CN101667623B - Organic photoelectric device and preparation method thereof - Google Patents

Abstract

the invention discloses an organic photoelectric device, comprising a substrate, a first electrode layer, a second electrode layer and a function layer arranged between the first electrode layer and the second electrode layer, wherein the first electrode layer or the second electrode layer is arranged on the surface of the substrate; the function layer comprises at least one layer of organic material layer relating to an organic polymer material with the function of transmitting electrons or separating excitons, thus improving electron mobility or exciton separating efficiency in devices and enhancing photoelectric or electro-optical conversion efficiency and service life of devices.

Description

A kind of organic optoelectronic device and preparation method thereof

technical field

The invention relates to the field of organic optoelectronic technology in electronic components, in particular to an organic optoelectronic device and a preparation method thereof.

Background technique

Organic optoelectronic devices can convert light energy into electrical energy or convert electrical energy into light energy. Including such as organic electroluminescence, organic solar cells and organic field effect tubes. Currently, a lot of research is being done on conductive polymer thin films in order to improve the efficiency of carrier transport and further optimize device performance.

Since the discovery of conductive acetylene by Japanese scientist Hideki Shirakawa in 1977, this conductive polymer material, known as the "fourth generation polymer material", has attracted the attention of many scientists for its outstanding photoelectric properties. Compared with inorganic materials with the same or similar applications, conductive polymers have the advantages of low density and easy processing. Due to the conjugation characteristics of this kind of material in structure, it can transport charge and stimulate light, so it can or may be used in many electronic or optoelectronic devices, such as light-emitting diodes, photovoltaic cells, field effect transistors and other fields. Potential application prospects and a wide range of application fields have prompted scientists to study this kind of conjugated polymer materials with photoelectric activity.

In general, the transport ability of holes in organic materials is much greater than that of electrons, and in general, the concentration of holes is much greater than that of electrons, and the recombination probability of electrons and holes is small. Therefore, a substantial increase in the electron concentration in the light-emitting layer of the OLED will effectively increase the recombination of electrons and holes, and effectively improve the efficiency of the device. This requires that the electron injection layer has a high electron injection ability, and the electron transport layer must also have a matching electron transport ability. In organic solar cells, materials with efficient electron transport capabilities can also effectively improve the energy conversion efficiency of devices. When the electron-hole pairs are separated at the interface between the donor material and the acceptor material, the electrons and holes must be transported to the electrode in time. If the material has poor carrier transport performance, the separated electrons and holes will be separated again Recombination, thereby reducing the effective separation efficiency of excitons. Electron transport materials are the main factors restricting the efficiency and lifetime of devices in materials, so the development of higher performance electron transport materials is currently the focus of many researchers.

Marco Mazzeo et al. developed an organic small molecule material, which is characterized in that the material can be prepared by a wet method, and the material has good electron injection and transport properties, and can be used in the light-emitting layer. The devices prepared by Marco showed high efficiency and outstanding photoelectric performance.

Contents of the invention

The problem to be solved by the present invention is: how to provide an organic optoelectronic device and its preparation method. The organic optoelectronic device uses a new type of organic polymer material to improve the electron mobility of the exciton dissociation inside the device and increase the electron mobility. The probability of recombination with holes improves the efficiency and life of the device.

The technical problem proposed by the present invention is solved in this way: provide an organic optoelectronic device, including a substrate, a first electrode layer and a second electrode layer, wherein the first electrode layer or the second electrode layer is located on the surface of the substrate, and also includes The functional layer arranged between the first electrode layer and the second electrode layer, the composition of the functional layer includes the following three situations: ① electron transport layer, light emitting layer, hole transport layer; ② electron donor layer, excitation layer sub-generation layer, exciton separation layer, electron acceptor layer; ③ insulating layer and organic semiconductor layer; it is characterized in that, electron transport layer or electron acceptor layer or exciton separation layer or organic semiconductor layer material is organic polymer material, The organic polymer material has good photoelectrochemical stability, and by introducing a group with an electron-absorbing function, the electron transport ability is effectively enhanced, thereby improving the efficiency and life of the device. The organic material has the chemical structure shown below:

Among them, R ₁ ~ R ₈ are substituent groups with the general formula -C _n H _2n+1 , R ₁₁ ~ R ₁₄ are substituent groups with the general formula -C _n H _2n+1 , R ₉ and R ₁₀ groups are the same or different, but they are all one or more of the following electron transport groups shown in (1) to (83):

