CN104192789B - A kind of nano/micron gold film and preparation method thereof - Google Patents

Abstract

The invention discloses a nano/micro gold film and a preparation method thereof. The nano/micro gold film includes a substrate and a nano/micro gold layer, the nano/micro metal layer is deposited from metal nanoparticles, the substrate surface has amino groups, and the metal nanoparticles and the substrate surface amino groups form a strong interaction. The preparation method comprises the following steps: (1) subjecting the substrate surface to oxygen plasma treatment or ultraviolet light irradiation; (2) immersing the surface-activated substrate in a 3-aminopropyltriethoxysilane solution; (3) taking The mixed solution of chloroauric acid and bicarbonate of strong alkali is evenly mixed with the glucose solution, and coated on the surface aminated substrate, and reacted in the dark to obtain the nanometer/micrometer metal film. The invention provides a nano/micro gold film, which has many types of substrates, can meet the requirements of different mechanical properties, is firmly bonded, and is not easy to break; the method provided by the invention has mild reaction and low cost.

Description

A kind of nano/micro gold film and preparation method thereof

technical field

The invention belongs to the field of nanomaterials, and more specifically relates to a nano/micro gold film and a preparation method thereof.

Background technique

The nano/micro gold film composed of nanoparticles has obvious surface effect, volume effect, small size effect, quantum effect and good biocompatibility. Its optical properties, electronic properties, sensing properties and biochemical properties have always been research hotspots. .

At present, the preparation methods of nano/micro gold layers mainly include electron beam evaporation, chemical vapor deposition (CVD), physical vapor deposition (PVD) and other methods. Although these methods can obtain relatively uniform nano gold layers, the equipment is expensive and the process is complicated. . In 2009, Chen Hongyuan and others invented a method for chemically depositing nano-gold on PDMS. This method deposits gold directly on PDMS, and the preparation is simple. However, this method can only use PDMS as the substrate, and its application range is limited. At the same time, the homogeneity of the obtained nano-gold layer cannot be guaranteed, the combination of gold and PDMS is not firm, and the gold is easy to break and fall off during the stretching and bending of PDMS.

Contents of the invention

Aiming at the above defects or improvement needs of the prior art, the present invention provides a nano/micro gold film and a preparation method thereof. The nano/micro gold film is obtained, thereby solving the technical problem that the nano/micro gold film prepared by the existing nano/micro gold film deposition method is not firmly bonded, and is easy to break and fall off during stretching/bending.

In order to achieve the above object, according to one aspect of the present invention, a nano/micro gold film is provided, including a substrate and a nano/micro gold layer, the nano/micro metal layer is deposited from metal nanoparticles, and the substrate surface With amino groups, the metal nanoparticles form a strong interaction with amino groups on the surface of the substrate, so that the nano/micro gold layer is firmly attached to the surface of the substrate.

Preferably, the matrix of the nano/micro metal film is a non-absorbent dense film, preferably polydimethylsiloxane, glass, indium tin oxide conductive glass, polyethylene terephthalate film, polyethylene Imide film, polyethylene film or Teflon film.

According to another aspect of the present invention, there is provided a method for preparing a nano/micro metal film, characterized in that it comprises the following steps:

(1) Substrate surface treatment: subject the substrate surface to oxygen plasma treatment or ultraviolet light irradiation, so that oxidized active groups are generated on the substrate surface, and a surface-activated substrate is obtained;

(2) Substrate surface amination: the surface-activated substrate obtained in step (1) is immersed in a 3-aminopropyltriethoxysilane solution for amination treatment to obtain a surface-aminated substrate;

(3) Deposit metal film: get the mixed solution of chloroauric acid and the bicarbonate of strong base and glucose solution and evenly mix, and apply on the substrate of the surface amination that obtains in step (2), make every 1cm Distribute Contains 3.58×10 ^-5 g to 2.87×10 ^-3 g of gold elements and 7.5×10 ^-4 g to 3×10 ^-3 g of glucose, at 20°C to 40°C, react in the dark for 2 hours to 4 hours, then wash and dry , to obtain the nano/micro metal film.

