CN113355665A - Composition for electroless gold plating - Google Patents
Composition for electroless gold plating Download PDFInfo
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- CN113355665A CN113355665A CN202110240282.2A CN202110240282A CN113355665A CN 113355665 A CN113355665 A CN 113355665A CN 202110240282 A CN202110240282 A CN 202110240282A CN 113355665 A CN113355665 A CN 113355665A
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- gold plating
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- 229910052737 gold Inorganic materials 0.000 title claims abstract description 188
- 239000010931 gold Substances 0.000 title claims abstract description 188
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 159
- 238000007747 plating Methods 0.000 title claims abstract description 102
- 239000000203 mixture Substances 0.000 title claims abstract description 67
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 104
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 104
- 239000010703 silicon Substances 0.000 claims abstract description 104
- 239000004065 semiconductor Substances 0.000 claims abstract description 78
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 75
- -1 hexafluorosilicic acid Chemical compound 0.000 claims abstract description 53
- 239000002253 acid Substances 0.000 claims abstract description 32
- 150000002222 fluorine compounds Chemical class 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims description 53
- 238000000151 deposition Methods 0.000 claims description 47
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 40
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims description 6
- 229910010271 silicon carbide Inorganic materials 0.000 claims description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 5
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 4
- MIMUSZHMZBJBPO-UHFFFAOYSA-N 6-methoxy-8-nitroquinoline Chemical compound N1=CC=CC2=CC(OC)=CC([N+]([O-])=O)=C21 MIMUSZHMZBJBPO-UHFFFAOYSA-N 0.000 claims description 4
- 230000008021 deposition Effects 0.000 abstract description 41
- 239000000758 substrate Substances 0.000 description 27
- 239000002244 precipitate Substances 0.000 description 17
- 230000000704 physical effect Effects 0.000 description 15
- 238000001556 precipitation Methods 0.000 description 14
- 238000006073 displacement reaction Methods 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 239000003638 chemical reducing agent Substances 0.000 description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 6
- 238000004090 dissolution Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- 239000010953 base metal Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 239000003960 organic solvent Substances 0.000 description 4
- JAJIPIAHCFBEPI-UHFFFAOYSA-N 9,10-dioxoanthracene-1-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)O JAJIPIAHCFBEPI-UHFFFAOYSA-N 0.000 description 3
- 229910021331 inorganic silicon compound Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 150000003961 organosilicon compounds Chemical class 0.000 description 3
- 230000001681 protective effect Effects 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- CYSGHNMQYZDMIA-UHFFFAOYSA-N 1,3-Dimethyl-2-imidazolidinon Chemical compound CN1CCN(C)C1=O CYSGHNMQYZDMIA-UHFFFAOYSA-N 0.000 description 2
- 241000722270 Regulus Species 0.000 description 2
- 229910052783 alkali metal Inorganic materials 0.000 description 2
- 150000001340 alkali metals Chemical class 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 235000011187 glycerol Nutrition 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 239000012454 non-polar solvent Substances 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- 241000555028 Sternidius alpha Species 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
Images
Classifications
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1635—Composition of the substrate
- C23C18/1639—Substrates other than metallic, e.g. inorganic or organic or non-conductive
- C23C18/1642—Substrates other than metallic, e.g. inorganic or organic or non-conductive semiconductor
-
- 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
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1675—Process conditions
- C23C18/1683—Control of electrolyte composition, e.g. measurement, adjustment
-
- 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 purpose of the present invention is to provide a composition for electroless gold plating on the surface of a silicon semiconductor, which can reduce the rate of gold deposition on the surface of a silicon semiconductor. The above object is achieved by providing a composition for electroless gold plating of a surface of a silicon semiconductor, which comprises a gold ion source, a fluorine compound and acetonitrile, a composition for electroless gold plating of a surface of a silicon semiconductor, which comprises a gold ion source and hexafluorosilicic acid and/or tetrafluoroboric acid, and the like.
Description
Technical Field
The present invention relates to a composition for electroless gold plating of a surface of a silicon semiconductor, and the like.
