CN113957441B - Etching solution and preparation method and application thereof - Google Patents

Etching solution and preparation method and application thereof Download PDF

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Publication number
CN113957441B
CN113957441B CN202111276160.5A CN202111276160A CN113957441B CN 113957441 B CN113957441 B CN 113957441B CN 202111276160 A CN202111276160 A CN 202111276160A CN 113957441 B CN113957441 B CN 113957441B
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China
Prior art keywords
etching solution
quinoline
aluminum
boric acid
fluoride
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CN202111276160.5A
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CN113957441A (en
Inventor
周志强
袁明军
李治文
杜小林
胡秋雨
刘彬云
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GUANGDONG GUANGHUA SCI-TECH CO LTD
Guangdong Toneset Science & Technology Co ltd
Guanghua Institute Of Science And Technology Guangdong Co ltd
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GUANGDONG GUANGHUA SCI-TECH CO LTD
Guangdong Toneset Science & Technology Co ltd
Guanghua Institute Of Science And Technology Guangdong 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
    • C23F1/16—Acidic compositions
    • C23F1/26—Acidic compositions for etching refractory metals
    • 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
    • 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
    • H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
    • H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
    • H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
    • H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
    • H01L21/76841—Barrier, adhesion or liner layers
    • H01L21/7685—Barrier, adhesion or liner layers the layer covering a conductive structure
    • 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

Abstract

The invention relates to an etching solution and a preparation method and application thereof, wherein the etching solution comprises water, fluoride salt, an aluminum corrosion inhibitor and an oxidant; the structure of the aluminum corrosion inhibitor contains nitrogen atoms and boron hydroxyl groups, or the structure of the aluminum corrosion inhibitor contains nitrogen atoms and boric acid pinacol ester groups. The etching solution can rapidly etch and corrode titanium, has small corrosion effect on aluminum and large etching coefficient, can meet the process requirement of manufacturing fine circuits by the current semiconductor wafer packaging process, is safe and reliable, has small environmental pollution and has wide application prospect.

Description

Etching solution and preparation method and application thereof
Technical Field
The invention belongs to the technical field of semiconductor wafer packaging, and particularly relates to an etching solution, a preparation method and application thereof.
Background
Currently, in the wafer level packaging process of semiconductor packages, a titanium barrier layer is deposited on the bottom layer of the copper lines, typically to a thickness less than the thickness of the copper lines, when new generation electrical contacts are manufactured. After the copper line is manufactured, etching the titanium metal layer outside the line to form an independent line. However, an aluminum metal layer is arranged between the substrate and the titanium metal layer, after the outermost copper metal layer is removed, the conventional hydrofluoric acid titanium etching solution is directly used to cause rapid corrosion of titanium metal, meanwhile, serious corrosion of the surface of aluminum occurs, if a phosphoric acid titanium etching solution is used, the corrosion of the titanium metal surface is slower, and if the titanium etching is incomplete, short circuit between copper circuits can be caused.
The commonly used hydrofluoric acid system is often too fast in corrosion rate, so that an aluminum metal layer below the titanium metal layer cannot be controlled to be corroded, and hydrofluoric acid is extremely acidic and has a great potential safety hazard. The phosphoric acid system has a lower titanium etching rate and a greater environmental pollution due to the phosphorus-containing compound, although the corrosion rate can be controlled compared with the hydrofluoric acid system.
Therefore, there is an urgent need in industry to find an etchant that has a high corrosion rate of titanium, hardly corrodes an aluminum metal layer, and has less environmental pollution.
Disclosure of Invention
In order to solve the problems, the invention provides the etching solution which has good titanium etching effect, high etching speed, small etching effect on aluminum and less environmental pollution.
The technical proposal is as follows:
an etching solution comprising: water, fluoride salt, aluminum corrosion inhibitor and oxidant;
the structure of the aluminum corrosion inhibitor contains nitrogen atoms and boron hydroxyl groups, or the structure of the aluminum corrosion inhibitor contains nitrogen atoms and boric acid pinacol ester groups.
In one embodiment, the aluminum corrosion inhibitor has a structure as shown in any one of formulas (I-1) - (I-4):
in one embodiment, the aluminum corrosion inhibitor is selected from at least one of quinoline-5-boronic acid, quinoline-3-boronic acid, 3-quinolineboronic acid pinacol ester, quinoline-4-boronic acid pinacol ester, 6-quinolineboronic acid pinacol ester, quinoline-8-boronic acid pinacol ester, 7-isoquinolineboronic acid pinacol ester, and 4-isoquinolineboronic acid.
In one embodiment, each liter of the etching solution comprises 1g to 20g of the fluorine salt, 1g to 20g of the aluminum corrosion inhibitor, and 1g to 20g of the oxidizing agent.
In one embodiment, each liter of the etching solution comprises 5g to 20g of the fluorine salt, 1g to 15g of the aluminum corrosion inhibitor, and 1g to 20g of the oxidant.
In one embodiment, the fluoride salt is selected from at least one of sodium fluoride, potassium fluoride, ammonium bifluoride, aluminum fluoride, and sodium fluorosilicate.