Preferably, in the preparation method, the substrate is a non-absorbent dense film, preferably polydimethylsiloxane, glass, indium tin oxide conductive glass, polyethylene terephthalate film, polyamide Imine film, polyethylene film or PTFE film.

Preferably, in the preparation method, when the substrate is a polyethylene film or a polytetrafluoroethylene film, the surface treatment of the substrate is irradiated with ultraviolet light.

Preferably, in the preparation method, the oxygen plasma treatment time of step (1) is 3 minutes to 5 minutes, and the ultraviolet light irradiation has an ultraviolet light intensity of 90uW/cm to 180uW/cm, and the irradiation time is 40 minutes to 90 minutes.

Preferably, the specific operation of the step (2) of the preparation method is:

The surface-activated matrix obtained in step (1) is immersed in the 3-aminopropyltriethoxysilane solution, reacted for 30 minutes to 120 minutes, washed with deionized water and dried.

Preferably, in the preparation method, the specific method of coating in step (3) is to reversibly bond a polydimethylsiloxane with a groove in the middle to the surface aminated substrate obtained in step (2). (PDMS) block, the groove is used to hold the deposition solution.

Preferably, in the preparation method, the mixed solution of chloroauric acid and strong base bicarbonate in step (3), wherein the concentration of chloroauric acid is from 10 ^-3 g/ml to 2×10 ^-2 g/ml Between, the concentration of bicarbonate is between 0.15mol/L and 0.5mol/L.

Generally speaking, compared with the prior art, the above technical solutions conceived by the present invention can achieve the following beneficial effects:

(1) The nano/micro gold film provided by the present invention can have multiple substrates, and different substrates have different mechanical properties, such as glass-based substrates with higher mechanical strength, and polydimethylsiloxane (PDMS) The matrix has good tensile properties, so the nano/micro gold film can meet different application requirements.

(2) The nano/micro gold film provided by the present invention uses the strong interaction between nano gold particles and amino groups, and the formed nano/micro gold layer can be firmly combined with the substrate evenly, and the gold is not easy to break and fall off during stretching and bending .

(3) The nano/micro gold film preparation method provided by the present invention adopts the chemical deposition method, does not need expensive equipment, the preparation method is simple, and the reaction conditions are mild, and can be applied to large-scale industrial production, greatly reducing the cost of the nano/micro gold film. Cost of production.

(4) nanometer/micron gold film preparation method provided by the present invention can be directly proportional to the thickness of the gold nanometer layer of deposition and the amount of deposition solution by controlling gold content in the bicarbonate of chloroauric acid and the strong alkali , the thickness of the nano-gold layer can be adjusted by controlling the amount of the deposition solution, and can be deposited multiple times to obtain gold layers of different thicknesses to meet different process requirements.

detailed description

In order to make the object, technical solution and advantages of the present invention more clear, the present invention will be further described in detail below in conjunction with the examples. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention. In addition, the technical features involved in the various embodiments of the present invention described below can be combined with each other as long as they do not constitute a conflict with each other.

The nano/micro gold film provided by the present invention comprises a substrate and a nano/micro gold layer, the nano/micro metal layer is formed by depositing metal nanoparticles, the surface of the substrate has amino groups, the metal nanoparticles and the substrate The surface amino groups form a strong interaction, so that the nano/micro gold layer is firmly attached to the surface of the substrate. The substrate is a dense film that does not absorb water, preferably polydimethylsiloxane, glass, indium tin oxide conductive glass, polyethylene terephthalate film, polyimide film, polyethylene film or polyester film. Tetrafluoroethylene membrane.

Described nano/micro gold film, its preparation method, comprises the following steps:

(1) Substrate surface treatment: the substrate surface is subjected to oxygen plasma treatment or ultraviolet light irradiation, so that the substrate surface produces oxidized active groups to obtain a surface-activated substrate; the substrate is a non-absorbent dense film, preferably polydimethylformaldehyde silicone, glass, indium tin oxide conductive glass, polyethylene terephthalate film, polyimide film, polyethylene film, or polytetrafluoroethylene film. The oxygen plasma treatment time in step (1) is 3 minutes to 5 minutes, the ultraviolet light intensity is 90uW/cm to 180uW/cm, and the irradiation time is 40 minutes to 90 minutes.