Background
Gold is used in various applications such as printed circuit boards, wire-bonding materials, and accessories as a substance having high conductivity, chemical stability, and ductility. The use is generally by gold plating.
As the gold plating method, an electrolytic gold plating method and an electroless gold plating method are known. As the electroless gold plating method, an autocatalytic electroless gold plating method, a substrate catalytic gold plating method, a displacement gold plating method, and the like are known. In particular, the displacement gold plating method is a gold plating method in which gold is deposited by an electrodisplacement reaction between a base metal on a surface to be plated and a gold ion and/or a gold ion complex.
In recent years, a method of performing electroless gold plating on the surface of silicon by a displacement gold plating method has been reported (patent document 1). The method employs a composition for gold plating comprising a source of gold ions and hydrofluoric acid. Hydrofluoric acid dissolves an oxide film on the surface of silicon, and silicon is ionized by a substitution reaction between silicon and gold to precipitate gold, thereby forming a gold plating layer on the surface of silicon. Further, a method of performing electroless gold plating on the surface of silicon carbide, not silicon, has also been reported (patent document 2).
The above-mentioned composition for gold plating is also used in a method for producing a polycrystalline silicon substrate for a solar cell and various composite materials (patent documents 3 to 7). On the other hand, a gold plating composition containing a gold ion source and an alkali metal hydroxide may be used instead (patent documents 8 and 9).
In recent years, a method of applying a gold plating layer formed by a displacement gold plating method to etching silicon has also been reported (patent document 10). Specifically, by forming gold on the surface of silicon, the gold precipitates exhibit a catalytic action, and silicon under the gold precipitates can be etched vertically.
Documents of the prior art
Patent document
Patent document 1 Japanese patent No. 5945429
Patent document 2 Japanese patent No. 6603491
Patent document 3 Japanese patent No. 4049329
Patent document 4 Japanese patent No. 5261475
Patent document 5 Japanese patent No. 5281847
Patent document 6 Japanese patent No. 5306670
Patent document 7 Japanese patent No. 5663625
Patent document 8 Japanese patent No. 6553596
Patent document 9 Japanese patent No. 6573603
Patent document 10 Japanese patent No. 6121959
Summary of the invention
Technical problem to be solved by the invention
The purpose of the present invention is to provide a composition for electroless gold plating on the surface of a silicon semiconductor, which can reduce the rate of gold deposition on the surface of a silicon semiconductor.
Technical scheme for solving technical problem
The present inventors confirmed the following phenomenon: in the case where a composition for gold plating containing a gold ion source and hydrofluoric acid is used in the electroless gold plating of the surface of a silicon semiconductor, the oxide film on the surface of the silicon semiconductor is very rapidly dissolved, and the deposition of gold proceeds very rapidly, so that gold is excessively deposited on the surface of the silicon semiconductor, and the control of the structure of the gold plating layer is difficult. Further, as a result of earnest studies for facilitating the control of the structure, it has been found that the rate of deposition of gold on the surface of a silicon semiconductor can be reduced by adding acetonitrile to the composition for gold plating or adding hexafluorosilicic acid and/or tetrafluoroboric acid instead of hydrofluoric acid, and the present invention has been completed.
That is, the present invention relates to the following.
[1] A composition for electroless gold plating of a surface of a silicon semiconductor comprising a source of gold ions, a fluorine compound and acetonitrile.
[2] The composition according to [1], wherein the fluorine compound is 1 or more fluorine compounds selected from hydrofluoric acid, ammonium fluoride, ammonium bifluoride, hexafluorosilicic acid and tetrafluoroboric acid.
[3] A composition for electroless gold plating of a surface of a silicon semiconductor comprising a source of gold ions and hexafluorosilicic acid and/or tetrafluoroboric acid.
[4] The composition according to [3], which further comprises acetonitrile.
[5] The composition according to any one of [1] to [4], wherein the silicon semiconductor is silicon, silicon oxide, and/or silicon carbide.
