CN115636923A - Polymer containing triazole structure, preparation method thereof and light-emitting device - Google Patents

Abstract

The application provides a polymer containing a triazole structure, a preparation method thereof and a light-emitting device, wherein the polymer containing the triazole structure is a cross-linked polymer containing the triazole structure, the polymer containing the triazole structure has good solvent resistance and thermal stability, and the polymer containing the triazole structure is applied to the light-emitting device, so that a film layer in the light-emitting device has good thermal stability and solvent resistance, and the film layer is prevented from being influenced by the next film layer when the light-emitting device is prepared by solution processing, and the performance of the light-emitting device is further improved.

Description

Polymer containing triazole structure and its preparation method and light-emitting device

technical field

The present application relates to the field of display technology, in particular to a polymer containing a triazole structure, a preparation method thereof, and a light-emitting device.

Background technique

Because the cost of preparing light-emitting diode devices by solution processing is low, and large-area light-emitting diode devices can be prepared, it is widely used by people. A light emitting diode device is composed of a carrier injection layer, a carrier transport layer and a light emitting layer stacked together. If the functional layer of the light-emitting diode device is prepared by the traditional solution processing method, the material of the functional layer is easily dissolved or mutually compatible by the solvent of the next functional layer during the solution processing process, thereby reducing the performance of the device.

Contents of the invention

The embodiments of the present application provide a polymer containing a triazole structure, a preparation method thereof, and a light-emitting device, so as to improve the thermal stability and solvent resistance of the film layer of the light-emitting device.

其中，所述X₁基团的结构式选自

所述X₂基团的结构式为

所述X₃基团的结构式为

所述n与所述m的比值为1：(1-99)，所述R₁基团、所述R₂基团、所述R₃基团、所述R₄基团和所述R₅基团选自-C_2yH_2y+1

所述R₆基团为C_2xH_2x+1，y为1-25，x为1-25。The application provides a polymer containing a triazole structure, the structural formula of the polymer containing a triazole structure is

Wherein, the structural formula _of the X1 group is selected from

The structural _formula of the X2 group is

The structural formula of the _X3 group is

The ratio of said n to said m is 1: (1-99), said R ₁ group, said R ₂ group, said R ₃ group, said R ₄ group and said R ₅ The group is selected from -C _2y H _2y+1

The R ₆ group is C _2x H _2x+1 , y is 1-25, and x is 1-25.

The application also provides a preparation method of a polymer containing a triazole structure, comprising:

providing a first reactant, a second reactant and a third reactant, the first reactant, the second reactant and the third reactant react to form a first intermediate product;

所述X₂基团的结构式为

所述X₃基团的结构式为

所述第一中间产物的结构式为

所述含三唑结构的聚合物的结构式为

所述n与所述m的比值为1：(1-99)，所述R₁基团、所述R₂基团、所述R₃基团、所述R₄基团和所述R₅基团选自-C_2yH_2y+1和

所述R₆基团为C_2xH_2x+1，y为1-25，x为1-25。Carrying out a first heat treatment to the first intermediate product to form a polymer containing a triazole structure, wherein the first reactant is _a compound comprising _an X group, and the structural formula of the X group is selected from

The structural _formula of the X2 group is

The structural formula of the _X3 group is

The structural formula of the first intermediate product is

The structural formula of the polymer containing triazole structure is

The ratio of said n to said m is 1: (1-99), said R ₁ group, said R ₂ group, said R ₃ group, said R ₄ group and said R ₅ The group is selected from -C _2y H _2y+1 and

The R ₆ group is C _2x H _2x+1 , y is 1-25, and x is 1-25.

The present application also provides a light emitting device, comprising:

substrate layer;

an electron transport layer disposed on the substrate layer; and

其中，所述X₁基团的结构式选自

所述X₂基团的结构式为

所述X₃基团的结构式为

所述n与所述m的比值为1：(1-99)，所述R₁基团、所述R₂基团、所述R₃基团、所述R₄基团和所述R₅基团分别独立地选自-C_2yH_2y+1和

所述R₆基团为C_2xH_2x+1，y为1-25，x为1-25。A light-emitting layer, the light-emitting layer is disposed on the electron transport layer, wherein the material of the electron transport layer and/or the material of the light-emitting layer includes a polymer containing a triazole structure, and the material containing a triazole structure The structure of the polymer is

Wherein, the structural formula _of the X1 group is selected from

The structural _formula of the X2 group is

The structural formula of the _X3 group is

The ratio of said n to said m is 1: (1-99), said R ₁ group, said R ₂ group, said R ₃ group, said R ₄ group and said R ₅ The groups are independently selected from -C _2y H _2y+1 and

The R ₆ group is C _2x H _2x+1 , y is 1-25, and x is 1-25.

