CN101603176B - Preparation method of surface metal-based nano-array ball array structure - Google Patents

Abstract

The invention relates to a preparation method of a surface metal base nano array ball distributing structure, belonging to the technical field of nano materials. The preparation method comprises the following steps: carrying out surface degreasing treatment, surface derusting treatment and acid pickling treatment to the metal base material in sequence; implementing plating to the metal base material; carrying out chemical plating to the metal base material; then obtaining the surface metal base nano array ball distributing structure. In the process of electro-deposition of the invention, the preparation method controls the quantity of active points by adding a crystal adjusting agent, leads the electrocrystallization to extend in the plating solution by being dependent on the active points at any time, leads crystal to grow in the direction vertical to the surface of the metal base material, namely one-dimensional longitudinal direction and forms a micronano needle-shaped crystal distributing structure. Then a chemical plating method is utilized, a reducing agent and a buffering agent are added so as to grow nano balls with a similar scale on the nano needle. The largest advantages of the method lies in no need of using any template, no need of any complex equipment and no special requirements for material and shape of the base material, thus being suitable for industrial batch production.

Description

Preparation method of surface metal-based nano-array ball array structure

technical field

The invention relates to a preparation method in the technical field of nanomaterials, in particular to a preparation method for a surface metal-based nano-array ball array structure.

Background technique

This nano-array structure refers to a composite ordered array structure with micro-nano scale on the metal or non-metal surface, with a longitudinal needle-like structure at the bottom and a spherical structure at the top of the needle, that is, a long ball on the needle. Due to the large real surface area and high reactivity of this structure, its checkers-like structure will generate many new properties, so the application range is very wide. For example: (1) In the field of microelectronic packaging, using its special structure, the bonding strength between the frame and the plastic packaging resin is greatly enhanced. (2) It can be used for composite materials between metal and metal, metal and ceramics. (3) The increased surface area makes it have good light scattering and absorption properties, and can be used as optical materials, laser stealth materials, and photothermal conversion materials. (4) Use nanospheres as templates (plates) to make materials with special structures. (5) The lotus leaf effect can be produced, and the good hydrophobicity can be used as a hydrophobic material. At present, the micro-nano array structure is mostly studied from the perspective of devices, and the general size is mostly between microns and millimeters. The relevant preparation methods are mainly template (plate) method and LIGA (soft X-ray deep layer photolithography electroforming technology) method. After searching the existing technology, it was found that Ma Di et al. mentioned in the article "Characterization and Electrochemical Behavior of Electrodeposited Nickel Nanowires by AAO Pattern Method" (Functional Materials, 1001-9731(2004) Supplement-2836-03) The template method is specifically a method in which a porous oxide film is used as a template, and then metal particles are electrodeposited on the template to prepare a nano-array, and then the template is dissolved by a chemical method. In addition, Wu Guangfeng and others mentioned the LIGA method in "LIGA process basis and its development trend" (Mechanical and Electrical Engineering Technology, 1009-9492 (2007) 12-0089-04), that is, the use of photolithography plate making, electroforming, and template removal and other complex steps for microstructure processing. However, both existing technologies have disadvantages such as complex process, low efficiency, high cost, large equipment investment, and strict requirements on the size and shape of the base material. Therefore, it is suitable only for micro-device fabrication or research purposes.

Contents of the invention

The present invention aims at the above-mentioned deficiencies in the prior art, and provides a method for preparing a surface metal-based nano-array ball array structure, using the principle of electrochemical deposition, placing a conductive metal substrate as a cathode in an electroplating solution containing a crystallization regulator , and apply current or voltage to make the electrocrystal grow vertically and one-dimensionally in the direction perpendicular to the surface, and then form a nano-array similar to needle-like structure on the metal surface. Then the metal substrate is placed in the electroless plating solution, and then a layer of spherical crystal structure is deposited on the nano-array.

The present invention is achieved through the following technical solutions, and the present invention comprises the following steps:

The first step is to select a suitable metal substrate, and then perform surface degreasing treatment, surface derusting treatment and pickling treatment on the metal substrate in sequence.

The surface degreasing treatment refers to removing the oily organic substances adhered to the surface of the metal substrate.

The surface derusting treatment refers to removing inorganic substances in the oxide layer on the surface of the metal substrate.

The pickling treatment refers to immersing the metal substrate in a corrosive solution.

The second step is to put the metal substrate into the electroplating tank as the cathode, and the nickel metal sheet or the insoluble plate as the anode, and connect the anode, the cathode, the electroplating power supply and the electroplating solution in series with a wire to form a circuit, and then pass the electroplating power supply to the metal substrate. Perform electroplating.

The components and concentrations of the electroplating solution are: 0.1-2.5mol/L metal ions, 0.1-2mol/L complexing agent, 0.5mol/L boric acid and 1-1000PPM crystal regulator, the solution temperature of the electroplating solution is 25 -60°C, pH3.5-6.0.