[6] The composition according to any one of [1] to [5], wherein the pH is 7 or less.
[7] A method for depositing gold, comprising a step of applying the composition according to any one of [1] to [6] to the surface of a silicon semiconductor.
ADVANTAGEOUS EFFECTS OF INVENTION
The composition for electroless gold plating on the surface of a silicon semiconductor of the present invention can reduce the rate of gold deposition on the surface of a silicon semiconductor. This makes it easy to control the structure of the gold plating layer on the surface of the silicon semiconductor, and thus desired physical properties of the precipitates can be obtained. Further, since an appropriate amount of gold can be deposited on the surface of the silicon semiconductor, the amount of gold consumed can be suppressed, and the method is economical. Further, the gold plating layer is formed accurately and densely on the surface of the silicon semiconductor, and the application to etching described in the background art is also facilitated. Further, since it is not necessary to use the composition for gold plating containing the hydroxide of an alkali metal described in the background art, it is possible to avoid adverse effects of the remaining alkali metal on semiconductor characteristics.
Brief description of the drawings
Fig. 1 shows a process of depositing gold on the surface of a patterned silicon semiconductor. Fig. 1A shows a cross-sectional view of a silicon semiconductor, and fig. 1B shows a top view of the silicon semiconductor viewed horizontally from above.
Modes for carrying out the invention
All technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art, unless otherwise defined herein. All patents, applications, and other publications and information referred to in this specification are herein incorporated in their entirety by reference into the specification, to the same extent as if each individual publication or information was specifically and individually indicated to be incorporated herein by reference.
[ composition (1) for electroless gold plating of the surface of a silicon semiconductor ]
One aspect of the present invention relates to a composition for electroless gold plating of a surface of a silicon semiconductor (hereinafter also referred to as "composition (1) of the present invention"), which contains a source of gold ions, a fluorine compound and acetonitrile.
The composition (1) of the present invention can also be suitably used for the surface of a patterned silicon semiconductor. The present inventors confirmed the following phenomenon: when a gold plating composition containing hydrofluoric acid is used in the electroless gold plating process on the surface of a silicon semiconductor, gold is excessively deposited on the surface of the silicon semiconductor, and gold is deposited outside the pattern (hereinafter also referred to as "out-of-pattern deposition") (fig. 1). By using the composition of the present invention, the rate of gold deposition on the surface of a silicon semiconductor can be reduced, and the deposition outside the pattern can be suppressed.
In the present invention, as the "gold ion source", a water-soluble gold salt such as chloroaurate can be specifically used. From the viewpoint of safety and waste liquid disposal problems, it is preferable to use a cyanide-free gold ion source. The concentration of the gold ion source is preferably 0.5 to 25mM, more preferably 1 to 10mM, and still more preferably 1.5 to 5mM, from the viewpoint of physical properties of the precipitate, particularly, precipitation property and economy.
In the present invention, the "fluorine compound" is 1 or more fluorine compounds selected from hydrofluoric acid, ammonium fluoride, ammonium bifluoride, hexafluorosilicic acid and tetrafluoroboric acid. From the viewpoint of reducing the rate of dissolution of the oxide film on the surface of the silicon semiconductor and reducing the rate of deposition of gold on the surface of the silicon semiconductor, hexafluorosilicic acid and/or tetrafluoroboric acid are preferred. From the viewpoint of physical properties of the precipitates, particularly reactivity and controllability, the concentration of the fluorine compound is preferably 0.1 to 2.7M, more preferably 0.5 to 2.0M, and still more preferably 0.7 to 1.2M.
In the present invention, from the viewpoint of suppressing the gold deposition rate and economy, "acetonitrile" is preferably at a concentration of 0.02 to 2M, particularly preferably at a concentration of 0.2 to 1.5M, and more preferably at a concentration of 0.5 to 1M.
In the present invention, the "silicon semiconductor" refers to a semiconductor containing an inorganic silicon compound having a siloxane bond and/or an organosilicon compound having a carbon-silicon bond. The silicon semiconductor is preferably silicon, silicon oxide, and/or silicon carbide from the viewpoint of physical properties of precipitates and the like.
