CN104312264B - Method for Microcontact Printing of Graphene/Silver Composite Pattern Using Nickel Phthalocyanine Complex - Google Patents

Abstract

The invention discloses the method utilizing Nickel Phthalocyanine title complex to carry out micro-contact printing Graphene/silver-colored composite pattern, this Nickel Phthalocyanine title complex is prestox Nickel Phthalocyanine, using the print paste of the dichloromethane solution of prestox Nickel Phthalocyanine as micro-contact printing, by the design transfer of PDMS seal to polyimide substrate, absorbing and reducing Graphene and silver again, finally obtains exquisite metal pattern in substrate.By micro-contact printing method is prepared graphene pattern, for micro-contact printing industry provides new approaches at the polyimide substrate surface that electron trade is conventional.

Description

Method for Microcontact Printing of Graphene/Silver Composite Pattern Using Nickel Phthalocyanine Complex

technical field

The invention belongs to the field of modern electronic technology, and particularly relates to the application of a nickel phthalocyanine complex as a green environmental protection ink in micro-contact printing.

Background technique

Surface micro-structuring technology is gradually showing important application value, especially micro-contact printing technology, which can be micro-patterned on a small scale, which is of great significance in many fields, especially in the field of modern electronic technology. At present, there are few microcontact printing inks to choose from, and the materials that can be printed on the surface are limited. A large number of materials cannot be prepared with surface patterns by microcontact printing. Therefore, it is of great significance to develop new and stable inks.

Utilizing the negative charge characteristics of graphene oxide and graphene sheets, using electrostatic self-assembly technology, it can be alternately deposited with polymer cations to prepare graphene films. However, the conductivity and light transmittance of the film cannot be improved at the same time. This is because although single-layer graphene has excellent electrical properties, but for multi-layer graphene films, the better the conductivity, the greater the thickness of the graphene film, but the lower the transmittance. Silver nanoparticles show unique thermal, electrical, optical, acoustic, magnetic, mechanical and catalytic properties due to their high surface energy and chemical activity, and have broad application prospects. Films prepared with silver-doped zinc oxide have good electrical conductivity and optical properties.

Contents of the invention

The purpose of the present invention is to provide a nickel phthalocyanine complex as a new ink for micro-contact printing on polyimide substrates. The technical scheme provided by the invention is: 1) the nickel phthalocyanine complex is octamethyl nickel phthalocyanine, which has the following structural formula:

The dichloromethane solution of nickel octamethylphthalocyanine is used as the printing agent for microcontact printing, and the pattern of the PDMS stamp is transferred to the polyimide substrate, and then graphene and silver are adsorbed and reduced, and finally a fine metal pattern is obtained on the substrate ;

Specific steps are as follows:

1. Soak the polyimide base in 5 wt% ethanol solution of 3-aminopropyltriethoxysilane, soak for 1 hour, wash with distilled water, and dry with _N2 ;

2. Dissolve carboxylated graphene oxide in water, and ultrasonically dissolve it for 1 minute to make it uniformly dissolved, with a concentration of 0.1-2g/L;

3. Dissolve nickel octamethylphthalocyanine in dichloromethane at a concentration of 1-10g/L;

4. Soak the PDMS stamp in the octamethylphthalocyanine nickel dichloromethane solution for 1-2 minutes, take it out and dry it in the N ₂ airflow for 30-60s, cover the above PDMS stamp on the substrate, press lightly for 10- 20s, transfer the PDMS stamp pattern to the surface of the substrate to obtain a patterned substrate;

5. Soak the patterned substrate in a mixed solution consisting of 1L graphene solution and 1L 5wt% silver nitrate, 7wt% sodium potassium tartrate, 5wt% sodium hydroxide, 40wt% formaldehyde and 43wt% distilled water for 3- After 5 minutes, a fine graphene/silver composite pattern can be obtained on the substrate after taking it out.

The beneficial effects of the present invention are:

1. By using the microcontact printing method to prepare graphene patterns on the surface of polyimide substrates commonly used in the electronics industry, it provides a new idea for the microcontact printing industry.

2. The graphene/silver composite pattern has better optical and electrical properties than single graphene.

3. The combination of phthalocyanine molecules and carboxylated graphene, including the π-π interaction between phthalocyanine and graphene, and the coordination bond between the carboxyl group of carboxylated graphene and phthalocyanine, so the combination is very tight .

4. The method has simple steps, easy-to-obtain raw materials, low cost and stability, and has great potential in industrial application.

detailed description

The present invention will be further described below in conjunction with the embodiments, so that those skilled in the art can implement it with reference to the description.

