A low defect Ti x Zn 1-x O composite cathode interface material and its preparation method and application in organic photoelectric devices

Abstract

The present invention discloses a low defect Ti x Zn 1‑x The invention discloses a composite cathode interface material and a preparation method thereof and an application thereof in an organic photoelectric device; the invention provides a TZO precursor solution by sequentially adding zinc acetate, isopropyl titanate, ethanolamine and methoxyethyl ether, heating and stirring, and then spin coating the TZO precursor solution, annealing, and obtaining a low-defect Ti x Zn 1‑x O composite cathode interface material. The organic photoelectric device of the present invention comprises a cathode substrate, a cathode interface layer, a photoactive layer, an anode interface layer and an anode in sequence; the cathode interface layer is the low-defect Ti x Zn 1‑x O composite cathode interface material. The low defect Ti x Zn 1‑x The O composite interface material has a significantly reduced surface defect concentration. When used as a cathode interface, it inhibits the recombination of carriers, reduces the dark current of the device and improves the light response of the device, thereby significantly improving the performance of the prepared organic photoelectric device.

Description

Technical Field

[0001] The present invention belongs to the technical field of organic photoelectric devices and particularly relates to a low-defect Ti x Zn 1-x O composite cathode interface material and its preparation method and application in organic optoelectronic devices. Background Art

[0002] Organic optoelectronic devices have attracted extensive attention from researchers due to their light weight, low cost, and large-area flexible preparation. At present, the performance of organic optoelectronic devices has been continuously improved through molecular structure design and device structure optimization. For example, the efficiency of single-junction organic solar cells has exceeded 19%, and organic detectors also show advantages such as fast response speed and large linear dynamic range. Organic optoelectronic devices usually adopt a stacked structure, in which the photoactive layer is responsible for absorbing sunlight and dissociating photogenerated excitons into free carriers. However, for the generated free carriers, their collection efficiency is seriously affected by the interface contact between the active layer and the electrode. Usually, direct contact between organic materials and metal electrodes will produce interface barriers due to energy level mismatch, which is not conducive to charge transfer and collection, resulting in reduced device efficiency. Introducing a suitable interface layer between the active layer and the electrode is an effective strategy to solve this problem. Therefore, forming a high-quality interface layer through interface optimization is crucial to improving device performance.

[0003] ZnO is widely used as the cathode interface layer of organic optoelectronic devices due to its high transmittance, low work function, simple synthesis and low cost. However, ZnO synthesized by solution method usually has a large number of surface defects, which will act as recombination centers for photogenerated carriers, thus affecting the charge transport and extraction process. In order to eliminate and improve this problem, researchers have proposed several strategies, such as using self-assembled monolayers (Adv. Energy Mater. 2019, 9, 190999), small molecules (Adv. Funct. Mater. 2014, 24, 7014–7024) and polyelectrolytes (J. Mater. Chem. A, 2019, 7, 3570-3576) as surface modifiers and coating them on the ZnO surface. However, the introduction of the passivation layer will complicate the device preparation process and the layer is relatively thin (usually only a few nanometers or even less), which is not conducive to large-scale commercial production. Therefore, the development of cathode interface materials with excellent performance and suitable for large-scale production is crucial to the realization of efficient and stable organic optoelectronic devices. Summary of the invention

[0004] In view of the shortcomings of the prior art, the present invention provides a low-defect Ti x Zn 1-x O composite cathode interface material and its preparation method and application in organic optoelectronic devices.

[0005] The present invention provides a low defect Ti x Zn 1-x The invention discloses a method for preparing a composite interface material of TiO, and successfully applies it to organic solar cells, organic photodetectors and other devices prepared by a solution method. The prepared organic photoelectric devices show more excellent performance. The organic photoelectric device adopts an inverted structure, including a transparent bottom electrode, a cathode interface layer, an active layer, an anode interface layer and a top electrode. The cathode interface layer is Ti x Zn 1-x The TZO (TZO) film is prepared by the sol-gel method, and has the advantages of high film quality, simple process flow, low production energy consumption to meet the requirements of large-scale production, low annealing temperature to prepare flexible electronic devices, etc. In addition, the surface defect concentration of the TZO film prepared by the present invention is significantly reduced, the work function and the energy level of the active layer are more matched, and when used as a cathode interface layer, the recombination of carriers is effectively suppressed, the leakage current of the device is reduced, and a good ohmic contact is formed between the electrode and the active layer, which improves the efficiency of charge transfer and extraction, and finally realizes a high-efficiency organic photoelectric device.