The application provides a polymer containing a triazole structure, a preparation method thereof, and a light-emitting device. The polymer containing a triazole structure is a cross-linked polymer containing a triazole structure. The polymer containing a triazole structure has good resistance Solvent properties and thermal stability, the application of polymers containing triazole structures in light-emitting devices makes the film layers in light-emitting devices have good thermal stability and solvent resistance, and avoids the film layer being damaged when the light-emitting device is prepared by solution processing. Affected by the next film layer, the performance of the light-emitting device is improved.

Description of drawings

In order to more clearly illustrate the technical solutions in the embodiments of the present application, the drawings that need to be used in the description of the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present application. For those skilled in the art, other drawings can also be obtained based on these drawings without any creative effort.

Fig. 1 is a schematic structural diagram of a light emitting device provided by an embodiment of the present application.

Detailed ways

The following will clearly and completely describe the technical solutions in the embodiments of the application with reference to the drawings in the embodiments of the application. Apparently, the described embodiments are only some of the embodiments of the application, not all of them. Based on the embodiments in this application, all other embodiments obtained by those skilled in the art without making creative efforts belong to the scope of protection of this application. In addition, it should be understood that the specific implementations described here are only used to illustrate and explain the present application, and are not intended to limit the present application. In this application, unless stated to the contrary, the used orientation words such as "up" and "down" usually refer to up and down in the actual use or working state of the device, specifically the direction of the drawing in the drawings ; while "inside" and "outside" refer to the outline of the device.

The application provides a polymer containing a triazole structure, a preparation method thereof, and a light-emitting device. Each will be described in detail below.

X₁基团的结构式选自

X₂基团的结构式为

X₃基团的结构式为

n与m的比值为1：(1-99)，R₁基团、R₂基团、R₃基团、R₄基团和R₅基团分别独立地选自-C_2yH_2y+1和

R₆基团为C_2xH_2x+1，y为1-25，x为1-25。The application provides a polymer containing a triazole structure, the structural formula of the polymer containing a triazole structure is

The structural formula _of the X1 group is selected from

The structural _formula of the X2 group is

The structural formula of the _X3 group is

The ratio of n to m is 1: (1-99), R ₁ group, R ₂ group, R ₃ group, R ₄ group and R ₅ group are independently selected from -C _2y H _2y+1 and

The R ₆ group is C _2x H _2x+1 , y is 1-25, and x is 1-25.

It should be noted that n and m do not represent the number of specific units of the polymer containing the triazole structure, that is, not the degree of polymerization, but reflect the molar weight of the two units.

基团的化合物包括contain

Group compounds include

one or a combination of several.

In one embodiment, the structural formula of the polymer containing triazole structure can be

等。

wait.

The present application provides a polymer containing a triazole structure, which is a cross-linkable polymer containing a triazole structure. The polymer containing a triazole structure is composed of a main chain structural unit, an electron-transporting structural unit and a cross-linkable structural unit. The main chain structural unit contains a fluorene structural unit or a phenyl-containing side chain structural unit, which has good stability. The electron-transporting structural unit contains a triazole structural unit, and the structural unit has good electron-transporting performance and good heat-resistant stability. The crosslinkable structural unit contains a triazole structure and a benzocyclobutene structure. With this structure, the introduction of the crosslinkable structural unit will not reduce the electron transport capability of the film layer material, and at the same time, the crosslinkable structural unit can It can be ring-opened and cross-linked to form a film layer that is insoluble in common solvents, so that the polymer containing the triazole structure has good solvent resistance. The polymer containing the triazole structure constructed by the three structural units of the main chain structural unit, the electron-transporting structural unit and the cross-linkable structural unit has good thermal stability at room temperature, while maintaining the good stability of the triazole structural unit. In addition, due to the ability to achieve cross-linking at high temperatures without generating any by-products, the polymers containing triazole structures can be used in light-emitting devices by solution processing.

The present application also provides a preparation method of a polymer containing a triazole structure. The preparation method of the polymer containing triazole structure comprises:

所述X₂基团的结构式为

所述X₃基团的结构式为，第一中间产物的结构式为

n与m的比值为1：(1-99)，R₁基团、R₂基团、R₃基团、R₄基团和R₅基团选自-C_2yH_2y+1和

R₆基团为C_2xH_2x+1，y为1-25，x为1-25。A. The first reactant, the second reactant and the third reactant are provided, and the first reactant, the second reactant and the third reactant are reacted to generate the first intermediate product. Wherein, the _first reactant is _a compound including X1 group, and the structural formula of X1 group is selected from

The structural _formula of the X2 group is

The structural formula of the _X3 group is, the structural formula of the first intermediate product is

The ratio of n to m is 1: (1-99), R ₁ group, R ₂ group, R ₃ group, R ₄ group and R ₅ group are selected from -C _2y H _2y+1 and

The R ₆ group is C _2x H _2x+1 , y is 1-25, and x is 1-25.

