CN113072309A

CN113072309A - Method suitable for jointing lens material and metal material

Info

Publication number: CN113072309A
Application number: CN202110300227.8A
Authority: CN
Inventors: 顾良; 毛军刚
Original assignee: Joymedicare Shanghai Medical Electronic Technology Co ltd
Current assignee: Joymedicare Shanghai Medical Electronic Technology Co ltd
Priority date: 2021-03-11
Filing date: 2021-03-22
Publication date: 2021-07-06

Abstract

The invention discloses a method suitable for jointing a lens material and a metal material, which comprises the following steps of pretreating a joint surface of the materials to be jointed to expose the materials of the joint surface; etching the exposed joint surface to generate a microstructure array pattern in dense arrangement on the surface; respectively carrying out replacement layer growth, seed crystal layer replacement and middle layer plating on the microstructure array pattern of the heterogeneous material to be jointed in sequence to obtain a composite plating layer; carrying out thermal oxidation treatment on the obtained composite coating, introducing an ion source, maintaining for a period of time, and cooling; preparing three electrodes, and performing electropolishing treatment on the joint surface in electrolyte containing a corrosion source by using reverse electroplating reaction; under vacuum environment, a certain voltage and current are applied to the joint surface after the joint surface is contacted, so that the joint effect is achieved. The composite coating of the invention is jointed by a dry anode, and the surface ions of the film layer are diffused by the surface coatings of the two workpieces under the pressure of voltage introduction and operating environment, so that the joint effect of the interface is achieved.

Description

Method suitable for jointing lens material and metal material

Technical Field

The invention belongs to the technical field of materials, and particularly relates to a method suitable for bonding a lens material and a metal material.

Background

In the aspect of medical related fields, regarding the medical behaviors and applications of medical instruments which are most suitable for the public, under the rapid development state of medical instruments, especially the invasive endoscope and other related technologies are most commonly used in various types of surgical operations or related medical behaviors, however, various endoscopes in medical instruments need to be adapted to the consideration of the harsh external physiological environment factors formed by the acid-base environment and the related physiological environment in the human body, so that establishing a tabling joint assembly technology which can form a high-safety endoscope is an important issue and a deeply-researched field in the field of endoscope assembly.

In various types of endoscope structure products, particularly those used in medical treatment, it is necessary to deal with severe environmental factors, such as physiological environment, acid-base environment, and bacterial environment, which may cause corrosion or potential structural damage to the endoscope structure and the related joint surface due to unexpected damage.

Disclosure of Invention

The invention aims to provide a method for jointing a semiconductor lens and a metal material in an endoscope structure, which can effectively overcome the limitations of external conditions such as different material characteristics, package shapes and the like, and completely resist the defects of incomplete package caused by corrosion behavior and related structural destruction behavior.

In order to achieve the purpose, the technical scheme is as follows:

a method for bonding a lens material to a metal material, comprising the steps of:

(1) surface treatment

Pretreating the joint surface of the materials to be jointed to expose the materials on the joint surface;

(2) microstructure array preparation

Etching the exposed joint surface to generate a microstructure array pattern in dense arrangement on the surface;

(3) preparation of composite coating

Respectively carrying out replacement layer growth, seed crystal layer replacement and middle layer plating on the microstructure array pattern of the heterogeneous material to be jointed in sequence to obtain a composite plating layer;

(4) ion implantation

Carrying out thermal oxidation treatment on the obtained composite coating, introducing an ion source, maintaining for a period of time, and cooling;

(5) planarization process

Preparing three electrodes, and performing electropolishing treatment on the joint surface in electrolyte containing a corrosion source by using reverse electroplating reaction;

(6) anodic bonding

Under vacuum environment, a certain voltage and current are applied to the joint surface after the joint surface is contacted, so that the joint effect is achieved.

According to the scheme, the lens material is a lens material with silicon oxide as a main body or a semiconductor lens material.

According to the scheme, the surface treatment process in the step 1 comprises corrosion or cleaning or corrosion plus cleaning.

According to the scheme, the microstructure array preparation in the step 2 adopts a wet etching and impressing array pattern, and the specific process is as follows:

preparing a mold with a microstructure array, carrying out catalytic corrosion by using an electrolytic reaction suitable for a joint surface material, and reversely etching and copying a microstructure array pattern of the mold on a joint surface.