In one embodiment, the oxidizing agent is selected from at least one of potassium hydrogen persulfate, m-chloroperoxybenzoic acid, hydrogen peroxide, and t-butyl hydroperoxide.
In one embodiment, the fluoride salt is potassium fluoride, the aluminum corrosion inhibitor is quinoline-5-boric acid, and the oxidizing agent is t-butyl hydroperoxide.
In one embodiment, the etching solution comprises water, 5 g-15 g of potassium fluoride, 5 g-15 g of quinoline-5-boric acid, and 10 g-20 g of tert-butyl hydroperoxide per liter.
In one embodiment, the etching solution comprises water, 5 g-8 g of potassium fluoride, 8 g-10 g of quinoline-5-boric acid, and 10 g-15 g of tert-butyl hydroperoxide per liter.
In one embodiment, the fluoride salt is potassium fluoride, the aluminum corrosion inhibitor is 4-isoquinolineboric acid, and the oxidizing agent is potassium hydrogen persulfate.
In one embodiment, the etching solution comprises water, 5g to 15g of potassium fluoride, 5g to 10g of 4-isoquinoline boric acid, and 10g to 20g of potassium hydrogen persulfate per liter.
In one embodiment, each liter of the etching solution comprises water, 8g to 10g of potassium fluoride, 5g to 10g of 4-isoquinoline boric acid, and 10g to 20g of potassium hydrogen persulfate.
In one embodiment, the fluoride salt is aluminum fluoride, the aluminum corrosion inhibitor is quinoline-5-boronic acid, and the oxidizing agent is potassium hydrogen persulfate.
In one embodiment, the etching solution comprises water, 5g to 15g of aluminum fluoride, 10g to 15g of quinoline-5-boric acid, and 1g to 10g of potassium hydrogen persulfate per liter.
In one embodiment, the etching solution comprises water, 5g to 15g of aluminum fluoride, 10g to 15g of quinoline-5-boric acid, and 1g to 8g of potassium hydrogen persulfate per liter.
In one embodiment, the fluoride salt is sodium fluosilicate, the aluminum corrosion inhibitor is at least one of 3-quinolineboronic acid pinacol ester and 4-isoquinolineeboronic acid, and the oxidizing agent is m-chloroperoxybenzoic acid.
In one embodiment, each liter of the etching solution comprises water, 5g to 15g of sodium fluosilicate, 10g to 15g of 3-quinoline boric acid pinacol ester, and 5g to 15g of m-chloroperoxybenzoic acid.
In one embodiment, each liter of the etching solution comprises 8g to 10g of sodium fluosilicate, 10g to 15g of 3-quinoline boric acid pinacol ester and 5g to 10g of m-chloroperoxybenzoic acid.
In one embodiment, each liter of the etching solution comprises water, 10 g-20 g of sodium fluosilicate, 10 g-15 g of 4-isoquinoline boric acid and 10 g-20 g of m-chloroperoxybenzoic acid.
In one embodiment, each liter of the etching solution comprises water, 15 g-20 g of sodium fluosilicate, 12 g-15 g of 4-isoquinoline boric acid and 15 g-20 g of m-chloroperoxybenzoic acid.
In one embodiment, the fluoride salt is ammonium bifluoride, the aluminum corrosion inhibitor is quinoline-3-boronic acid, and the oxidizing agent is hydrogen peroxide.
In one embodiment, the etching solution comprises 10 g-20 g of ammonium bifluoride, 1 g-15 g of quinoline-3-boronic acid and 10 g-20 g of hydrogen peroxide per liter of the etching solution.
In one embodiment, the etching solution comprises 15 g-20 g of ammonium bifluoride, 5 g-15 g of quinoline-3-boric acid and 15 g-20 g of hydrogen peroxide per liter of the etching solution.
In one embodiment, the fluoride salt is aluminum fluoride, the aluminum corrosion inhibitor is 3-quinolineboronic acid pinacol ester, and the oxidizing agent is t-butyl hydroperoxide.
In one embodiment, the etching solution comprises water, 10 g-20 g of aluminum fluoride, 10 g-15 g of 3-quinolineboronic acid pinacol ester, and 10 g-20 g of tert-butyl hydroperoxide per liter.
In one embodiment, the etching solution comprises water, 15 g-20 g of aluminum fluoride, 12 g-15 g of 3-quinolineboronic acid pinacol ester, and 15 g-20 g of tert-butyl hydroperoxide per liter.
The invention also provides a preparation method of the etching solution, which comprises the following steps:
mixing the water, the fluoride salt, the aluminum corrosion inhibitor and the oxidant.
The invention also provides an application of the etching solution in etching titanium-containing components.
In one embodiment, the titanium-containing component is a titanium metal barrier layer used in semiconductor packaging.
The invention also provides a method of etching a titanium-containing component comprising the steps of:
the titanium-containing member is immersed in the etching solution as described above.
The invention has the following beneficial effects:
the etching solution disclosed by the invention comprises water, fluoride salt, an aluminum corrosion inhibitor and an oxidant, and through the synergistic cooperation of the raw materials, the etching solution disclosed by the invention can rapidly corrode titanium and has a small corrosion effect on aluminum, the etching coefficient is large, the etching solution is safe and reliable, and the environmental pollution is small.
