CN115558931B - Refining method of copper surface crystal flower, corrosive liquid combination and application thereof - Google Patents

Refining method of copper surface crystal flower, corrosive liquid combination and application thereof Download PDF

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CN115558931B
CN115558931B CN202211317254.7A CN202211317254A CN115558931B CN 115558931 B CN115558931 B CN 115558931B CN 202211317254 A CN202211317254 A CN 202211317254A CN 115558931 B CN115558931 B CN 115558931B
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copper
corrosive liquid
corrosion
crystal
etching
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CN115558931A (en
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徐俊
陈志钊
马文珍
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Guangdong Huazhixin Electronic Technology Co ltd
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Guangdong Huazhixin Electronic Technology Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/32—Alkaline compositions
    • C23F1/34—Alkaline compositions for etching copper or alloys thereof
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00—Etching metallic material by chemical means
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/16—Acidic compositions
    • C23F1/18—Acidic compositions for etching copper or alloys thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
    • H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
    • H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

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Abstract

The application relates to a refining method of crystal flowers on a copper surface, which comprises the following steps: sequentially adopting a first etching solution and a second etching solution to etch the surface of the copper material twice; the first corrosive liquid comprises ammonia water and hydrogen peroxide; the second corrosive liquid comprises sulfuric acid and sodium persulfate. The method can realize the effects of reducing the size of the copper crystal flower and refining the copper crystal flower with a coarse shape, obviously enhance the difference between the imaging of the shape of the copper crystal flower and the imaging effect formed by dispensing or welding line processing, and can clearly identify and distinguish the glue or solder area and the copper surface area in the imaging graph through automatic equipment after the copper material subjected to the copper surface crystal flower refining treatment is subsequently subjected to the processing such as dispensing, welding line and the like, so that the processing effect of a product can be accurately detected and judged.

Description

Refining method of copper surface crystal flower, corrosive liquid combination and application thereof
Technical Field
The application relates to the technical field of metal surface treatment, in particular to a refining method of copper surface crystal flowers, a corrosive liquid combination and application thereof.
Background
In the processing technology of semiconductor materials, copper metal is the most common material, and dispensing and wire bonding processing by taking copper metal as a base material are also processes which are often required in the processing process of semiconductor materials. In particular, in the processing technology of high-power semiconductor products, the sintering effect of the glue and the Bonding Wire effect of Wire Bonding (Wire Bonding) are required to be higher, and automation equipment is generally required to be adopted to identify and detect the glue-dispensing and Bonding Wire processing effects.
In the prior process, the metal copper has internal stress after processing, so that the stress is required to be released through annealing, and the high-temperature annealing process is accompanied with the growth of copper crystal flowers, and after the copper crystal flowers grow to a certain degree, the appearance of the copper crystal flowers is displayed on the surface, so that the visual recognition is influenced. Although the nickel-gold plating is usually performed on the surface of the metal copper to ensure the application of the metal copper on the semiconductor, the thickness of the plated nickel-gold plating is usually only a few micrometers, after the nickel-gold plating, the texture and texture of the copper surface, namely the crystal flower shape of the copper can be still observed under a high-resolution camera, and if the crystal flower shape is thick, the imaging of the crystal flower shape of the copper is close to the imaging effect formed by dispensing or welding line processing, so that the accuracy of identifying and detecting the dispensing and welding line processing effects by the automatic equipment can be affected. For example, the glue formed by the dispensing process is black through a high-resolution camera image, coarse crystal flowers on the copper surface also show a large black area, and the imaging result is close to the black area, so that the automatic equipment can be influenced to judge whether the processing effect of the product is qualified.
Disclosure of Invention
Based on this, it is necessary to provide a method for refining the crystal flower on the copper surface, a corrosive liquid combination and application thereof, which can reduce the crystal flower size on the copper surface.
An embodiment of the application provides a refining method of crystal flowers on a copper surface, which comprises the following steps:
sequentially adopting a first etching solution and a second etching solution to etch the surface of the copper material twice;
the first corrosive liquid comprises ammonia water and hydrogen peroxide;
the second corrosive liquid comprises sulfuric acid and sodium persulfate.
