Conjugated polymer materials and organic optoelectronic components using them

Abstract

An organic optoelectronic component, wherein the active layer comprises a conjugated polymer material with a structure of formula 1: wherein X 1 With X 2 Independently selected from one of the following groups: N, CH and -CR 1 A 2 and A 3 It is an electron-withdrawing group, and A 2 and A 3 Not at the same time as A 1 Same. D 1 D 2 and D 3 For electron-donating groups. sp 1 to sp 6 It is independently selected from aromatic and heteroaryl groups. a, b, and c are all real numbers, and 0

Description

Technical Field

[0001] This invention relates to a conjugated polymer material for use in organic optoelectronic components, and an organic optoelectronic component comprising this conjugated polymer material. Background Technology

[0002] Global warming has made climate change a common challenge facing the international community. The Kyoto Protocol, proposed by the Parties to the United Nations Framework Convention on Climate Change (UNFCCC) in 1997, officially came into effect in 2005, aiming to reduce carbon dioxide emissions. In response, countries have focused on developing renewable energy to reduce the use of fossil fuels. Among renewable energy sources, solar power generation has received significant attention because the sun provides far more than enough to meet current and future energy needs. Organic photovoltaic (OPV) modules, which convert sunlight into electricity, have become a primary development target in solar power technology.

[0003] In recent years, in addition to the application of organic photovoltaic (OPV), there has been an emerging application area of ​​organic photodetector (OPD).

[0004] In the application of organic solar cells, the current absorption wavelength range of solar cells is 320–900 nm. However, the absorption wavelength of current solar cells is mainly concentrated in the visible light range of 400–700 nm, and they do not have the ability to absorb infrared light exceeding 900 nm. In other words, a portion of photons in sunlight are still in the infrared region, which have not yet been utilized and converted into current or signals.

[0005] In the application of organic photodetectors, the adjustable absorption range of organic materials allows for effective absorption of specific wavelengths, achieving selective detection. Furthermore, the high extinction coefficient of organic materials significantly improves detection efficiency. In recent years, the development of organic photodetectors has expanded from ultraviolet (UV) and visible light to near-infrared (NIR). Therefore, the wavelength range required for detection by organic photodetectors is no longer limited to below 1000nm. For example, autonomous driving and drones require better penetration and long-distance detection, necessitating wavelengths exceeding 1000nm. Water absorbs light at 1350nm, allowing for the detection of moisture levels in food or medicine, preventing accidental ingestion and potential harm. Light above 1000nm has greater penetrating power in biological detection, improving image contrast. The good flexibility of organic photodetectors also facilitates the fabrication of wearable health sensors. Additionally, to reduce interference, the components must exhibit low dark current and high detectability.

[0006] As mentioned above, developing organic polymer materials with a wide absorption wavelength range (visible and near-infrared range) and adjustable absorption wavelength, allowing for adjustment of the absorption wavelength range according to the desired application, is a very important current research topic. Furthermore, considering future commercial applications and environmental friendliness, organic polymer materials also need to have good solubility in non-halogen solvents. Summary of the Invention

[0007] In view of this, one scope of the present invention is to provide a conjugated polymer material that achieves a wide absorption wavelength range (visible and near-infrared range) and has wavelength tuning properties. According to a specific embodiment of the present invention, the conjugated polymer material comprises a structure of formula one:

[0008]

[0009] in X 1 With X 2 They may be the same or different, and are independently selected from one of the following groups: N, CH, and -CR. 1 R 1 Selected from one of the following groups: halogens, -C(O)R x1 -CF2R x1 and -CN,R x1 Selected from one of the following groups: alkyl groups having C1 to C20 and haloalkyl groups having C1 to C20; A 2 and A 3may be the same or different electron-withdrawing groups, which are polycyclic structures containing at least one five-membered ring and at least one six-membered ring, or polycyclic structures of at least two five-membered rings, and A 2 and A 3 are not simultaneously the same as A 1 ; D 1 , D 2 and D 3 may be the same or different electron-donating groups from each other, and are independently selected from one of the following groups: aromatic groups with or without substituents, polycyclic aromatic groups with or without substituents, heteroaryl groups with or without substituents, and polycyclic heteroaryl groups with or without substituents; sp 1 to sp 6 may be the same or different from each other, and are independently selected from one of the following groups: aromatic groups with or without substituents, and heteroaryl groups with or without substituents; a, b, and c are all real numbers, and 0 < a ≤ 1, 0 ≤ b ≤ 1, 0 ≤ c ≤ 1, a + b + c = 1; and d, e, f, g, h, and i may be the same or different from each other, and are independently selected from one of 0, 1, and 2.

[0010] Among them, b and c are not simultaneously 0.

[0011] Among them, a is in the range of 0.1 to 0.9.

[0012] Among them, D 1 , D 2 and D 3 are independently selected from the following structures of polycyclic aromatic groups or polycyclic heteroaryl groups having 11 to 24 members:

[0013]

[0014] Among them, Ar 1 , Ar 2 and Ar 3 may be the same or different from each other, and are independently selected from one of the following groups: five-membered aromatic groups with or without substituents, five-membered heteroaryl groups with or without substituents, six-membered aromatic groups with or without substituents, and six-membered heteroaryl groups with or without substituents.

[0015] Among them, D 1 , D 2 and D 3 are independently selected from the following structures:

[0016]

[0017] Among them, R 2 and R3 They may be the same or different, and are independently selected from one of the following groups: H, F, R x2 -OR x2 -SR x2 -C(=O)R x2 -C(=O)-OR x2 and -S(=O)2R x2 And R x2 Selected from one of the following groups: C1-C30 alkyl groups having or not having substituents, wherein the substituent is independently selected from one of the following groups: O, S, aryl, and heteroaryl; and U 1 Selected from one of the following groups: CR 4 R 5 SiR 4 R 5 GeR 4 R 5 NR 4 And C=O, R 4 and R 5 It may be the same or different, and is independently selected from one of the following groups: C1 to C30 alkyl groups having or not having substituents, and the substituent is independently selected from one of the following groups: O, S, aromatic group and heteroaryl group.

[0018] Among them, A 2 and A 3 It is an electron-withdrawing group with or without substituents, and the structure of the electron-withdrawing group includes at least one of the following groups: S, N, Si, Se, C=O, CN and SO2.

[0019] Among them, A 2 and A 3 Independently selected from one of the following groups and their mirror structures:

[0020]

[0021] Among them, X 3 Selected from one of the following groups: S, Se, O, NR x3 and R x3 And R x3 Selected from one of the following groups: C1-C30 alkyl groups having or not having substituents, wherein the substituent is independently selected from one of the following groups: O, S, aryl, and heteroaryl; X 4 Selected from one of the following groups: S, Se, and O; and R 6 and R 7 They may be the same or different, and are independently selected from one of the following groups: H, F, R x4 -ORx4 -SR x4 -C(=O)R x4 -C(=O)-OR x4 and -S(=O)2R x4 And R x4 Selected from one of the following groups: C1 to C30 alkyl groups having or not having substituents, wherein the substituent is independently selected from one of the following groups: O, S, aromatic group and heteroaryl group.

[0022] Among them, A 2 and A 3 Independently selected from one of the following groups and their mirror structures:

[0023]

[0024] Among them, R x1 R 6 R 7 and R x3 Same as the definition above.

[0025] Among them, sp 1 to sp 6 Independently selected from one of the following groups:

[0026]

[0027] Among them, R 8 and R 9 They may be the same or different, and are independently selected from one of the following groups: H, F, R x5 -OR x5 -SR x5 -C(=O)R x5 -C(=O)-OR x5 and -S(=O)2R x5 And R x5 Selected from one of the following groups: C1 to C30 alkyl groups having or not having substituents, wherein the substituent is independently selected from one of the following groups: O, S, aromatic group and heteroaryl group.

[0028] Another aspect of this invention relates to providing an organic optoelectronic component comprising a first electrode, a first carrier transport layer, an active layer, a second carrier transport layer, and a second electrode. The first electrode is a transparent electrode. The active layer comprises at least one of the aforementioned conjugated polymer materials. The first carrier transport layer is located between the first electrode and the active layer, the active layer is located between the first carrier transport layer and the second carrier transport layer, and the second carrier transport layer is located between the active layer and the second electrode.