In the present invention, "electroless gold plating" means gold plating using, for example, an autocatalytic type electroless gold plating method, a substrate catalytic gold plating method, and a displacement gold plating method. The autocatalytic electroless gold plating method is a method of performing gold deposition by using a reducing agent using gold as a catalyst. The substrate catalytic gold plating method is a method for carrying out gold precipitation by using a substrate metal as a catalyst through a reducing agent. Displacement gold plating is a method of depositing gold by an electrodisplacement reaction between a base metal on a surface to be plated and a gold ion and/or a gold ion complex. These plating methods may be used in combination of 2 or more. The electroless gold plating is preferably a displacement gold plating method from the viewpoint of physical properties of the precipitates and the like.
In the present invention, the "pattern" refers to a fine structure having a portion where a mask is present and a portion where no mask is present. From the viewpoint of physical properties of the precipitates, the width of the gap between the mask and the mask is preferably 0.5 to 20 μm, particularly preferably 1 to 10 μm. For example, the pattern is a resist pattern.
In the present invention, the "mask" refers to a protective film for gold plating treatment. In the case where the mask is present, the gold plating treatment does not occur, and the surface of the silicon semiconductor under the mask does not change before and after the gold plating treatment. The components constituting the mask are not particularly limited as long as they are selected according to the treatment chemicals used in the gold plating treatment. The mask is, for example, a resist.
From the viewpoints of stability of the composition, precipitation rate and the like, the pH of the composition (1) of the present invention is preferably 7 or less, particularly preferably 4 or less, more preferably less than 3.
[ composition (2) for electroless gold plating of the surface of a silicon semiconductor ]
Another aspect of the present invention relates to a composition for electroless gold plating of a surface of a silicon semiconductor (hereinafter also referred to as "composition (2) of the present invention"), which comprises a source of gold ions and hexafluorosilicic acid and/or tetrafluoroboric acid. From the viewpoint of reducing the rate of gold deposition on the surface of a silicon semiconductor, the composition (2) of the present invention preferably further contains acetonitrile.
The composition (2) of the present invention can also be suitably used for the surface of a patterned silicon semiconductor. By using the composition of the present invention, the rate of dissolution of the oxide film on the surface of the silicon semiconductor is reduced, and the rate of deposition of gold on the surface of the silicon semiconductor is reduced, whereby deposition outside the pattern can be suppressed.
In the present invention, as the "gold ion source", a water-soluble gold salt such as chloroaurate can be specifically used. From the viewpoint of safety and waste liquid disposal problems, it is preferable to use a cyanide-free gold ion source. The concentration of the gold ion source is preferably 0.5 to 25mM, more preferably 1 to 10mM, and still more preferably 1.5 to 5mM, from the viewpoint of physical properties of the precipitate, particularly, precipitation property and economy.
In the present invention, from the viewpoint of reducing the rate of dissolution of the oxide film on the surface of the silicon semiconductor and the rate of deposition of gold on the surface of the silicon semiconductor, "hexafluorosilicic acid" and/or "tetrafluoroboric acid" is/are preferably at a concentration of 0.1 to 2.7M, more preferably at a concentration of 0.5 to 2.0M, and still more preferably at a concentration of 0.7 to 1.2M.
In the present invention, the "silicon semiconductor" refers to a semiconductor containing an inorganic silicon compound having a siloxane bond and/or an organosilicon compound having a carbon-silicon bond. The silicon semiconductor is preferably silicon, silicon oxide, and/or silicon carbide from the viewpoint of physical properties of precipitates and the like.