When the substrate is a plastic substrate, such as a polyethylene film or a polytetrafluoroethylene film, since it is easily deformed when treated with oxygen plasma, the surface treatment of the substrate should be irradiated with ultraviolet light.

(2) Substrate surface amination: the surface-activated substrate obtained in step (1) is immersed in a 3-aminopropyltriethoxysilane solution for amination treatment to obtain a surface-aminated substrate; the specific operations are as follows: :

The surface-activated matrix obtained in step (1) is immersed in the 3-aminopropyltriethoxysilane solution, reacted for 30 minutes to 120 minutes, washed with deionized water and dried.

(3) Deposit metal film: get the mixed solution of chloroauric acid and the bicarbonate of strong alkali and glucose solution and evenly mix, and be coated on the substrate of the surface amination that obtains in step ( ² ), make every 1cm Distributed with 3.58×10 ^-5 g to 2.87×10 ^-3 g of gold elements and 7.5×10 ^-4 g to 3×10 ^-3 g of glucose, at 20°C to 40°C, react in the dark for 2 hours to 4 hours and then wash drying to obtain the nano/micro metal film. The mixed solution of chloroauric acid and bicarbonate of strong base, wherein the concentration of chloroauric acid is between 10 ^-3 g/ml and 2×10 ^-2 g/ml, and the concentration of bicarbonate is 0.15mol/L to 0.5mol/L.

The specific method of coating is to reversibly bond a polydimethylsiloxane (PDMS) block with a groove in the middle on the surface aminated substrate obtained in step (2), and the groove is used to hold deposition solution.

The gold nano/micro film prepared by the method can be applied to electrochemical sensing, biological sensing, and acquisition of cell patterns, and can be further applied to the fields of medical diagnosis, tissue engineering, and the like.

The following are examples:

Example 1

The nano/micro gold film provided by the present invention comprises a substrate and a nano/micro gold layer, the nano/micro metal layer is formed by depositing metal nanoparticles, the surface of the substrate has amino groups, the metal nanoparticles and the substrate The surface amino groups form a strong interaction, so that the nano/micro gold layer is firmly attached to the surface of the substrate. The matrix is a non-absorbent dense film, which is polydimethylsiloxane.

Described nano/micro gold film, its preparation method, comprises the following steps:

(1) Substrate surface treatment: The surface of the polydimethylsiloxane substrate is subjected to oxygen plasma treatment, so that oxidized active groups are generated on the substrate surface, and a surface-activated substrate is obtained. The oxygen plasma treatment time was 3 minutes.

(2) Substrate surface amination: the surface-activated substrate obtained in step (1) is immersed in a 3-aminopropyltriethoxysilane solution for amination treatment to obtain a surface-aminated substrate; the specific operations are as follows: :

The surface-activated substrate obtained in step (1) was immersed in the 3-aminopropyltriethoxysilane solution, reacted for 120 minutes, washed with deionized water and dried.

(3) Deposit metal film: get the mixed solution of chloroauric acid and the bicarbonate of strong alkali and glucose solution and evenly mix, and be coated on the substrate of the surface amination that obtains in step ( ² ), make every 1cm 3.58×10 ^-5 g of gold element and 7.5×10 ^-4 g of glucose are distributed, and the nano/micro metal film is obtained after reacting in the dark for 4 hours at 25°C. The mixed solution of chloroauric acid and bicarbonate of strong base, wherein the concentration of chloroauric acid is between 10 ⁻³ g/ml and the concentration of bicarbonate is 0.15 mol/L.

The specific method of coating is to reversibly bond a polydimethylsiloxane (PDMS) block with a groove in the middle on the surface aminated substrate obtained in step (2), and the groove is used to hold deposition solution.

The gold film can be deposited multiple times by repeating step (3), thereby controlling the thickness of the gold film.

Example 2

The nano/micro gold film provided by the present invention comprises a substrate and a nano/micro gold layer, the nano/micro metal layer is formed by depositing metal nanoparticles, the surface of the substrate has amino groups, the metal nanoparticles and the substrate The surface amino groups form a strong interaction, so that the nano/micro gold layer is firmly attached to the surface of the substrate. The matrix is a non-water-absorbing dense film, which is glass.