The metal ion refers to one or a combination of nickel, copper, iron or aluminum.

The complexing agent refers to: one of citrate, malate, ethylenediaminetetraacetate, acetate, ethylenediamine or a combination thereof.

The crystal regulator is composed of Cu, Ag, Pd, Au, Zn, Sn, Ca and Y, La, Ce, Eu rare earth metal ions.

The electroplating performed is DC electroplating, single pulse electroplating or double pulse current electroplating.

In the third step, the electroplated metal substrate is placed in another plating tank containing an electroless plating solution for 2 minutes, and the surface metal-based nano-array ball array structure is prepared after electroless plating.

The composition and concentration of the electroless plating solution are: 0.1-2.5 mol/L of deposited metal ions of metals and alloys thereof, 0.1-2.5 mol/L of reducing agent, 0.1-2.5 mol/L of trisodium citrate and sodium acetate 0.1-2.5mol/L, the solution temperature of the electroless plating solution is 5°C-150°C, and the pH is 3.5-6.0.

The metal ion refers to one or a combination of nickel, copper, iron or aluminum.

Described reducing agent refers to sodium dihydrogen phosphite.

In the process of electrodeposition, the present invention controls the number of active points and makes the electrocrystallization depend on the active points to extend into the plating solution at every moment by adding a crystallization regulator, so that the crystallization is one-dimensional in a direction perpendicular to the surface of the metal substrate. Longitudinal growth, forming a micro-nano needle-like crystal array structure. Afterwards, the electroless plating method is used to add reducing agents and buffers to grow nanospheres of similar size on the nanoneedles. The biggest advantage of this method is that it does not require any templates, complex equipment, and no special requirements on the shape and material of the substrate, and is suitable for industrialized mass production.

Detailed ways

The embodiments of the present invention are described in detail below. This embodiment is implemented on the premise of the technical solution of the present invention, and detailed implementation methods and specific operating procedures are provided, but the protection scope of the present invention is not limited to the following implementation example.

Example 1

(1) Degreasing, derusting and pickling treatment are performed on the surface of the copper sheet that needs to be hydrophobically treated.

(2) Place the metal substrate processed in step (1) in the electroplating solution, the metal substrate is used as the cathode, and the nickel plate is used as the anode, and the two, the power supply, and the electroplating solution are used to form a circuit through wires. The composition of the electroplating solution is: 0.1 mol/L nickel chloride, 0.1 mol/L triammonium citrate, 0.5 mol/L boric acid, 1 ppm copper chloride crystallization regulator, solution temperature 60°C, pH 6.

(3) Adjust the current density to 1A/min, and electroplate for 20 minutes.

(4) Place the metal base material processed through (3) in the electroless plating solution, the solution consists of: nickel sulfate hexahydrate 0.1mol/L, sodium dihydrogen phosphite 0.1mol/L, trisodium citrate 0.1 mol/L, sodium acetate 0.2mol/L, solution temperature 60°C, pH 7.5, time 2min.

Results: By SEM observation, the height of the nano-plated needles is 0.05-0.4 microns, the diameter of the bottom is 0.05-0.2 microns, and the diameter of the nanospheres is 0.05-0.2 microns.

Example 2

(1) Degreasing, derusting and pickling treatment are performed on the surface of the copper sheet that needs to be hydrophobically treated.

(2) Place the metal substrate processed in step (1) in the electroplating solution, the metal substrate is used as the cathode, and the nickel plate is used as the anode, and the two, the power supply, and the electroplating solution are used to form a circuit through wires. The electroplating solution is composed of: 2.5 mol/L nickel chloride, 2 mol/L triammonium citrate, 0.5 mol/L boric acid, 1000 ppm copper chloride as a crystal regulator, solution temperature 25°C, Ph 3.5.

(3) Adjust the current density to 1A/min, and electroplate for 20 minutes.

(4) Place the metal base material treated in step (3) in the electroless plating solution, the solution consists of: nickel sulfate hexahydrate 0.5mol/L, sodium dihydrogen phosphite 0.5mol/L, trisodium citrate 0.5 mol/L, sodium acetate 1.5mol/L, solution temperature 80°C, pH 8, time 2min.

Results: By SEM observation, the height of the nano-plated needles is 0.05-0.4 microns, the diameter of the bottom is 0.05-0.2 microns, and the diameter of the nanospheres is 0.05-0.2 microns.

Example 3

(1) Degreasing, derusting and pickling treatment are performed on the surface of the copper sheet that needs to be hydrophobically treated.

(2) Place the metal substrate processed in step (1) in the electroplating solution, the metal substrate is used as the cathode, and the nickel plate is used as the anode, and the two, the power supply, and the electroplating solution are used to form a circuit through wires. The electroplating solution is composed of: 1.3 mol/L nickel chloride, 1 mol/L triammonium citrate, 0.5 mol/L boric acid, 500 ppm copper chloride as a crystal regulator, solution temperature 40°C, pH 4.