[0006] In order to achieve the above-mentioned invention object, the following technical scheme is adopted:

[0007] A low defect Ti x Zn 1-x The preparation method of O composite cathode interface material comprises the following steps:

[0008] (1) adding zinc acetate, isopropyl titanate, ethanolamine and methoxyethyl ether in sequence, heating and stirring, to obtain a TZO precursor solution;

[0009] (2) Spin coating the TZO precursor solution of step (1), annealing, and obtaining a low-defect Ti x Zn 1-x O composite cathode interface material.

[0010] Preferably, the low-defect Ti x Zn 1-x The value of x in the O composite cathode interface material is 0.05 to 0.15.

[0011] Further preferably, the low-defect Ti x Zn 1-x The value of x in the O composite cathode interface material is 0.1.

[0012] Preferably, the zinc acetate in step (1) is zinc acetate dihydrate.

[0013] Preferably, the total concentration of zinc acetate and isopropyl titanate in the TZO precursor solution in step (1) is 0.3-0.5 mol / L;

[0014] Further preferably, the total concentration of zinc acetate and isopropyl titanate in the TZO precursor solution in step (1) is 0.45 mol / L;

[0015] Preferably, the molar ratio of zinc acetate to isopropyl titanate in step (1) is 0.95-0.85:0.05-0.15;

[0016] Further preferably, the molar ratio of zinc acetate to isopropyl titanate in step (1) is 0.9:0.1;

[0017] Preferably, the solubility of ethanolamine in the TZO precursor solution in step (1) is 25-35 mg / ml;

[0018] Preferably, the heating and stirring in step (1) is performed at a temperature of 50-60° C. for 8-12 h.

[0019] Further preferably, the time is 10h;

[0020] Preferably, the spin coating speed in step (2) is 2000-4000 rpm, and the time is 20-40 s;

[0021] Further preferably, the spin coating speed in step (2) is 3000 rpm and the time is 30 s;

[0022] Preferably, the annealing treatment in step (2) is performed at a temperature of 150-250° C. and for a time of 0.5-1.5 h.

[0023] Further preferably, the temperature of the annealing treatment in step (2) is 200° C. and the time is 1 hour.

[0024] The low-defect Ti prepared by the above preparation method x Zn 1-x O composite cathode interface material.

[0025] An organic photoelectric device, the organic photoelectric device comprises a cathode substrate, a cathode interface layer, a photoactive layer, an anode interface layer and an anode in sequence; the cathode interface layer is the low-defect Ti x Zn 1-x O composite cathode interface material.

[0026] Preferably, the thickness of the cathode interface layer is 30 nm.

[0027] Preferably, the cathode substrate is indium tin oxide glass (ITO), a transparent substrate material with good electrical conductivity.

[0028] Preferably, the polymer donor material of the photoactive layer is PM6:Y6, and the mass ratio of PM6 to Y6 is 1.2-1.6; the thickness of the photoactive layer is 100-200 nm;

[0029] Further preferably, the total concentration of PM6 and Y6 is 16-20 mg / ml, and the solvent is chloroform.

[0030] Preferably, the material of the anode interface layer is MoO 3 , the thickness of the anode interface layer is 6-10nm;

[0031] Preferably, the material of the anode is Ag or Al, and the thickness of the anode is 80-100 nm.

[0032] The method for preparing the organic optoelectronic device comprises the following steps:

[0033] (a) cleaning and drying the cathode substrate, and performing a surface plasma treatment on the cathode substrate;

[0034] (b) spin coating a cathode interface layer and a photoactive layer sequentially on the cathode substrate of step (a);

[0035] (c) Sequentially evaporating an anode interface layer and an anode to obtain an organic photoelectric device.