In the present invention, "electroless gold plating" means gold plating using, for example, an autocatalytic type electroless gold plating method, a substrate catalytic gold plating method, and a displacement gold plating method. The autocatalytic electroless gold plating method is a method of performing gold deposition by using a reducing agent using gold as a catalyst. The substrate catalytic gold plating method is a method for carrying out gold precipitation by using a substrate metal as a catalyst through a reducing agent. Displacement gold plating is a method of depositing gold by an electrodisplacement reaction between a base metal on a surface to be plated and a gold ion and/or a gold ion complex. These plating methods may be used in combination of 2 or more. The electroless gold plating is preferably a displacement gold plating method from the viewpoint of physical properties of the precipitates and the like.
In the present invention, from the viewpoint of suppressing the gold deposition rate and economy, "acetonitrile" is preferably at a concentration of 0.02 to 2M, particularly preferably at a concentration of 0.2 to 1.5M, and more preferably at a concentration of 0.5 to 1M.
In the present invention, the "pattern" refers to a fine structure having a portion where a mask is present and a portion where no mask is present. From the viewpoint of physical properties of the precipitates, the width of the gap between the mask and the mask is preferably 0.5 to 20 μm, particularly preferably 1 to 10 μm. For example, the pattern is a resist pattern.
In the present invention, the "mask" refers to a protective film for gold plating treatment. In the case where the mask is present, the gold plating treatment does not occur, and the surface of the silicon semiconductor under the mask does not change before and after the gold plating treatment. The components constituting the mask are not particularly limited as long as they are selected according to the treatment chemicals used in the gold plating treatment. The mask is, for example, a resist.
From the viewpoints of stability of the composition, precipitation rate and the like, the pH of the composition (2) of the present invention is preferably 7 or less, particularly preferably 4 or less, more preferably less than 3.
[ composition (3) for electroless gold plating of the surface of a silicon semiconductor ]
Another aspect of the present invention relates to a composition for electroless gold plating of a surface of a patterned silicon semiconductor (hereinafter also referred to as "composition (3) of the present invention"), which comprises a source of gold ions and a fluorine compound. From the viewpoint of reducing the rate of dissolution of the oxide film on the surface of the silicon semiconductor and reducing the rate of deposition of gold on the surface of the silicon semiconductor, hexafluorosilicic acid and/or tetrafluoroboric acid are preferred. From the viewpoint of reducing the rate of gold deposition on the surface of a silicon semiconductor, the composition (3) of the present invention preferably further contains acetonitrile.
In the present invention, as the "gold ion source", a water-soluble gold salt such as chloroaurate can be specifically used. From the viewpoint of safety and waste liquid disposal problems, it is preferable to use a cyanide-free gold ion source. The concentration of the gold ion source is preferably 0.5 to 25mM, more preferably 1 to 10mM, and still more preferably 1.5 to 5mM, from the viewpoint of physical properties of the precipitate, particularly, precipitation property and economy.
In the present invention, the "fluorine compound" is 1 or more fluorine compounds selected from hydrofluoric acid, ammonium fluoride, ammonium bifluoride, hexafluorosilicic acid and tetrafluoroboric acid. From the viewpoint of reducing the rate of dissolution of the oxide film on the surface of the silicon semiconductor and reducing the rate of deposition of gold on the surface of the silicon semiconductor, hexafluorosilicic acid and/or tetrafluoroboric acid are preferred. From the viewpoint of physical properties of the precipitates, particularly reactivity and controllability, the concentration of the fluorine compound is preferably 0.1 to 2.7M, more preferably 0.5 to 2.0M, and still more preferably 0.7 to 1.2M.
In the present invention, the "pattern" refers to a fine structure having a portion where a mask is present and a portion where no mask is present. From the viewpoint of physical properties of the precipitates, the width of the gap between the mask and the mask is preferably 0.5 to 20 μm, particularly preferably 1 to 10 μm. For example, the pattern is a resist pattern.
In the present invention, the "mask" refers to a protective film for gold plating treatment. In the case where the mask is present, the gold plating treatment does not occur, and the surface of the silicon semiconductor under the mask does not change before and after the gold plating treatment. The components constituting the mask are not particularly limited as long as they are selected according to the treatment chemicals used in the gold plating treatment. The mask is, for example, a resist.