The etching solution disclosed by the invention is simple in preparation method, simple and convenient to operate, high in production efficiency, capable of saving time and energy consumption, low in production cost and suitable for industrial production.
The etching solution disclosed by the invention is simple in use method, and in the application process, only titanium-containing materials are immersed in the etching solution, so that the etching time is short, the effect is good, and the application prospect is wide.
If the etching solution is used for etching titanium-containing components, such as a titanium metal barrier layer in a wafer packaging process, fluoride salt can accelerate corrosion of metal, so that the etching solution has a larger etching coefficient and can be used for efficiently etching the titanium-containing components; the oxidant can lead the titanium metal to be corroded rapidly under the condition of normal temperature, thereby improving the production efficiency and simultaneously reducing the cost required by production; the aluminum corrosion inhibitor is matched, so that the etching solution has little side etching to aluminum metal, and the integrity of a circuit can be well ensured.
Drawings
FIG. 1 is a schematic diagram of an etching process of a titanium metal layer;
fig. 2 is a diagram showing a comparison of a metallographic microscope before and after etching a semiconductor integrated circuit package circuit by using an etching solution according to an embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The present invention 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 invention belongs. The terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used herein includes any and all combinations of one or more of the associated listed items.
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.
Unless mentioned to the contrary, singular terms may include plural and are not to be construed as being one in number.
In the present invention, a single bond to which a substituent is attached extends through the corresponding ring, meaning that the substituent may be attached to an optional position on the ring, e.gR represents 2 Attached to any substitutable site of the benzene ring, -, is a group of amino acids>R represents 2 Is attached to any substitutable site on the naphthalene ring.
In the present invention, at least one means one, or a mixture of plural. For example, the aluminum corrosion inhibitor is at least one of 3-quinolineboronic acid pinacol ester and 4-isoquinolinoboric acid, including: the aluminum corrosion inhibitor is 3-quinoline pinacol borate or 4-isoquinoline boric acid, and the aluminum corrosion inhibitor is 3-quinoline pinacol borate and 4-isoquinoline boric acid mixture.
The invention provides the etching solution which has good titanium etching effect, high etching speed, small etching effect on aluminum and less environmental pollution.
The technical proposal is as follows:
an etching solution comprising: water, fluoride salt, aluminum corrosion inhibitor and oxidant;
the structure of the aluminum corrosion inhibitor contains nitrogen atoms and boron hydroxyl groups, or the structure of the aluminum corrosion inhibitor contains nitrogen atoms and boric acid pinacol ester groups.
In one embodiment, the aluminum corrosion inhibitor has a structure as shown in any one of formulas (I-1) - (I-4):
in one embodiment, the aluminum corrosion inhibitor is selected from quinoline-5-boronic acidQuinoline-3-boronic acid3-quinolineboronic acid pinacol ester +.>Quinoline-4-boronic acid pinacol ester->6-quinolineboronic acid pinacol ester +.>Quinoline-8-boronic acid pinacol ester->7-Isoquinolineboronic acid pinacol ester +.>And 4-isoquinolineboronic acid->At least one of them.
In one embodiment, each liter of the etching solution comprises 1g to 20g of the fluorine salt, 1g to 20g of the aluminum corrosion inhibitor, and 1g to 20g of the oxidizing agent.
In one embodiment, each liter of the etching solution comprises 5g to 20g of the fluorine salt, 1g to 15g of the aluminum corrosion inhibitor, and 1g to 20g of the oxidant.
In one embodiment, the fluoride salt is selected from at least one of sodium fluoride, potassium fluoride, ammonium bifluoride, aluminum fluoride, and sodium fluorosilicate.
In one embodiment, the oxidizing agent is selected from at least one of potassium hydrogen persulfate, m-chloroperoxybenzoic acid, hydrogen peroxide, and t-butyl hydroperoxide.
In one embodiment, the fluoride salt is potassium fluoride, the aluminum corrosion inhibitor is quinoline-5-boric acid, and the oxidizing agent is t-butyl hydroperoxide.
In one embodiment, the etching solution comprises water, 5 g-15 g of potassium fluoride, 5 g-15 g of quinoline-5-boric acid, and 10 g-20 g of tert-butyl hydroperoxide per liter.
In one embodiment, the etching solution comprises water, 8 g-10 g of potassium fluoride, 8 g-10 g of quinoline-5-boric acid, and 10 g-15 g of tert-butyl hydroperoxide per liter.
In one embodiment, the etchant comprises water, 5g of potassium fluoride, 10g of quinoline-5-boronic acid, and 10g of tert-butyl hydroperoxide per liter of the etchant.
In one embodiment, the fluoride salt is potassium fluoride, the aluminum corrosion inhibitor is 4-isoquinolineboric acid, and the oxidizing agent is potassium hydrogen persulfate.
In one embodiment, the etching solution comprises water, 5g to 15g of potassium fluoride, 5g to 10g of 4-isoquinoline boric acid, and 10g to 20g of potassium hydrogen persulfate per liter.