In one embodiment, when the first reactant, the second reactant and the third reactant are reacted to form a first intermediate product, the molar amount of the first reactant, the first The corresponding relationship between the molar weight of the reactant and the molar weight of the third reactant is that 4-7 mmol of the first reactant corresponds to 0.1-2 mmol of the second reactant and 2 millimolar to 5 millimolar of said third reactant.

In one embodiment, the first reactant, the second reactant and the third reactant react in a solvent to generate the first intermediate product, and the solvent includes toluene, ethanol, ethylene, perchlorethylene, trichloroethylene, acetone, ethylene One or more combinations of glycol ether and triethanolamine.

In the step that the first reactant, the second reactant and the third reactant are reacted to generate the first intermediate product, comprising:

performing a second heat treatment on the first reactant, the second reactant, and the third reactant to generate a second intermediate product;

A third heat treatment is performed on the second intermediate product to form the first intermediate product.

In one embodiment, the temperature of the second heat treatment is 100°C-120°C.

In one embodiment, the time for the second heat treatment is 5 hours to 24 hours.

In one embodiment, the temperature of the third heat treatment is 85°C-110°C.

第二反应物的结构式可以为

第三反应物的结构式可以为

In one embodiment, the structural formula of the first reactant can be

The structural formula of the second reactant can be

The structural formula of the third reactant can be

In one embodiment, the reaction formula of the first reactant, the second reactant and the third reactant to generate the first intermediate product may be:

4.4毫摩的

0.8毫摩的苯并环丁烯衍生物

然后，加入27.04微摩的三(2-甲氧基苯基)膦作为催化剂配体；然后，加入5.1微摩的醋酸钯Pd(OAc)2作为催化剂；然后，进行抽真空换氮气操作，重复3次；然后，用注射器加入20wt％的四乙基氢氧化铵溶液；然后，加入60毫升的甲苯，氮气氛围下110摄氏度回流6小时；然后，在混合液中加入苯基硼酸3.2毫摩，继续反应12小时；反应完成后将二乙基二硫代氨基甲酸钠溶液加入到混合液中，并在85摄氏度搅拌2小时；然后，对油相进行多次水洗，并用色谱柱进行分离提纯；提纯后，采用甲醇对其进行沉淀，并过滤，烘干。得到第一中间产物。使用高效凝胶色谱来测定其分子量，测得其Mn＝69000，Mw＝160000。In one embodiment, 5.3 millimolar boronate derivatives of fluorene are sequentially added to a 100 ml two-necked bottle

4.4 mmol

0.8 mmol of benzocyclobutene derivative

Then, add 27.04 micromoles of tris (2-methoxyphenyl) phosphine as catalyst ligand; then, add 5.1 micromoles of palladium acetate Pd (OAc) as catalyst; then, carry out vacuuming for nitrogen operation, repeat 3 times; then, add 20wt% tetraethylammonium hydroxide solution with a syringe; then, add 60 ml of toluene, and reflux at 110 degrees Celsius for 6 hours under a nitrogen atmosphere; then, add 3.2 mmoles of phenyl boric acid in the mixed solution, Continue to react for 12 hours; after the reaction is completed, add sodium diethyldithiocarbamate solution into the mixed solution, and stir at 85 degrees Celsius for 2 hours; then, wash the oil phase with water several times, and use a chromatographic column to separate and purify; purify Finally, it was precipitated with methanol, filtered, and dried. A first intermediate product is obtained. Its molecular weight was measured by high performance gel chromatography, and its Mn=69000 and Mw=160000 were measured.

In this application, the addition of phenylboronic acid can be used to terminate the active bromine end group, thereby improving the stability of the first intermediate product and avoiding luminescence quenching.