According to the scheme, the preparation of the microstructure array in the step 2 adopts a dry-type imprinting and transfer printing array pattern, and the specific process is as follows:

preparing a mold with a microstructure array, and forming a microstructure array pattern of the mold on a joint surface by dry electrolytic imprinting suitable for the joint surface material.

According to the scheme, the replacement layer in the step 3 grows, and the method comprises the following steps:

immersing the joint surface into catalytic electrolytic metal complex solution to enable the metal complex to form a catalytic ion layer on the surface of the microstructure array; the complex liquid is a complex solution of tin dioxide and glycine, cysteine, arginine or serine.

According to the scheme, the seed layer replacement in the step 3 comprises the following steps:

and soaking the joint surface into chloride solution of gold, silver, palladium or platinum, and performing displacement under the catalysis of the catalytic ion layer, so that the catalytic ion layer on the surface of the microstructure array absorbs and displaces to form a metal coating.

According to the scheme, the intermediate layer plating layer in the step 3 comprises the following steps:

and electroplating nickel, copper, zinc, chromium or titanium on the metal coating on the surface of the microstructure array through three electrodes to obtain an intermediate coating.

According to the scheme, the ion source in the step 4 is sodium ions, aluminum ions, potassium ions, phosphorus or boron.

According to the scheme, the vacuum degree of the anode joint in the step 6 is 0-10^-5torr; the voltage is 1-5V; the current is 1-10A.

Compared with the prior art, the beneficial effects are as follows:

the method for jointing the semiconductor lens and the metal material in the endoscope structure can be directly used for jointing the surfaces of heterogeneous special-shaped structures, and the structural shape of the method is not limited to a circle, a ring, a square or a related specific shape; is particularly suitable for assembling and manufacturing the lens and the shell of the endoscope.

The invention relates to a composite coating layer by dry type anode joint, in particular to a dry type method similar to high temperature and high pressure anode joint reaction. The planarization is used to provide the high flatness requirement necessary for anode bonding, voltage and current flow in the junction of two workpieces to provide effective interface bonding, and then voltage drop is performed to gradually adjust the bonding strength of the junction to increase, so as to achieve the bonding effect.

Detailed Description

The following examples further illustrate the technical solutions of the present invention, but should not be construed as limiting the scope of the present invention.

Take the example of stainless steel and sapphire lens material bonding for endoscope construction.

(1) And removing the original film layer, namely performing surface treatment.

The process is mainly used for removing a workpiece surface layer material needing plating treatment, such as a thin film with a protective effect on the surface of a metal or alloy material, and any corrosion, etching or plating treatment needs to be carried out by removing the film first so as to be beneficial to the execution of subsequent actions.

Taking stainless steel alloy as an example, a chromized film which is easy to be oxidized is generated on the surface due to the components of iron, nickel, gold and chromium metal, before cleaning and corrosion are carried out to a certain depth, a chromium oxide film is continuously generated for protection, and the film needs to be effectively removed through the corrosion effect, so that the subsequent process is facilitated.

(2) And (4) preparing a microstructure.

The process action is mainly to prepare a surface microstructure on the joint surface of a workpiece to be jointed after the original film layer is removed or the original film layer is not required to be removed, wherein the microstructure can be prepared by adopting wet-type impression etching or dry-type impression transfer printing, so that a densely arranged ordered array pattern is generated on the surface of the microstructure, and the subsequent process of treating a coating can be facilitated to coat the coating on the surface of the pattern according to the basic shape of the pattern.

Wet etching imprint patterning: by utilizing the micro-structure array which is precisely processed, an electrolytic reaction which is suitable for the materials of the workpieces to be jointed and can carry out catalytic corrosion is formulated, the pattern of the precise die can be directly reversely etched and copied on the joint surface of the workpieces to be jointed, and the array micro-structure pattern to be formed can be formed.