Formula 1 Formula 2

Equation 3 Equation 4

Equation 5 Equation 6

Equation 7 Equation 8

Formula 9 Formula 10

Equation 11 Equation 12

Equation 13 Equation 14

Equation 15 Equation 16

Equation 17 Equation 18

Equation 19 Equation 20

Equation 21 Equation 22

Equation 23 Equation 24

Equation 25 Equation 26

Equation 27 Equation 28

Equation 29 Equation 30

Equation 31 Equation 32

Equation 33 Equation 34

Equation 35 Equation 36

Formula 37 Formula 38

Equation 39 Equation 40

Equation 41 Equation 42

Equation 43 Equation 44

Equation 45 Equation 46

Equation 47 Equation 48

Equation 49 Equation 50

Equation 51 Equation 52

Equation 53 Equation 54

Equation 55 Equation 56

Equation 57 Equation 58

Equation 59 Equation 60

Equation 61 Equation 62

Equation 63 Equation 64

Equation 65 Equation 66

Equation 67 Equation 68

Formula 69 Formula 70

Equation 71 Equation 72

Equation 73 Equation 74

Equation 75 Equation 76

Equation 77 Equation 78

Formula 79 Formula 80

Formula 81 Formula 82

Equation 83

Where R is C _1-30 alkyl, C _2-30 alkenyl, C _1-30 alkoxy, C _6-30 aryl, C _6-30 aryloxy, C _3-30 heteroaryl, C _{1 -30} heteroalkyl, X is O, S, or NR', R' is C _1-30 alkyl, C _6-30 aryl, C _3-30 heteroaryl, C _1-30 heteroalkyl or combination.

The organic optoelectronic device provided by the present invention is characterized in that the device is an organic electroluminescent device, an organic solar cell or an organic field effect tube.

According to the organic optoelectronic device provided by the present invention, it is characterized in that, when the device is an organic electroluminescent device and an organic solar cell, the substrate is glass or a flexible substrate or a metal sheet, wherein the flexible substrate is an ultra-thin glass , polyester or polyimide compound, the first electrode layer is metal oxide film or metal film or PEDOT:PSS or PANI organic conductive polymer, the metal oxide film is ITO film or zinc oxide film Or tin-zinc oxide film, the metal film is gold, copper, silver metal film with higher work function, the second electrode layer material is metal film or alloy film, the metal film is lithium or magnesium or calcium or strontium or aluminum Or metal films with low work functions such as indium or alloy films of them with copper or gold or silver.

According to the organic optoelectronic device provided by the present invention, it is characterized in that the device is an organic electroluminescent device and an organic solar cell, the material of the light-emitting layer or the material of the exciton generating layer is an organic polymer, and the organic polymer The molecular weight is 10,000-100,000, and it can be formed into a film by spin coating and inkjet printing, such as polyphenylene vinylene (PPV).

According to the organic optoelectronic device provided by the present invention, it is characterized in that the device is an organic electroluminescent device and an organic solar cell, and the material of the hole transport layer or the electron donor layer has a low highest occupied energy level (HOMO) energy grade organic polymers. The organic polymer compound is tri-[4-(5-phenyl-2-thienyl)phenyl]amine (PTDATA series), polyvinylcarbazole (PVK), poly 3,4-ethylenedioxythiophene (PEDOT ).

The organic optoelectronic device provided by the present invention is characterized in that the device is an organic solar cell, and the electron acceptor material has electron transport and exciton separation capabilities.

According to the organic optoelectronic device provided by the present invention, it is characterized in that the device is an organic field effect transistor, and the substrate is a rigid substrate or a flexible substrate, which is one of Si, ultra-thin glass, polymer film and metal foil. kind.

The organic optoelectronic device provided by the present invention is characterized in that the device is an organic field effect transistor, the material contained in the organic semiconductor layer is an organic polymer material, and the organic semiconductor layer can be prepared by spin coating or inkjet printing.

According to the organic optoelectronic device provided by the present invention, it is characterized in that the device is an organic field effect transistor, the first electrode layer is a grid, and its material is one of gold, silver, aluminum, nickel and indium tin oxide. The second electrode layer is a drain electrode and a source electrode, and its material is a metal or a conductive film, such as Al metal, Au metal, Cu metal, Cr metal, etc., or a conductive film with good physical properties and chemical properties such as indium tin oxide ( ITO) or zinc tin oxide (IZO), etc.