[0036] Preferably, the cleaning of the cathode substrate in step (a) comprises: adding detergent and deionized water to the cathode substrate and cleaning it once for 20 minutes; then, cleaning it with deionized water 4 times, each time for 15 minutes; and finally, cleaning it with isopropyl alcohol once for 20 minutes.

[0037] Preferably, the drying temperature in step (a) is 70° C. and the drying time is 12 hours; and the surface plasma treatment time is 1 minute.

[0038] Preferably, the preparation process of the photoactive layer in step (b) is: dissolving the photoactive layer material in a solvent and preparing it on the cathode interface layer by a dynamic spin coating method.

[0039] Preferably, the pressure range of the vapor-deposited anode interface layer and the anode in step (c) is 1x10 -4 to 4x10 -4 Pa.

[0040] The beneficial effects of the present invention are:

[0041] Ti in the present invention x Zn 1-xThe TZO composite material is prepared by the sol-gel method, which has the advantages of low cost, simple process flow, compatibility with large-scale industrial production, low preparation temperature, and compatibility with flexible substrates for preparation into flexible electronic devices compared to magnetron sputtering and atomic layer deposition. In addition, the prepared TZO film has a work function that is more matched with the active layer material, which is conducive to forming a good ohmic contact between the electrode and the active layer, and improving the charge transfer and extraction efficiency; in addition, compared with the ZnO film, the TZO film has a significantly reduced surface defect concentration, which inhibits the recombination of carriers when used as a cathode interface, reduces the dark current of the device and improves the light response of the device, thereby significantly improving the performance of the prepared organic optoelectronic device. Therefore, the TiO film of the present invention x Zn 1-x O cathode interface materials have a certain role in promoting the commercial development of organic optoelectronic devices. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 is a schematic diagram of the device structure of the organic photoelectric device of the present invention;

[0043] Figure 2 For the present invention Ti x Zn 1-x Preparation flow chart of organic optoelectronic devices with O composite materials as cathode interface layer;

[0044] Figure 3 Graph showing the relationship between current density and voltage of the devices of Example 2 (curve 2) and Comparative Example 1 (curve 1) under illumination conditions;

[0045] Figure 4 Graph showing the relationship between current density and voltage of the devices of Example 2 (curve 2) and Comparative Example 1 (curve 1) under dark conditions;

[0046] Figure 5 PL spectra of ZnO thin films of Comparative Example 1 (curve 1) and TZO thin films of Example 2 (curve 2);

[0047] Figure 6 O1s XPS spectra of ZnO thin films of Comparative Example 1 (curve 1) and TZO thin films of Example 2 (curve 2);

[0048] Among them, there are cathode substrate 01, cathode interface layer 02, photoactive layer 03, anode interface layer 04 and anode 05. DETAILED DESCRIPTION

[0049] The present invention is described in more detail below in conjunction with specific embodiments and drawings. The embodiments described herein are only intended to explain the present invention and are not intended to limit the present invention.

[0050] The present invention provides a low-defect TixZn1-xO composite interface material for an organic optoelectronic device and a preparation method thereof. The device structure is as follows: Figure 1 As shown, it includes a cathode substrate 01, a cathode interface layer 02, a photoactive layer 03, an anode interface layer 04 and an anode 05.

[0051] The above Ti x Zn 1-x Preparation technology of organic optoelectronic devices with O composite materials as cathode interface layer Figure 2 As shown, the following steps are included:

[0052] Step 1: Clean the ITO glass, and then perform surface plasma treatment on the cleaned and dried ITO glass;

[0053] Step 2: Spin-coat the cathode interface layer on the ITO glass treated in step 1, and the cathode interface layer is Ti x Zn 1-x O thin film, wherein x = 0.05 to 0.15;

[0054] Step 3: Spin coating an active layer on the cathode interface layer processed in step 2;

[0055] Step 4: sequentially evaporate an anode interface layer and an anode on the photoactive layer treated in step 3.