[0029] The first carrier transport layer is either an electron transport layer or a hole transport layer, while the second carrier transport layer is the other.

[0030] Compared to existing technologies, the organic optoelectronic components made from the conjugated polymer materials of this invention exhibit a wide absorption wavelength range. Furthermore, the absorption wavelength range of these organic optoelectronic components can be adjusted by modifying their band gap through structural adjustments, allowing for customization to suit specific applications. In other words, the organic optoelectronic components made from the conjugated polymer materials of this invention exhibit excellent absorption in the infrared region, along with low dark current and high detectability. Moreover, the conjugated polymer materials of this invention demonstrate good solubility in non-halogen solvents, leading to better commercial and environmentally friendly applications. Attached Figure Description

[0031] Figure 1 A schematic diagram illustrating a specific embodiment of the organic optoelectronic component of the present invention is shown.

[0032] Figure 2 The absorption spectra of a specific embodiment P1 of the conjugated polymer material of the present invention in solution and thin film states are shown.

[0033] Figure 3 The absorption spectra of a specific embodiment P2 of the conjugated polymer material of the present invention in solution and thin film states are shown.

[0034] Figure 4 The absorption spectra of specific embodiment P3 of the conjugated polymer material of the present invention in solution and thin film states are shown.

[0035] Figure 5 The absorption spectra of specific embodiment P4 of the conjugated polymer material of the present invention in solution and thin film states are shown.

[0036] Figure 6 The absorption spectra of specific embodiment P5 of the conjugated polymer material of the present invention in solution and thin film states are shown.

[0037] Figure 7 The absorption spectra of specific embodiment P6 of the conjugated polymer material of the present invention in solution and thin film states are shown.

[0038] Figure 8 The absorption spectra of specific embodiment P7 of the conjugated polymer material of the present invention in solution and thin film states are shown.

[0039] Figure 9 The absorption spectra of specific embodiment P8 of the conjugated polymer material of the present invention in solution and thin film states are shown.

[0040] Figure 10The diagram shows the energy level positions of specific embodiments P1 to P8 of the conjugated polymer material of the present invention.

[0041] Figure 11 The JV diagram of component P1, a specific embodiment of the organic optoelectronic component of the present invention, is shown.

[0042] Figure 12 The JV diagram of component P2, a specific embodiment of the organic optoelectronic component of the present invention, is shown.

[0043] Figure 13 The EQE test results of component P1, a specific embodiment of the organic optoelectronic component of the present invention, are shown.

[0044] Figure 14 The PCE error diagrams of P1 and P2 components, specific embodiments of the organic optoelectronic components of the present invention, are shown.

[0045] Figure 15 The JV diagram shows a specific embodiment of the organic optoelectronic component of the present invention, the P4 component (active layer thickness of 100 nm).

[0046] Figure 16 The JV diagram shows a specific embodiment of the organic optoelectronic component of the present invention, the P4 component (active layer thickness of 450 nm).

[0047] Figure 17 The EQE test results of the P4 module (active layer thickness of 100 nm), a specific embodiment of the organic optoelectronic module of the present invention, are shown.

[0048] Figure 18 The EQE test results of the P4 module (active layer thickness of 450 nm), a specific embodiment of the organic optoelectronic module of the present invention, are shown.

[0049] Figure 19 The JV diagram of component P7, a specific embodiment of the organic optoelectronic component of the present invention, is shown.

[0050] Figure 20 The EQE test results of component P7, a specific embodiment of the organic optoelectronic component of the present invention, are shown.

[0051] Figure 21 The JV diagram of component P8, a specific embodiment of the organic optoelectronic component of the present invention, is shown.

[0052] Figure 22 The EQE test results of the P8 component, a specific embodiment of the organic optoelectronic component of the present invention, are shown. Detailed Implementation

[0053] To make the advantages, spirit, and features of the present invention more readily and clearly understood, detailed descriptions and discussions will follow with reference to the accompanying drawings. It is important to note that these embodiments are merely representative examples of the present invention. However, they can be implemented in many different forms and are not limited to the embodiments described herein. Rather, these embodiments are provided to make the disclosure of the present invention more thorough and comprehensive.

[0054] The terminology used in the various embodiments disclosed herein is for the purpose of describing particular embodiments only and is not intended to limit the various embodiments disclosed herein. Singular forms used herein also include plural forms unless the context clearly indicates otherwise. Unless otherwise specified, all terms used in this specification (including technical and scientific terms) have the same meaning as commonly understood by one of ordinary skill in the art to which the various embodiments disclosed herein pertain. The foregoing terms (such as those defined in commonly used dictionaries) are to be interpreted as having the same meaning as in the context of the same technical field and are not to be interpreted as having an idealized or overly formal meaning unless clearly defined in the various embodiments disclosed herein.

[0055] In the description of this specification, references to terms such as "an embodiment," "a specific embodiment," etc., indicate that a specific feature, structure, material, or characteristic described in connection with that embodiment is included in at least one embodiment of the invention. In this specification, the illustrative expressions of the above terms do not necessarily refer to the same embodiment. Furthermore, the specific features, structures, materials, or characteristics described may be combined in any suitable manner in one or more embodiments.

[0056] definition:

[0057] As used herein, "donor" material refers to a semiconductor material, such as an organic semiconductor material, that possesses holes as primary current or charge carriers. In some embodiments, when a P-type semiconductor material is deposited on a substrate, it can provide more than about 10 -5 cm 2 / Vs hole mobility. In the case of field-effect components, P-type semiconductor materials can exhibit current on / off ratios exceeding approximately 10.

[0058] The term "acceptor" as used herein refers to a semiconductor material, such as an organic semiconductor material, which possesses electrons as the primary current or charge carriers. In some embodiments, when an N-type semiconductor material is deposited on a substrate, it can provide more than about 10 -5 cm 2 Electron mobility of / Vs. In the case of field-effect components, N-type semiconductor materials can exhibit current on / off ratios exceeding approximately 10.

[0059] As used in this article, "mobility" refers to the measurement of the rate at which charge carriers move through a material under the influence of an electric field, such as holes (positive charges) in P-type semiconductors and electrons (negative charges) in N-type semiconductors. This parameter depends on the architecture of the component and can be measured using field-effect components or space charge confinement current.

[0060] The compounds used in this article are considered "environmentally stable" or "stable under environmental conditions," meaning that when a transistor incorporating the compound as its semiconductor material is exposed to environmental conditions, such as air, ambient temperature, and humidity, for a period of time, the carrier mobility remains at its initial value. For example, a compound can be considered environmentally stable if, in a transistor incorporating the compound, after exposure to environmental conditions including air, humidity, and temperature for 3, 5, or 10 days, the change in carrier mobility does not exceed 20% or 10% of the initial value.

[0061] The fill factor (FF) used in this paper refers to the actual maximum achievable power (P). m or V mp *J mp The ratio of ) to theoretical (not practically available) power (J) sc *V oc Therefore, the fill factor can be determined by the following formula: FF = (V mp *J mp ) / (J sc *V oc ); where J mp and V mp These represent the points at maximum power (P) m The current density and voltage at this point are obtained by varying the resistance in the circuit until J*V reaches its maximum value; J sc and V oc These represent the short-circuit current density and open-circuit voltage, respectively. The fill factor is a key parameter for evaluating solar cells. Commercial solar cells typically have a fill factor of approximately 60% or higher. The open-circuit voltage (V) used in this paper... oc The potential difference between the anode and cathode of a component when no external load is connected.

[0062] The power conversion efficiency (PCE) of solar cells used in this article refers to the percentage of power converted from incident light into electrical energy. The PCE of a solar cell can be expressed as the maximum power point (P0). m Divide by the incident light irradiance (E; W / m²) under standard test conditions (STC). 2 ) and the surface area of ​​solar cells (A) c m 2 ) is calculated. STC usually refers to the temperature at 25℃ and the irradiance at 1000W / m². 2Air quality 1.5 (AM 1.5) spectrum.

[0063] The external quantum efficiency (EQE) used in this paper is calculated by converting the spectral response (Amp / Watt), the amperes (Amp) to electrons per second (electron / sec), and the watts (Watt) to photons per second (photons / sec), and then substituting these values ​​into the formula above. Generally, quantum efficiency (QE) refers to the external quantum efficiency (EQE), also known as the incident photon-electron conversion efficiency (IPCE).