In one embodiment, each liter of the etching solution comprises water, 8g to 10g of potassium fluoride, 5g to 10g of 4-isoquinoline boric acid, and 10g to 20g of potassium hydrogen persulfate.
In one embodiment, the etching solution comprises water, 10g of potassium fluoride, 5g of 4-isoquinoline boric acid, and 10g of potassium hydrogen persulfate per liter.
In one embodiment, the fluoride salt is aluminum fluoride, the aluminum corrosion inhibitor is quinoline-5-boronic acid, and the oxidizing agent is potassium hydrogen persulfate.
In one embodiment, the etching solution comprises water, 5g to 15g of aluminum fluoride, 10g to 15g of quinoline-5-boric acid, and 1g to 10g of potassium hydrogen persulfate per liter.
In one embodiment, the etching solution comprises water, 5g to 15g of aluminum fluoride, 10g to 15g of quinoline-5-boric acid, and 1g to 8g of potassium hydrogen persulfate per liter.
In one embodiment, the etching solution comprises water, 15g of aluminum fluoride, 15g of quinoline-5-boronic acid, and 1g of potassium hydrogen persulfate per liter.
In one embodiment, the fluoride salt is sodium fluosilicate, the aluminum corrosion inhibitor is at least one of 3-quinolineboronic acid pinacol ester and 4-isoquinolineeboronic acid, and the oxidizing agent is m-chloroperoxybenzoic acid.
In one embodiment, each liter of the etching solution comprises water, 5g to 15g of sodium fluosilicate, 10g to 15g of 3-quinoline boric acid pinacol ester, and 5g to 15g of m-chloroperoxybenzoic acid.
In one embodiment, each liter of the etching solution comprises 8g to 10g of sodium fluosilicate, 10g to 15g of 3-quinoline boric acid pinacol ester and 5g to 10g of m-chloroperoxybenzoic acid.
In one embodiment, the etchant comprises water, 10g of sodium fluorosilicate, 10g of 3-quinolineboronic acid pinacol ester, and 5g of m-chloroperoxybenzoic acid per liter of the etchant.
In one embodiment, each liter of the etching solution comprises water, 10 g-20 g of sodium fluosilicate, 10 g-15 g of 4-isoquinoline boric acid and 10 g-20 g of m-chloroperoxybenzoic acid.
In one embodiment, each liter of the etching solution comprises water, 15 g-20 g of sodium fluosilicate, 12 g-15 g of 4-isoquinoline boric acid and 15 g-20 g of m-chloroperoxybenzoic acid.
In one embodiment, each liter of the etching solution comprises water, 20g of sodium fluorosilicate, 15g of 4-isoquinoline boric acid, and 15g of m-chloroperoxybenzoic acid.
In one embodiment, the fluoride salt is ammonium bifluoride, the aluminum corrosion inhibitor is quinoline-3-boronic acid, and the oxidizing agent is hydrogen peroxide.
In one embodiment, the etching solution comprises 10 g-20 g of ammonium bifluoride, 1 g-15 g of quinoline-3-boronic acid and 10 g-20 g of hydrogen peroxide per liter of the etching solution.
In one embodiment, the etching solution comprises 15 g-20 g of ammonium bifluoride, 5 g-15 g of quinoline-3-boric acid and 15 g-20 g of hydrogen peroxide per liter of the etching solution.
In one embodiment, the etchant comprises water, ammonium bifluoride 20g, quinoline-3-boronic acid 5g, and hydrogen peroxide 15g per liter.
In one embodiment, the etchant comprises 20g of ammonium bifluoride, 5g of quinoline-3-boronic acid, and 20g of hydrogen peroxide per liter of the etchant.
In one embodiment, the etchant comprises water, ammonium bifluoride 20g, quinoline-3-boronic acid 10g, and hydrogen peroxide 15g per liter.
In one embodiment, the etchant comprises water, ammonium bifluoride 20g, quinoline-3-boronic acid 15g, and hydrogen peroxide 15g per liter of the etchant.
In one embodiment, the etching solution comprises 15 g-20 g of ammonium bifluoride, 1 g-3 g of quinoline-3-boronic acid and 15 g-18 g of hydrogen peroxide per liter of the etching solution.
In one embodiment, the etchant comprises water, ammonium bifluoride 20g, quinoline-3-boronic acid 1g, and hydrogen peroxide 15g per liter.
In one embodiment, the fluoride salt is aluminum fluoride, the aluminum corrosion inhibitor is 3-quinolineboronic acid pinacol ester, and the oxidizing agent is t-butyl hydroperoxide.
In one embodiment, the etching solution comprises water, 10 g-20 g of aluminum fluoride, 10 g-15 g of 3-quinolineboronic acid pinacol ester, and 10 g-20 g of tert-butyl hydroperoxide per liter.
In one embodiment, the etching solution comprises water, 15 g-20 g of aluminum fluoride, 12 g-15 g of 3-quinolineboronic acid pinacol ester, and 15 g-20 g of tert-butyl hydroperoxide per liter.
In one embodiment, the etchant comprises water, 20g of aluminum fluoride, 15g of 3-quinolineboronic acid pinacol ester, and 15g of t-butyl hydroperoxide per liter of the etchant.