In one embodiment, the mass fraction of the ammonia water in the first corrosive liquid is 23-27%, and the mass fraction of the hydrogen peroxide is 1-5%;
optionally, the mass fraction of the ammonia water in the first corrosive liquid is 25%, and the mass fraction of the hydrogen peroxide is 3%.
In one embodiment, the mass fraction of the sulfuric acid in the second corrosive liquid is 1-4%, and the mass fraction of the sodium persulfate is 0.5-2.5%;
optionally, the mass fraction of sulfuric acid in the second corrosive liquid is 2.5%, and the mass fraction of sodium persulfate is 1.5%.
In one embodiment, the step of performing the etching twice on the copper material sequentially with the first etching solution and the second etching solution includes:
firstly, immersing the copper material in the first etching solution to perform first etching, taking out the copper material, cleaning, and then immersing the copper material in the second etching solution to perform second etching;
optionally, the first etching is performed for a period of 3min to 8min.
Optionally, the second etching is performed for a period of 2min to 3min.
In one embodiment, the method further comprises the following steps:
and (3) sealing the surface of the copper material subjected to the twice corrosion.
In one embodiment, the sealing material for sealing the surface of the copper material subjected to the twice corrosion is green oil.
The embodiment of the application also provides an etching solution combination for refining the crystal flowers on the copper surface, wherein the etching solution combination comprises a first etching solution and a second etching solution, the first etching solution comprises ammonia water and hydrogen peroxide, and the second etching solution comprises sulfuric acid and sodium persulfate.
In one embodiment, the mass fraction of the ammonia water in the first corrosive liquid is 23-27%, and the mass fraction of the hydrogen peroxide is 1-5%;
optionally, the mass fraction of the ammonia water in the first corrosive liquid is 25%, and the mass fraction of the hydrogen peroxide is 3%.
In one embodiment, the mass fraction of the sulfuric acid in the second corrosive liquid is 1-4%, and the mass fraction of the sodium persulfate is 0.5-2.5%;
optionally, the mass fraction of sulfuric acid in the second corrosive liquid is 2.5%, and the mass fraction of sodium persulfate is 1.5%.
An embodiment of the present application further provides a method for refining the crystal flowers on the copper surface according to any one of the above embodiments or an application of the etching solution combination for refining the crystal flowers on the copper surface according to any one of the above embodiments in a semiconductor material processing process.
According to the method, the copper surface is sequentially corroded twice by the first corrosive liquid and the second corrosive liquid, after the copper surface is corroded by the first corrosive liquid, tiny micro-gaps which are uniformly distributed are formed on the copper surface by micro-corrosion, and then the copper surface is corroded by the second corrosive liquid for the second time, so that the original tiny micro-gaps are deepened, corrosion to a certain extent is also caused at the positions where the micro-gaps are not formed on the copper surface, the effects of reducing the size of copper crystal flowers and refining the copper crystal flowers in the thick shape are achieved, and the imaging of the shape of the copper crystal flowers is obviously enhanced, and the imaging effect difference is formed by dispensing or welding line processing. After the copper material subjected to the copper surface crystal pattern refinement treatment is subjected to subsequent processing such as dispensing, welding lines and the like, glue or solder areas and copper surface areas in the imaging patterns can be clearly identified and distinguished through automatic equipment, and the processing effect of the product can be accurately detected and judged.
Drawings
Fig. 1 is a black-and-white visual recognition device recognition picture of the surface of a copper material with crystal patterns not refined.
Fig. 2 is a microscopic observation appearance image of the copper surface with crystal flowers not refined.
Fig. 3 is a microscopic view of the surface of the copper material after the grain refinement treatment in one embodiment.
