阅读说明：本技术 一种柔性电子器件透明衬底膜的制备方法 (Preparation method of transparent substrate film of flexible electronic device ) 是由 刘俊稚 葛亚明 杨家顺 韩厚峰 于 2019-08-14 设计创作，主要内容包括：本发明提出了一种柔性电子器件透明衬底膜的制备方法,包括以下步骤：S1.掺杂石墨烯的制备：在反应器中依次加入浓酸和石墨烯,超声搅拌下将其加入冰醋酸中,倒入大量水中进行稀释,过滤,滤饼用去离子水洗涤至中性,备用；所述掺杂石墨烯的收率为大于85％；S2.柔性电子器件透明衬底膜的制备：将羧甲基纤维素钠加入醋酸溶液中,研磨,搅拌下加入掺杂石墨烯,超声,离心,取上清液,用去离子水稀释,转入玻璃皿中,水浴下将水分蒸干,制得柔性电子器件透明衬底膜。本发明制备方法简单、原料来源广、成本低,将不导电的羧甲基纤维素钠做成力学性能和电学性能均很优异的柔性电子器件透明衬底膜,具有广阔的市场前景。(The invention provides a preparation method of a transparent substrate film of a flexible electronic device, which comprises the following steps: s1, preparation of doped graphene: sequentially adding concentrated acid and graphene into a reactor, adding the concentrated acid and the graphene into glacial acetic acid under ultrasonic stirring, pouring a large amount of water for dilution, filtering, and washing a filter cake to be neutral by using deionized water for later use; the yield of the doped graphene is more than 85%; s2, preparing a transparent substrate film of the flexible electronic device: adding sodium carboxymethylcellulose into an acetic acid solution, grinding, adding doped graphene under stirring, performing ultrasonic treatment and centrifugation, taking supernatant, diluting with deionized water, transferring into a glass dish, and evaporating water in a water bath to dryness to obtain the transparent substrate film of the flexible electronic device. The preparation method is simple, the raw material source is wide, the cost is low, and the non-conductive sodium carboxymethyl cellulose is made into the flexible electronic device transparent substrate film with excellent mechanical property and electrical property, so that the preparation method has wide market prospect.)

1. A preparation method of a transparent substrate film of a flexible electronic device is characterized by comprising the following steps:

s1, preparation of doped graphene: sequentially adding concentrated acid and graphene into a reactor, uniformly stirring, performing ultrasonic treatment at 25 ℃ for 6h, adding the mixture into glacial acetic acid while stirring, stirring for 10-20min, pouring a large amount of water for dilution, filtering, and washing a filter cake to be neutral by using deionized water for later use;

the yield of the doped graphene is more than 85%;

s2, preparing a transparent substrate film of the flexible electronic device: adding sodium carboxymethylcellulose into an acetic acid solution, grinding for 2h by using a stone mortar grinder, adding doped graphene into the ground mixed solution under stirring, carrying out ultrasonic treatment for 20-30min, centrifuging, taking a supernatant, diluting the supernatant by 10 times with deionized water, transferring the diluted supernatant into a glass vessel, and evaporating water in a water bath at 100 ℃ to dryness to obtain the transparent substrate film of the flexible electronic device.

2. The method for preparing a transparent substrate film for a flexible electronic device as claimed in claim 1, wherein the concentrated acid is selected from one of concentrated sulfuric acid, chlorosulfonic acid, perchloric acid, permanganic acid and nitric acid with a mass fraction of more than 90%.

3. The method for preparing the transparent substrate film for the flexible electronic device as claimed in claim 1, wherein the ratio of the amount of the concentrated acid to the amount of the substance of the graphene in the step S1 is 50 (12-25).

4. The method for preparing the transparent substrate film for the flexible electronic device as claimed in claim 1, wherein the mass ratio of the sodium carboxymethyl cellulose to the doped graphene in step S2 is 10 (1-2); the mass concentration of the acetic acid solution is 1-2 mol/L; the ultrasonic power is 500-700W; the centrifugal rotating speed is 1000-2000 r/min.

5. A flexible electronic device transparent substrate film obtained by the production method as set forth in any one of claims 1 to 4, characterized in that the tensile strength of the flexible electronic device transparent substrate film is not less than 375MPa and the dielectric constant is not higher than 3.3.