In the present invention, the "silicon semiconductor" refers to a semiconductor containing an inorganic silicon compound having a siloxane bond and/or an organosilicon compound having a carbon-silicon bond. The silicon semiconductor is preferably silicon, silicon oxide, and/or silicon carbide from the viewpoint of physical properties of precipitates and the like.
In the present invention, "electroless gold plating" means gold plating using, for example, an autocatalytic type electroless gold plating method, a substrate catalytic gold plating method, and a displacement gold plating method. The autocatalytic electroless gold plating method is a method of performing gold deposition by using a reducing agent using gold as a catalyst. The substrate catalytic gold plating method is a method for carrying out gold precipitation by using a substrate metal as a catalyst through a reducing agent. Displacement gold plating is a method of depositing gold by an electrodisplacement reaction between a base metal on a surface to be plated and a gold ion and/or a gold ion complex. These plating methods may be used in combination of 2 or more. The electroless gold plating is preferably a displacement gold plating method from the viewpoint of physical properties of the precipitates and the like.
In the present invention, from the viewpoint of suppressing the gold deposition rate and economy, "acetonitrile" is preferably at a concentration of 0.02 to 2M, particularly preferably at a concentration of 0.2 to 1.5M, and more preferably at a concentration of 0.5 to 1M.
From the viewpoints of stability of the composition, precipitation rate and the like, the pH of the composition (3) of the present invention is preferably 7 or less, particularly preferably 4 or less, more preferably less than 3.
[ method of precipitating gold ]
Another aspect of the present invention relates to a method for depositing gold (hereinafter also referred to as "the method of the present invention"), which comprises a step of applying any one of the compositions (1) to (3) of the present invention to the surface of a silicon semiconductor.
The use temperature of any of the compositions (1) to (3) of the present invention in the above step is preferably 10 to 50 ℃ from the viewpoint of the deposition rate, more preferably 15 to 30 ℃.
The amount of any one of the compositions (1) to (3) of the present invention used in the above step is not particularly limited as long as it is an amount sufficient for application to the surface of a silicon semiconductor. For example, the amount used is an amount sufficient to impregnate the surface of the silicon semiconductor.
The above-mentioned step may be carried out under a static condition, or may be carried out under a stirring condition. The stirring conditions are not particularly limited, but from the viewpoint of the precipitation rate, the stirring conditions are preferably 50 to 1500rpm, more preferably 100 to 1000 rpm.
The time of the step is not particularly limited, but is preferably 15 seconds to 10 minutes, more preferably 30 seconds to 5 minutes, from the viewpoint of the deposition rate.
Examples
Example 1 Effect of reducing the speed of gold deposition on the surface of a silicon semiconductor
Unpatterned silicon substrates (n-Si (100) Low < 0.02. omega. cm, Nilac Corporation) were cut to a size of 0.5cm by 1 cm. A silicon substrate was immersed in each composition (0.1L) of example 1 (3 mM tetrachloroauric (III) acid, 1M hydrofluoric acid, 1M acetonitrile, pH 2-3), example 2 (3 mM tetrachloroauric (III) acid, 1M hexafluorosilicic acid, pH < 1), example 3 (3 mM tetrachloroauric (III) acid, 1M hexafluorosilicic acid, 1M acetonitrile, pH < 1), and comparative example 1 (3 mM tetrachloroauric (III) acid, 1M hydrofluoric acid, pH 2-3) at room temperature (25 ℃) under a static condition for 1 minute to precipitate gold. Then, the silicon substrate was showered for 10 seconds (overflow with pure water) and dried with a nitrogen flow. The amount of gold deposited on the silicon substrate was evaluated by measuring the fluorescent X-ray intensity of gold deposited on the silicon substrate with a fluorescent X-ray film thickness meter (measurement time: 30 seconds, excitation voltage: 45kV, tube current: 1000. mu.A, measurement element: gold, analytical radiation: L.alpha., ROI (energy range for obtaining fluorescent X-ray intensity): 9.52 to 9.89 keV).