According to the organic optoelectronic device provided by the present invention, it is characterized in that the device is an organic field effect transistor, the material of the insulating layer is not particularly limited, and the insulating layer can be formed by an insulating film formed from the following materials: an inorganic insulating material such as silicon dioxide, Silicon nitride, oxygen-containing silicon dioxide, and oxygen-containing silicon nitride, organic insulating materials such as acrylic or polyimide, or materials composed of a skeleton structure formed by bonds between silicon and oxygen (which contain at least hydrogen Organic groups (such as alkyl or aromatic hydrocarbons), fluorinated groups, or organic groups containing at least hydrogen and fluorine groups are included as substituents), that is, siloxane-type materials.

A method for preparing an organic electroluminescent device and an organic solar cell, characterized in that it comprises the following steps:

①Use acetone, ethanol solution and deionized water to ultrasonically clean the substrate, and dry it with high-pressure nitrogen after cleaning;

②The substrate is prepared in a vacuum evaporation chamber for electrodes, and the electrodes include a first electrode layer or a second electrode layer;

③ Move the prepared electrode substrate into the vacuum chamber and perform pretreatment under the oxygen pressure environment;

④Put the treated substrate into a homogenizer, spin-coat the organic thin film in the homogenizer, and spin-coat the organic functional layers sequentially according to the device structure. The organic functional layers include a light-emitting layer or an exciton generating layer, Electron transport layer or electron acceptor layer, hole transport layer or electron donor layer, wherein the structural formula of electron acceptor layer material is:

⑤ After the spin coating of the organic layer is completed, another electrode is prepared in a high-vacuum evaporation chamber;

⑥Encapsulate the finished device in a glove box, and the glove box is a nitrogen atmosphere;

⑦Test the current-voltage-brightness characteristics and luminescence spectrum parameters of organic electroluminescent devices; test the current-voltage curves of organic solar cells under the conditions of no light and light.

A method for preparing an organic field effect tube is characterized by comprising the following steps: ① using a mixed solution of H ₂ SO ₄ : _{H 2} O ₂ =7:3, H ₂ O:NH ₃ =5:1 and ultrapure Clean the substrate ultrasonically with water, and dry it with high-pressure nitrogen after cleaning;

②Gate electrodes are prepared on the surface of the substrate by vacuum evaporation, spin coating or sputtering;

③ Etching the pattern of the gate electrode by photolithography;

④ Prepare an insulating layer on the surface of the substrate coated with a gate electrode by vacuum evaporation or spin coating or sputtering, and prepare an organic semiconductor layer by spin coating, wherein the structural formula of the organic semiconductor layer material is:

⑤Then prepare a source electrode and a drain electrode on the organic semiconductor layer by evaporation or spin coating or sputtering;

⑥ Form source electrode and drain electrode patterns by photolithography.

In the organic photoelectric device provided by the present invention, the organic material used is a high molecular polymer material, and the polymer material has better solubility, effectively prevents the generation of exciplexes and excimer associations in small molecule materials, and improves the Device efficiency, the material has good electron transport ability and exciton separation ability, and can be used as the exciton separation layer and electron transport layer in polymer solar cells or the electron injection layer or light emitting layer in organic electroluminescent devices. The organic material can be applied in an organic electroluminescent device, an organic solar cell or an organic field effect tube, and plays the role of an electron transport layer or a light emitting layer or a hole blocking layer or an exciton blocking layer in an organic electroluminescent device. Function, it plays the role of electron acceptor layer or exciton generation layer or exciton separation layer or exciton blocking layer in organic solar cells, and plays the role of n-type organic layer in organic field effect transistor. In addition, it can be prepared by wet method, which can effectively simplify the preparation process and control cost of organic photoelectric devices, and facilitate large-scale production. Through the design, assembly and tailoring of the structure of the electron transport material or electron acceptor material used, it can meet the requirements of organic electroluminescence. Devices, organic solar cells and organic field effect transistors have different demands on the material.