The invention also provides a preparation method of the etching solution, which comprises the following steps:
mixing the water, the fluoride salt, the aluminum corrosion inhibitor and the oxidant.
The invention also provides an application of the etching solution in etching titanium-containing components.
In one embodiment, the titanium-containing component is a titanium metal barrier layer used in semiconductor packaging.
The invention also provides a method of etching a titanium-containing component comprising the steps of:
the titanium-containing member is immersed in the etching solution as described above.
The invention relates to a method for manufacturing a semiconductor integrated circuit packaging circuit, which comprises the following steps:
(1) Removing a dry film between electroplated copper on the substrate by exposure and development;
(2) Etching physical vapor deposited copper using a copper etchant;
(3) The physical vapor deposition titanium is etched using the titanium etchant of the present invention.
The etching process of the titanium metal layer of the present invention can be schematically shown in fig. 1.
Fig. 2 is a diagram showing a comparison of a metallographic microscope before and after etching a semiconductor integrated circuit package circuit by using an etching solution according to an embodiment of the present invention. As can be seen from fig. 2, if a corrosion inhibitor having a corrosion inhibition effect on aluminum is not added to the etching solution, the titanium metal layer is etched and simultaneously the aluminum metal layer is etched; and a corrosion inhibitor with corrosion inhibition effect on aluminum is added into the etching solution, only the titanium metal layer is etched, and the aluminum metal layer is not etched.
The invention will be further illustrated with reference to specific examples.
Example 1
The embodiment provides an etching solution and a preparation method thereof.
(1) The composition of each liter of the etching solution is as follows:
(2) The preparation method of the etching solution in the embodiment comprises the following steps:
at normal temperature, adding 0.5L deionized water into a reaction vessel, slowly adding potassium fluoride, quinoline-5-boric acid and tert-butyl hydroperoxide, stirring until the solution is clear, adding deionized water to 1L, stirring uniformly, and standing for standby.
Example 2
The embodiment provides an etching solution and a preparation method thereof.
(1) The composition of each liter of the etching solution is as follows:
(2) The preparation method of the etching solution in the embodiment comprises the following steps:
at normal temperature, adding 0.5L of deionized water into a reaction vessel, slowly adding potassium fluoride, 4-isoquinoline boric acid and potassium hydrogen persulfate, stirring until the solution is clear, adding deionized water to 1L, stirring uniformly, and standing for later use.
Example 3
The embodiment provides an etching solution and a preparation method thereof.
(1) The composition of each liter of the etching solution is as follows:
(2) The preparation method of the etching solution in the embodiment comprises the following steps:
at normal temperature, adding 0.5L of deionized water into a reaction vessel, slowly adding aluminum fluoride, quinoline-5-boric acid and potassium hydrogen persulfate, stirring until the solution is clear, adding deionized water to 1L, stirring uniformly, and standing for later use.
Example 4
The embodiment provides an etching solution and a preparation method thereof.
(1) The composition of each liter of the etching solution is as follows:
(2) The preparation method of the etching solution in the embodiment comprises the following steps:
at normal temperature, adding 0.5L of deionized water into a reaction container, slowly adding sodium fluosilicate, 3-quinoline boric acid pinacol ester and m-chloroperoxybenzoic acid, stirring until the solution is clear, adding deionized water to 1L, stirring uniformly, and standing for later use.
Example 5
The embodiment provides an etching solution and a preparation method thereof.
(1) The composition of each liter of the etching solution is as follows:
(2) The preparation method of the etching solution in the embodiment comprises the following steps:
at normal temperature, adding 0.5L of deionized water into a reaction container, slowly adding ammonium bifluoride, quinoline-3-boric acid and hydrogen peroxide, stirring until the solution is clear, adding deionized water to 1L, stirring uniformly, and standing for later use.
Example 6
The embodiment provides an etching solution and a preparation method thereof.
(1) The composition of each liter of the etching solution is as follows:
(2) The preparation method of the etching solution in the embodiment comprises the following steps:
at normal temperature, adding 0.5L of deionized water into a reaction container, slowly adding ammonium bifluoride, quinoline-3-boric acid and hydrogen peroxide, stirring until the solution is clear, adding deionized water to 1L, stirring uniformly, and standing for later use.
Example 7
The embodiment provides an etching solution and a preparation method thereof.
(1) The composition of each liter of the etching solution is as follows:
(2) The preparation method of the etching solution in the embodiment comprises the following steps:
at normal temperature, adding 0.5L of deionized water into a reaction container, slowly adding ammonium bifluoride, quinoline-3-boric acid and hydrogen peroxide, stirring until the solution is clear, adding deionized water to 1L, stirring uniformly, and standing for later use.
Example 8
The embodiment provides an etching solution and a preparation method thereof.
(1) The composition of each liter of the etching solution is as follows:
(2) The preparation method of the etching solution in the embodiment comprises the following steps:
at normal temperature, adding 0.5L of deionized water into a reaction container, slowly adding ammonium bifluoride, quinoline-3-boric acid and hydrogen peroxide, stirring until the solution is clear, adding deionized water to 1L, stirring uniformly, and standing for later use.