6. A preparation method of a transparent substrate film of a flexible electronic device is characterized by comprising the following steps:

s1, preparing graphene oxide: the preparation method adopts an improved Hummers method;

s2, preparing a transparent substrate film of the flexible electronic device: adding sodium carboxymethylcellulose into an acetic acid solution, grinding for 2h by using a stone mortar type grinder, adding a silane coupling agent into the ground mixed solution, reacting for 2-3h, adding graphene oxide while stirring, stirring for reacting for 1-2h, centrifuging, taking a supernatant, diluting the supernatant by 10 times by using deionized water, transferring the diluted supernatant into a glass vessel, and evaporating water in a water bath at 100 ℃ to dryness to obtain the transparent substrate film of the flexible electronic device.

7. The method for preparing the transparent substrate film of the flexible electronic device as claimed in claim 6, wherein the mass ratio of the sodium carboxymethyl cellulose to the graphene oxide to the silane coupling agent in step S2 is 10 (1-2): (0.1-0.2).

8. The method for preparing a transparent substrate film for a flexible electronic device according to claim 6, wherein the substance of the acetic acid solution in step S2 has a concentration of (1-2) mol/L.

9. The method as claimed in claim 6, wherein the stirring speed is 300-500 r/min; the centrifugal rotating speed is 1000-2000 r/min.

10. A flexible electronic device transparent substrate film produced by the production method according to any one of claims 6 to 9, characterized in that the tensile strength of the flexible electronic device transparent substrate film is not less than 345MPa and the dielectric constant is not higher than 3.6.

Technical Field

The invention relates to the technical field of flexible electronic materials, in particular to a preparation method of a transparent substrate film of a flexible electronic device.

Background

Flexible electronics can be summarized as a new electronic technology for manufacturing organic/inorganic material electronic devices on flexible/ductile plastics or thin metal substrates, and has wide application prospects in the fields of information, energy, medical treatment, national defense and the like, such as flexible electronic displays, Organic Light Emitting Diodes (OLEDs), printed RFIDs, thin-film solar panels, surface-mounted electronics (Skin Patches) and the like, due to unique flexibility/ductility, high efficiency and low cost manufacturing processes. As with conventional IC technology, manufacturing processes and equipment are also a major driver in the development of flexible electronic technology. The key to the technical level of flexible electronic manufacturing technology, including chip feature size and substrate area size, is how to manufacture flexible electronic devices with smaller feature size on larger substrates at lower cost.

Compared with the conventional electronic device, the flexible electronic device has many advantages, such as lower energy consumption, light weight, breakage resistance, long service life, and the like. As a new technology, the related technology of the flexible electronic device is expected to be applied to high-tech products such as mobile phones, liquid crystal televisions, computers, automobiles, wearable intelligent devices and the like on a large scale within 3 to 5 years in the future. Organic transparent substrates are important components of flexible electronic devices. At present, the preparation raw materials of the organic transparent substrate mainly take chemical raw materials as main raw materials, and the raw materials have high cost and can not be continuously developed.

Disclosure of Invention

The invention provides a preparation method of a flexible electronic device transparent substrate film, which aims to provide the flexible electronic device transparent substrate film, wherein sodium carboxymethylcellulose is used as a raw material, is mixed with doped graphene, and is prepared through a film forming process, the conductivity and the mechanical property are greatly improved, the yield is improved by 0.5-1%, and the conductivity is improved by increasing the carrier density and reducing the contact resistance through a dopant concentrated acid.

The invention provides a preparation method of a transparent substrate film of a flexible electronic device, which comprises the following steps:

s1, preparation of doped graphene: sequentially adding concentrated acid and graphene into a reactor, uniformly stirring, performing ultrasonic treatment at 25 ℃ for 6h, adding the mixture into glacial acetic acid while stirring, stirring for 10-20min, pouring a large amount of water for dilution, filtering, and washing a filter cake to be neutral by using deionized water for later use;

the yield of the doped graphene is more than 85%;

s2, preparing a transparent substrate film of the flexible electronic device: adding sodium carboxymethylcellulose into an acetic acid solution, grinding for 2h by using a stone mortar grinder, adding doped graphene into the ground mixed solution under stirring, carrying out ultrasonic treatment for 20-30min, centrifuging, taking a supernatant, diluting the supernatant by 10 times with deionized water, transferring the diluted supernatant into a glass vessel, and evaporating water in a water bath at 100 ℃ to dryness to obtain the transparent substrate film of the flexible electronic device.