[0056] After completing the above steps, we get Ti x Zn 1-x O composite material as the cathode interface layer of organic optoelectronic devices.

[0057] Example 1

[0058] In this embodiment 1, Ti x Zn 1-x The structure of organic solar cell device with ITO / TiO composite material as cathode interface layer is as follows: x Zn 1-x O / PM6:Y6 / MoO 3 / Ag, where x = 0.05. The preparation process is as follows:

[0059] Step 1: Clean the ITO glass. First, place the ITO in a special cleaning basket, add detergent and deionized water to clean it once for about 20 minutes; then, clean it 4 times with deionized water, 15 minutes each time; finally, clean it once with isopropyl alcohol for about 20 minutes. After that, put the cleaned ITO glass in a 70℃ oven and dry it for at least 12 hours before use.

[0060] Step 2: Prepare TZO precursor solution in situ, weigh 0.19 g zinc acetate dihydrate, then add 16 μl isopropyl titanate, 56 μl ethanolamine and 2 ml methoxyethyl ether in sequence, heat and stir at 60°C for 10 h until the solution is completely clear and transparent.

[0061] Step 3: Plasma treat the cleaned ITO surface for 1 minute, then spin-coat the precursor solution in step 2 on the ITO at 3000 rpm for 30 seconds, and then anneal on a 200°C hot plate for 1 hour. The thickness of the cathode interface layer is about 30 nm.

[0062] Step 4: Spin-coat the active layer solution on the cathode interface layer at a speed of 3000 rpm, wherein the active layer material is PM6:Y6, the mass ratio is 1:1.2, the total concentration is 16 mg / ml, the solvent is chloroform, and the thickness is 100 nm.

[0063] Step 5: Move the above devices into the evaporation chamber and place them in a 4x10 -4 Pa pressure evaporation 10nm MoO 3 As the anode interface modification layer, 100nm of metal Ag was then evaporated as the anode top electrode.

[0064] Example 2

[0065] In this embodiment 1, Ti x Zn 1-x The structure of organic solar cell device with ITO / TiO composite material as cathode interface layer is as follows: x Zn 1-x O / PM6:Y6 / MoO 3 / Ag, where x = 0.1. The preparation process is as follows:

[0066] Step 1: Clean the ITO glass. First, place the ITO in a special cleaning basket, add detergent and deionized water to clean it once for about 20 minutes; then, clean it 4 times with deionized water, 15 minutes each time; finally, clean it once with isopropyl alcohol for about 20 minutes. After that, put the cleaned ITO glass in a 70℃ oven and dry it for at least 12 hours before use.

[0067] Step 2: In situ prepare Ti-doped ZnO precursor solution, weigh 0.18 g zinc acetate dihydrate, then add 32 μl titanium tetraisopropoxide, 56 μl ethanolamine and 2 ml methoxyethyl ether in sequence, heat and stir at 60°C for 10 h until the solution is completely clear and transparent for use.

[0068] Step 3: Plasma treat the cleaned ITO surface for 1 minute, then spin-coat the precursor solution in step 2 on the ITO at 3000 rpm for 30 seconds, and then anneal on a 200°C hot plate for 1 hour. The thickness of the cathode interface layer is about 30 nm.

[0069] Step 4: Spin-coat the active layer solution on the cathode interface layer at a speed of 3000 rpm, wherein the active layer material is PM6:Y6, the mass ratio is 1:1.2, the total concentration is 16 mg / ml, the solvent is chloroform, and the thickness is 100 nm.

[0070] Step 5: Move the above devices into the evaporation chamber and place them in a 4x10 -4 Pa pressure evaporation 10nm MoO 3 As the anode interface modification layer, 100nm of metal Ag was then evaporated as the anode top electrode.

[0071] Example 3

[0072] In this embodiment 1, Ti x Zn 1-x The structure of organic solar cell device with ITO / TiO composite material as cathode interface layer is as follows: x Zn 1-x O / PM6:Y6 / MoO 3 / Ag, where x = 0.15. The preparation process is as follows:

[0073] Step 1: Clean the ITO glass. First, place the ITO in a special cleaning basket, add detergent and deionized water to clean it once for about 20 minutes; then, clean it 4 times with deionized water, 15 minutes each time; finally, clean it once with isopropyl alcohol for about 20 minutes. After that, put the cleaned ITO glass in a 70℃ oven and dry it for at least 12 hours before use.