[0064] The dark current used in this article (J) d (Also known as non-illuminated current), refers to the current flowing in an optoelectronic component in the absence of light.

[0065] The responsivity (R) and detectivity (D) used in this paper are calculated based on the measured dark current and external quantum efficiency (EQE) of the organic photosensitive sensor, using the following formulas:

[0066]

[0067] Where λ is the wavelength and q is the elementary charge (1.602 × 10⁻⁶). -19 Coulombs), where h is Planck's constant (6.626 × 10⁻⁶). -34 m 2 kg / s), c is the speed of light (3×10⁻⁶ kg / s), and c is the speed of light (3×10⁻⁶ kg / s). 8 m / sec), J D This represents the dark current density.

[0068] The components used in this article (such as thin film layers) that contain one or more compounds that can absorb photons to generate excitons for generating photocurrent can be considered "photoactive".

[0069] As used in this article, "solution processing" refers to processes in which compounds (e.g., polymers), materials, or components can be used in a solution state, such as spin coating, printing methods (e.g., inkjet printing, gravure printing, offset printing, etc.), spraying, electrospraying, drop casting, dip coating, and blade coating.

[0070] As used herein, "annealing" refers to the post-deposition heat treatment of a semi-crystalline polymer film for a certain duration in an environment or under reduced or increased pressure. "Annealing temperature" refers to the temperature at which small-scale molecular movement and rearrangement can occur in the polymer film or the mixed thin film of the polymer and other molecules during the annealing process. Without being bound by any specific theory, it is believed that annealing can, where possible, increase the crystallinity in the polymer film, enhance the material carrier mobility of the polymer film or the mixed thin film of the polymer and other molecules, and form a molecular interaction arrangement to achieve the effect of independent transfer paths for effective electrons and holes.

[0071] In a specific embodiment, the conjugated polymer material of the present invention comprises a structure of Formula I:

[0072]

[0073] Wherein X 1 and X 2 may be the same or different, and are independently selected from one of the following groups: N, CH, and -CR 1 , R 1 is selected from one of the following groups: halogen, -C(O)R x1 , -CF2R x1 and -CN, R x1 is selected from one of the following groups: alkyl having C1 to C20 and haloalkyl having C1 to C20; A 2 and A 3 may be the same or different electron-withdrawing groups, the electron-withdrawing group being a polycyclic structure containing at least one five-membered ring and at least one six-membered ring, or a polycyclic structure of at least two five-membered rings, and A 2 and A 3 are not simultaneously the same as A 1 ; D 1 , D 2 and D 3 may be the same or different electron-donating groups among each other, and are independently selected from one of the following groups: aromatic group with or without substituents, polycyclic aromatic group with or without substituents, heteroaryl group with or without substituents, and polycyclic heteroaryl group with or without substituents; sp 1 to sp 6 may be the same or different among each other, and are independently selected from one of the following groups: aromatic group with or without substituents, and heteroaryl group with or without substituents; a, b, and c are all real numbers, and 0 < a ≤ 1, 0 ≤ b ≤ 1, 0 ≤ c ≤ 1, a + b + c = 1; and d, e, f, g, h, and i may be the same or different among each other, and are independently selected from one of 0, 1, and 2.

[0074] The electron-withdrawing groups mentioned above are groups or atoms with a stronger electron-withdrawing ability than hydrogen, i.e., they exhibit an electron-withdrawing inductive effect; while electron-donating groups are groups or atoms with a stronger electron-donating ability than hydrogen, i.e., they exhibit an electron-donating inductive effect. The inductive effect is the effect of the bonding electron cloud shifting in a certain direction along the atomic bond due to the difference in polarity (electronegativity) of atoms or groups in the molecule. The electron cloud shifts towards the group or atom with stronger electronegativity.

[0075] It should be noted that the "*" or "*" in the structures listed in this specification represent the locations where the structures can be bonded, but are not limited thereto.

[0076] In one specific embodiment, D 1 D 2 and D 3 The following structures are independently selected from those having 11 to 24 members of a polycyclic aromatic group or a polycyclic heteroaryl group:

[0077]

[0078] Among them, Ar 1 Ar 2 and Ar 3 They may be the same or different from each other, and are independently selected from one of the following groups: five-membered aromatic groups with or without substituents, five-membered heteroaryl groups with or without substituents, six-membered aromatic groups with or without substituents, and six-membered heteroaryl groups with or without substituents.

[0079] In one specific embodiment, D 1 D 2 and D 3 Independently selected from the following structures:

[0080]

[0081] Among them, R 2 and R 3 They may be the same or different, and are independently selected from one of the following groups: H, F, R x2 -OR x2 -SR x2 -C(=O)R x2 -C(=O)-OR x2 and -S(=O)2R x2 And R x2 Selected from one of the following groups: C1-C30 alkyl groups having or not having substituents, wherein the substituent is independently selected from one of the following groups: O, S, aryl, and heteroaryl; and U 1 Selected from one of the following groups: CR 4R 5 SiR 4 R 5 GeR 4 R 5 NR 4 And C=O, R 4 and R 5 It may be the same or different, and is independently selected from one of the following groups: C1 to C30 alkyl groups having or not having substituents, and the substituent is independently selected from one of the following groups: O, S, aromatic group and heteroaryl group.

[0082] In one specific embodiment, A 2 and A 3 It is an electron-withdrawing group with or without substituents, and the structure of the electron-withdrawing group includes at least one of the following groups: S, N, Si, Se, C=O, CN and SO2.

[0083] In practical applications, A 2 and A 3 Independently selected from one of the following groups and their mirror structures:

[0084]

[0085] Among them, X 3 Selected from one of the following groups: S, Se, O, NR x3 and R x3 And R x3 Selected from one of the following groups: C1-C30 alkyl groups having or not having substituents, wherein the substituent is independently selected from one of the following groups: O, S, aryl, and heteroaryl; X 4 Selected from one of the following groups: S, Se, and O; and R 6 and R 7 They may be the same or different, and are independently selected from one of the following groups: H, F, R x4 -OR x4 -SR x4 -C(=O)R x4 -C(=O)-OR x4 and -S(=O)2R x4 And R x4 Selected from one of the following groups: C1 to C30 alkyl groups having or not having substituents, wherein the substituent is independently selected from one of the following groups: O, S, aromatic group and heteroaryl group.

[0086] Furthermore, A 2 and A 3 Independently selected from one of the following groups and their mirror structures:

[0087]

[0088] Among them, R x1 R 6 R 7 and R x3 Same as the definition above.

[0089] In one specific embodiment, sp 1 to sp 6 Independently selected from one of the following groups:

[0090]

[0091] Among them, R 8 and R 9 They may be the same or different, and are independently selected from one of the following groups: H, F, R x5 -OR x5 -SR x5 -C(=O)R x5 -C(=O)-OR x5 and -S(=O)2R x5 And R x5 Selected from one of the following groups: C1 to C30 alkyl groups having or not having substituents, wherein the substituent is independently selected from one of the following groups: O, S, aromatic group and heteroaryl group.

[0092] In practical applications, the conjugated polymer material of the present invention may contain the following structure:

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103] It should be understood that the embodiments listed above are only intended to give those skilled in the art a clearer understanding of the structural composition of the present invention, and are not intended to limit it.

[0104] In practical applications, when A 1 =A 2 =A 3 At this time, the organic optoelectronic components made from this conjugated polymer material have an absorption wavelength range limited to the visible light region. Therefore, the conjugated polymer material of this invention utilizes the adjustment of A... 2 and A 3 The structure is adjusted to change the bandgap of the material, thereby expanding the absorption wavelength range.

[0105] In one specific embodiment, b and c are not both 0. This is because when both b and c are 0, only the structure of part a remains, resulting in the organic optoelectronic component made from the conjugated polymer material having an absorption wavelength range limited to the visible light region. Therefore, in practical applications, in the structure of the conjugated polymer material of this invention, b and c are not both 0.

[0106] In one specific embodiment, 'a' is between 0.1 and 0.9. In practical applications, 'a' is between 0.3 and 0.9. In further applications, 'a' is between 0.3 and 0.6. Taking the above embodiments P1 to P28 as examples, when c = 0, 'a' is between 0.2 and 0.9. In further applications, 'a' is between 0.3 and 0.9, and may even be between 0.4 and 0.7. When 'a', 'b', and 'c' are all non-zero, 'a' is between 0.1 and 0.9. In further applications, 'a' is between 0.2 and 0.5. It should be noted that this invention relates to a conjugated polymer material, and the structure of Formula 1 is the smallest repeating unit of this conjugated polymer material. Therefore, the ratio of 'a', 'b', and 'c' is the equivalent ratio within the smallest repeating unit.