Detailed Description
In order that the application may be readily understood, a more complete description of the application will be rendered by reference to the embodiments that are illustrated in the appended drawings. This application may be embodied in many different forms and is not limited to the embodiments described herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein in the description of the application is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
The terms "first," "second," "third," "fourth," and the like, as used herein, are used for descriptive purposes only and not necessarily for describing particular sequences or sequences, and are not to be construed as indicating or implying any relative importance or number of such features. Thus, a feature defining "a first" or "a second" may explicitly or implicitly include at least one such feature. In the description of the present application, the meaning of "plurality" means at least two, for example, two, three, etc., unless specifically defined otherwise.
Where the terms "comprising," "having," and "including" are used herein, it is intended to cover a non-exclusive inclusion, unless a specifically defined term is used, such as "consisting of … … only," etc., another component may be added.
The words "optionally," "preferably," "more preferably," and the like in this application refer to embodiments of the invention that may provide certain benefits in some instances. However, other embodiments may be optional or preferred under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful, nor is it intended to exclude other embodiments from the scope of the application.
When a range of values is disclosed in this application, the range is considered to be continuous and includes both the minimum and maximum values of the range, as well as each value between such minimum and maximum values. Further, when a range refers to an integer, each integer between the minimum and maximum values of the range is included. Further, when multiple range description features or characteristics are provided, the ranges may be combined. In other words, unless otherwise indicated, all ranges disclosed herein are to be understood to encompass any and all subranges subsumed therein.
Unless mentioned to the contrary, singular terms may include plural and are not to be construed as being one in number.
In the present application, the technical features described in an open manner include a closed technical scheme composed of the listed features, and also include an open technical scheme including the listed features.
An embodiment of the application provides a refining method of crystal flowers on a copper surface, which comprises the following steps:
sequentially adopting a first etching solution and a second etching solution to etch the surface of the copper material twice;
the first corrosive liquid comprises ammonia water and hydrogen peroxide;
the second etching solution comprises sulfuric acid and sodium persulfate.
Referring to fig. 1 and fig. 2, it can be seen that the sizes of crystal flowers on the copper surface after the high-temperature annealing treatment are larger, and the imaging of the shapes of the crystal flowers of copper is close to the imaging effect formed by the dispensing or bonding wire processing, for example, the glue formed by the dispensing process is black through a high-resolution camera image, and coarse crystal flowers on the copper surface also show a large black area, so that the imaging result is close to the imaging effect, which can influence the automation equipment to judge whether the processing effect of the product is qualified or not.
As shown in fig. 3, the method for refining the crystal flowers on the copper surface provided in the foregoing embodiment sequentially etches the copper surface twice by using the first etching solution and the second etching solution, after the copper is etched by the first etching solution, the copper surface is micro-etched to form uniformly distributed fine micro-cracks, and then etched by the second etching solution for the second time, so that the original fine micro-cracks are deepened, and a certain degree of corrosion is also generated at the position where the micro-cracks do not appear on the copper surface, thereby realizing the effects of reducing the size of the copper crystal flowers and refining the copper crystal flowers in coarse shapes, and obviously enhancing the difference between the imaging of the shapes of the copper crystal flowers and the imaging effect formed by dispensing or bonding wire processing. After the copper material subjected to the copper surface crystal pattern refinement treatment is subjected to subsequent processing such as dispensing, welding lines and the like, glue or solder areas and copper surface areas in the imaging patterns can be clearly identified and distinguished through automatic equipment, and the processing effect of the product can be accurately detected and judged.
The first corrosive liquid comprises ammonia water and hydrogen peroxide, the second corrosive liquid comprises sulfuric acid and sodium persulfate, the first corrosive liquid is weaker than the second corrosive liquid in corrosion capability of the first corrosive liquid to the surface of the copper material, after the first corrosive liquid is adopted to carry out corrosion treatment on the copper material, tiny micro-cracks which are uniformly distributed are formed on the surface of the copper material, the second corrosive liquid is stronger in corrosion capability of the second corrosive liquid to the surface of the copper material, the original micro-cracks are deepened by further penetrating into the tiny micro-cracks formed after the first corrosive liquid is corroded, and corrosion to a certain extent can be generated at the position of the surface of the copper material which is not corroded by the first corrosive liquid, so that the effects of reducing the size of copper crystal flowers and refining the coarse copper crystal flowers are achieved.