Example 9
The embodiment provides an etching solution and a preparation method thereof.
(1) The composition of each liter of the etching solution is as follows:
(2) The preparation method of the etching solution in the embodiment comprises the following steps:
at normal temperature, adding 0.5L of deionized water into a reaction container, slowly adding ammonium bifluoride, quinoline-3-boric acid and hydrogen peroxide, stirring until the solution is clear, adding deionized water to 1L, stirring uniformly, and standing for later use.
Example 10
The embodiment provides an etching solution and a preparation method thereof.
(1) The composition of each liter of the etching solution is as follows:
(2) The preparation method of the etching solution in the embodiment comprises the following steps:
at normal temperature, adding 0.5L of deionized water into a reaction vessel, slowly adding aluminum fluoride, 3-quinoline pinacol borate and tert-butyl hydroperoxide, stirring until the solution is clear, adding deionized water to 1L, stirring uniformly, and standing for standby.
Example 11
The embodiment provides an etching solution and a preparation method thereof.
(1) The composition of each liter of the etching solution is as follows:
(2) The preparation method of the etching solution in the embodiment comprises the following steps:
at normal temperature, adding 0.5L of deionized water into a reaction container, slowly adding sodium fluosilicate, 4-isoquinoline boric acid and m-chloroperoxybenzoic acid, stirring until the solution is clear, adding deionized water to 1L, stirring uniformly, and standing for later use.
Example 12
The embodiment provides an etching solution and a preparation method thereof.
(1) The composition of each liter of the etching solution is as follows:
(2) The preparation method of the etching solution in the embodiment comprises the following steps:
at normal temperature, adding 0.5L deionized water into a reaction vessel, slowly adding potassium fluoride, quinoline-5-boric acid, 3-quinoline pinacol borate and tert-butyl hydroperoxide, stirring until the solution is clear, adding deionized water to 1L, stirring uniformly, and standing for standby.
Example 13
The embodiment provides an etching solution and a preparation method thereof.
(1) The composition of each liter of the etching solution is as follows:
(2) The preparation method of the etching solution in the embodiment comprises the following steps:
at normal temperature, adding 0.5L deionized water into a reaction vessel, slowly adding potassium fluoride, sodium fluoride, quinoline-5-boric acid and tert-butyl hydroperoxide, stirring until the solution is clear, adding deionized water to 1L, stirring uniformly, and standing for standby.
Example 14
The embodiment provides an etching solution and a preparation method thereof.
(1) The composition of each liter of the etching solution is as follows:
(2) The preparation method of the etching solution in the embodiment comprises the following steps:
at normal temperature, adding 0.5L deionized water into a reaction vessel, slowly adding potassium fluoride, quinoline-5-boric acid, m-chloroperoxybenzoic acid and tert-butyl hydroperoxide, stirring until the solution is clear, adding deionized water to 1L, stirring uniformly, and standing for later use.
Example 15
The embodiment provides an etching solution and a preparation method thereof.
(1) The composition of each liter of the etching solution is as follows:
(2) The preparation method of the etching solution in the embodiment comprises the following steps:
at normal temperature, adding 0.5L deionized water into a reaction vessel, slowly adding potassium fluoride, sodium fluoride, quinoline-5-boric acid and tert-butyl hydroperoxide, stirring until the solution is clear, adding deionized water to 1L, stirring uniformly, and standing for standby.
Example 16
The embodiment provides an etching solution and a preparation method thereof.
(1) The composition of each liter of the etching solution is as follows:
/>
(2) The preparation method of the etching solution in the embodiment comprises the following steps:
at normal temperature, adding 0.5L deionized water into a reaction vessel, slowly adding potassium fluoride, quinoline-5-boric acid and tert-butyl hydroperoxide, stirring until the solution is clear, adding deionized water to 1L, stirring uniformly, and standing for standby.
Comparative example 1
The comparative example provides an etching solution and a method for preparing the same.
(1) The composition of each liter of the etching solution is as follows:
20g of hydrogen fluoride, and the concentration of the hydrogen fluoride,
15g of hydrogen peroxide;
the balance being water.
(2) The etching solution in this comparative example was prepared by:
at normal temperature, adding 0.5L deionized water into a reaction vessel, slowly adding hydrogen fluoride, cooling, slowly adding hydrogen peroxide, stirring until the solution is clear, adding deionized water to 1L, stirring uniformly, and standing for standby.
Comparative example 2
The comparative example provides an etching solution and a method for preparing the same.
(1) The composition of each liter of the etching solution is as follows:
(2) The etching solution in this comparative example was prepared by:
at normal temperature, adding 0.5L of deionized water into a reaction container, slowly adding phosphoric acid, phosphonic acid and hydrogen peroxide, stirring until the solution is clear, adding deionized water to 1L, stirring uniformly, and standing for standby.
Comparative example 3
The comparative example provides an etching solution and a method for preparing the same.
(1) The composition of each liter of the etching solution is as follows:
(2) The etching solution in this comparative example was prepared by:
at normal temperature, adding 0.5L deionized water into a reaction vessel, slowly adding ammonium bifluoride, hydrogen peroxide and N, N-dimethylacetamide, stirring until the solution is clear, adding deionized water to 1L, stirring uniformly, and standing for standby.