Description of drawings

Fig. 1 is the structural representation of organic electroluminescent device provided by the present invention;

Fig. 2 is a schematic structural view of an organic solar cell provided by the present invention;

Fig. 3 is the structural representation of organic field effect tube provided by the present invention;

Figure 4 is a schematic structural view of the electron transport or electron acceptor material provided by the present invention;

Figure 5 is a schematic structural view of Embodiments 1, 2, 3, and 4 provided by the present invention;

Figure 6 is a schematic structural view of Embodiment 5 provided by the present invention;

Figure 7 is a performance comparison diagram of Example 5 provided by the present invention: 7-1 is a device prepared by using a conventional acceptor material, 7-2 is a device prepared in Example 5, and the two devices have the same structure;

Fig. 8 is a schematic structural diagram of Embodiment 6 provided by the present invention.

Among them, 1. substrate, 2. anode layer, 3. organic functional layer, 31. hole transport layer, 32 light-emitting layer and electron transport layer, 4. cathode layer, 5. external power supply, 61. electron donor layer and Exciton generation layer, 62, electron acceptor layer, 7, cathode layer, 8, Si substrate, 9, gate electrode, 10, insulating layer, 11, organic semiconductor layer, 12, source electrode, 13, drain electrode.

Detailed ways

The present invention will be further described below in conjunction with accompanying drawing:

The technical solution of the present invention is to provide a kind of organic optoelectronic device with novel organic material as electron transport layer or electron acceptor layer or organic semiconductor layer, as shown in Figure 5, the structure of device comprises substrate 1, anode layer 2, organic Functional layer 3, cathode layer 4, wherein the anode layer 2 is located on the surface of the substrate 1, the organic functional layer 3 is located between the anode layer 2 and the cathode layer 4, the organic functional layer 3 may include a hole transport layer 31, a light-emitting layer and an electron transport layer layer 32 , the device emits light under the drive of an external power supply 5 . Fig. 1 is a schematic structural diagram of an organic electroluminescent device, Fig. 2 is a schematic structural diagram of an organic solar cell, and Fig. 3 is a schematic structural diagram of an organic field effect transistor.

As shown in Figure 6, the structure of the device includes a substrate 1, an anode layer 2, an organic functional layer 6, and a cathode 7, wherein the anode layer 2 is located on the surface of the substrate 1, and the organic functional layer 6 is located between the anode layer 2 and the cathode layer 7 , the organic functional layer 6 may include an electron donor layer 61 and an electron acceptor layer 62, and the electrodes of the device generate voltage under light.

As shown in FIG. 8 , the structure of the device includes a substrate 1 , a gate 2 , an insulating layer 3 , an organic semiconductor layer 4 , a source electrode 5 , and a drain electrode 6 .

In the organic electroluminescent device and the organic solar cell of the present invention, the substrate 1 is the support of the electrodes and the organic thin film layer, and it has good light transmission performance in the visible light region, has a certain ability of waterproofing and oxygen penetration, and has relatively Good surface smoothness, it can be glass or flexible substrate, flexible substrate adopts one of polyester, polyimide compound or thinner metal.

The anode layer 2 in the organic electroluminescent device and the organic solar cell of the present invention is used as the connecting layer for the forward voltage of the organic electroluminescent device, and it requires better electrical conductivity, visible light transparency and higher work function. Inorganic metal oxides (such as indium tin oxide ITO, zinc oxide ZnO, etc.), organic conductive polymers (such as PEDOT:PSS, PANI, etc.) or high work function metal materials (such as gold, copper, silver, platinum, etc.) are usually used.

Cathode layer 4 in the organic electroluminescence device among the present invention and cathode layer 7 in the organic solar cell are as the connecting layer of negative voltage of device, and it requires to have better electrical conductivity and lower work function, and cathode is usually low work function. Functional metal materials Lithium, magnesium, calcium, strontium, aluminum, indium and other metals with low work functions or their alloys with copper, gold, silver; or a very thin buffer insulating layer (such as LiF, _MgF2, etc.) and The previously raised metal or alloy.

The organic electroluminescent device and the organic solar cell in the present invention are inorganic or organic compounds with a low highest occupied energy level (HOMO) as the materials for the hole transport layer and the electron donor layer 31 . The compound may be copper phthalocyanine (CuPc), N, N'-bis-(3-methylphenyl)-N, N'-diphenyl-[1,1'-biphenyl]-4, 4'-diamine (TPD) or N,N'-bis(3-naphthyl)-N,N'-diphenyl-[1,1'-diphenyl]-4,4'-diamine ( NPB), the star-shaped triphenylamine compound can be three-[4-(5-phenyl-2-thienyl)phenyl]amine (PTDATA series), polyvinylcarbazole (PVK).