In one embodiment of the present application, the first etching solution and the second etching solution are sequentially used to etch the copper surface twice. Further, the surface of the copper material is corroded by the first corrosive liquid and then corroded by the second corrosive liquid. Because the second corrosive liquid is stronger than the first corrosive liquid, if the second corrosive liquid is adopted to corrode the copper surface in the step of refining the crystal flowers on the copper surface, then the first corrosive liquid is adopted to corrode the copper surface, the corrosion of the second corrosive liquid with stronger corrosiveness can play a leading role on the copper surface, and the corrosion treatment effect is difficult to control, for example, if the second corrosive liquid is adopted to corrode the copper surface first, if the corrosion treatment time is too short, micro-cracks can only appear at weak positions on the copper surface and further corrode the copper surface, and the overall surface uniformity after corrosion is poor; the corrosion treatment time is too long, and the second corrosive liquid has stronger corrosiveness and can generate irreversible damage to the surface of the copper material. Therefore, in one embodiment of the present application, the copper surface is etched with a first etching solution and then etched with a second etching solution.
In one embodiment, the mass fraction of the ammonia water in the first corrosive liquid is 23% -27%, and the mass fraction of the hydrogen peroxide is 1% -5%. The first corrosive liquid is a mixed liquid comprising ammonia water and hydrogen peroxide, the ammonia water and the hydrogen peroxide are matched with each other in a specific mass fraction range, a better micro-corrosion effect can be achieved, and after the copper surface is corroded, fine micro-cracks which are uniformly distributed can be formed on the copper surface. If the concentration of the ammonia water and/or the hydrogen peroxide in the first corrosive liquid is low, the corrosion density of the copper surface is reduced, the corrosion effect is not ideal, if the concentration of the ammonia water and/or the hydrogen peroxide in the first corrosive liquid is high, the reaction is severe, micro-cracks generated on the copper surface are further and rapidly deepened, the deepened micro-crack areas are preferentially corroded when the second corrosive liquid is adopted for corrosion subsequently, the final treatment effect of corroding the copper surface is reduced, and the treatment cost is increased. It is understood that the mass fraction of the aqueous ammonia in the first etching solution may be, for example, but not limited to, 23%, 23.3%, 23.5%, 23.8%, 24%, 24.2%, 24.4%, 24.6%, 25%, 25.4%, 25.5%, 25.8%, 26%, 26.5%, 27%, etc. It is understood that the mass fraction of hydrogen peroxide in the first etching solution may be, for example, but not limited to, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.3%, 2.5%, 2.8%, 3%, 3.2%, 3.6%, 3.7%, 3.9%, 4%, 4.1%, 4.3%, 4.5%, 4.6%, 4.8%, 4.9%, 5%, etc. It is understood that the mass fraction of the aqueous ammonia and the mass fraction of the hydrogen peroxide in the first etching liquid may be any combination within the above-described range.
In one embodiment, the mass fraction of the ammonia water in the first corrosive liquid is 25%, and the mass fraction of the hydrogen peroxide is 3%. When the specific mass fraction combination is adopted by the mass fraction of the ammonia water and the mass fraction of the hydrogen peroxide in the first corrosive liquid, the corrosion effect on the surface of the copper material is best, and fine micro-cracks which are uniformly distributed can be formed on the surface of the copper material.
In one embodiment, the mass fraction of the sulfuric acid in the second corrosive liquid is 1% -4%, and the mass fraction of the sodium persulfate is 0.5% -2.5%. The second corrosive liquid comprises sulfuric acid and sodium persulfate which are matched with each other in a specific mass fraction range, so that the second corrosive liquid can be ensured to permeate into tiny micro-gaps formed on the surface of the copper material after being corroded by the first corrosive liquid, the depth of the micro-gaps is further increased, corrosion can be generated on other micro-corroded surfaces to a certain extent, and the crystal flower size of the copper surface is promoted to be refined. If the concentration of the sulfuric acid and/or sodium persulfate in the second corrosive liquid is low, the corrosion effect is too weak, the corrosion depth and corrosion density are reduced, the refining effect on copper crystal patterns is not good, if the concentration of the sulfuric acid and/or sodium persulfate in the second corrosive liquid is too high, the corrosion is excessive, irreversible damage is generated on the copper surface, and the copper cannot be used for normal subsequent processing. It is understood that the mass fraction of sulfuric acid in the second etching solution may be, for example, but not limited to, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.3%, 2.5%, 2.8%, 3%, 3.2%, 3.6%, 3.7%, 3.9%, 4%, etc. It is understood that the mass fraction of sodium persulfate in the second etching solution may be, for example, but not limited to, 0.5%, 0.6%, 0.8%, 0.9%, 1%, 1.2%, 1.3%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, etc.