[0074] Step 2: Prepare Ti-doped ZnO precursor solution, weigh 0.17 g zinc acetate dihydrate, then add 48 μl titanium tetraisopropoxide, 56 μl ethanolamine and 2 ml methoxyethyl ether in sequence, heat and stir at 60°C for 10 h until the solution is completely clear and transparent.

[0075] Step 3: Plasma treat the cleaned ITO surface for 1 minute, then spin-coat the precursor solution in step 2 on the ITO at 3000 rpm for 30 seconds, and then anneal on a 200°C hot plate for 1 hour. The thickness of the cathode interface layer is about 30 nm.

[0076] Step 4: Spin-coat the active layer solution on the cathode interface layer at a speed of 3000 rpm, wherein the active layer material is PM6:Y6, the mass ratio is 1:1.2, the total concentration is 16 mg / ml, the solvent is chloroform, and the thickness is 100 nm.

[0077] Step 5: Move the above devices into the evaporation chamber and place them in a 4x10 -4 Pa pressure evaporation 10nm MoO 3 As the anode interface modification layer, 100nm of metal Ag was then evaporated as the anode top electrode.

[0078] Comparative Example 1

[0079] The preparation conditions of Comparative Example 1 are basically the same as those of Example 1, except that the cathode interface layer is ZnO, and the device structure is: ITO / ZnO / PM6:Y6 / MoO 3 / Ag. The preparation steps of the ZnO interface layer are as follows:

[0080] Step 1: Prepare ZnO precursor solution, weigh 0.2g zinc acetate dihydrate, then add 56μl ethanolamine and 2ml methoxyethyl ether, heat and stir at 60℃ for 10h until the solution is completely clear and transparent.

[0081] Step 2: Plasma treat the cleaned ITO surface for 1 minute, then spin-coat the precursor solution in step 1 on the ITO at 3000 rpm for 30 seconds, and then anneal on a 200°C hot plate for 1 hour. The thickness of the cathode interface layer is about 30 nm.

[0082] The performance parameters of Examples 1-3 and Comparative Example 1 are shown in Table 1. It can be seen that compared with pure ZnO devices, Ti x Zn 1-x O-based devices have improved in performance. 2 With the increase of TiO 2 As the value of Ti increases, the performance of the device begins to decline. 0.1 Zn 0.9 The open circuit voltage, short circuit current, fill factor and power conversion efficiency of the device with TiO as the cathode interface layer are improved most significantly. This may be because when the Ti content is low, the surface defect states in the ZnO film are suppressed; when the Ti content is too high, the generated TiO 2 This results in poor conductivity of the interface, reduced charge transfer capability, and decreased device performance.

[0083] Table 1 Device performance parameters of various embodiments and comparative examples

[0084]

[0085] Figure 3 and Figure 4 The current density and voltage relationship diagrams of Example 2 and the comparative example under light and dark conditions are shown respectively. Curve 1 represents the experimental data measured by the comparative example, and curve 2 represents the experimental data measured by Example 2. Figure 3 From Table 1, it can be seen that the open circuit voltage of the device with ZnO as the cathode interface layer in the comparative example is 0.830 V and the short circuit current is 25.80 mA / cm 2 The fill factor is 66.52%. The device with TZO as the cathode interface modification layer has an open circuit voltage of 0.839V and a short circuit current of 26.59mA / cm 2 , the fill factor is 70.09%. The relationship between the current density and voltage curve under dark conditions further proves the reason why the device performance of Example 1 and Comparative Example 1 is different. Figure 4 As shown in the figure, compared with the pure ZnO cathode interface layer, the reverse saturation current of the device with TZO as the cathode interface layer is greatly suppressed, while the forward output current of the two devices is basically the same, indicating that the TZO cathode interface layer has better charge selectivity and charge transport capability, thereby increasing the device efficiency from 14.28% to 15.64%.