Comparative example 4
The comparative example provides an etching solution and a method for preparing the same.
(1) The composition of each liter of the etching solution is as follows:
(2) The etching solution in this comparative example was prepared by:
at normal temperature, adding 0.5L of deionized water into a reaction container, slowly adding ammonium bifluoride, hydrogen peroxide and quinaldic acid, stirring until the solution is clear, adding deionized water to 1L, stirring uniformly, and standing for standby.
Comparative example 5
The comparative example provides an etching solution and a method for preparing the same.
(1) The composition of each liter of the etching solution is as follows:
(2) The etching solution in this comparative example was prepared by:
at normal temperature, adding 0.5L deionized water into a reaction vessel, slowly adding potassium fluoride, fluoboric acid and hydrogen peroxide, stirring until the solution is clear, adding deionized water to 1L, stirring uniformly, and standing for standby.
Comparative example 6
The comparative example provides an etching solution and a method for preparing the same.
(1) The composition of each liter of the etching solution is as follows:
(2) The etching solution in this comparative example was prepared by:
at normal temperature, adding 0.5L of deionized water into a reaction vessel, slowly adding potassium fluoride, phenylboronic acid and hydrogen peroxide, stirring until the solution is clear, adding deionized water to 1L, stirring uniformly, and standing for standby.
The etching solutions of examples 1 to 16 and comparative examples 1 to 6 were formulated as shown in Table 1, and the total volume of the etching solutions was 1L, and they contained deionized water (raw material 1).
TABLE 1
/>
Test example:
the test method is as follows:
after preparing the titanium etching solution, the dried pure metal titanium block and pure metal aluminum block were weighed at normal temperature, and the areas thereof were measured, respectively, and then the etching solutions of the above-mentioned examples 1 to 16 and comparative examples 1 to 6 were immersed for 5 minutes, respectively, taken out, washed with purified water, dried and weighed, and the weight loss was calculated, and the titanium etching rate and the aluminum etching rate were calculated, respectively, using a formula.
The calculation formula is as follows: lost weight (g)/{ 2 etched metal area (cm) 2 ) Metal density (g/cm) 3 ) Etching time (min)*10000 Etch rate (μm/min).
Wherein, the metal density of the pure metal titanium block is 4.506g/cm 3 The metal density of the pure metal aluminum block is 2.7g/cm 3 。
The selectivity is the ratio of the titanium etching rate to the aluminum etching rate, and the larger the value of the selectivity is, the better the selectivity is, which shows that the etching solution is more prone to etch titanium and less corrosion to aluminum, and the titanium etching performance is better. The titanium etching rate is higher, the aluminum etching rate is lower, the selectivity is good, and the etching effect is optimal.
The test results are shown in table 2:
TABLE 2
As can be seen from table 2, the etching solutions of examples 1 to 16 of the present invention have strong etching effect on titanium metal, have a fast etching rate, have a smaller etching effect on aluminum metal, and have a better etching performance on titanium than titanium. In contrast, the etching solutions of comparative examples 1, 3 to 4 did not produce the effect of inhibiting aluminum, but the surface of aluminum was severely corroded while etching titanium. The etching solutions of comparative examples 2 and 5 to 6 have weak effects of inhibiting aluminum, and the surface of aluminum is obviously corroded during titanium etching.
The technical features of the above-described embodiments may be arbitrarily combined, and all possible combinations of the technical features in the above-described 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 above examples merely represent a few embodiments of the present invention, which facilitate a specific and detailed understanding of the technical solutions of the present invention, but are not to be construed as limiting the scope of the invention. It should be noted that it will be apparent to those skilled in the art that several variations and modifications can be made without departing from the spirit of the invention, which are all within the scope of the invention. It should be understood that, based on the technical solutions provided by the present invention, those skilled in the art may obtain technical solutions through logic analysis, reasoning or limited experiments, which are all within the scope of protection of the appended claims. The scope of the patent is therefore intended to be covered by the appended claims, and the description and drawings may be interpreted as illustrative of the contents of the claims.

Claims (8)

1. An etching solution for a titanium-containing member, comprising: water, fluoride salt, aluminum corrosion inhibitor and oxidant;
the aluminum corrosion inhibitor has a structure shown in any one of formulas (I-1) - (I-4):
（I-1）、/>（I-2）、
（I-3）、/>（I-4）；
the fluoride salt is at least one selected from sodium fluoride, potassium fluoride, ammonium bifluoride, aluminum fluoride and sodium fluosilicate;
the oxidant is at least one selected from potassium hydrogen persulfate, m-chloroperoxybenzoic acid, hydrogen peroxide and tert-butyl hydroperoxide.
2. The etching solution according to claim 1, wherein the aluminum corrosion inhibitor is at least one selected from the group consisting of quinoline-5-boric acid, quinoline-3-boric acid, 3-quinolineboronic acid pinacol ester, quinoline-4-boronic acid pinacol ester, 6-quinolineboronic acid pinacol ester, quinoline-8-boronic acid pinacol ester, 7-isoquinolinoboric acid pinacol ester, and 4-isoquinolinoboric acid.