In one embodiment, the second etching solution has a mass fraction of sulfuric acid of 2.5% and the sodium persulfate has a mass fraction of 1.5%. When the specific mass fraction combination is adopted for the mass fraction of the sulfuric acid and the mass fraction of the sodium persulfate in the second corrosive liquid, the corrosion effect on the surface of the copper material is best, the refinement of the crystal pattern size of the copper surface can be ensured, and adverse effects on the copper material can be avoided.
In one embodiment, the step of performing the two corrosions on the copper material sequentially using the first etching solution and the second etching solution includes:
firstly, immersing a copper material in a first etching solution to perform first etching, taking out the copper material, cleaning, and then immersing the copper material in a second etching solution to perform second etching.
It is understood that the cleaning agent used in the cleaning may be, for example, water.
It will be appreciated that after the second etching has ended, the step of cleaning the copper material again may also be included after removal of the copper material.
In one embodiment, the first etching is performed for a period of 3 to 8 minutes. The first corrosive liquid has weaker corrosion capability on the surface of the copper material, so that the first corrosive liquid can be used for corroding the surface of the copper material for a longer time, excessive damage can not be generated on the surface of the copper material in the longer-time corrosion process due to weaker corrosiveness of the first corrosive liquid, the time of the first corrosion is properly prolonged, and the corrosion density and the corrosion uniformity on the surface of the copper material can be improved. However, it is understood that the appropriate extension of the first etching time referred to herein is also an extension within a suitable range, and if the first etching time is outside the suitable range, the material processing efficiency is significantly affected. It is understood that, if the time for performing the first etching is too short, the etching density on the copper surface may be lowered, and the final treatment effect may be affected. It is understood that the time for performing the first etch may be, for example, but not limited to, 3min, 3.3min, 3.5min, 3.7min, 4min, 4.5min, 5min, 5.3min, 5.6min, 6min, 6.5min, 7min, 7.5min, 8min, and the like. Preferably, the first etching is performed for a period of 4 to 6 minutes. Preferably, the first etching is performed for a period of 5 minutes.
In one embodiment, the second etching is performed for a period of 2 to 3 minutes. Since the second etching liquid has a strong etching capability, the time for performing the second etching needs to be controlled more strictly and shorter than the time for performing the first etching. If the second etching time is too short, the etching depth and the etching density are not ideal, the thinning of crystal flowers on the copper surface is unfavorable, and if the second etching time is too long, excessive etching can be generated on the copper material, and the application of the copper material is affected. It is understood that the time for performing the second etch may be, for example, but not limited to, 2min, 2.1min, 2.2min, 2.3min, 2.4min, 2.5min, 2.6min, 2.7min, 2.8min, 2.9min, 3min. Preferably, the second etching is performed for a period of 2min to 2.5min.
In one embodiment, the method further comprises the following steps:
and (3) sealing the surface of the copper material subjected to the twice corrosion.
It is understood that after the copper surface is corroded twice, the grain boundary density is increased, and the copper surface is prevented from being oxidized by sealing the normal surface.
It is understood that the sealing material for sealing the copper surface after the two corrosions may be, for example, but not limited to, green oil. Green oil is a good metal surface sealing material, and can effectively prevent the contact between the copper surface and external oxygen. It will be appreciated that prior to actual use, the copper surface may be subjected to subsequent processing after removal of the capping material. The process of removing the sealing material on the copper surface may be, for example, electroplating or the like, but is not limited thereto.