The material of the light-emitting layer 32 in the organic electroluminescent device and the exciton generating layer 62 in the organic solar cell in the present invention is a polymer material. The molecular weight of the polymer is 10,000-100,000, and it can be formed into a film by methods such as spin coating and inkjet printing, such as polyphenylene vinylene (PPV).

The substrate 1 in the organic field effect tube of the present invention is a rigid substrate or a flexible substrate, which is one of Si, ultra-thin glass, polymer film and metal foil.

The material of the gate 2 in the organic field effect transistor of the present invention is one of gold, silver, aluminum, nickel and indium tin oxide. The source electrode 5 and the drain electrode 6 are metal or conductive films, such as Al metal, Au metal, Cu metal, Cr metal, etc., or films with good physical and chemical properties such as indium tin oxide (ITO) or zinc tin oxide (IZO) and other conductive films.

The material of the insulating layer 3 in the organic field effect tube in the present invention is not particularly limited, and the insulating layer can be formed by an insulating film formed from the following materials: inorganic insulating materials such as silicon dioxide, silicon nitride, silicon dioxide containing oxygen , and oxygen-containing silicon nitride, organic insulating materials such as acrylic or polyimide, or materials composed of a skeleton structure formed by bonds between silicon and oxygen (organic groups containing at least hydrogen (such as alkyl or aromatic hydrocarbons), fluorinated groups, or organic groups containing at least hydrogen and fluorine groups are included as substituents), that is, siloxane-type materials.

The electron transport layer (32) or electron acceptor layer (62) material or organic semiconductor material in the present invention is a new type of organic material, and the material has good thermal stability and better ability to accept electrons, and at the same time Depression can effectively transfer electrons. Listed below are specific examples of the organic material of the present invention, but the present invention is not limited to these specific examples.

Formula 1 Material 1

Formula 2 Material 2

Formula 3 Material 3

Formula 4 Material 4

Formula 5 Material 5

Formula 6 Material 6

The structure of the organic photoelectric device prepared by the present invention is exemplified as follows:

Glass/ITO/luminescent layer/electron transport layer/electron injection layer/cathode layer

Glass/ITO/hole injection layer/hole transport layer/luminescent layer/cathode layer

Glass/ITO/hole transport layer/luminescent layer/electron transport layer/cathode layer

Glass/ITO/hole transport layer/luminescent layer/electron transport layer/electron injection layer/cathode layer

Glass/ITO/hole injection layer/hole transport layer/light emitting layer/electron transport layer/cathode layer

Glass/conductive polymer/hole transport layer/emissive layer/cathode layer

Glass/conductive polymer/emissive layer/electron transport layer/electron injection layer/cathode layer

Glass/conductive polymer/hole injection layer/hole transport layer/emissive layer/cathode layer

Glass/conductive polymer/hole transport layer/emissive layer/electron transport layer/cathode layer

Glass/conducting polymer/hole injection layer/hole transport layer/emissive layer/electron transport layer/cathode layer

Flexible substrate/ITO/hole transport layer/luminescent layer/electron transport layer/cathode layer

Flexible substrate/ITO/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode layer

Flexible substrate/ITO/hole transport layer/luminescent layer/electron transport layer/cathode layer

Flexible substrate/ITO/hole transport layer/light emitting layer/electron transport layer/electron injection layer/cathode layer

Glass/ITO/electron donor layer and exciton generation layer/electron acceptor layer/cathode layer

Example 1

As shown in FIG. 5 , the organic functional layer 3 in the structure of the device includes a hole injection layer 31 , a light emitting layer and an electron transport layer 32 .

The material of the hole transport layer of the device is PEDOT:PSS, the material of the light emitting layer and the electron transport material are material 1, and the cathode layer is made of Mg:Ag alloy. The entire device structure is described as:

Glass substrate/ITO/PEDOT:PSS(100nm)/Material 1(30nm)/Mg:Ag(100nm)

The preparation method is as follows:

①Use detergent, ethanol solution and deionized water to ultrasonically clean the transparent conductive substrate ITO glass, and dry it with dry nitrogen after cleaning. Wherein the ITO film on the glass substrate is used as the anode layer of the device, the square resistance of the ITO film is 10Ω/sq, and the film thickness is 180nm.