第二反应物的结构式可以为

第三反应物的结构式可以为

In one embodiment, the structural formula of the first reactant can be

The structural formula of the second reactant can be

The structural formula of the third reactant can be

In one embodiment, the reaction formula of the first reactant, the second reactant and the third reactant to generate the first intermediate product may be:

3毫摩的

1毫摩的苯并环丁烯衍生物

然后，加入27.04微摩的三(2-甲氧基苯基)膦作为催化剂配体；然后，加入5.1微摩的醋酸钯Pd(OAc)2作为催化剂；然后，进行抽真空换氮气操作，重复3次；然后，用注射器加入20wt％的四乙基氢氧化铵溶液；然后，加入60毫升的甲苯，氮气氛围下115摄氏度回流8小时；然后，在混合液中加入苯基硼酸3.2毫摩，继续反应20小时；反应完成后将二乙基二硫代氨基甲酸钠溶液加入到混合液中，并在90摄氏度搅拌3小时；然后，对油相进行多次水洗，并用色谱柱进行分离提纯；提纯后，采用甲醇对其进行沉淀，并过滤，烘干。得到第一中间产物。使用高效凝胶色谱来测定其分子量，测得其Mn＝72000，Mw＝159000。In one embodiment, 4.5 millimolar boronate derivatives of fluorene were added successively in a 100 ml two-necked flask

3mM

1 mmol of benzocyclobutene derivative

Then, add 27.04 micromoles of tris (2-methoxyphenyl) phosphine as catalyst ligand; then, add 5.1 micromoles of palladium acetate Pd (OAc) as catalyst; then, carry out vacuuming for nitrogen operation, repeat 3 times; then, add 20wt% tetraethylammonium hydroxide solution with a syringe; then, add 60 ml of toluene, and reflux at 115 degrees Celsius for 8 hours under a nitrogen atmosphere; then, add 3.2 mmoles of phenyl boric acid in the mixed solution, Continue to react for 20 hours; after the reaction is completed, add the sodium diethyldithiocarbamate solution into the mixed solution, and stir at 90 degrees Celsius for 3 hours; then, wash the oil phase with water several times, and use a chromatographic column to separate and purify; purify Finally, it was precipitated with methanol, filtered, and dried. A first intermediate product is obtained. Its molecular weight was measured by high performance gel chromatography, and its Mn=72000 and Mw=159000 were measured.

第二反应物的结构式可以为

第三反应物的结构式可以为

In one embodiment, the structural formula of the first reactant can be

The structural formula of the second reactant can be

The structural formula of the third reactant can be

In one embodiment, the reaction formula of the first reactant, the second reactant and the third reactant to generate the first intermediate product may be:

2.5毫摩的

1.6毫摩的苯并环丁烯衍生物

然后，加入27.04微摩的三(2-甲氧基苯基)膦作为催化剂配体；然后，加入5.1微摩的醋酸钯Pd(OAc)2作为催化剂；然后，进行抽真空换氮气操作，重复3次；然后，用注射器加入20wt％的四乙基氢氧化铵溶液；然后，加入60毫升的甲苯，氮气氛围下105摄氏度回流8小时；然后，在混合液中加入苯基硼酸3.2毫摩，继续反应15小时；反应完成后将二乙基二硫代氨基甲酸钠溶液加入到混合液中，并在95摄氏度搅拌1.5小时；然后，对油相进行多次水洗，并用色谱柱进行分离提纯；提纯后，采用甲醇对其进行沉淀，并过滤，烘干。得到第一中间产物。使用高效凝胶色谱来测定其分子量，测得其Mn＝75000，Mw＝170000。In one embodiment, 6 millimolar boronate derivatives of fluorene were successively added to a 100 ml two-necked flask

2.5 mmol

1.6 mmoles of benzocyclobutene derivatives

Then, add 27.04 micromoles of tris (2-methoxyphenyl) phosphine as catalyst ligand; then, add 5.1 micromoles of palladium acetate Pd (OAc) as catalyst; then, carry out vacuuming for nitrogen operation, repeat 3 times; then, add 20wt% tetraethylammonium hydroxide solution with a syringe; then, add 60 ml of toluene, and reflux at 105 degrees Celsius for 8 hours under a nitrogen atmosphere; then, add 3.2 mmoles of phenyl boric acid in the mixed solution, Continue to react for 15 hours; after the reaction is completed, add the sodium diethyldithiocarbamate solution to the mixed solution, and stir at 95 degrees Celsius for 1.5 hours; then, wash the oil phase with water several times, and use a chromatographic column to separate and purify; purify Finally, it was precipitated with methanol, filtered, and dried. A first intermediate product is obtained. Using high performance gel chromatography to measure its molecular weight, its Mn=75000, Mw=170000.