3. The etching solution according to claim 1, wherein each liter of the etching solution comprises water, 1g to 20g of the fluorine salt, 1g to 20g of the aluminum corrosion inhibitor, and 1g to 20g of the oxidizing agent.
4. The etching solution according to claim 1, wherein the fluorine salt is potassium fluoride, the aluminum corrosion inhibitor is quinoline-5-boric acid, and the oxidizing agent is tert-butyl hydroperoxide; or (b)
The fluorine salt is potassium fluoride, the aluminum corrosion inhibitor is 4-isoquinoline boric acid, and the oxidant is potassium hydrogen persulfate; or (b)
The fluorine salt is aluminum fluoride, the aluminum corrosion inhibitor is quinoline-5-boric acid, and the oxidant is potassium hydrogen persulfate; or (b)
The fluorine salt is sodium fluosilicate, the aluminum corrosion inhibitor is at least one of 3-quinoline boric acid pinacol ester and 4-isoquinoline boric acid, and the oxidant is m-chloroperoxybenzoic acid; or (b)
The fluorine salt is ammonium bifluoride, the aluminum corrosion inhibitor is quinoline-3-boric acid, and the oxidant is hydrogen peroxide; or (b)
The fluorine salt is aluminum fluoride, the aluminum corrosion inhibitor is 3-quinoline boric acid pinacol ester, and the oxidant is tert-butyl hydroperoxide.
5. The etching solution according to claim 4, wherein each liter of the etching solution comprises water, 5g to 15g of potassium fluoride, 5g to 15g of quinoline-5-boric acid, and 10g to 20g of t-butyl hydroperoxide; or (b)
Each liter of the etching solution comprises 5 g-15 g of potassium fluoride, 5 g-10 g of 4-isoquinoline boric acid and 10 g-20 g of potassium hydrogen persulfate; or (b)
Each liter of the etching solution comprises 5g to 15g of aluminum fluoride, 10g to 15g of quinoline-5-boric acid and 1g to 10g of potassium hydrogen persulfate; or (b)
Each liter of the etching solution comprises 5 g-15 g of sodium fluosilicate, 10 g-15 g of 3-quinoline boric acid pinacol ester and 5 g-15 g of m-chloroperoxybenzoic acid; or (b)
Each liter of the etching solution comprises 10 g-20 g of ammonium bifluoride, 1 g-15 g of quinoline-3-boric acid and 10 g-20 g of hydrogen peroxide; or (b)
Each liter of the etching solution comprises 10 g-20 g of aluminum fluoride, 10 g-15 g of 3-quinoline boric acid pinacol ester and 10 g-20 g of tert-butyl hydroperoxide; or (b)
Each liter of the etching solution comprises 10 g-20 g of sodium fluosilicate, 10 g-15 g of 4-isoquinoline boric acid and 10 g-20 g of m-chloroperoxybenzoic acid.
6. A method for preparing the etching solution for a titanium-containing member according to any one of claims 1 to 5, comprising the steps of:
mixing the water, the fluoride salt, the aluminum corrosion inhibitor and the oxidant.
7. Use of the etching solution for etching a titanium-containing member according to any one of claims 1 to 5 for etching a titanium-containing member.
8. A method of etching a titanium-containing component, comprising the steps of:
immersing the titanium-containing member in the etching liquid for titanium-containing members according to any one of claims 1 to 5.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1025157A (en) * 1964-04-18 1966-04-06 Distillers Co Yeast Ltd Boron modified quinolated metalloxane polymers
US6465433B1 (en) * 1994-10-28 2002-10-15 Millennium Pharmaceuticals, Inc. Boronic ester and acid compounds, synthesis and uses
CN101750914A (en) * 2008-12-05 2010-06-23 安集微电子（上海）有限公司 Photoresist detergent composition
CN104599956A (en) * 2013-08-21 2015-05-06 加利福尼亚大学董事会 Doping of a substrate via a dopant containing polymer film
WO2016079757A2 (en) * 2014-11-19 2016-05-26 Symed Labs Limited Novel processes for preparing 5-hydroxymethyl-oxazolidin-2-one derivatives
CN113265660A (en) * 2021-04-30 2021-08-17 光华科学技术研究院(广东)有限公司 Etching solution and application thereof

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1025157A (en) * 1964-04-18 1966-04-06 Distillers Co Yeast Ltd Boron modified quinolated metalloxane polymers
US6465433B1 (en) * 1994-10-28 2002-10-15 Millennium Pharmaceuticals, Inc. Boronic ester and acid compounds, synthesis and uses
CN101750914A (en) * 2008-12-05 2010-06-23 安集微电子（上海）有限公司 Photoresist detergent composition
CN104599956A (en) * 2013-08-21 2015-05-06 加利福尼亚大学董事会 Doping of a substrate via a dopant containing polymer film
WO2016079757A2 (en) * 2014-11-19 2016-05-26 Symed Labs Limited Novel processes for preparing 5-hydroxymethyl-oxazolidin-2-one derivatives
CN113265660A (en) * 2021-04-30 2021-08-17 光华科学技术研究院(广东)有限公司 Etching solution and application thereof

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