[0107] Please see Figure 1 , Figure 1 A schematic diagram illustrating the structure of a specific embodiment of the organic optoelectronic component 1 of the present invention is shown. Figure 1As shown, in another embodiment, the present invention further provides an organic optoelectronic component 1, which includes a first electrode 11, a second electrode 15, and an active layer 13. The active layer 13 is located between the first electrode 11 and the second electrode 15, wherein the active layer 13 includes the aforementioned conjugated polymer material of formula one. In this specific embodiment, the organic optoelectronic component 1 may be a stacked structure, sequentially including a substrate 10, a first electrode 11 (transparent electrode), a first carrier transport layer 12, an active layer 13, a second carrier transport layer 14, and a second electrode 15. The first carrier transport layer is either an electron transport layer or a hole transport layer, while the second carrier transport layer is the other. Specifically, when the first carrier transport layer is an electron transport layer, the second carrier transport layer is a hole transport layer, which is an inverse stacked structure; when the first carrier transport layer is a hole transport layer, the second carrier transport layer is an electron transport layer, which is a formal stacked structure. In practice, organic optoelectronic component 1 may include organic photovoltaic component, organic photosensing component, organic light-emitting diode and organic thin film transistor (OTFT).

[0108] To more clearly illustrate the conjugated polymer material of the present invention, eight specific embodiments P1 to P8 will be used as P-type materials for the active layer, and further prepared into organic optoelectronic components or organic photosensing components for experiments.

[0109] Preparation of the active layer:

[0110] Synthetic M3:

[0111]

[0112] Place M1 (20.0 g, 169 mmol) into a 250 mL three-necked reaction flask. Under nitrogen atmosphere, dissolve in 100 mL anhydrous THF and cool to below 15 °C. Slowly add n-BuLi (2.5 M in 45.0 mL hexane, 113 mmol) dropwise over approximately 30 minutes, until the solution turns pale orange and the temperature does not exceed 18 °C. Allow to cool to room temperature and stir for 1 hour. At 15 °C, add M2 (39.8 g, 113 mmol) dropwise. Allow to cool to room temperature and stir for 20 hours. Stop the reaction by adding 50 mL H2O. After removing the organic solvent by vacuum rotary evaporation, add 100 mL heptane and extract three times with 100 mL H2O. Remove the organic layer to remove water, and concentrate by vacuum rotary evaporation to obtain the crude product. Remove the starting material and impurities by vacuum distillation (0.25 torr, 170-200 °C). The residue was purified by column chromatography, and the extract was heptane. The main fraction was collected, the organic solvent was removed, and the product was dried under vacuum to give 16 g of pale yellow oil M3 (yield 41.3%). 1H NMR (500MHz, CDCl3) δ7.09 (d, J = 6.5 Hz, 1H), 6.85 (d, J = 6.5 Hz, 1H), 2.72 (d, J = 7.0 Hz, 2H), 1.68 (m, 1H), 1.27 (m, 24H), 0.88 (m, 6H).

[0113] Synthesize M5:

[0114]

[0115] Place M3 (19.7 g, 57 mmol) into a 500 mL three-necked reaction flask. Under nitrogen atmosphere, dissolve in 160 mL of anhydrous THF and cool to below 10 °C. Slowly add n-BuLi (2.5 M in hexane, 22.8 mL, 57 mmol) dropwise and stir for 1 hour. Place CuBr (cuprous bromide) (8.2 g, 57 mmol) and LiBr (lithium bromide) (5.0 g, 57 mmol) into a 250 mL three-necked reaction flask. Under nitrogen atmosphere, dissolve in 160 mL of anhydrous THF. At 10 °C, add the above reactants to the CuBr and LiBr solutions and stir for 1 hour. At 10 °C, add M4 (3.3 g, 25.9 mmol) to the above mixed solution. Return to room temperature and stir for 18 hours. Stop the reaction by adding 50 mL of H2O, remove the organic solvent by vacuum rotary evacuation, add 200 mL of heptane, and extract three times with 100 mL of H2O. The organic layer was dehydrated and concentrated under vacuum to remove the organic solvent, yielding a crude product. The crude product was purified by column chromatography with a heptane:DCM ratio of 4:1 as the eluent. The major product was collected, the organic solvent removed, and dried under vacuum to give 13.3 g of a yellow oil, M5 (yield: 71.5%). 1 H NMR (500MHz, CDCl3) δ7.88 (s, 2H), 2.80 (d, J = 7.0Hz, 4H), 1.76 (m, 2H), 1.29 (m, 48H), 0.88 (m, 12H).

[0116] Synthesize M8:

[0117]

[0118] Place M6 (2.0 g, 5.2 mmol) in a 250 mL double-necked reaction flask, add 60 mL of glacial acetic acid, and stir at room temperature. Add 5.8 g of iron powder under nitrogen. Heat to 120 °C and stir overnight. Cool the reaction to room temperature and add 150 g of ice water to stop the reaction. Filter the solid and wash with ice water, collecting the yellowish-brown solid. Dissolve the yellowish-brown solid in 150 mL of THF, and filter off the residual gray solid. Concentrate under vacuum to remove the organic solvent, and dry under vacuum to obtain 1.35 g of the greenish-brown crude product M7. Place M7 (1.3 g, 4.1 mmol) and M5 (2.7 g, 3.8 mmol) in a 250 mL single-necked reaction flask, add 60 mL of glacial acetic acid. Heat to 120 °C under nitrogen and stir overnight. Cool the reaction to room temperature and add 100 mL of H2O to stop the reaction. Extract three times with 100 mL of DCM, and collect the organic layer. Extract three times with 100 mL H2O to remove glacial acetic acid. Remove water from the organic layer and concentrate under vacuum to remove the organic solvent, yielding the crude product. Purify by column chromatography with a heptane:DCM ratio of 4:1 as the eluent. Collect the major product, remove the organic solvent, and dry under vacuum to give 2.4 g of bright red solid M8 (yield 61.6%). 1 H NMR (500MHz, CDCl3) δ7.45 (s, 2H), 2.83 (d, J = 7.0Hz, 4H), 1.83 (m, 2H), 1.30 (m, 48H), 0.89 (m, 12H).

[0119] Synthetic M10:

[0120]

[0121] M8 (2 g, 1.942 mmol) and M9 (1.60 g, 4.287 mmol) were placed in a 100 mL double-necked reaction flask, and 40 mL of THF was added. The mixture was deoxygenated under argon atmosphere for 15 minutes. Pd2(dba)3 (tris(dibenzylacetone)dipalladium) (0.071 g, 0.078 mmol) and P(o-tol)3 (tris(2-tolyl)phosphine) (0.095 g, 0.311 mmol) were added, and the mixture was heated to 66 °C and stirred for 2 hours. After cooling, the mixture was filtered through Celite (diatomaceous earth), washed with Heptane, and concentrated under vacuum to remove the organic solvent. The mixture was then subjected to column chromatography, with the eluent being Heptane:DCM = 9:1. The main product was collected and concentrated to give 1.81 g of a brown viscous liquid M10 (yield 90.1%). 1HNMR(600MHz, CDCl3) δ8.88(d,J=4.8Hz,2H),7.71(d,J=4.8Hz,2H),7.43(s,2H),7. 34(t,J=6.0Hz,2H),2.85(d,J=8.4Hz,4H),1.83(m,2H),1.30(m,48H),0.88(m,12H).

[0122] Synthetic M11:

[0123]

[0124] Place M10 (1.81 g, 1.75 mmol) into a 100 mL three-necked reaction flask. Under nitrogen atmosphere, add 107 mL of THF. Under ice bath conditions (<10 °C), add NBS (N-bromosuccinimide) (0.716 g, 4.023 mmol). Stir at room temperature for 18 hours. Remove the organic solvent by vacuum rotary evacuation. Perform column chromatography, using a heptane:DCM ratio of 19:1 as the eluent. Collect the main fraction and concentrate to give a dark brown viscous liquid M11, 1.88 g (yield 89.8%). 1 H NMR (600MHz, CDCl3) δ8.73 (d, J = 5.4 Hz, 2H), 7.38 (s, 2H), 7.21 (t, J = 4.8 Hz, 2H), 2.88 (d, J = 8.4 Hz, 4H), 1.87 (m, 2H), 1.29 (m, 48H), 0.85 (m, 12H).