第五反应物的结构式为

In one embodiment, the second reactant is formed from the fourth reactant and the fifth reactant. The structural formula of the fourth reactant is

The structural formula of the fifth reactant is

In one embodiment, the reaction formula of the fourth reactant and the fifth reactant to generate the second reactant may be:

的甲苯溶液，然后逐滴把10毫摩的POCl₃滴到反应液中，待反应完全后，恢复到室温，然后加入5毫摩的

然后，在烧瓶中通氮气使之处于氮气氛围，加热反应液回流反应8h；然后，把反应液冷却到室温。反应结束后对反应液进行过滤；然后，进行萃取分离，接着对反应液用硅胶色谱柱进行分离提纯，用正己烷/乙酸乙酯作洗脱剂，旋蒸除去溶剂收集产物，最后室温真空干燥12h，得到第二反应物，称重，产率约为61％。In one embodiment, 30 mmol of

Toluene solution, then drop 10 mmol of POCl ₃ dropwise into the reaction solution, after the reaction is complete, return to room temperature, then add 5 mmol of POCl 3

Then, nitrogen gas was passed through the flask to make it in a nitrogen atmosphere, and the reaction solution was heated to reflux for 8 hours; then, the reaction solution was cooled to room temperature. After the reaction, the reaction solution was filtered; then, extraction and separation were carried out, followed by separation and purification of the reaction solution with a silica gel chromatography column, using n-hexane/ethyl acetate as the eluent, rotary evaporation to remove the solvent to collect the product, and finally vacuum drying at room temperature After 12 hours, the second reactant was obtained and weighed, and the yield was about 61%.

1H NMR (300 MHz, DMSO), (TMS, ppm): 7.68 (s, 2H), 7.66-7.62 (m, 8H), 7.20 (d, 1H), 7.07 (d, 1H), 2.88 (s, 4H).

第六反应物的结构式为

In one embodiment, the third reactant is formed from the fourth reactant and the sixth reactant. The structural formula of the fourth reactant is

The structural formula of the sixth reactant is

In one embodiment, the reaction formula of the reaction between the fourth reactant and the sixth reactant to generate the third reactant may be:

的甲苯溶液，然后逐滴把10毫摩的POCl₃滴到反应液中，待反应完全后，恢复到室温，然后加入5毫摩的

然后，在烧瓶中通氮气使之处于氮气氛围，加热反应液回流反应8h；然后，把反应液冷却到室温。反应结束后对反应液进行过滤，然后进行萃取分离，接着对反应液用硅胶色谱柱进行分离提纯，用正己烷/乙酸乙酯作洗脱剂，旋蒸除去溶剂收集产物，最后室温真空干燥12h，得到第三反应物，称重，产率约为60％。In one embodiment, 30 mmol of

Toluene solution, then drop 10 mmol of POCl ₃ dropwise into the reaction solution, after the reaction is complete, return to room temperature, then add 5 mmol of POCl 3

Then, nitrogen gas was passed through the flask to make it in a nitrogen atmosphere, and the reaction solution was heated to reflux for 8 hours; then, the reaction solution was cooled to room temperature. After the reaction, the reaction solution was filtered, then extracted and separated, and then the reaction solution was separated and purified with a silica gel column, using n-hexane/ethyl acetate as the eluent, and the solvent was removed by rotary evaporation to collect the product, and finally vacuum-dried at room temperature for 12 hours , to obtain the third reactant, weighed, and the yield was about 60%.

1HNMR (300MHz, DMSO), (TMS, ppm):

7.66-7.62(m, 8H), 7.32(d, 1H), 7.17(d, 2H), 2.55(m, 1H), 1.52(m, 2H), 1.16(m, 3H), 0.76(m, 3H) .

B, carry out the first heat treatment to the first intermediate product to form the polymkeric substance containing triazole structure, the structural formula of the polymkeric substance containing triazole structure is:

In one embodiment, the temperature of the first heat treatment is 110°C-250°C.

In one embodiment, the general reaction formula for performing the first heat treatment on the first intermediate product to form a polymer containing a triazole structure can be:

In one embodiment, the structural formula of the first intermediate product can be

In one embodiment, the reaction formula of the first intermediate product to generate a polymer containing a triazole structure can be:

The first intermediate product is baked at 120 degrees Celsius for 10 minutes to remove residual solvent; then, it is subjected to a first heat treatment to form a polymer containing a triazole structure.

The temperature of the first heat treatment is 110°C-250°C. Specifically, the temperature of the first heat treatment may be 110 degrees Celsius, 150 degrees Celsius, 200 degrees Celsius, 220 degrees Celsius, or 250 degrees Celsius. In this embodiment, the temperature of the first heat treatment is 200 degrees Celsius.

The time for the first heat treatment is 30 minutes to 60 minutes. Specifically, the time for the first heat treatment may be 30 minutes, 33 minutes, 40 minutes, 50 minutes or 60 minutes, etc.

It should be noted that n and m do not represent the number of specific units of the polymer containing the triazole structure, that is, not the degree of polymerization, but reflect the molar weight of the two units.