② Move the dried substrate into a vacuum chamber, and pretreat the ITO glass with low-energy oxygen plasma for 10 minutes under an oxygen pressure environment with an air pressure of 20Pa, and the sputtering power is ~20W.

③ Spin-coat the treated transparent substrate with an organic thin film in a spin-coater, and spin-coat organic functional layers sequentially according to the device structure, and the organic functional layers include a light-emitting layer, a carrier transport layer and (or) an injection layer and buffer layers.

④ After the evaporation of the organic layer is completed, the metal electrode is prepared. The gas pressure is 3×10 ^-3 Pa, the evaporation rate is ~1nm/s, the Mg:Ag ratio in the alloy is ~10:1, and the film thickness is 100nm. The evaporation rate and thickness are monitored by a film thickness meter installed near the substrate.

⑤Transfer the finished device to the glove box for packaging, and the glove box is 99.9% nitrogen atmosphere.

⑥Test the current-voltage-brightness characteristics of the device, and test the emission spectrum parameters of the device.

Example 2

As shown in FIG. 5 , the organic functional layer 3 in the structure of the device includes a hole injection layer 31 , a light emitting layer and an electron transport layer 32 .

The material of the hole transport layer of the device is PEDOT:PSS, the material of the light emitting layer and the electron transport material are material 2, and the cathode layer is made of Mg:Ag alloy. The entire device structure is described as:

Glass substrate/ITO/PEDOT:PSS(100nm)/Material 2(30nm)/Mg:Ag(100nm)

The fabrication process of the device is similar to that of Example 1.

Example 3

As shown in FIG. 5 , the organic functional layer 3 in the structure of the device includes a hole transport layer 31 , a light emitting layer and an electron transport layer 32 .

The material of the hole transport layer of the device is PEDOT:PSS, the material of the light emitting layer and the electron transport material are material 3, and the cathode layer is made of Mg:Ag alloy. The entire device structure is described as:

Glass substrate/ITO/PEDOT:PSS(100nm)/Material 3(15nm)/Mg:Ag(100nm)

The fabrication process of the device is similar to that of Example 1.

Example 4

As shown in FIG. 5 , the organic functional layer 3 in the structure of the device includes a hole transport layer 31 , a light emitting layer and an electron transport layer 32 .

The material of the hole transport layer of the device is PEDOT:PSS, the material of the light emitting layer and the electron transport material are material 4, and the cathode layer is made of Mg:Ag alloy. The entire device structure is described as:

Glass substrate/ITO/PEDOT:PSS(100nm)/Material 4(30nm)/Mg:Ag(100nm)

The fabrication process of the device is similar to that of Example 1.

Example 5

As shown in FIG. 6 , the organic functional layer 3 in the structure of the device includes an electron donor layer 61 , an electron acceptor layer and an exciton generating layer 62 .

The electron donor layer of the device is PEDOT:PSS, the electron acceptor layer material and exciton generation layer material is material 5, and the cathode layer is made of Ag alloy. The two device structures are the same, and the entire device structure is described as:

Glass substrate/ITO/PEDOT:PSS(100nm)/Material 5(30nm)/Ag(100nm)

Device Fabrication Process

①Use detergent, ethanol solution and deionized water to ultrasonically clean the transparent conductive substrate ITO glass, and dry it with dry nitrogen after cleaning. Wherein the ITO film on the glass substrate is used as the anode layer of the device, the square resistance of the ITO film is 10Ω/sq, and the film thickness is 180nm.

② Move the dried substrate into a vacuum chamber, and pretreat the ITO glass with low-energy oxygen plasma for 10 minutes under an oxygen pressure environment with an air pressure of 20Pa, and the sputtering power is ~20W.

③ Spin-coat the treated transparent substrate with an organic thin film in a spin-coater, and spin-coat organic functional layers sequentially according to the device structure, and the organic functional layers include a light-emitting layer, a carrier transport layer and (or) an injection layer and buffer layers.

④ After the evaporation of the organic layer is completed, the metal electrode is prepared. The gas pressure is 3×10 ^-3 Pa, the evaporation rate is ~1nm/s, and the film thickness is 100nm. The evaporation rate and thickness are monitored by a film thickness meter installed near the substrate.

⑤Transfer the finished device to the glove box for packaging, and the glove box is 99.9% nitrogen atmosphere.