The specific operation is as follows:

1. an ultra-precise mold is adopted, the pyramid structure of the mold is 0.1-0.3um, the interval is 0.05-0.1um, and the mold is made of high-rigidity materials such as stainless steel, silicon base, tungsten steel and the like;

2. preparing special etching liquid, and preparing hydrofluoric acid, hydrogen peroxide, isopropanol and water in a ratio of 1:5:0.5: 10;

3. forming an electrochemical etching reaction, and configuring an electrode (mold) for etching, a carbon electrode (processing workpiece) and a reference electrode;

4. carrying out wet micro-nano imprinting, keeping pressure between the workpiece and the mold, and conducting current to form electrochemical etching reaction;

5. adjusting voltage to 0.01-1.37-2.0V and 0.05-0.1A, observing potential output to a descending trend with reference to an electrochemical workstation, wherein the operation time can be 0-60 seconds;

6. after the reaction, the reaction solution is washed, and ultrasonic oscillation washing is sequentially carried out for 1 minute, 1 minute and 5 minutes by using purified water/IPA/purified water, and then drying is carried out.

Dry imprint transfer: the micro-structure array is precisely processed, the joint surface of the workpieces to be jointed is impacted by electrolysis to form a two-phase interface capable of being dissolved and diffused temporarily, and the array micro-structure pattern is formed on the joint surface by dry electrolytic imprinting. Or the micro-structure array which is precisely processed is used for making imprinting which is suitable for the materials of the workpieces to be jointed and can carry out thermoplastic physical contact surface softening and solidification, and the pattern of the precise mould can be directly reversely etched and copied on the jointing surface of the workpieces to be jointed, so that the array micro-structure pattern to be formed can be formed.

The specific operation is as follows:

2. cleaning a mould, preparing isopropanol, cleaning for 1 minute by ultrasonic oscillation, and cleaning for 1 minute by ultrasonic oscillation with ultrapure water;

3. carrying out vacuum drying on the mold to ensure that no residue is left after removing surface moisture;

4. heating the mould for reaction, and configuring and maintaining the temperature in the range of 5-10 ℃ greater than the melting point of the material to be imprinted;

5. carrying out dry-method micro-nano imprinting, keeping pressure between the workpiece and the mold, and heating to form a thermoplastic imprinting reaction;

6. adjusting the temperature and holding the temperature for 10-30 seconds, and then cooling, curing and shaping, wherein the operation time can be 300 seconds;

7. after the reaction, the reaction solution is washed, and ultrasonic oscillation washing is sequentially carried out for 1 minute, 1 minute and 5 minutes by using purified water/IPA/purified water, and then drying is carried out.

(3) And (4) preparing a composite coating.

The process is used for coating the prepared microstructure array of the workpiece to be jointed so as to facilitate the subsequent heterogeneous jointing, and the composite coating needs to be sequentially subjected to three steps.

Growing a replacement layer: after the prepared microstructure array of the workpieces to be jointed is cleaned, an active catalytic electrolysis metal complex solution, which is usually a complex solution of tin dioxide and specific amino acid, is put into the microstructure array of the workpieces, so that the microstructure array of the workpieces is immersed in the liquid, and the metal complex (such as copper glycine complex Cu-Gly, copper serine complex Cu-Ser and copper cysteine complex Cu-Cys) can form an active catalytic ion layer on the surface of the microstructure array.

The specific operation is as follows:

1. ultrasonically cleaning the workpiece with the surface hardening film removed in purified water for 5 minutes to ensure that the microstructure array is clean;

2. placing the mixture into an IPA cleaning solution ultrasonic cleaning tank for cleaning for 5 minutes to ensure that organic matters are removed;

3. cleaning in a purified water ultrasonic cleaning tank for 5 min to ensure removal of IPA;

4. with tin dioxide SnCl₂And preparing 0.1M solution by using dilute hydrochloric acid and amino acid, and soaking the workpiece microstructure array in the solution for 1 minute to ensure that the surface of the workpiece is filled with tin ions to obtain the catalytic ion layer.

Seed layer replacement: the microstructure array for growing the replacement layer is immersed in chloride solution containing noble metal such as gold, silver, palladium, platinum and the like, so that metal source ions of the type are replaced by catalysis of a catalytic ion layer, and are directly adsorbed and replaced by a pure metal plating layer on the surface, wherein the plating layer usually selects a crystal phase matched with the next step, and the seed crystal layer is mainly selected to correspond to a metal film to be coated and has a substrate layer capable of catalyzing the plating film, so that effective plating layer joint force and catalytic growth effects are generated.