In this application, the ratio of n and m is set to 1 because the ratio of n in the entire main chain can mainly control the ratio of crosslinkable structural units and the solubility of polymers containing triazole structures: (1- 99), the crosslinkability and stability of the first intermediate product can be improved. If the proportion of the cross-linkable structural unit is too high, it is easy to cause incomplete reaction of some cross-linkable structural units, thereby leading to quenching of luminescence and increase of instability of the first intermediate product.

The present application provides a method for preparing a polymer containing a triazole structure. The polymer containing a triazole structure is a cross-linked polymer containing a triazole structure. The polymer containing a triazole structure is applied to a light-emitting device, so that The film layer in the light-emitting device has good thermal stability and solvent resistance, which prevents the film layer from being affected by the next film layer when the light-emitting device is prepared by solution processing, thereby improving the performance of the light-emitting device.

Please refer to FIG. 1 . FIG. 1 is a schematic structural diagram of a light emitting device provided by an embodiment of the present application. The present application also provides a light emitting device. The light emitting device 10 includes a substrate layer 100 , an electron transport layer 200 and a light emitting layer 300 . The specific description is as follows.

In one embodiment, the light emitting device 10 further includes a cathode 400 . The cathode 400 is disposed on the substrate layer 100 .

In one embodiment, the material of the cathode 400 includes one or a combination of indium tin oxide, indium zinc oxide, zinc aluminum oxide, and indium gallium zinc oxide. In this embodiment, the material of the cathode 400 is indium tin oxide.

In one embodiment, the light emitting device 10 further includes an electron injection layer 500 . The electron injection layer 500 is disposed on the cathode 400 .

The electron transport layer 200 is disposed on the electron injection layer 500 .

The light emitting layer 300 is disposed on the electron transport layer 200 .

In one embodiment, the material of the electron transport layer 200 includes the above-mentioned polymer containing a triazole structure.

In this application, the electron transport layer 200 is prepared by using a polymer containing a triazole structure, so that the electron transport layer 200 can improve the thermal stability and solvent resistance of the electron transport layer 200 while ensuring its own performance, so that the light-emitting device 10 adopts When prepared by solution processing, the electron transport layer 200 can be prevented from being affected by the next film layer pair, thereby improving the performance of the light emitting device 10 .

In one embodiment, the material of the electron transport layer 200 does not contain the above-mentioned polymer containing a triazole structure, but the material of the light-emitting layer 300 contains the above-mentioned polymer containing a triazole structure.

In this application, the light-emitting layer 300 is prepared by using a polymer containing a triazole structure, so that the light-emitting layer 300 can improve the thermal stability and solvent resistance of the light-emitting layer 300 while ensuring its own performance, so that the light-emitting device 10 adopts a solution processing process During the preparation, the light-emitting layer 300 can be prevented from being affected by the next film layer on the light-emitting layer 300 , that is, the light-emitting layer 300 can be prevented from being dissolved by the solvent of the next film layer, thereby improving the performance of the light-emitting device 10 .

In one embodiment, both the material of the light-emitting layer 300 and the material of the electron transport layer 200 contain the above-mentioned polymer containing a triazole structure.

In this application, polymers containing a triazole structure are used to prepare the light-emitting layer 300 and the electron transport layer 200, so that the light-emitting layer 300 and the electron transport layer 200 can improve the performance of the light-emitting layer 300 and the electron transport layer 200 while ensuring their own performance. thermal stability and solvent resistance, so that when the light-emitting device 10 is prepared by a solution processing process, the light-emitting layer 300 and the electron transport layer 200 can be prevented from being affected by the next film layer on the light-emitting layer, that is, the light-emitting layer 300 and the electron transport layer can be avoided. 200 is dissolved by the solvent of the next film layer, thereby improving the performance of the light emitting device 10 .

In one embodiment, the light emitting device 10 further includes a hole transport layer 600 , a hole injection layer 700 and an anode 800 . The hole transport layer 600 , the hole injection layer 700 and the anode 800 are sequentially stacked on the light emitting layer 300 .

The present application provides a light emitting device 10 , which includes a substrate layer 100 and an electron transport layer 200 and a light emitting layer 300 sequentially stacked on the substrate layer 100 . The material of the electron transport layer 200 and/or the material of the light emitting layer 300 is a polymer containing a triazole structure as described in this application, so that the electron transport layer 200 and/or the light emitting layer 300 can improve the performance of the electron transport layer 200 while ensuring its own performance. And/or thermal stability and solvent resistance of the light emitting layer 300, thereby improving the performance of the light emitting device 10.

The present application also provides a method for preparing a light-emitting device. The preparation method of the light-emitting device 10 of the present application is described by taking the electron transport layer 200 formed from a polymer containing a triazole structure as an example. The specific description is as follows.