According to the method for refining the crystal flowers on the copper surface, provided by any one of the embodiments, the first corrosive liquid is used for corroding the copper surface, so that the crystal flowers on the copper surface are corroded at the weak positions of the crystal boundaries of the crystal flowers to form fine network-shaped micro-cracks, and further, the time for corroding by the first corrosive liquid can be properly prolonged within a proper range due to the fact that the corrosion effect of the first corrosive liquid is softer, and the corrosion density is improved and the corrosion effect is more uniform. Then the second corrosive liquid is used for continuously corroding the surface of the copper material, the corrosiveness of the second corrosive liquid is relatively equal and strong, the surface of the copper crystal flower can be deeply corroded, on one hand, micro-cracks which are good in corrosion of the first corrosive liquid can be continuously deeply corroded, crystal grains of the crystal flower become finely crushed, meanwhile, the second corrosive liquid has a stronger microetching effect on the surface of the metal, and can continuously corrode the peripheral positions along the grain boundary position, so that a denser netlike corrosion structure is formed, and crystal grains of the crystal flower are changed to be finely crushed. Further, after the crystal patterns on the copper surface are thinned, when the copper material is used as a base material to process semiconductor materials such as dispensing or welding, glue or welding line areas can be accurately identified through automatic equipment, confusion between the glue or welding line areas and the crystal pattern areas on the copper surface is reduced, processing quality can be accurately detected and judged, quality control level of a semiconductor material processing technology is improved, and for example, the problem of controlling silver paste and welding flux during silver paste sintering and welding flux sintering can be solved.
The embodiment of the application also provides a corrosion solution combination for refining the crystal flowers on the copper surface, wherein the corrosion solution combination comprises a first corrosion solution and a second corrosion solution, the first corrosion solution comprises ammonia water and hydrogen peroxide, and the second corrosion solution comprises sulfuric acid and sodium persulfate.
Further, ammonia water and hydrogen peroxide in the first corrosive liquid and sulfuric acid and sodium persulfate in the second corrosive liquid are low in concentration, so that the solution can be prepared in advance for mass treatment, and the method has mass production.
Further, the acid in the second corrosive liquid is sulfuric acid, so that compared with other inorganic acids such as hydrochloric acid, nitric acid and the like, the volatility of the sulfuric acid is weaker, and the health hazard to operators can be effectively reduced.
In one embodiment, the mass fraction of the ammonia water in the first corrosive liquid is 23% -27%, and the mass fraction of the hydrogen peroxide is 1% -5%. It is understood that the mass fraction of the aqueous ammonia in the first etching solution may be, for example, but not limited to, 23%, 23.3%, 23.5%, 23.8%, 24%, 24.2%, 24.4%, 24.6%, 25%, 25.4%, 25.5%, 25.8%, 26%, 26.5%, 27%, etc. It is understood that the mass fraction of hydrogen peroxide in the first etching solution may be, for example, but not limited to, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.3%, 2.5%, 2.8%, 3%, 3.2%, 3.6%, 3.7%, 3.9%, 4%, 4.1%, 4.3%, 4.5%, 4.6%, 4.8%, 4.9%, 5%, etc. It is understood that the mass fraction of the aqueous ammonia and the mass fraction of the hydrogen peroxide in the first etching liquid may be any combination within the above-described range. Preferably, the mass fraction of the ammonia water in the first corrosive liquid is 25%, and the mass fraction of the hydrogen peroxide is 3%.
In one embodiment, the mass fraction of the sulfuric acid in the second corrosive liquid is 1% -4%, and the mass fraction of the sodium persulfate is 0.5% -2.5%. It is understood that the mass fraction of sulfuric acid in the second etching solution may be, for example, but not limited to, 1%, 1.2%, 1.5%, 1.8%, 2%, 2.3%, 2.5%, 2.8%, 3%, 3.2%, 3.6%, 3.7%, 3.9%, 4%, etc. It is understood that the mass fraction of sodium persulfate in the second etching solution may be, for example, but not limited to, 0.5%, 0.6%, 0.8%, 0.9%, 1%, 1.2%, 1.3%, 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, etc. Preferably, the mass fraction of sulfuric acid in the second corrosive liquid is 2.5%, and the mass fraction of sodium persulfate is 1.5%.