[0125] Synthetic M14:

[0126]

[0127] M12 (1.0 g, 2.226 mmol) and M13 (2.4 g, 5.779 mmol) were placed in a 100 mL three-necked flask, and 45 mL of THF was added. The mixture was deoxygenated under argon atmosphere for 15 minutes. Pd2(dba)3 (0.082 g, 0.090 mmol) and P(o-tolyl)3 (0.108 g, 0.355 mmol) were added, and the mixture was heated to 66 °C and stirred for 2 hours. After cooling, the mixture was filtered through Celite, washed with Heptane, and the organic solution was concentrated under vacuum by rotary cyclohexane. The extract was then subjected to column chromatography, with a DCM / Hep ratio of 1 / 4. The main fraction was collected and concentrated to give 1.64 g of a dark blue solid, M14 (93.2% yield). 1H NMR (600MHz, CDCl3) δ8.69 (s, 2H), 7.23 (s, 2H), 4.91 (d, J = 7.2Hz, 2H), 2.76 (m,4H),2.38(s,1H),1.74(m,4H),1.38(m,2H),1.07(m,42H),0.89(m,12H).

[0128] Synthetic M15:

[0129]

[0130] Place 1.0 g (1.265 mmol) of M14 into a 100 mL three-necked reaction flask and add 45 mL of THF under nitrogen atmosphere. Cool to 10 °C and add NBS (0.450 g, 2.528 mmol). Stir at room temperature for 18 hours. Remove the organic solvent by vacuum rotary evacuation. Perform column chromatography, with a DCM / Hep ratio of 1 / 4. Collect the main fraction and concentrate to give 1.15 g of dark blue solid M15 (95.6% yield). 1 H NMR (600MHz, CDCl3) δ8.54(s,2H),4.95(m,2H),2.70(m,4H),2.38(s,1H),1.74(m,4H),1.38(m,2H),1.07(m,42H),0.88(m,12H).

[0131] Synthesize P1:

[0132]

[0133] Starting materials M16 (0.32 g, 0.27 mmol), M17 (0.066 g, 0.13 mmol), and M18 (0.10 g, 0.13 mmol) were placed in a double-necked flask, 30 mL of chlorobenzene was added, and the mixture was stirred for 30 minutes under argon protection. Pd₂(dba)₃ (0.0098 g, 0.011 mmol) and P(o-tol)₃ (0.013 g, 0.043 mmol) were added under argon protection. The mixture was heated overnight in an oil bath at 130 °C. After cooling to room temperature, the mixture was poured into methanol to precipitate. The polymer was purified by Soxhlet extraction, using methanol and dichloromethane successively. The purified solid was dissolved in chlorobenzene and then precipitated in methanol. After drying, 0.28 g of product (79.3% yield) was obtained.

[0134] Synthesis of P2:

[0135]

[0136]

[0137] Starting materials M16 (0.31 g, 0.26 mmol), M17 (0.065 g, 0.13 mmol), and M19 (0.12 g, 0.13 mmol) were placed in a double-necked flask, 30 mL of chlorobenzene was added, and argon gas was bubbled through the flask while stirring for 30 minutes. Under argon protection, Pd2(dba)3 (0.0096 g, 0.011 mmol) and P(o-tol)3 (0.013 g, 0.042 mmol) were added. The mixture was heated overnight in an oil bath at 130 °C. After cooling to room temperature, the mixture was poured into methanol to precipitate the product. The polymer was purified by Soxhlet extraction, using methanol and dichloromethane sequentially. The purified solid was dissolved in chlorobenzene and then precipitated in methanol. After drying the solid, 0.18 g of product (51.8% yield) was obtained.

[0138] Synthesize P3:

[0139]

[0140] Starting materials M16 (0.50 g, 0.42 mmol), M17 (0.062 g, 0.126 mmol), M20 (0.10 g, 0.126 mmol), and M18 (0.13 g, 0.17 mmol) were placed in a double-necked flask, 50 mL of chlorobenzene was added, and argon gas was bubbled through the flask while stirring for 30 minutes. Under argon protection, Pd2(dba)3 (0.015 g, 0.017 mmol) and P(o-tol)3 (0.020 g, 0.067 mmol) were added. The mixture was heated in an oil bath at 130 °C for 6 hours. After cooling to room temperature, the mixture was poured into methanol to precipitate the product. The polymer was purified by Soxhlet extraction, using methanol and dichloromethane sequentially. The purified solid was dissolved in chlorobenzene and then precipitated in methanol. After drying the solid, 0.48 g of product (yield 80.8%) was obtained.

[0141] Synthesize P4:

[0142]

[0143] Starting materials M21 (0.20 g, 0.17 mmol), M17 (0.043 g, 0.088 mmol), and M11 (0.10 g, 0.088 mmol) were placed in a double-necked flask, 20 mL of xylene was added, and the mixture was stirred for 30 minutes under argon protection. Pd2(dba)3 (0.0064 g, 0.007 mmol) and P(o-tol)3 (0.0085 g, 0.028 mmol) were added under argon protection. The mixture was heated overnight in an oil bath at 130 °C. After cooling to room temperature, the mixture was poured into methanol to precipitate the product. The polymer was purified by Soxhlet extraction, using methanol and dichloromethane sequentially. The purified solid was dissolved in chlorobenzene and then precipitated in methanol. After drying the solid, 0.147 g of product (56.6% yield) was obtained.

[0144] Synthesize P5:

[0145]

[0146] Starting materials M16 (0.20 g, 0.17 mmol), M17 (0.041 g, 0.084 mmol), and M11 (0.10 g, 0.084 mmol) were placed in a double-necked flask, 20 mL of chlorobenzene was added, and the mixture was stirred for 30 minutes under argon protection. Pd2(dba)3 (0.0062 g, 0.007 mmol) and P(o-tol)3 (0.0082 g, 0.027 mmol) were added under argon protection. The mixture was heated overnight in an oil bath at 130 °C. After cooling to room temperature, the mixture was poured into methanol to precipitate. The polymer was purified by Soxhlet extraction, using methanol and ethyl acetate successively. The purified solid was dissolved in chlorobenzene and then precipitated in methanol. After drying the solid, 0.22 g of product (84% yield) was obtained.

[0147] Synthesize P6:

[0148]

[0149]

[0150] Starting materials M22 (0.150 g, 0.24 mmol), M23 (0.128 g, 0.12 mmol), and M15 (0.115 g, 0.12 mmol) were placed in a double-necked flask, and 10.5 mL of chlorobenzene was added. Argon gas was bubbled through the flask and the mixture was stirred for 30 minutes. Under argon protection, Pd2(dba)3 (0.0022 g, 0.0024 mmol) and P(o-tol)3 (0.0030 g, 0.0097 mmol) were added. The mixture was heated in an oil bath at 130 °C for 13.5 minutes. After cooling to room temperature, the mixture was poured into methanol to precipitate the product. The polymer was purified by Soxhlet extraction, using methanol and dichloromethane sequentially. The purified solid was dissolved in chlorobenzene and then precipitated in methanol. After drying the solid, 0.176 g of product (64.1% yield) was obtained.

[0151] Synthesize P7:

[0152]

[0153] Starting materials M22 (0.150 g, 0.24 mmol), M23 (0.128 g, 0.12 mmol), and M11 (0.149 g, 0.12 mmol) were placed in a double-necked flask, and 10.5 mL of chlorobenzene was added. Argon gas was bubbled through the flask and the mixture was stirred for 30 minutes. Under argon protection, Pd2(dba)3 (0.0022 g, 0.0024 mmol) and P(o-tol)3 (0.0030 g, 0.0097 mmol) were added. The mixture was heated in an oil bath at 130 °C for 1 hour. After cooling to room temperature, the mixture was poured into methanol to precipitate the product. The polymer was purified by Soxhlet extraction, using methanol and dichloromethane sequentially. The purified solid was dissolved in chlorobenzene and then precipitated in methanol. After drying the solid, 0.158 g of product (51.9% yield) was obtained.