Example

A substrate layer 100 is provided. Then, a cathode 400 is formed on the substrate layer 100 .

Then, the substrate layer 100 and the cathode 400 were cleaned in the following order: 5% potassium hydroxide solution for 15 minutes, pure water for 15 minutes, isopropanol for 15 minutes, and oven drying for 1 hour. Then, transfer the substrate layer 100 and the cathode 400 to an ultraviolet light ozone cleaning device for surface treatment for 15 minutes. Transfer to the glove box immediately after handling. A layer of zinc oxide nanoparticles is spin-coated on the clean cathode 400 . Then, bake for 15 minutes at a temperature of 120 degrees Celsius.

Then, after dissolving the first intermediate product with a solvent (such as o-xylene), the first intermediate product is spin-coated on the zinc oxide nano-layer, and the first intermediate product is first baked at 120 degrees Celsius for 10 minutes to remove residual solvent. Then, the ring-opening and cross-linking of the first intermediate product is carried out at 200 degrees Celsius to form a polymer containing a triazole structure, that is, the electron transport layer 200 is formed. The crosslinking time is 30 minutes to 60 minutes.

Wherein, the structural formula of the first intermediate product may be (Formula 1)-(Formula 16). In this embodiment, the electron transport layer is prepared by formula 1 to formula 16 respectively.

Then, the luminescent layer 300 ink is spin-coated. Then, the hole transport layer 600 , the hole injection layer 700 and the anode 800 are formed by vacuum evaporation. Finally, the encapsulation is cured by ultraviolet light and heated and baked for 20 minutes to prepare the light emitting device 10 .

comparative example

A substrate layer is provided. Then, an anode is formed on the substrate layer.

Then, the substrate layer and the anode were cleaned in the following order: 5% potassium hydroxide solution for 15 minutes, pure water for 15 minutes, isopropanol for 15 minutes, and oven drying for 1 hour. Then, the substrate layer and the anode were transferred to ultraviolet light ozone cleaning equipment for surface treatment for 15 minutes. Transfer to the glove box immediately after handling. A layer of zinc oxide nanoparticles was spin-coated on a clean anode. Then, bake for 15 minutes at a temperature of 120 degrees Celsius.

Then, the electron transport layer material is evaporated by vacuum evaporation. The electron transport layer material is TPBi. The evaporation rate was 0.1 nm/s.

Then, after spin-coating the emissive layer ink. Then, a hole transport layer, a hole injection layer, and a cathode are formed by vacuum evaporation. Finally, the encapsulation is cured by ultraviolet light and heated and baked for 20 minutes to prepare a light-emitting device.

Please refer to Table 1. Table 1 shows the data of light-emitting devices using polymers containing triazole structures to form electron transport layers and/or light-emitting layers.

Table 1

The structure of devices 1-16 is Al/ZnO(35nm)/Formula 1-Formula 16(20nm)/mCP:Ir(ppy)2acac, 7wt%(30nm)/TAPC(30nm)/NPB(10nm)/HAT-CN (10nm)/ITO(120nm), where Al is the cathode material. ZnO is an electron injection layer material. Formula 1-Formula 16 are electron transport layer materials. mCP is used as the host material of the light-emitting layer, and Ir(ppy)2acac is the guest material of the light-emitting layer. TAPC and NPB are hole transport layer materials. HAT-CN is the hole injection layer material. ITO is the anode material.

The structure of the light-emitting device in the comparative example is Al/ZnO(35nm)/TPBi(20nm)/mCP:Ir(ppy)2acac,7wt%(30nm)/TAPC(30nm)/NPB(10nm)/HAT-CN(10nm) /ITO (120nm), where Al is the cathode material. ZnO is an electron injection layer material. TPBi is an electron transport layer material. mCP is used as the host material of the light-emitting layer, and Ir(ppy)2acac is the guest material of the light-emitting layer. TAPC and NPB are hole transport layer materials. HAT-CN is the hole injection layer material. ITO is the anode material.

It should be noted that CIEx and CIEy are numerical values of color coordinates. It can be seen from Table 1 that the first intermediate product is used to form a polymer containing a triazole structure, that is, the electron transport layer 200 is formed, so that the electron transport layer 200 has good thermal stability and solvent resistance, and does not affect the light-emitting device 10. The current efficiency and luminous performance are improved, thereby improving the performance of the light emitting device 10 .

This application provides a method for preparing a light-emitting device, using a polymer containing a triazole structure to form an electron transport layer. Because the polymer containing a triazole structure has high thermal stability and solvent resistance, it is used for the electron transport layer In 200, the electron transport layer 200 has good thermal stability and solvent resistance while ensuring its own performance, thereby improving the performance of the light emitting device 10 .