(3) Adjust the current density to 1A/min, and electroplate for 20 minutes.

(4) Place the metal substrate processed through (3) in the electroless plating solution, the solution consists of: nickel sulfate hexahydrate 2.5mol/L, sodium dihydrogen phosphite 1.3mol/L, trisodium citrate 1.3 mol/L, sodium acetate 1.3mol/L, solution temperature 40°C, pH 9.5, time 2min.

Results: By SEM observation, the height of the nano-plated needles is 0.05-0.4 microns, the diameter of the bottom is 0.05-0.2 microns, and the diameter of the nanospheres is 0.05-0.2 microns.

Example 4

(1) Degreasing, derusting and pickling treatment are performed on the surface of the copper sheet that needs to be hydrophobically treated.

(2) Place the metal substrate processed in step (1) in the electroplating solution, the metal substrate is used as the cathode, and the nickel plate is used as the anode, and the two, the power supply, and the electroplating solution are used to form a circuit through wires. The electroplating solution is composed of: 0.7 mol/L nickel chloride, 0.5 mol/L triammonium citrate, 0.5 mol/L boric acid, 100 ppm copper chloride as a crystal regulator, solution temperature 30°C, pH 4.5.

(3) Adjust the current density to 1A/min, and electroplate for 20 minutes.

(4) Place the metal substrate processed through (3) in the electroless plating solution, and the solution consists of: 0.7 mol/L of nickel sulfate hexahydrate, 0.7 mol/L of sodium dihydrogen phosphite, and 0.7 mol/L of trisodium citrate. mol/L, sodium acetate 0.7mol/L, solution temperature 90°C, pH 9, time 2min.

Results: By SEM observation, the height of the nano-plated needles is 0.05-0.4 microns, the diameter of the bottom is 0.05-0.2 microns, and the diameter of the nanospheres is 0.05-0.2 microns.

Example 5

(1) Degreasing, derusting and pickling treatment are performed on the surface of the copper sheet that needs to be hydrophobically treated.

(2) Place the metal substrate processed in step (1) in the electroplating solution, the metal substrate is used as the cathode, and the nickel plate is used as the anode, and the two, the power supply, and the electroplating solution are used to form a circuit through wires. The composition of the electroplating solution is: 1.9 mol/L nickel chloride, 1.5 mol/L triammonium citrate, 0.5 mol/L boric acid, 800 ppm copper chloride crystallization regulator, solution temperature 50°C, pH 5.

(3) Adjust the current density to 1A/min, and electroplate for 20 minutes.

(4) Place the metal substrate processed through (3) in the electroless plating solution, the solution consists of: nickel sulfate hexahydrate 1.9mol/L, sodium dihydrogen phosphite 1.9mol/L, trisodium citrate 1.9 mol/L, sodium acetate 1.9mol/L, solution temperature 70°C, pH 10.0, time 2min.

Results: By SEM observation, the height of the nano-plated needles is 0.05-0.4 microns, the diameter of the bottom is 0.05-0.2 microns, and the diameter of the nanospheres is 0.05-0.2 microns.

Claims (4)

1. the preparation method of a surface metal base nano array ball distributing structure is characterized in that, may further comprise the steps:

The first step, choose suitable metal base, metal base is carried out successively surface degreasing is handled, surface derusting is handled and cleanup acid treatment;

Second step, metal base is put into plating tank as negative electrode, nickel tinsel or insoluble pole plate be as anode, and with lead anode, negative electrode, electroplating power supply and electroplate liquid series connection are constituted the loop, by electroplating power supply metal base implemented to electroplate then;

The 3rd step, the metal base after will electroplating are put into the coating bath 2min that another contains chemical plating fluid, carry out making surface metal base nano array ball distributing structure after the electroless plating;

Described metal base is a copper sheet;

The component of described electroplate liquid and concentration are: nickelous chloride 0.1-2.5mol/L, triammonium citrate 0.1-2mol/L, boric acid 0.5mol/L and cupric chloride 1-1000ppm;

The component of described chemical plating fluid and concentration are: six hydration nickel sulfate 0.1-2.5mol/L, sodium dihydrogen phosphite 0.1-2.5mol/L, trisodium citrate 0.1-2.5mol/L and sodium acetate 0.1-2.5mol/L.

2. the preparation method of surface metal base nano array ball distributing structure according to claim 1 is characterized in that, described surface degreasing is handled and is meant: the adherent greasy dirt organic substance of metallic substrate surface is removed.

3. the preparation method of surface metal base nano array ball distributing structure according to claim 1 is characterized in that, described surface derusting is handled and is meant: the zone of oxidation inorganic substance of metallic substrate surface are removed.

4. the preparation method of surface metal base nano array ball distributing structure according to claim 1 is characterized in that, described cleanup acid treatment is meant metal base is soaked in having corrosive solution.