[0086] Example 4

[0087] In this embodiment 1, Ti x Zn 1-x The device structure of the organic photodetector with ITO / TiO composite material as the cathode interface layer is: x Zn 1-x O / PM6:Y6 / MoO 3 / Al, where x = 0.1. The preparation process is as follows:

[0088] Step 1: Clean the ITO glass. First, place the ITO in a special cleaning basket, add detergent and deionized water to clean it once for about 20 minutes; then, clean it 4 times with deionized water, 15 minutes each time; finally, clean it once with isopropyl alcohol for about 20 minutes. After that, put the cleaned ITO glass in a 70℃ oven and dry it for at least 12 hours before use.

[0089] Step 2: Prepare Ti-doped ZnO precursor solution, weigh 0.18 g zinc acetate dihydrate, then add 32 μl titanium tetraisopropoxide, 56 μl ethanolamine and 2 ml methoxyethyl ether in sequence, heat and stir at 60°C for 10 h until the solution is completely clear and transparent.

[0090] Step 3: Plasma treat the cleaned ITO surface for 1 minute, then spin-coat the precursor solution in step 2 on the ITO at 3000 rpm for 30 seconds, and then anneal on a 200°C hot plate for 1 hour. The thickness of the cathode interface layer is about 30 nm.

[0091] Step 4: Spin-coat the active layer solution on the cathode interface layer at a speed of 3000 rpm, wherein the active layer material is PM6:Y6, the mass ratio is 1:1.2, the total concentration is 20 mg / ml, the solvent is chloroform, and the thickness is 200 nm.

[0092] Step 5: Move the above devices into the evaporation chamber and place them in a 4x10 -4 Pa pressure evaporation 10nm MoO 3 As the anode interface modification layer, 100nm of metal Al was then evaporated as the anode top electrode.

[0093] Comparative Example 2

[0094] The preparation conditions of Comparative Example 2 are basically the same as those of Example 4, except that the cathode interface layer is ZnO, and the device structure is: ITO / ZnO / PM6:Y6 / MoO 3 / Al. The preparation steps of the ZnO interface layer are the same as those of the aforementioned comparative example 1.

[0095] Table 2 Comparison of main parameters of Example 4 and Comparative Example 2

[0096]

[0097] The device characterization data of Example 4 and Comparative Example 2 are shown in Table 2, from which it can be seen that the organic photodetector using the TZO composite interface has a smaller dark current under negative bias and a larger rectification ratio. Compared with Comparative Example 2, the specific detection rate of Example 4 is improved by an order of magnitude. This shows that in addition to having a good device modification effect in organic solar cells, the TZO composite interface still has good performance in organic photodetectors.

[0098] Figure 5 For ZnO (curve 1) and Ti 0.1 Zn 0.9The PL spectrum of the TZO film (curve 2) shows that there are two emission peaks in the film, the first peak is in the ultraviolet region, and the second peak is in the visible light region. Among them, the luminescence peak in the ultraviolet region is mainly derived from the quenching process of near-band edge (NBE) photoexcitons, because the energy of this peak is almost equal to the band gap value of ZnO, and the wider luminescence peak at 530nm is believed to be mainly caused by the defect-assisted recombination in the ZnO crystal. From the PL spectrum, it can be seen that the luminescence peak intensity of the TZO film in the visible light region is significantly reduced, indicating that the defect concentration in the TZO film is significantly reduced.

[0099] Figure 6 For ZnO (curve 1) and Ti 0.1 Zn 0.9 O1s XPS spectrum of the original ZnO film (curve 2). Gaussian fitting of the O1s spectrum of the original ZnO can obtain two Gaussian component peaks located near the binding energy of 530.4eV and 531.8eV. The peak at the higher binding energy is formed by oxygen defects, and the peak at the lower binding energy comes from the lattice oxygen (Zn-O bond) in ZnO (Angew. Chem. 2022, 134, e202207397). Gaussian fitting of the O1s spectrum of TZO shows that in addition to the above two Gaussian component peaks, a new peak appears at the binding energy of 531.1eV, which can be attributed to TiO 2 In addition, it can be observed from the figure that compared with the ZnO film, the peak intensity of lattice oxygen in the TZO film increases, and the peak intensity of defect oxygen decreases. The ratios of defect oxygen to lattice oxygen before and after modification are calculated from the corresponding peak areas to be 0.98 and 0.71, respectively, indicating that the concentration of oxygen defects in TZO is significantly reduced, which is consistent with the results observed in the aforementioned PL spectrum.