[0154] Synthesize P8:

[0155]

[0156] Starting materials M22 (0.150 g, 0.24 mmol), M23 (0.102 g, 0.10 mmol), M11 (0.149 g, 0.12 mmol), and M24 (0.022 g, 0.02 mmol) were placed in a double-necked flask, and 10.5 mL of chlorobenzene was added. Argon gas was bubbled through the flask and the mixture was stirred for 30 minutes. Under argon protection, Pd2(dba)3 (0.0022 g, 0.0024 mmol) and P(o-tol)3 (0.0030 g, 0.0097 mmol) were added. The mixture was heated in an oil bath at 130 °C for 16 minutes. After cooling to room temperature, the mixture was poured into methanol to precipitate the product. The polymer was purified by Soxhlet extraction, using methanol and dichloromethane sequentially. The purified solid was dissolved in chlorobenzene and then precipitated in methanol. After drying the solid, 0.256 g of product (85.0% yield) was obtained.

[0157] Material property testing of conjugated polymer materials P1 to P8:

[0158] Please see Figures 2 to 10 And Table 1, Figure 2 The absorption spectra of specific embodiment P1 of the conjugated polymer material of the present invention in solution and thin film states are shown. Figure 3 The absorption spectra of specific embodiment P2 of the conjugated polymer material of the present invention in solution and thin film states are shown. Figure 4 The absorption spectra of specific embodiment P3 of the conjugated polymer material of the present invention in solution and thin film states are shown. Figure 5 The absorption spectra of specific embodiment P4 of the conjugated polymer material of the present invention in solution and thin film states are shown. Figure 6 The absorption spectra of specific embodiment P5 of the conjugated polymer material of the present invention in solution and thin film states are shown. Figure 7 The absorption spectra of specific embodiment P6 of the conjugated polymer material of the present invention in solution and thin film states are shown. Figure 8 The absorption spectra of specific embodiment P7 of the conjugated polymer material of the present invention in solution and thin film states are shown. Figure 9 The absorption spectra of specific embodiment P8 of the conjugated polymer material of the present invention in solution and thin film states are shown. Figure 10 The diagram shows the energy level positions of specific embodiments P1 to P8 of the conjugated polymer material of the present invention. Table 1 shows... Figures 2 to 10 The data results.

[0159] Table 1: Figures 2 to 10 Data results

[0160]

[0161] Examples P1 to P8 used cyclic voltammetry to measure oxidation properties, and the results were calculated (HOMO = -|4.71+E). ox -E ferroncene The highest occupied molecular orbital (HOMO) is determined by |eV), and then the absorption onset position (λ) is obtained through the absorption spectrum of the material in thin film state. film onset From this, we can determine the optical bandgap (E) of the material. g =1241 / λ film onset eV) and the lowest unoccupied molecular orbital (LUMO, LUMO = HOMO + E). g eV). By Figures 2 to 9 The absorption spectrum clearly shows three patterns and absorption ranges: P1 to P3, P4 and P5, and P6 to P8. Figure 10 Furthermore, it can be observed that they can be categorized according to their bandgap size into wide bandgap P1 to P3, narrow bandgap P4 and P5, and ultra-narrow bandgap P6 to P8. Therefore, from Figure 10 It is quite clear that different A values ​​are introduced into the structure of Equation 1. 2 and A 3 The structure can effectively alter the material's bandgap and light absorption range, thus verifying the purpose of this invention: the conjugated polymer material can arbitrarily control the material's light absorption range. P1 to P3 can be applied to organic solar cells (OPVs) that require a wide bandgap, i.e., an absorption range primarily falling within the visible light region. P4 to P8, however, are used because they incorporate A molecules with different electron-withdrawing capabilities. 2 and A 3The structure alters the charge transfer effect of conjugated polymers, extending their absorption range to over 1000 nm. Therefore, P4 to P8 polymers can be applied to organic photosensitive devices (OPDs) requiring narrower band gaps, i.e., absorption ranges encompassing the visible and near-infrared regions. Figures 2 to 10 As can be seen from Table 1, conjugated polymer materials can be formulated according to different combinations of A... 2 and A 3 The structure allows for adjustment of the light absorption range from the visible to the near-infrared region, meaning its bandgap can vary from 1.76 to 0.74 eV. In other words, the conjugated polymer material of this invention allows for the design and control of its bandgap size to suit different applications. In other words, the bandgap of the conjugated polymer material of this invention is tunable, allowing for adjustments to appropriate bandgap specifications for different applications. Combined with corresponding N-type materials, it can be used to fabricate high-efficiency organic electronic components, such as high-efficiency OPVs or high-detectability OPDs, but not limited to these.

[0162] In practical applications, once the basic properties of the materials (i.e., the bandgap range) are known, the next step is to select suitable N-type materials to pair with these P-type materials and test the component's performance.

[0163] besides, Figures 2 to 9 The solution test showed that the material dissolved in o-xylene, thus demonstrating that the conjugated polymer material of the present invention can be coated using o-xylene. In this field, the use of non-halogenated green solvents is an industry trend. Green solvents are generally derived from renewable resources or can be degraded by soil organisms or other substances, have short half-lives, and easily decay into low-toxicity or non-toxic substances. Therefore, compared to general solvents that are easily chlorinated or highly toxic, green solvents generally pose less harm to biological health and the environment. Green solvents are also called environmentally friendly solvents. O-xylene is a non-halogenated green solvent.

[0164] Fabrication and testing of organic solar cells (OPV):

[0165] A pre-patterned indium tin oxide (ITO) coated glass with a sheet resistance of ~15 Ω / sq was used as the substrate. The substrate was sequentially ultrasonically treated in deionized water containing soap, acetone, and isopropanol, cleaning for 15 minutes in each step. The washed substrate was further treated with a UV-ozone cleaner for 30 minutes. A top coating of ZnO was spin-coated onto the ITO substrate at 5000 rpm for 30 seconds, and then baked in air at 120°C for 10 minutes to form the electron transport layer (ETL). An active layer solution was prepared in o-xylene. The active layer contained the aforementioned organic semiconductor material. To completely dissolve the active layer, the solution was stirred on a hot plate at 120°C for at least 1 hour. The active layer was then returned to room temperature for spin-coating. Finally, the film formed by the coated active layer was thermally annealed at 120°C for 5 minutes and then transferred to a thermal evaporation machine. (3 × 10⁻⁶) - 6 Under Torr vacuum, a thin layer (8 nm) of MoO3 was deposited as a hole transport layer (HTL), followed by the deposition of a 100 nm thick silver layer as the top electrode. All cells were encapsulated in epoxy resin within a glove box to fabricate an organic optoelectronic assembly (ITO / ETL / active layer / MoO3 / Ag). A solar simulator (a xenon lamp with an AM1.5G filter) was used in air and at room temperature at AM1.5G (100 mW cm⁻¹). -2 At 1000W / m 2 The JV characteristics of the component were measured under AM1.5G light intensity. The calibration cell used to calibrate the light intensity was a standard silicon diode with a KG5 filter, which was calibrated by a third party before use. The JV characteristics were recorded using a Keithley 2400 source meter. The P1 component was configured with a P1:N1:PC ratio. 61 BM = 1:1:0.2, at a concentration of 7 mg / mL, was prepared in o-xylene; the P2 component was prepared using P2:N2:PC. 61 The BM (Blank-Bulk Interchange) was prepared in o-xylene at a concentration of 14 mg / mL (1:1:0.2). The active layer thickness was approximately 100 nm, and the organic optoelectronic component had a structure of glass / ITO / ETL / ATL / MoO3 / Ag.