The specific operation is as follows:

1. taking a platinum coating as a case, preparing 0.1M solution by chloroplatinic acid and dilute hydrochloric acid;

2. placing the replacement layer on the surface of the microstructure array of the workpiece into the displacement layer for displacement reaction, wherein Sn ions on the surface of the workpiece and platinum ions generate displacement reduction reaction, and a platinum metal coating is directly formed on the surface;

3. ensuring that the stable plating layer can adopt the subsequent platinum electroplating process;

4. preparing 0.1N-0.5N chloroplatinic acid/dilute hydrochloric acid/water electrolyte;

5. a plating electrode (workpiece), a carbon electrode and a reference electrode are configured;

6. adjusting the voltage to 0.01-1.10V and 0.05-0.1A, referring to the electrochemical workstation, and observing the potential output to a descending trend to complete the platinum coating process. The plating process can be selected from evaporation or sputtering.

And (3) intermediate layer plating: after the metal plating layer such as gold, silver, palladium, platinum and the like is finished, the plating film generation process of the middle layer is carried out. The selection of the plating layer can be generally selected to be matched with the crystal phase selection of a bonding layer of a seed crystal layer and a next layer, and the selection of the following related metal ion sources such as nickel, copper, zinc, chromium, titanium and the like is generally selected based on the selection of strength, rigidity and toughness, and the plating reaction can directly utilize pure electroplating reaction. The method comprises the steps of configuring a three-phase electrode, a cathode, an anode and a reference electrode, configuring one electrode as a clamping object workpiece and the other electrode as a carbon electrode in an electrolyte containing a metal source, selecting an electrochemical oxidation-reduction potential suitable for a coating as a basic voltage, adjusting proper current input, carrying out staged coating of the coating, improving input of adjusting current when the coating is nearly finished, stabilizing the strength and the bonding force of the coating, and then carrying out slow adjusting current to control the quality of the coating (sintering is not needed in electroplating).

The preparation process comprises the following steps:

1. taking a platinum coating as a case, preparing 0.1-0.5M solution by nickel nitrate, chromium nitrate, dilute hydrochloric acid and dilute nitric acid;

2. placing a workpiece into the reaction vessel for a displacement reaction, wherein a noble metal layer such as platinum on the surface of the workpiece and nickel ions generate a displacement reduction reaction, and a nickel metal coating is directly formed on the surface;

3. ensuring that the stable plating layer can adopt the subsequent nickel electroplating process;

4. preparing 0.1N-0.5N of nickel nitrate/chromium nitrate/dilute hydrochloric acid/amino acid/water electrolyte;

6. adjusting the voltage to 0.01-1.10V and 0.05-0.1A, referring to the electrochemical workstation, and observing the potential output to a descending trend to complete the platinum coating process.

(4) And (4) ion implantation.

The process carries out ion implantation process on the lattice matching degree of the stainless steel alloy material and the lens material. After the film layer is treated, thermal oxidation treatment is carried out, ion sources are introduced, ions such as sodium ions, aluminum ions, potassium ions, phosphorus ions, boron ions and the like are added into the surface coating layer in the thermal oxidation process to implant ions into the surface of the coating layer, so that the surface coating layer of the stainless steel alloy workpiece can be matched with a lens material to effectively carry out anodic bonding, and the bonding strength is enhanced.

1. Confirming the cleaning and drying process of the surface of the workpiece to ensure the perfection;

2. providing an organometallic or semiconducting compound having a source of ions;

3. vacuum treatment is carried out on the thermal oxidation equipment to ensure that the vacuum degree reaches 10^-3~10^-5torr；

4. Placing the workpiece in a thermal oxidation device, heating a device heating pipe to a preposed preparation temperature of the ionization starting temperature of the ion source, and judging the temperature to be lower than 95% of the ionization temperature;

5. ensuring that the temperature reaches 97-98% of the temperature point, opening a vent valve for releasing the ion source, and introducing the ion source for maintaining the process for 30 minutes;

6. and (3) completing the process, starting slow cooling, and maintaining three-stage cooling: the first stage is to control the temperature to be reduced by 50 percent within 30 minutes, the second stage is to reduce the temperature by 20 percent within 30 minutes, and the third stage is to reduce the temperature by 30 percent within 1 hour;

7. releasing the pressure to restore the vacuum degree to normal air pressure; and (4) standing the thermal oxidation equipment for 1 minute, and taking out the workpiece after the completion of the thermal oxidation equipment under the temperature and the pressure.