[0100] It can be seen that the TZO film prepared by the sol-gel method has a lower surface defect state concentration. When it is used as a cathode interface layer, it can significantly reduce the carrier recombination inside the device, improve the charge transfer and extraction efficiency, and the organic photoelectric device exhibits higher performance.

[0101] The above embodiments are several implementation forms of the present invention and are described in more detail, but they should not be understood as limiting the scope of the present invention. For researchers engaged in this field, without departing from the main idea of ​​the design of the present invention, making several changes and improvements should all belong to the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on the attached claims.

Claims

1. An organic optoelectronic device, It is characterized in that The organic photoelectric device comprises a cathode substrate, a cathode interface layer, a photoactive layer, an anode interface layer and an anode in sequence; the cathode interface layer is a low-defect Ti x Zn 1-x O composite cathode interface material; the low defect Ti x Zn 1-x The value of x in the O composite cathode interface material is 0.1; The cathode substrate is indium tin oxide glass; The polymer donor material of the photoactive layer is PM6:Y6, and the mass ratio of PM6 to Y6 is 1.2-1.6; the thickness of the photoactive layer is 100-200 nm; The material of the anode interface layer is MoO 3 , the thickness of the anode interface layer is 6-10 nm; The material of the anode is Ag or Al, and the thickness of the anode is 80-100 nm; The low defect Ti x Zn 1-x The preparation method of O composite cathode interface material comprises the following steps: (1) adding zinc acetate, isopropyl titanate, ethanolamine and methoxyethyl ether in sequence, heating and stirring to obtain a TZO precursor solution; (2) Spin coating the TZO precursor solution in step (1), annealing, and obtaining a low-defect Ti x Zn 1-x O composite cathode interface material.

2. The organic optoelectronic device according to claim 1, It is characterized in that The total concentration of zinc acetate and isopropyl titanate in the TZO precursor solution of step (1) is 0.3-0.5 mol / L; In step (1), the molar ratio of zinc acetate to isopropyl titanate is 0.95-0.85:0.05-0.15; The solubility of ethanolamine in the TZO precursor solution in step (1) is 25-35 mg / ml; The heating and stirring in step (1) is performed at a temperature of 50-60°C and for a time of 8-12 h.

3. The organic optoelectronic device according to claim 1, It is characterized in that The spin coating speed in step (2) is 2000-4000 rpm and the time is 20-40 s; The annealing treatment in step (2) is performed at a temperature of 150-250° C. and for a time of 0.5-1.5 h.

4. The method for preparing the organic optoelectronic device according to any one of claims 1 to 3, It is characterized in that The following steps are involved: (a) cleaning and drying the cathode substrate, and performing a surface plasma treatment on the cathode substrate; (b) spin coating a cathode interface layer and a photoactive layer sequentially on the cathode substrate of step (a); (c) The anode interface layer and the anode are sequentially evaporated to obtain an organic photoelectric device.

5. The preparation method according to claim 4, It is characterized in that The cleaning of the cathode substrate in step (a) comprises: adding detergent and deionized water to the cathode substrate and cleaning it once for 20 minutes; then, cleaning it with deionized water 4 times, each time for 15 minutes; and finally, cleaning it with isopropyl alcohol once for 20 minutes; The drying temperature is 70° C. and the drying time is 12 hours; the surface plasma treatment time is 1 minute.

6. The preparation method according to claim 4, It is characterized in that The pressure range of the vapor-deposited anode interface layer and the anode in step (c) is 1x10 -4 to 4x10 -4 Pa.

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