[0166] It should be noted that, in practical applications, the first electrode should ideally have good light transmittance. The first electrode is often made of a transparent conductive material, preferably one of the following groups of conductive materials: indium oxide, tin oxide, halogen-doped tin oxide derivatives (Florine Doped Tin Oxide, FTO), or composite metal oxides such as indium tin oxide (ITO) and indium zinc oxide (IZO). The second electrode is made of a conductive metal, preferably silver or aluminum, and more preferably silver. Suitable and preferred materials for ETL include, but are not limited to, metal oxides, such as ZnO. x Aluminum-doped ZnO (AZO) and TiO x Or its nanoparticles, salts (e.g., LiF, NaF, CsF, CsCO3), amines (e.g., primary, secondary, or tertiary amines), conjugated polymer electrolytes (e.g., polyethyleneimine), conjugated polymers (e.g., poly[3-(6-trimethylammonium hexyl)thiophene], poly(9,9)-bis(2-ethylhexyl-fluorene)-b-poly[3-(6-trimethylammonium hexyl)thiophene] or poly[(9,9-bis(3′-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)], and organic compounds (e.g., tris(8-quinolinyl)-aluminum(III)(Al) q3 (4,7-diphenyl-1,10-phenanthroline), or a combination of one or more of the above substances. Suitable and preferred materials for HTL include, but are not limited to, metal oxides, such as ZnO, MoO. x WO x NiO x Or its nanoparticles, conjugated polymer electrolytes such as PEDOT:PSS, polymeric acids such as polyacrylates, conjugated polymers such as polytriarylamine (PTAA), insulating polymers such as nanofeneral films, polyethyleneimine or polystyrene sulfonates, organic compounds such as N,N'-diphenyl-N,N'-bis(1-naphthyl)(1,1'-biphenyl)-4,4'-diamine (NPB), N,N'-diphenyl-N,N'-(3-methylphenyl)-1,1'-biphenyl-4,4'-diamine (TPD), or combinations of one or more of the above materials.

[0167] Among them, N1, N2 and PC 61 The structure of BM is as follows:

[0168]

[0169] Performance analysis of organic optoelectronic components:

[0170] Please see Figures 11 to 14 and Table 2, Figure 11 The JV diagram of component P1, a specific embodiment of the organic optoelectronic component of the present invention, is shown. Figure 12 The JV diagram of component P2, a specific embodiment of the organic optoelectronic component of the present invention, is shown. Figure 13 The EQE test results of component P1, a specific embodiment of the organic optoelectronic component of the present invention, are shown. Figure 14 Table 2 shows the PCE error diagrams of P1 and P2 components, specific embodiments of the organic optoelectronic module of the present invention. Table 2 shows the component efficiency test results of P1 and P2 components, specific embodiments of the organic optoelectronic module of the present invention.

[0171] Table 2. Component efficiency test results of P1 and P2 components in specific embodiments of the organic optoelectronic components of the present invention.

[0172]

[0173] As shown in Table 2, Figures 11 to 13 As shown, the conjugated polymer materials P1 and P2 of this invention are paired with acceptor materials N1 and PC. 61 The organic optoelectronic components fabricated by BM, namely components P1 and P2, both exhibit a power conversion efficiency (PCE) of over 15% when using halogen-free solvents. Because the conjugated polymer material of this invention possesses excellent photoelectric conversion efficiency and the component fabrication process does not use highly toxic halogen-containing solvents, it holds great potential for large-scale production applications. Furthermore, as... Figure 14 As shown, the errors between the P1 and P2 components in each test data are small. In other words, the test results are very similar each time, which indicates that the specific embodiments of the organic optoelectronic components of this invention, P1 and P2 components, have good material stability. This also means that the characteristics of the conjugated polymer material of this invention are conducive to obtaining good and stable film quality, thus making the organic optoelectronic component manufacturing process stable.

[0174] Fabrication and testing of organic photosensitive components (OPD):

[0175] A pre-patterned indium tin oxide (ITO) coated glass with a sheet resistance of ~15 Ω / sq was used as the substrate. The substrate was sequentially ultrasonically treated in deionized water containing soap, deionized water, acetone, and isopropanol, cleaning for 15 minutes in each step. The washed substrate was further treated with a UV-ozone cleaner for 30 minutes. A top coating of AZO (aluminum-doped zinc oxide) solution was applied to the ITO substrate at 3000 rpm for 40 seconds, followed by baking in air at 120°C for 5 minutes. An active layer solution was prepared in o-xylene. The active layer contained the aforementioned organic semiconductor material. To ensure complete dissolution of the active layer, the solution was stirred on a hot plate at 100°C for at least 1 hour. The active layer solution was then cooled to room temperature for spin coating. Finally, the film formed by the coated active layer was thermally annealed at 100°C for 5 minutes and then transferred to a thermal evaporation machine. The coating was applied at 3 × 10⁻⁶ ppm. -6 Under Torr vacuum conditions, a thin layer (8 nm) of MoO3 was deposited as a hole transport layer, followed by a 100 nm thick layer of silver as the top electrode. All cells were encapsulated in an epoxy resin box to fabricate an organic optoelectronic assembly (ITO / ETL / active layer / MoO3 / Ag). Keithley was used. TM The 2400 sourcemeter instrument recorded the dark current (ID) under no-light conditions, followed by the use of a sunlight simulator (a xenon lamp with an AM1.5G filter and a 100mW cm⁻¹ lamp). -2 The photocurrent (Iph) characteristics of the components were measured in air and at room temperature. A standard silicon diode with a KG5 filter was used as a reference cell to calibrate the light intensity, ensuring consistency in spectral mismatches. External quantum efficiency (EQE) was measured using an external quantum efficiency meter, with a measurement range of 300–1800 nm (bias voltage 0–-8 V). Light source calibration used silicon (300–1100 nm) and germanium (1100–1800 nm). The P4 component was prepared using a P4:N2 ratio of 1:1 at a concentration of 14 or 18 mg / mL in o-xylene; the P7 component was prepared using a P7:N2 ratio of 1:1 at a concentration of 10 mg / mL in o-xylene; and the P8 component was prepared using a P8:N2 ratio of 1:1 at a concentration of 12 mg / mL in o-xylene. The structure of the aforementioned organic photosensing component is glass / ITO / AZO / ATL / MoO3 / Ag.

[0176] Performance analysis of organic optoelectronic components:

[0177] When the organic optoelectronic component of this invention is applied in an organic photosensing component, the performance analysis mainly focuses on the external quantum efficiency (EQE) and dark current (J). d ) to conduct analysis.

[0178] Generally speaking, quantum efficiency (QE) refers to external quantum efficiency (EQE). Quantum efficiency / spectral response reflects the photoelectric conversion efficiency of an organic optoelectronic component at different wavelengths, that is, its ability to effectively convert photons into electrons when illuminated. The conversion efficiency of an organic optoelectronic component is affected by factors such as its materials, manufacturing process, and structure, resulting in different conversion efficiencies at different wavelengths. In organic photosensitive applications, a higher external quantum efficiency (EQE) indicates a better signal from the organic photosensitive sensor.

[0179] Dark current (J) d Dark current, also known as unlit current, refers to the current flowing in an optoelectronic component when there is no light exposure. In dark current testing, a bias voltage is applied to the organic optoelectronic component when it is not illuminated. In organic photosensitive applications, a larger dark current results in greater noise within the photosensitive component.

[0180] Please see Figures 15 to 18 and Table 3, Figure 15 The JV diagram shows a specific embodiment of the organic optoelectronic component of the present invention, the P4 component (active layer thickness of 100 nm). Figure 16 The JV diagram shows a specific embodiment of the organic optoelectronic component of the present invention, the P4 component (active layer thickness of 450 nm). Figure 17 The EQE test results of the P4 module (active layer thickness of 100 nm), a specific embodiment of the organic optoelectronic module of the present invention, are shown. Figure 18 The table shows the EQE test results of the P4 module (active layer thickness of 450nm) of the organic optoelectronic module of the present invention. Table 3 shows the module efficiency test results of the P4 module of the organic optoelectronic module of the present invention under different active layer thicknesses.

[0181] Table 3. Specific embodiments of the organic optoelectronic module of the present invention. P4 Module efficiency test results under different active layer thicknesses.

[0182]

[0183] As shown in Table 3, Figure 15 and Figure 16 As shown, the organic photosensitive module P4, fabricated by combining P4 and N2, exhibits good EQE values ​​in the 1050nm wavelength band, achieving a 20% EQE at -8V. Furthermore, increasing the active layer thickness from 100nm to 450nm effectively reduces the module's dark current to 3.2 × 10⁻⁶.-8 A / cm 2 This effectively reduces noise generated during detection. Detectability, calculated using a formula, can reach 10 across different active layer thicknesses. 11 The grade is evidence of good detection capability. For example... Figure 17 and Figure 18 As shown, the P4 component exhibits good EQE even at -8V, indicating that the organic optoelectronic component of this invention has a wide voltage tolerance range. Based on the above experimental results, the conjugated polymer material of this invention is not only soluble in non-halogen solvents (environmentally friendly solvents), but its light absorption range can also reach over 1000nm. Furthermore, the organic optoelectronic component prepared with this conjugated polymer material exhibits good EQE and dark current performance in both the visible and infrared regions.