As a further improvement of the invention, the concentrated acid is selected from one of concentrated sulfuric acid, chlorosulfonic acid, perchloric acid, permanganic acid and nitric acid with the mass fraction of more than 90%.

As a further improvement of the invention, the ratio of the amount of the concentrated acid to the amount of the substance of the graphene in the step S1 is 50 (12-25).

As a further improvement of the invention, the mass ratio of the sodium carboxymethyl cellulose to the doped graphene in the step S2 is 10 (1-2); the mass concentration of the acetic acid solution is 1-2 mol/L; the ultrasonic power is 500-700W; the centrifugal rotating speed is 1000-2000 r/min.

The invention further protects the flexible electronic device transparent substrate film prepared by the preparation method, wherein the tensile strength of the flexible electronic device transparent substrate film is not less than 375MPa, and the dielectric constant is not higher than 3.3.

The invention further provides a preparation method of the transparent substrate film of the flexible electronic device, which comprises the following steps:

s1, preparing graphene oxide: the preparation method adopts an improved Hummers method;

s2, preparing a transparent substrate film of the flexible electronic device: adding sodium carboxymethylcellulose into an acetic acid solution, grinding for 2h by using a stone mortar type grinder, adding a silane coupling agent into the ground mixed solution, reacting for 2-3h, adding graphene oxide while stirring, stirring for reacting for 1-2h, centrifuging, taking a supernatant, diluting the supernatant by 10 times by using deionized water, transferring the diluted supernatant into a glass vessel, and evaporating water in a water bath at 100 ℃ to dryness to obtain the transparent substrate film of the flexible electronic device.

As a further improvement of the invention, the mass ratio of the sodium carboxymethyl cellulose to the graphene oxide to the silane coupling agent is 10 (1-2): (0.1-0.2).

As a further improvement of the invention, the mass ratio of the sodium carboxymethyl cellulose to the graphene oxide to the silane coupling agent in the step S2 is 10 (1-2): (0.1-0.2); the mass concentration of the acetic acid solution is (1-2) mol/L.

As a further improvement of the invention, the stirring rotating speed is 300-500 r/min; the centrifugal rotating speed is 1000-2000 r/min.

The invention further protects the flexible electronic device transparent substrate film prepared by the preparation method, wherein the tensile strength of the flexible electronic device transparent substrate film is not less than 345MPa, and the dielectric constant is not higher than 3.6.

The invention has the following beneficial effects:

according to the invention, sodium carboxymethylcellulose is used as a raw material, is mixed with doped graphene, and is subjected to a film forming process to prepare the transparent substrate film of the flexible electronic device, the conductivity and the mechanical property are greatly improved, the yield is improved by 0.5-1%, and the conductivity is improved by increasing the carrier density and reducing the contact resistance through a dopant concentrated acid;

the invention also prepares the film which takes sodium carboxymethylcellulose as a raw material, is coupled by graphene oxide, and the silane coupling agent is connected with the oxygen-containing group chemical bond on the carboxymethyl cellulose through the hydroxyl on the graphene oxide, so that the film has good stability and uniform distribution, the graphene oxide further improves the electrical property of the transparent substrate film of the flexible electronic device, the yield is improved by 0.7-1.2%, and the film has good application prospect;

the preparation method is simple, the raw material source is wide, the cost is low, and the non-conductive sodium carboxymethyl cellulose is made into the flexible electronic device transparent substrate film with excellent mechanical property and electrical property, so that the preparation method has wide market prospect.

Drawings

FIG. 1 is a graph showing a comparison of mechanical properties of each group in test example 1 of the present invention;

FIG. 2 is a graph showing a comparison of electrical properties of the respective groups in test example 1 of the present invention;

FIG. 3 is a graph showing a comparison of mechanical properties of the respective groups in test example 2 of the present invention;

FIG. 4 is a graph showing a comparison of electrical properties of the groups in test example 2 of the present invention.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is obvious that the embodiments described are only some representative embodiments of the present invention, rather than all embodiments, and all other embodiments obtained by a person skilled in the art without creative efforts belong to the protection scope of the present invention.