An embodiment of the application also provides a refining method of the copper surface crystal flower in any embodiment or application of the etching solution combination for refining the copper surface crystal flower in any embodiment in a semiconductor material processing process.
The following are specific examples.
Example 1
Step one:
preparing a first corrosive liquid and a second corrosive liquid: the first corrosive liquid comprises 25% of ammonia water and 3% of hydrogen peroxide by mass, and the second corrosive liquid comprises 2.5% of sulfuric acid by mass and 1.5% of sodium persulfate by mass.
Step two:
firstly, immersing a copper material in a first corrosive liquid for first corrosion, wherein the first corrosion time is 5min, then taking out the copper material, cleaning, then immersing the copper material in a second corrosive liquid for second corrosion, wherein the second corrosion time is 2min, and then taking out the copper material and cleaning.
Step three:
and (3) sealing and blocking oxygen on the surface of the copper material subjected to the twice corrosion treatment by using green oil.
Comparative example 1
The procedure was substantially the same as in example 1, except that the first etching was performed with the first etching liquid and the second etching was performed with the second etching liquid in the order of the first etching.
Step one:
preparing a first corrosive liquid and a second corrosive liquid: the first corrosive liquid comprises 25% of ammonia water and 3% of hydrogen peroxide by mass, and the second corrosive liquid comprises 2.5% of sulfuric acid by mass and 1.5% of sodium persulfate by mass.
Step two:
firstly, immersing a copper material in a second corrosive liquid for second corrosion, wherein the second corrosion time is 2min, then taking out the copper material, cleaning, then immersing the copper material in a first corrosive liquid for first corrosion, wherein the first corrosion time is 5min, and then taking out the copper material and cleaning.
Step three:
and (3) sealing and blocking oxygen on the surface of the copper material subjected to the twice corrosion treatment by using green oil.
Comparative example 2
The procedure was substantially the same as in example 1, except that the first etching was performed using only the first etching liquid, and the second etching was performed using no second etching liquid.
Step one:
preparing a first corrosive liquid: the first corrosive liquid comprises 25% of ammonia water and 3% of hydrogen peroxide.
Step two:
firstly, immersing a copper material in a first corrosive liquid for first corrosion, wherein the time of the first corrosion is 7min, and then taking out the copper material for cleaning.
Step three:
and sealing and blocking oxygen on the surface of the copper material subjected to the first corrosion treatment by using green oil.
Comparative example 3
The procedure was substantially the same as in example 1, except that the second etching was performed using only the second etching liquid, and the first etching was performed using no first etching liquid.
Step one:
preparing a second corrosive liquid: the second corrosive liquid comprises sulfuric acid with the mass fraction of 2.5% and sodium persulfate with the mass fraction of 1.5%.
Step two:
firstly, immersing the copper material in a second corrosive liquid for second corrosion, wherein the second corrosion time is 7min, and then taking out the copper material for cleaning.
Step three:
and sealing and blocking oxygen on the surface of the copper material subjected to the second corrosion treatment by using green oil.
Comparative example 4
The procedure is substantially the same as in example 1, except that the formulation concentration of the first etching solution is different.
Step one:
preparing a first corrosive liquid and a second corrosive liquid: the first corrosive liquid comprises ammonia water with the mass fraction of 20% and hydrogen peroxide with the mass fraction of 6%, and the second corrosive liquid comprises sulfuric acid with the mass fraction of 2.5% and sodium persulfate with the mass fraction of 1.5%.
Step two:
firstly, immersing a copper material in a first corrosive liquid for first corrosion, wherein the first corrosion time is 5min, then taking out the copper material, cleaning, then immersing the copper material in a second corrosive liquid for second corrosion, wherein the second corrosion time is 2min, and then taking out the copper material and cleaning.
