability was analyzed after light irradiation for 1000 hours and 1 sun condition, and the results are shown in Table 5 below.

Polymer LS Time Voc [V] Jsc [mA/cm ² ] FF
[%] PCE
[%] % Drop in PCE J _D @ -2V
[A/cm ² ] EQEmax
@λ [nm] Responsivity/R [A/W]

)Detectivity/D*
[Jones or cm

) Comparative Example 1 × 0.76 17.90
(17.52*) 66 9.19 7.27×10 ^-4 77.5%
@620nm 0.3875 2.54×10 ¹⁰ √ 0.76 15.12
(14.60*) 49 5.71 ↓37.86% 1.14×10 ^-3 65.5%
@620nm 0.3275 1.71×10 ¹⁰ Example 1 × 0.77 18.39
(18.73*) 69 9.87 1.42×10 ^-6 81.5%
@640nm 0.4206 6.24×10 ¹¹ √ 0.77 16.27
(16.11*) 60 7.67 ↓22.28% 5.54×10 ^-6 71.2%
@640nm 0.3674 2.76×10 ¹¹ Example 2 × 0.78 18.41
(17.75*) 69 10.06 3.52×10 ^-7 78.7%
@620nm 0.3935 1.17×10 ¹² √ 0.76 15.56
(15.51*) 60 7.22 ↓28.23% 4.35×10 ^-6 69.5%
@620nm 0.3475 2.94×10 ¹¹ Example 3 × 0.77 18.45
(17.78*) 66 9.48 4.81×10 ^-5 79.0%
@620nm 0.3950 1.00×10 ¹¹ √ 0.76 15.80
(15.59*) 59 7.25 ↓23.52% 4.68×10 ^-4 70.6%
@620nm 0.3530 2.88×10 ¹⁰ Example 4 × 0.77 17.11
(16.68*) 72 9.66 1.80×10 ^-9 77.1%
@560nm 0.3481 1.45×10 ¹³ √ 0.77 14.64
(14.48*) 61 6.90 ↓28.57% 2.31×10 ^-8 67.5%
@560nm 0.3048 3.54×10 ¹² Example 5 × 0.77 16.61
(17.08*) 72 9.52 2.01×10 ^-9 77.1%
@640nm 0.3979 1.56×10 ¹³ √ 0.77 14.81
(14.44*) 62 7.16 ↓15.96% 6.51×10 ^-9 67.2%
@640nm 0.3468 7.59×10 ¹² Example 6 × 0.78 19.03
(18.48*) 70 10.47 2.24×10 ^-9 81.7%
@620nm 0.4085 1.52×10 ¹³ √ 0.77 16.13
(16.15*) 61 7.76 ↓25.88% 3.52×10 ^-8 72.5%
@620nm 0.3625 3.41×10 ¹²

Referring to Table 6, all of Comparative Example 1, Example 2, and Example 5 showed increased photostability with the introduction of OH, and in particular, in the case of Example 5, the dark current was maintained without increasing even after 1000 hours, resulting in a photodiode having high stability. was implemented.

Claims (13)

A photoactive layer for an organic photodiode comprising a polymer including a repeating unit represented by Formula 1 and a repeating unit represented by Formula 2:
[Formula 1]

[Formula 2]

Here, R ¹¹ , R ¹² and R ¹³ are each independently hydrogen or C1-C30 alkyl;
R ² and R ⁴ are each independently hydrogen or halogen;
Z is a sulfur element (S) or -C(R ³³ )=C(R ³⁴ )-,
R ³¹ , R ³² , R ³³ and R ³⁴ are each independently hydrogen or C1-C10 alkyl substituted with one or more hydroxy groups, but at least one is C1-C10 alkyl substituted with one or more hydroxy groups;
Each R ⁵ is independently hydrogen or C1-C30 alkyl.
According to claim 1,
R ¹¹ are each independently C1-C30 alkyl;
R ¹² and R ¹³ are each hydrogen;
R ² and R ⁴ are each independently halogen;
Z is a sulfur element (S) or -C(R ³³ )=C(R ³⁴ )-,
R ³¹ and R ³⁴ are each independently C1-C10 alkyl substituted with one or more hydroxyl groups;
R ³² and R ³³ are each hydrogen;
R ⁵ is hydrogen, a photoactive layer for an organic photodiode.
According to claim 1,
R ¹¹ are each independently C4-C30 alkyl;
R ¹² and R ¹³ are each hydrogen;
R ² and R ⁴ are each independently fluoro, chloro and bromo;
Z is a sulfur element (S) or -C(R ³³ )=C(R ³⁴ )-,
R ³¹ and R ³⁴ are each independently C1-C6alkyl substituted with 1 to 2 hydroxyl groups;
R ³² and R ³³ are each hydrogen;
R ⁵ is hydrogen, a photoactive layer for an organic photodiode.
According to claim 1,
R ¹¹ are each independently C8-C24 alkyl;
R ¹² and R ¹³ are each hydrogen;
R ² and R ⁴ are each fluoro;
Z is a sulfur element (S) or -C(R ³³ )=C(R ³⁴ )-,
R ³¹ and R ³⁴ are each independently C1-C4alkyl substituted with 1 hydroxyl group;
R ³² and R ³³ are each hydrogen;
R ⁵ is hydrogen, a photoactive layer for an organic photodiode.
According to claim 1,
R ¹¹ are each independently C14-C18 alkyl;
R ¹² and R ¹³ are each hydrogen;
R ² and R ⁴ are each fluoro;
Z is a sulfur element (S) or -C(R ³³ )=C(R ³⁴ )-,
R ³¹ and R ³³ are each independently C1-C4alkyl substituted with 1 hydroxyl group;
R ³² and R ³³ are each hydrogen;
R ⁵ is hydrogen, a photoactive layer for an organic photodiode.
According to claim 1,
R ¹¹ are each independently C14-C18 alkyl;
R ¹² and R ¹³ are each hydrogen;
R ² and R ⁴ are each fluoro;
Z is a sulfur element (S) or -C(R ³³ )=C(R ³⁴ )-,
R ³¹ and R ³³ are each independently C1-C4alkyl substituted with 1 hydroxyl group;
R ³² and R ³³ are each hydrogen;
R ⁵ is hydrogen, a photoactive layer for an organic photodiode.
An organic photodiode comprising the photoactive layer of claim 1.
7. The organic photodiode according to claim 6, wherein the photoactive layer further comprises fullerene or a fullerene derivative.
The organic photodiode according to claim 6, wherein the organic photodiode has a D ^* (Specific detectivity) value of 1x10 ¹¹ Jones or more when measured by further including PC71BM in the photoactive layer.
According to claim 6,
The organic photodiode may include a transparent electrode;
The photoactive layer of claim 1 laminated on the transparent electrode; and
an electrode on the photoactive layer; structure, an organic photodiode.
preparing a transparent electrode;
Laminating the photoactive layer of claim 1 on the transparent electrode; and
A method of manufacturing an organic photodiode comprising the step of stacking an electrode on the photoactive layer.
A photodetector comprising the organic photodiode of claim 6 .
An image sensor comprising the organic photodiode of claim 6 .

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