Described nano/micro gold film, its preparation method, comprises the following steps:

(1) Substrate surface treatment: The surface of the glass substrate is treated with oxygen plasma to generate oxidized active groups on the surface of the substrate to obtain a surface-activated substrate. The oxygen plasma treatment time was 4 minutes.

(2) Substrate surface amination: the surface-activated substrate obtained in step (1) is immersed in a 3-aminopropyltriethoxysilane solution for amination treatment to obtain a surface-aminated substrate; the specific operations are as follows: :

The surface-activated substrate obtained in step (1) was immersed in the 3-aminopropyltriethoxysilane solution, reacted for 90 minutes, washed with deionized water and dried.

(3) Deposit metal film: get the mixed solution of chloroauric acid and the bicarbonate of strong alkali and glucose solution and evenly mix, and be coated on the substrate of the surface amination that obtains in step ( ² ), make every 1cm 3.5×10 ^-4 g of gold element and 1.2×10 ^-3 g of glucose are distributed, and reacted at 20° C. for 3 hours in the dark, washed and dried to obtain the nano/micro metal film. The mixed solution of chloroauric acid and bicarbonate of strong base, wherein the concentration of chloroauric acid is between 10 ⁻² g/ml and the concentration of bicarbonate is 0.3 mol/L.

The specific method of coating is to reversibly bond a polydimethylsiloxane (PDMS) block with a groove in the middle on the surface aminated substrate obtained in step (2), and the groove is used to hold deposition solution.

Example 3

The nano/micro gold film provided by the present invention comprises a substrate and a nano/micro gold layer, the nano/micro metal layer is formed by depositing metal nanoparticles, the surface of the substrate has amino groups, the metal nanoparticles and the substrate The surface amino groups form a strong interaction, so that the nano/micro gold layer is firmly attached to the surface of the substrate. The matrix is a non-water-absorbing dense film, which is indium tin oxide conductive glass.

Described nano/micro gold film, its preparation method, comprises the following steps:

(1) Substrate surface treatment: The surface of the indium tin oxide conductive glass substrate is subjected to oxygen plasma treatment, so that oxidized active groups are generated on the substrate surface, and a surface-activated substrate is obtained. The oxygen plasma treatment time was 5 minutes.

(2) Substrate surface amination: the surface-activated substrate obtained in step (1) is immersed in a 3-aminopropyltriethoxysilane solution for amination treatment to obtain a surface-aminated substrate; the specific operations are as follows: :

The surface-activated substrate obtained in step (1) was immersed in the 3-aminopropyltriethoxysilane solution, reacted for 30 minutes, washed with deionized water and dried.

(3) Deposit metal film: get the mixed solution of chloroauric acid and the bicarbonate of strong alkali and glucose solution and evenly mix, and be coated on the substrate of the surface amination that obtains in step ( ² ), make every 1cm 2.87×10 ^-3 g of gold element and 3×10 ^-3 g of glucose are distributed, and reacted at 40° C. for 2 hours in the dark, washed and dried to obtain the nano/micro metal film. The mixed solution of chloroauric acid and bicarbonate of strong base, wherein the concentration of chloroauric acid is between 2×10 ⁻² g/ml, and the concentration of bicarbonate is 0.5 mol/L.

The specific method of coating is to reversibly bond a polydimethylsiloxane (PDMS) block with a groove in the middle on the surface aminated substrate obtained in step (2), and the groove is used to hold deposition solution.

Example 4

The nano/micro gold film provided by the present invention comprises a substrate and a nano/micro gold layer, the nano/micro metal layer is formed by depositing metal nanoparticles, the surface of the substrate has amino groups, the metal nanoparticles and the substrate The surface amino groups form a strong interaction, so that the nano/micro gold layer is firmly attached to the surface of the substrate. The substrate is a non-absorbent dense film, which is a polyethylene terephthalate film.

Described nano/micro gold film, its preparation method, comprises the following steps:

(1) Substrate surface treatment: irradiating the surface of the polyethylene terephthalate film substrate with ultraviolet light, so that oxidized active groups are generated on the substrate surface, and a surface-activated substrate is obtained. The intensity of ultraviolet light is 90uW/cm, and the irradiation time is 90 minutes.