Example 1:

Soak the polyimide substrate in an ethanol solution of 5 wt% 3-aminopropyltriethoxysilane, soak for 1 hour, wash it with distilled water, and dry it with _N2 ; dissolve the carboxylated graphene oxide in water, Ultrasound for 1 minute to dissolve it uniformly, with a concentration of 0.1g/L; dissolve nickel octamethylphthalocyanine in dichloromethane, with a concentration of 1g/L; soak the PDMS stamp in the nickel octamethylphthalocyanine dichloride Put it in methane solution for 1 minute, take it out and dry it in _N2 air flow for 30s, cover the above PDMS stamp on the substrate, press lightly for 10s, transfer the pattern of PDMS stamp to the surface of the substrate, and obtain the substrate with printed pattern; Soak the substrate in a mixed solution consisting of 1L graphene solution and 1L 5wt% silver nitrate, 7wt% sodium potassium tartrate, 5wt% sodium hydroxide, 40wt% formaldehyde and 43wt% distilled water for 3 minutes, and put it on the substrate after taking it out Get a nice graphene/silver pattern.

Example 2:

Soak the polyimide substrate in an ethanol solution of 5 wt% 3-aminopropyltriethoxysilane, soak for 1 hour, wash it with distilled water, and dry it with _N2 ; dissolve the carboxylated graphene oxide in water, Ultrasound for 1 minute to make it dissolve evenly, the concentration is 2g/L; dissolve nickel octamethylphthalocyanine in dichloromethane, the concentration is 10g/L; soak the PDMS stamp in the nickel octamethylphthalocyanine dichloromethane Put in the solution for 2 minutes, take it out and dry it in _N2 air flow for 60s, put the above PDMS stamp on the substrate, press lightly for 20s, transfer the PDMS stamp pattern to the surface of the substrate, and obtain the substrate with the pattern printed; the substrate with the pattern printed Soak in a mixed solution consisting of 1L graphene solution and 1L 5wt% silver nitrate, 7wt% sodium potassium tartrate, 5wt% sodium hydroxide, 40wt% formaldehyde and 43wt% distilled water for 5 minutes, and get it on the substrate after taking it out Beautiful graphene/silver pattern.

Example 3:

Soak the polyimide substrate in an ethanol solution of 5 wt% 3-aminopropyltriethoxysilane, soak for 1 hour, wash it with distilled water, and dry it with _N2 ; dissolve the carboxylated graphene oxide in water, Ultrasound for 1 minute to dissolve it evenly, with a concentration of 0.8g/L; dissolve nickel octamethylphthalocyanine in dichloromethane, with a concentration of 7g/L; soak the PDMS stamp in the nickel octamethylphthalocyanine dichloride Put in methane solution for 1.5 minutes, take it out and dry it in _N2 air flow for 40s, cover the above PDMS stamp on the substrate, press lightly for 15s, transfer the PDMS stamp pattern to the surface of the substrate, and obtain the substrate with printed pattern; Soak the substrate in a mixed solution consisting of 1L graphene solution, 1L 5wt% silver nitrate, 7wt% sodium potassium tartrate, 5wt% sodium hydroxide, 40wt% formaldehyde and 43wt% distilled water for 4 minutes, and put it on the substrate after taking it out Get a nice graphene/silver pattern.

Although the embodiment of the present invention has been disclosed as above, it is not limited to the use listed in the specification and implementation, it can be applied to various fields suitable for the present invention, and it can be easily understood by those skilled in the art Therefore, the invention is not limited to the specific details and examples shown and described herein without departing from the general concept defined by the claims and their equivalents.

Claims (1)

1. Utilize nickel phthalocyanine complex to carry out the method for microcontact printing graphene/silver composite pattern, it is characterized in that: The nickel phthalocyanine complex is octamethyl nickel phthalocyanine and has the following structural formula: The dichloromethane solution of nickel octamethylphthalocyanine is used as the printing agent for microcontact printing, and the pattern of the PDMS stamp is transferred to the polyimide substrate, and then graphene and silver are adsorbed and reduced, and finally a fine metal pattern is obtained on the substrate ; Specific steps are as follows: 1. Soak the polyimide base in 5 wt% ethanol solution of 3-aminopropyltriethoxysilane, soak for 1 hour, wash with distilled water, and dry with _N2 ; 2. Dissolve carboxylated graphene oxide in water, and ultrasonically dissolve it for 1 minute to make it uniformly dissolved, with a concentration of 0.1-2g/L; 3. Dissolve nickel octamethylphthalocyanine in dichloromethane at a concentration of 1-10g/L; 4. Soak the PDMS stamp in the octamethylphthalocyanine nickel dichloromethane solution for 1-2 minutes, take it out and dry it in the N ₂ airflow for 30-60s, cover the above PDMS stamp on the substrate, press lightly for 10- 20s, transfer the PDMS stamp pattern to the surface of the substrate to obtain a patterned substrate; 5. Soak the patterned substrate in a mixed solution consisting of 1L graphene solution and 1L 5wt% silver nitrate, 7wt% sodium potassium tartrate, 5wt% sodium hydroxide, 40wt% formaldehyde and 43wt% distilled water for 3- After 5min, a fine graphene/silver pattern can be obtained on the substrate after taking it out.