(5) And (7) carrying out planarization treatment.

The process action is to carry out planarization treatment on the workpiece to ensure complete surface polishing of the workpiece, and can be achieved by adopting an electropolishing process. Directly utilizing reverse electroplating reaction to prepare a three-phase electrode, and placing an anode and a reference electrode in an electrolyte containing a corrosion source; the first electrode is a workpiece to be processed, the other electrode is a carbon electrode, the electrochemical oxidation-reduction potential suitable for the coating is selected as the basic voltage, the proper current input is adjusted, the polishing staged coating is carried out, the input of the adjusting current is improved when the coating is nearly finished, the polishing effect is stabilized, then the slow adjusting current is carried out, and the final planarization quality is determined.

1. Preparing 0.1N-0.5N/dilute hydrochloric acid/dilute sulfuric acid/water/acetic acid electrolyte;

2. a plating object electrode (workpiece), a carbon electrode and a reference electrode are configured;

3. adjusting the voltage to 0.01-1.10V and 0.05-0.1A, referring to the electrochemical workstation, and observing the potential output to a descending trend so as to finish the electro-polishing coating process.

(6) And (6) anode jointing.

The workpiece to be bonded is fixed on two conductive substrates, and a specific voltage and an atmospheric pressure are applied, wherein the voltage is usually configured at 1-5V, the current is configured at 1-10A, and the atmospheric pressure is usually in a vacuum environment state.

The process flow is an electroforming jointing reaction, a method for improving crystal orientation matching degree through ion implantation and forming process ionization is achieved, and the whole environment is constructed to be capable of being excited by ionization to form rapid interface jointing by utilizing the ion jointing process of the reaction.

When the electroforming reaction is about to be completed, the voltage drop is required to stabilize the reaction, the critical state of the charge is made to be a stable state, the junction is stabilized, the control of the charge conduction rate and the atmospheric pressure is required to be gradually reduced, the overall operation background environment is made to be stable, and the state of the junction surface is made to be a condensed state.

The vacuum degree is 0-10^-5Controlling the release time to release pressure for 10 minutes in an torr interval; when the electrochemical reaction for anodic bonding is about to terminate; if the voltage is 1.5V, the trend of the electrochemical workstation approaches to 1.2-1.0V, and the current needs to be regulated and controlled to be slowly reduced to 1.0V at the rate of 0.05A/min. The voltage is 1.00V, the trend of the electrochemical workstation approaches to 1.00-0.50V, and the current needs to be regulated and controlled to be slowly reduced to 0.05-0.37V at the rate of 0.01A/min. If the voltage is 0.37V, the trend of the electrochemical workstation approaches to 0.37-0.01-0V, and the current needs to be regulated and controlled to slowly decrease to 0.00V at the rate of 0.01A/min.

Claims

1. A method for bonding a lens material and a metal material, comprising the steps of:

(1) surface treatment

(2) microstructure array preparation

(3) preparation of composite coating

(4) ion implantation

(5) planarization process

(6) anodic bonding

2. The method of claim 1, wherein the lens material is a silica-based lens material or a semiconductor lens material.

3. The method of claim 1, wherein the surface treatment process of step 1 comprises etching or cleaning or etching plus cleaning.

4. The method of claim 1, wherein the microstructure array preparation in step 2 is performed by wet etching of an embossed array pattern, and the specific process is as follows:

5. The method of claim 1, wherein the step 2 of preparing the microstructure array uses dry imprint transfer printing of the array pattern, and the specific process is as follows:

6. The method of claim 1, wherein the step 3 of growing the displacement layer comprises the steps of:

7. The method of claim 1, wherein the step 3 of replacing the seed layer comprises the steps of:

8. The method of claim 1, wherein the step 3 of plating the intermediate layer comprises the steps of:

9. The method of claim 1, wherein the ion source of step 4 is selected from the group consisting of sodium, aluminum, potassium, phosphorus, and boron.

10. The method of claim 1, wherein the step 6 of applying the positive electrode to the lens material is performed under a vacuum of 0-10 ° to obtain a positive electrode bonding^-5torr; the voltage is 1-5V; the current is 1-10A.