[0184] Please see Figures 19 to 22 and Table 4, Figure 19 The JV diagram of component P7, a specific embodiment of the organic optoelectronic component of the present invention, is shown. Figure 20 The EQE test results of component P7, a specific embodiment of the organic optoelectronic component of the present invention, are shown. Figure 21 The JV diagram of component P8, a specific embodiment of the organic optoelectronic component of the present invention, is shown. Figure 22 The table shows the EQE test results of the P8 component, a specific embodiment of the organic optoelectronic component of the present invention. Table 4 shows the performance comparison of the P7 and P8 components, specific embodiments of the organic optoelectronic component of the present invention, with the prior art.

[0185] Table 4. Performance comparison of specific embodiments of the organic optoelectronic components of the present invention, P7 and P8, with existing technologies.

[0186]

[0187]

[0188] The structures of TQ-T, Y6, DPP, and DTT are as follows:

[0189]

[0190]

[0191] like Figures 19 to 22 As shown in Table 4, the organic optoelectronic components P7 and P8, fabricated using P7 and P8 respectively with N2 as the N-type material, have EQE values ​​of 5.4% and 8.7% at a wavelength of 1350 nm. The dark current reaches 10 at -2V. -6 The level reaches 10 at -4V. -5Level. The detection accuracy of P7 and P8 components, after conversion, is 2.2 × 10⁻⁶. 10 and 2.7×10 10 (Jones). It is evident that, compared to existing technologies, the P7 and P8 components exhibit superior performance, with significantly higher detectability, dark current, and EQE compared to prior art. The various embodiments of this invention demonstrate the versatility of its material variations, from the adjustment and control of material energy levels to applications in different downstream fields. The organic optoelectronic device of this invention extends the wavelength response range from the visible light region to the infrared region, overcoming the limitation of previous materials that could not simultaneously possess such a wide design range.

[0192] As shown in Table 4, Small 2022,2200580 uses a non-fullerene acceptor Y6 combined with TQ-T as the P-type material to fabricate OPD modules. Compared with the previous work, the P7 and P8 modules of this invention have EQE and dark current results that are more than 10 times higher, and the detectivity is more than 100 times higher. This shows that although the Y6 structure of the previous work is similar to the N-type structure used in this invention, the difference in P-type material results in a significant difference in module efficiency. While another previous work, Adv. Sci. 2020,7,2000444, also uses a non-fullerene acceptor combined with DPP as the P-type material, the dark current and detectivity of the P7 and P8 modules of this invention are significantly better than those of the previous work.

[0193] Based on the above experimental results, the conjugated polymer material of this invention is not only soluble in non-halogen solvents (environmentally friendly solvents), but it can also be adjusted according to A. 2 and A 3 The structure of conjugated polymer materials is adjusted to change the band gap size, thereby adjusting their absorption characteristics and spectral appearance.

[0194] It should be noted that, unless otherwise specified, the substituents in the above specification are independently selected from one of the following groups: C1-C30 alkyl groups, C3-C30 branched alkyl groups, C1-C30 silyl groups, C2-C30 ester groups, C1-C30 alkoxy groups, C1-C30 alkylthio groups, C1-C30 haloalkyl groups, C2-C30 alkenes, C2-C30 alkynes, C2-C30 carbon chains containing cyano groups, C1-C30 carbon chains containing nitro groups, C1-C30 carbon chains containing hydroxyl groups, C3-C30 carbon chains containing ketone groups, halogens, cyano groups, and hydrogen atoms.

[0195] The detailed description of the specific embodiments above is intended to more clearly illustrate the features and spirit of the present invention, and is not intended to limit the scope of the invention to the specific embodiments disclosed above. Rather, the aim is to cover various modifications and equivalent arrangements within the scope of the patent claims made by the present invention.

[0196] Symbol Explanation

[0197] 1: Organic optoelectronic components

[0198] 10: Substrate

[0199] 11: First electrode

[0200] 12: First Carrier Transfer Layer

[0201] 13: Active Layer

[0202] 14: Second Carrier Transfer Layer

[0203] 15: Second electrode

Claims

1. A conjugated polymer material having a constituent formula-1 structure: (Formula 1) in ; Where X 1 With X 2 They may be the same or different, and are independently selected from one of the following groups: CH and -CR 1 R 1 Selected from one of the following groups: halogens, -C(O)R x1 -CF2R x1 and -CN,R x1 Selected from one of the following groups: alkyl groups having C1 to C20 and haloalkyl groups having C1 to C20; A 2 and A 3 Independently selected from one of the following groups and their mirror structures: in, X 3 Selected from one of the following groups: S, Se, O; X 4 Selected from one of the following groups: S, Se, and O; and R 6 and R 7 They may be the same or different, and are independently selected from one of the following groups: H, F, R x4 -OR x4 -SR x4 -C(=O)R x4 -C(=O)-OR x4 and -S(=O)2R x4 And R x4 Selected from one of the following groups: C1 to C30 alkyl groups having or not having substituents, wherein the substituent is independently selected from one of the following groups: O, S, aromatic group and heteroaryl group; D 1 D 2 and D 3 They may be the same or different electron-donating groups and are independently selected from one of the following groups: aromatic groups with or without substituents, polycyclic aromatic groups with or without substituents, heteroaryl groups with or without substituents, and polycyclic heteroaryl groups with or without substituents. sp 1 to sp 6 They may be the same or different from each other, and are independently selected from one of the following groups: aromatic groups with or without substituents, and heteroaryl groups with or without substituents; a, b, and c are all real numbers, and d, e, f, g, h, and i are all 1.

2. The conjugated polymer material as described in claim 1, wherein a is in the range of 0.1 to 0.

9.

7. An organic optoelectronic component, comprising:

3. The conjugated polymer material as described in claim 1, wherein D 1 D 2 and D 3 The following structures are independently selected from those having 11 to 24 members of a polycyclic aromatic group or a polycyclic heteroaryl group: in, Ar 1 Ar 2 and Ar 3 They may be the same or different from each other, and are independently selected from one of the following groups: five-membered aromatic groups with or without substituents, five-membered heteroaryl groups with or without substituents, six-membered aromatic groups with or without substituents, and six-membered heteroaryl groups with or without substituents.

4. The conjugated polymer material as described in claim 3, wherein D 1 D 2 and D 3 Independently selected from the following structures: in, R 2 and R 3 They may be the same or different, and are independently selected from one of the following groups: H, F, R x2 -OR x2 -SR x2 -C(=O)R x2 -C(=O)-OR x2 and -S(=O)2R x2 And R x2 Selected from one of the following groups: C1-C30 alkyl groups having or not having substituents, wherein the substituent is independently selected from one of the following groups: O, S, aryl, and heteroaryl; and U 1 Selected from one of the following groups: CR 4 R 5 SiR 4 R 5 GeR 4 R 5 NR 4 And C=O, R 4 and R 5 It may be the same or different, and is independently selected from one of the following groups: C1 to C30 alkyl groups having or not having substituents, and the substituent is independently selected from one of the following groups: O, S, aromatic group and heteroaryl group.

5. The conjugated polymer material as described in claim 1, wherein A 2 and A 3 Independently selected from one of the following groups and their mirror structures: in, R 6 R 7 Same as the definition in claim 1.

6. The conjugated polymer material as described in claim 1, wherein sp 1 to sp 6 Independently selected from one of the following groups: in, R 8 and R 9 They may be the same or different, and are independently selected from one of the following groups: H, F, R x5 -OR x5 -SR x5 -C(=O)R x5 -C(=O)-OR x5 and -S(=O)2R x5 And R x5 Selected from one of the following groups: C1 to C30 alkyl groups having or not having substituents, wherein the substituent is independently selected from one of the following groups: O, S, aromatic group and heteroaryl group. The first electrode includes a transparent electrode; First carrier transfer layer; The active layer comprises at least one conjugated polymer material as described in claim 1; Second carrier transport layer; and The second electrode, wherein the first carrier transport layer is located between the first electrode and the active layer, the active layer is located between the first carrier transport layer and the second carrier transport layer, and the second carrier transport layer is located between the active layer and the second electrode. ​

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