Step three:
and (3) sealing and blocking oxygen on the surface of the copper material subjected to the twice corrosion treatment by using green oil.
Comparative example 5
The procedure is substantially the same as in example 1, except that the recipe concentration of the second etching solution is different.
Step one:
preparing a first corrosive liquid and a second corrosive liquid: the first corrosive liquid comprises 25% of ammonia water and 3% of hydrogen peroxide by mass, and the second corrosive liquid comprises 1% of sulfuric acid by mass and 4.5% of sodium persulfate by mass.
Step two:
firstly, immersing a copper material in a first corrosive liquid for first corrosion, wherein the first corrosion time is 5min, then taking out the copper material, cleaning, then immersing the copper material in a second corrosive liquid for second corrosion, wherein the second corrosion time is 2min, and then taking out the copper material and cleaning.
Step three:
and (3) sealing and blocking oxygen on the surface of the copper material subjected to the twice corrosion treatment by using green oil.
Comparative example 5
Copper material which does not corrode the surface.
The copper materials obtained after the treatment of example 1 and comparative examples 1 to 5 were subjected to morphology observation and black-and-white visual recognition, and the test results are shown in table 1 below.
Wherein: the morphology observation method comprises the following steps: observing the appearance of the copper surface under the condition of a microscope 10X;
black and white visual recognition: and (3) performing black and white visual identification by using automatic equipment, selecting an area on the identified image, and measuring the proportion of the area of the black area caused by the crystal flowers in the selected area.
TABLE 1 appearance of copper Material and Black-white visual recognition Effect
Figure BDA0003909898420000151
As can be seen from table 1, compared with comparative examples 1 to 5, in example 1, after the copper material is subjected to the crystal flower refinement treatment in example 1, the crystal flower appearance is significantly refined, and the copper material is judged by black and white visual recognition of an automation device, so that the quality requirement that the proportion of the area of the black area caused by the crystal flower is less than 5% is satisfied.
The technical features of the above embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above embodiments are not described for brevity of description, however, as long as there is no contradiction between the combinations of the technical features, they should be considered as the scope of the description.
The foregoing examples represent only a few embodiments of the present application, which are described in more detail and are not thereby to be construed as limiting the scope of the invention. It should be noted that it would be obvious to those skilled in the art that various modifications and improvements could be made without departing from the inventive concept of the present application, which would be within the scope of the present application. Accordingly, the scope of protection of the present application is to be determined by the claims appended hereto.

Claims (7)

1. The refining method of the crystal flower on the copper surface is characterized by comprising the following steps of:
carrying out first corrosion on the surface of the copper material by adopting a first corrosion liquid, and then carrying out second corrosion by adopting a second corrosion liquid;
the first corrosive liquid comprises 23-27% of ammonia water and 1-5% of hydrogen peroxide by mass;
the second corrosive liquid comprises 1-4% of sulfuric acid by mass and 0.5-2.5% of sodium persulfate by mass;
the first etching is carried out for 3-8 min; and the second etching is carried out for 2 min-3 min.
2. The method for refining the crystal flowers on the copper surface according to claim 1, wherein the mass fraction of the ammonia water in the first corrosive liquid is 25%, and the mass fraction of the hydrogen peroxide is 3%.
3. The method for refining the crystal flowers on the copper surface according to claim 1, wherein the mass fraction of sulfuric acid in the second corrosive liquid is 2.5%, and the mass fraction of sodium persulfate is 1.5%.
4. A method for refining a copper surface crystal flower according to any one of claims 1 to 3, wherein the time for performing the first etching is 4min to 6min; the second etching is performed for 2 to 2.5 minutes.
5. The method for refining the crystal flowers on the copper surface according to any one of claims 1 to 3, further comprising the following steps:
and (3) sealing the surface of the copper material subjected to the twice corrosion.
6. The method for refining crystal flowers on a copper surface according to claim 5, wherein the sealing material for sealing the copper surface after two times of corrosion is green oil.
7. Use of the method for refining crystal flowers on copper surfaces according to any one of claims 1-6 in a semiconductor material processing technology.
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