(2) Substrate surface amination: the surface-activated substrate obtained in step (1) is immersed in a 3-aminopropyltriethoxysilane solution for amination treatment to obtain a surface-aminated substrate; the specific operations are as follows: :

The surface-activated substrate obtained in step (1) was immersed in the 3-aminopropyltriethoxysilane solution, reacted for 120 minutes, washed with deionized water and dried.

(3) Deposit metal film: get the mixed solution of chloroauric acid and the bicarbonate of strong alkali and glucose solution and evenly mix, and be coated on the substrate of the surface amination that obtains in step ( ² ), make every 1cm 3.58×10 ^-5 g of gold element and 7.5×10 ^-4 g of glucose are distributed, and the nano/micro metal film is obtained after reacting in the dark for 3 hours at 25°C and then washing and drying. The mixed solution of chloroauric acid and bicarbonate of strong base, wherein the concentration of chloroauric acid is between 10 ⁻³ g/ml and the concentration of bicarbonate is 0.15 mol/L.

The specific method of coating is to reversibly bond a polydimethylsiloxane (PDMS) block with a groove in the middle on the surface aminated substrate obtained in step (2), and the groove is used to hold deposition solution.

Example 5

The nano/micro gold film provided by the present invention comprises a substrate and a nano/micro gold layer, the nano/micro metal layer is formed by depositing metal nanoparticles, the surface of the substrate has amino groups, the metal nanoparticles and the substrate The surface amino groups form a strong interaction, so that the nano/micro gold layer is firmly attached to the surface of the substrate. The substrate is a non-absorbent dense film, which is a polyimide film.

Described nano/micro gold film, its preparation method, comprises the following steps:

(1) Substrate surface treatment: irradiate the surface of the polyimide membrane substrate with ultraviolet light, so that oxidized active groups are generated on the substrate surface, and a surface-activated substrate is obtained. The ultraviolet light intensity is 120uW/cm, and the irradiation time is 60 minutes.

(2) Substrate surface amination: the surface-activated substrate obtained in step (1) is immersed in a 3-aminopropyltriethoxysilane solution for amination treatment to obtain a surface-aminated substrate; the specific operations are as follows: :

The surface-activated matrix obtained in step (1) was immersed in the 3-aminopropyltriethoxysilane solution, reacted for 60 minutes, washed with deionized water and dried.

(3) Deposit metal film: get the mixed solution of chloroauric acid and the bicarbonate of strong alkali and glucose solution and evenly mix, and be coated on the substrate of the surface amination that obtains in step ( ² ), make every 1cm 3.7×10 ^-4 g of gold element and 1.3×10 ^-3 g of glucose are distributed, and the nano/micro metal film is obtained after reacting in the dark for 4 hours at 20° C. and then washing and drying. The mixed solution of chloroauric acid and bicarbonate of strong base, wherein the concentration of chloroauric acid is between 10 ⁻² g/ml and the concentration of bicarbonate is 0.3 mol/L.

The specific method of coating is to reversibly bond a polydimethylsiloxane (PDMS) block with a groove in the middle on the surface aminated substrate obtained in step (2), and the groove is used to hold deposition solution.

The gold film can be deposited multiple times by repeating step (3), thereby controlling the thickness of the gold film.

Example 6

The nano/micro gold film provided by the present invention comprises a substrate and a nano/micro gold layer, the nano/micro metal layer is formed by depositing metal nanoparticles, the surface of the substrate has amino groups, the metal nanoparticles and the substrate The surface amino groups form a strong interaction, so that the nano/micro gold layer is firmly attached to the surface of the substrate. The matrix is a non-absorbent dense film, which is a polytetrafluoroethylene film.

Described nano/micro gold film, its preparation method, comprises the following steps:

(1) Substrate surface treatment: irradiate the surface of the polytetrafluoroethylene membrane substrate with ultraviolet light, so that oxidized active groups are generated on the substrate surface, and a surface-activated substrate is obtained. The ultraviolet light intensity is 180uW/cm, and the irradiation time is 40 minutes.