⑥Test the current-voltage characteristics of the device, and test the absorption spectrum of the device.

See Figure 7 for performance comparison: 7-1 is a device prepared using conventional receptor materials, and 7-2 is a device prepared in this example.

Example 6

As shown in FIG. 8 , the structure of the device includes a substrate 1 , a gate electrode 2 , an insulating layer 3 , an organic semiconductor layer 4 , a source electrode 5 , and a drain electrode 6 .

The substrate of the device is Si, the gate is Au, the insulating layer is PVP, the material 6 for the organic semiconductor layer, and the source and drain electrodes are Au.

The preparation method is as follows:

①. Put the Si substrate into hot H ₂ SO ₄ : _{H 2} O ₂ (7: 3) and sonicate for 1 hour, and then wash it with ultrapure water;

②. After heating H ₂ O:NH ₃ (5:1) to 70°C, add 1 volume of H ₂ O ₂ , add the substrate and soak for 15 minutes, wash it with ultrapure water, and finally dry it with dry nitrogen;

③. On the surface of the Si substrate, the gate electrode Au is evaporated by vacuum evaporation or sputtering;

④. Etching the pattern of the gate electrode by photolithography;

⑤. On the other side of the Si plate coated with the gate electrode, the organic insulating layer PVP is spin-coated by spin-coating. The organic insulating layer PVP can be spin-coated into a film at one time, or it can be spin-coated on the Si substrate multiple times;

⑥. Put in the vacuum evaporation organic conductor film material 6, the air pressure is 3×10 ^-4 Pa, the evaporation rate is 0.1nm/s, and the evaporation rate and thickness are monitored by a film thickness meter installed near the substrate.

Then, Au is vapor-deposited on the organic semiconductor layer for the source electrode and the drain electrode. Source electrode and drain electrode patterns are formed by photolithography.

Claims (9)

1. An organic optoelectronic device, comprising a substrate, a first electrode layer and a second electrode layer, wherein the first electrode layer or the second electrode layer is located on the substrate surface, and also includes a substrate arranged on the first electrode layer and the second electrode layer The functional layer between the layers, the composition of the functional layer includes the following three situations: ① electron transport layer, light-emitting layer, hole transport layer; ② electron donor layer, exciton generation layer, exciton separation layer, electron acceptor layer 3. insulating layer and organic semiconductor layer; it is characterized in that, electron transport layer or electron acceptor layer or exciton separation layer or organic semiconductor layer material is organic polymer material, and the chemical structure of this organic polymer material is as follows: Among them, R ₁ ~ R ₈ are substituent groups with the general formula -C _n H _2n+1 , R ₁₁ ~ R ₁₄ are substituent groups with the general formula -C _n H _2n+1 , R ₉ and R The ₁₀ groups are the same or different, but they are all one or more of the electron-transporting groups shown in the following formulas 1 to 83:

Formula 1 Formula 2

Formula 3 Formula 4

Equation 5 Equation 6 Equation 7 Equation 8

Formula 9 Formula 10

Formula 11 Formula 12

Equation 13 Equation 14

Equation 15 Equation 16 Equation 17 Equation 18 Formula 19 Formula 20

Equation 21 Equation 22

Equation 23 Equation 24

Equation 25 Equation 26

Equation 27 Equation 28

Equation 29 Equation 30

Equation 31 Equation 32

Equation 33 Equation 34

Equation 35 Equation 36

Equation 37 Equation 38

Equation 39 Equation 40

Equation 41 Equation 42

Equation 43 Equation 44

Equation 45 Equation 46

Equation 47 Equation 48

Equation 49 Equation 50 Equation 51 Equation 52

Equation 53 Equation 54

Equation 55 Equation 56 Equation 57 Equation 58

Equation 59 Equation 60

Equation 61 Equation 62

Equation 63 Equation 64

Equation 65 Equation 66

Equation 67 Equation 68

Equation 69 Equation 70

Equation 71 Equation 72

Equation 73 Equation 74

Equation 75 Equation 76                        

Formula 77 Formula 78

Formula 79 Formula 80

Formula 81 Formula 82

Formula 83 Where R is C _1-30 alkyl, C _2-30 alkenyl, C _1-30 alkoxy, C _6-30 aryl, C _6-30 aryloxy, C _3-30 heteroaryl, C _{1 -30} heteroalkyl, X is O, S, or NR', R' is C _1-30 alkyl, C _6-30 aryl, C _3-30 heteroaryl, C _1-30 heteroalkyl or combination. 2. The organic optoelectronic device according to claim 1, characterized in that the device is an organic electroluminescence device, an organic solar cell or an organic field effect transistor. 3. The organic optoelectronic device according to claim 1 or 2, wherein when the device is an organic electroluminescent device and an organic solar cell, the substrate is glass or a flexible substrate or a metal sheet, wherein the flexible substrate The sheet is ultra-thin glass, polyester or polyimide compound, the first electrode layer is metal oxide film or metal film or PEDOT:PSS or PANI organic conductive polymer, the metal oxide film is ITO Film or zinc oxide film or tin zinc oxide film, the metal film is gold, copper, silver metal film, the second electrode layer material is metal film or alloy film, the metal film is lithium or magnesium or calcium or strontium or aluminum Or indium metal film or their alloy film with copper or gold or silver. 4. The organic optoelectronic device according to claim 1 or 2, wherein the device is an organic electroluminescence device and an organic solar cell, and the material of the light-emitting layer or the material of the exciton generating layer is an organic polymer, the The molecular weight of the organic polymer is 10,000-100,000. the 5. The organic optoelectronic device according to claim 1 or 2, wherein the device is an organic electroluminescence device and an organic solar cell, and the hole transport layer or electron donor layer material has a low highest occupied energy Level (HOMO) energy level organic polymers. The organic polymer compound is tri-[4-(5-phenyl-2-thienyl)phenyl]amine (PTDATA series), polyvinylcarbazole (PVK), poly 3,4-ethylenedioxythiophene (PEDOT ). 6. The organic optoelectronic device according to claim 1 or 2, wherein the device is an organic field effect transistor, and the substrate is a rigid substrate or a flexible substrate, which is Si, ultra-thin glass, polymer film and A type of metal foil. 7. The organic optoelectronic device according to claim 1 or 2, wherein the device is an organic field effect transistor, the first electrode layer is a gate, and its material is gold, silver, aluminum, nickel and indium tin oxide. The second electrode layer is a drain electrode and a source electrode, and its material is a conductive film. 8. A method for preparing an organic electroluminescent device and an organic solar cell, comprising the following steps: ①Use acetone, ethanol solution and deionized water to ultrasonically clean the substrate, and dry it with high-pressure nitrogen after cleaning; ②The substrate is prepared in a vacuum evaporation chamber for electrodes, and the electrodes include a first electrode layer or a second electrode layer; ③ Move the prepared electrode substrate into the vacuum chamber and perform pretreatment under the oxygen pressure environment; ④Put the treated substrate into a homogenizer, spin-coat the organic thin film in the homogenizer, and spin-coat the organic functional layers sequentially according to the device structure. The organic functional layers include a light-emitting layer or an exciton generating layer, Electron transport layer or electron acceptor layer, hole transport layer or electron donor layer, wherein the structural formula of electron acceptor layer material is:

⑤ After the spin coating of the organic layer is completed, another electrode layer is prepared in a high-vacuum evaporation chamber; ⑥Encapsulate the finished device in a glove box, and the glove box is a nitrogen atmosphere; ⑦Test the current-voltage-brightness characteristics and luminescence spectrum parameters of organic electroluminescent devices; test the current-voltage curves of organic solar cells under the conditions of no light and light. 9. A preparation method for an organic field effect tube, comprising the following steps: ①Use a mixed solution of H ₂ SO ₄ : _{H 2} O ₂ =7:3, H ₂ O:NH ₃ =5:1 and ultrapure water to ultrasonically clean the substrate, and dry it with high-pressure nitrogen after cleaning; ②Gate electrodes are prepared on the surface of the substrate by vacuum evaporation, spin coating or sputtering; ③ Etching the pattern of the gate electrode by photolithography; ④ Prepare an insulating layer on the surface of the substrate coated with a gate electrode by vacuum evaporation or spin coating or sputtering, and prepare an organic semiconductor layer by spin coating, wherein the structural formula of the organic semiconductor layer material is:

⑤Then prepare a source electrode and a drain electrode on the organic semiconductor layer by evaporation or spin coating or sputtering; ⑥ Form source electrode and drain electrode patterns by photolithography. the

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