The application provides a polymer containing a triazole structure, a preparation method thereof, and a light-emitting device. The polymer containing a triazole structure is a cross-linked polymer containing a triazole structure. The polymer containing a triazole structure is used in light emitting In the device, the film layer in the light-emitting device has good thermal stability and solvent resistance, which prevents the film layer from being affected by the next film layer when the light-emitting device is prepared by solution processing, thereby improving the performance of the light-emitting device.

A polymer containing a triazole structure and its preparation method and light-emitting device provided in the examples of the present application have been described in detail above. In this paper, specific examples are used to illustrate the principles and implementation methods of the present application. The above examples The description is only used to help understand the method of the present application and its core idea; at the same time, for those skilled in the art, according to the idea of the present application, there will be changes in the specific implementation and application scope, in summary , the contents of this specification should not be construed as limiting the application.

Claims (10)

1. The polymer containing the triazole structure is characterized in that the structural formula of the polymer containing the triazole structure is shown in the specification

Wherein, X is ₁ The structural formula of the group is selected from

Said X ₂ The structural formula of the radical is

Said X ₃ The structural formula of the radical is

The ratio of n to m is 1: (1-99), said R ₁ Group, said R ₂ Group, said R ₃ Group, said R ₄ Group and said R ₅ Each independently selected from-C _2y H _2y+1 And

said R is ₆ The radical being C _2x H _2x+1 Y is 1 to 25, x is 1 to 25.

2. The polymer having a triazole structure according to claim 1, which contains the compound

The compounds of the group include

One or a combination of several of them.

3. The triazole structure-containing polymer according to claim 2, wherein the structural formula of the triazole structure-containing polymer comprises

One or a combination of several of them.

4. A method for preparing a polymer containing a triazole structure, which comprises the following steps:

providing a first reactant, a second reactant and a third reactant, wherein the first reactant, the second reactant and the third reactant react to form a first intermediate product;

subjecting the first intermediate product to a first heat treatment to form a polymer containing a triazole structure, wherein the first reactant comprises X ₁ Compound of the group X ₁ The structural formulas of the groups are respectively and independently selected from

The second reactant is a compound comprising X ₂ Compound of group X ₂ The structural formula of the group is

The third reactant is a compound comprising X ₃ Compound of group X ₃ The structural formula of the group is

The structural formula of the first intermediate product is

The structural formula of the polymer containing the triazole structure is shown in the specification

The ratio of n to m is 1: (1-99), said R ₁ Group, said R ₂ Group, said R ₃ Group, said R ₄ Group and said R ₅ Each independently selected from-C _2y H _2y+1 And

the R is ₆ The radical being C _2x H _2x+1 Y is 1 to 25, x is 1 to 25.

5. The method of claim 4, wherein the first reactant, the second reactant, and the third reactant are reacted to form a first intermediate product, and wherein the molar amount of the first reactant, and the molar amount of the third reactant correspond to each other in a range of 4 mmol to 7 mmol of the first reactant to 0.1 mmol to 2 mmol of the second reactant and in a range of 2 mmol to 5 mmol of the third reactant.

6. The method for producing a polymer having a triazole structure according to claim 5, wherein the temperature of the first heat treatment is 110 degrees celsius to 250 degrees celsius.

7. The method as claimed in claim 4, wherein the first reactant, the second reactant and the third reactant react in a solvent to form the first intermediate, and the solvent comprises one or more of toluene, ethanol, ethylene, perchloroethylene, trichloroethylene, acetone, ethylene glycol ether and triethanolamine.

8. A light emitting device, comprising:

a substrate layer;

an electron transport layer disposed on the substrate layer; and

the light-emitting layer is arranged on the electron transport layer, wherein the material of the electron transport layer and/or the material of the light-emitting layer comprises a polymer containing a triazole structure, and the structural formula of the polymer containing the triazole structure is shown in the specification

Wherein, X is ₁ The structural formula of the group is selected from

Said X ₂ The structural formula of the group is

Said X ₃ The structural formula of the group is

The ratio of n to m is 1: (1-99), said R ₁ Group, said R ₂ Group, said R ₃ Group, said R ₄ Group and said R ₅ The group is selected from-C _2y H _2y+1 And

the R is ₆ The radical being C _2x H _2x+1 Y is 1 to 25, x is 1 to 25.

9. The light-emitting device according to claim 8, comprising the above-mentioned compound

The compounds of the group include

One or a combination of several of them.

10. The light-emitting device according to claim 9, wherein the structural formula of the polymer having a triazole structure comprises

One or a combination of several of them.

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