(2) Substrate surface amination: the surface-activated substrate obtained in step (1) is immersed in a 3-aminopropyltriethoxysilane solution for amination treatment to obtain a surface-aminated substrate; the specific operations are as follows: :

The surface-activated substrate obtained in step (1) was immersed in the 3-aminopropyltriethoxysilane solution, reacted for 30 minutes, washed with deionized water and dried.

(3) Deposit metal film: get the mixed solution of chloroauric acid and the bicarbonate of strong alkali and glucose solution and evenly mix, and be coated on the substrate of the surface amination that obtains in step ( ² ), make every 1cm 2.87×10 ^-3 g of gold element and 3×10 ^-3 g of glucose are distributed, and reacted at 40° C. for 2 hours in the dark, then washed and dried to obtain the nano/micro metal film. The mixed solution of chloroauric acid and bicarbonate of strong base, wherein the concentration of chloroauric acid is between 2×10 ⁻² g/ml, and the concentration of bicarbonate is 0.5 mol/L.

The specific method of coating is to reversibly bond a polydimethylsiloxane (PDMS) block with a groove in the middle on the surface aminated substrate obtained in step (2), and the groove is used to hold deposition solution.

It is easy for those skilled in the art to understand that the above descriptions are only preferred embodiments of the present invention, and are not intended to limit the present invention. Any modifications, equivalent replacements and improvements made within the spirit and principles of the present invention, All should be included within the protection scope of the present invention.

Claims (9)

1. a preparation method of nano/micro metal film, is characterized in that, comprises the following steps: (1) Substrate surface treatment: subject the substrate surface to oxygen plasma treatment or ultraviolet light irradiation, so that oxidized active groups are generated on the substrate surface, and a surface-activated substrate is obtained; (2) Substrate surface amination: the surface-activated substrate obtained in step (1) is immersed in a 3-aminopropyltriethoxysilane solution for amination treatment to obtain a surface-aminated substrate; (3) Deposit metal film: get the mixed solution of chloroauric acid and the bicarbonate of strong base and glucose solution and evenly mix, and apply on the substrate of the surface amination that obtains in step (2), make every 1cm Distribute Contains 3.58×10 ^-5 g to 2.87×10 ^-3 g of gold elements and 7.5×10 ^-4 g to 3×10 ^-3 g of glucose, at 20°C to 40°C, react in the dark for 2 hours to 4 hours, then wash and dry , to obtain the nano/micro metal film. 2. The preparation method according to claim 1, wherein the matrix is a non-absorbent dense film. 3. the preparation method as claimed in claim 2 is characterized in that, described matrix is polydimethylsiloxane, glass, polyethylene terephthalate film, polyimide film, polyethylene film or PTFE membrane. 4. The preparation method according to claim 3, wherein the glass is an indium tin oxide conductive glass. 5. The preparation method according to claim 1, wherein when the substrate is a polyethylene film or a polytetrafluoroethylene film, the surface treatment of the substrate is irradiated with ultraviolet light. 6. The preparation method according to claim 1, characterized in that, the oxygen plasma treatment time of step (1) is 3 minutes to 5 minutes, and the ultraviolet light irradiation has an ultraviolet light intensity of 90uW/cm to 180uW/cm cm, and the irradiation time ranges from 40 minutes to 90 minutes. 7. preparation method as claimed in claim 1, is characterized in that, the concrete operation of described step (2) is: The surface-activated substrate obtained in step (1) is immersed in the 3-aminopropyltriethoxysilane solution, reacted for 30 minutes to 120 minutes, washed with deionized water and dried. 8. The preparation method as claimed in claim 1, characterized in that, the specific method of coating in the step (3) is, on the surface aminated substrate obtained in the step (2), reversibly bond a The polydimethylsiloxane block of the groove is used to hold the solution obtained by uniformly mixing the mixed solution of chloroauric acid and strong alkali bicarbonate and the glucose solution. 9. preparation method as claimed in claim 1, is characterized in that, the mixed solution of the bicarbonate of chloroauric acid and strong base described in step (3), wherein chloroauric acid concentration is at 10 ^-3 g/ml to 2 ×10 ^-2 g/ml, the concentration of bicarbonate is between 0.15mol/L and 0.5mol/L.