As a result, it was confirmed that the fluorescent X-ray intensities (232, 222, 227cps) of examples 1 to 3 were lower than the fluorescent X-ray intensity value (246cps) of the comparative example. The above results are summarized in Table 1. The value of the fluorescent X-ray intensity was an average value of 5 measurements.
[ Table 1]
TABLE 1 Effect of reducing the rate of gold precipitation on the surface of a silicon semiconductor
From this, it is found that the rate of gold deposition on the surface of the silicon semiconductor is reduced by adding acetonitrile to the composition for gold plating containing hydrofluoric acid. Further, it is found that the use of hexafluorosilicic acid instead of hydrofluoric acid as the fluorine compound reduces the rate of gold deposition on the surface of the silicon semiconductor. Further, it is known that the combined use of hexafluorosilicic acid and acetonitrile reduces the rate of gold deposition on the surface of a silicon semiconductor.
In each of the compositions of examples 1 and 3, in addition to the above-mentioned discussion, a study was made to replace acetonitrile with another organic solvent (polar solvent: isopropyl alcohol, diethylene glycol, methanol, ethylene glycol, glycerin, water, N-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, dimethyl sulfoxide), but the stability of the gold-plating composition is lowered regardless of the organic solvent, and therefore, the composition is not practical. Further, the nonpolar solvent has low solubility in water and is not mixed with the composition for gold plating, and therefore, it is not practical.
From the above results, it is considered that the use of acetonitrile and/or hexafluorosilicic acid as a fluorine compound reduces the rate of gold deposition on the surface of the silicon semiconductor, and facilitates the control of the structure of the gold plating layer on the surface of the silicon semiconductor.
Example 2 Effect of suppressing extrapattern deposition Using acetonitrile
A silicon substrate (n-Si (100) Low < 0.02. omega. cm, Niake corporation) on which a resist pattern (OFPR-800LB, film thickness of about 1.8 μm, Tokyo Kasei) having an L/S of 1 μm/1 μm was formed was cut into a size of 0.5cm × 1 cm. The silicon substrate was immersed in each composition (0.1L) of example 4 (3 mM of tetrachloroauric (III) acid, 1M of hydrofluoric acid, 1M of acetonitrile, pH2 to 3), example 5 (3 mM of tetrachloroauric (III) acid, 1M of hexafluorosilicic acid, 1M of acetonitrile, pH < 1), and comparative example (3 mM of tetrachloroauric (III) acid, 1M of hydrofluoric acid, pH2 to 3) for 2 minutes while stirring (100rpm) at room temperature (25 ℃ C.) to precipitate gold. Then, the silicon substrate was showered for 10 seconds (overflow with pure water) and dried with a nitrogen flow. The surface of the silicon substrate was observed with a field emission scanning electron microscope (Regulus 8230, hitachi high-tech co.) to confirm the presence or absence of the off-pattern deposition.
As a result, although a large amount of the off-pattern deposition was observed in the comparative example, only a small amount was observed in example 4, and only a very small amount was observed in example 5. In addition, in examples 4 and 5 and comparative example, it was confirmed that a large amount of gold was precipitated on the silicon substrate, and the precipitation of gold was not hindered. The above results are summarized in Table 2.
[ Table 2]
TABLE 2 inhibition effect of acetonitrile-based pattern extrication
From this, it was found that the addition of acetonitrile to a composition for gold plating containing hydrofluoric acid suppressed the deposition of an outer pattern. Furthermore, it is also found that when hexafluorosilicic acid is used as the fluorine compound in the composition instead of hydrofluoric acid, the deposition outside the pattern can be further suppressed.
In addition to the above-mentioned studies, the replacement of acetonitrile with other organic solvents (polar solvents: isopropyl alcohol, diethylene glycol, methanol, ethylene glycol, glycerin, water, N-methyl-2-pyrrolidone, 1, 3-dimethyl-2-imidazolidinone, and dimethyl sulfoxide) has been studied, but it is not practical because the stability of the gold-plating composition is lowered regardless of the organic solvent. Further, the nonpolar solvent has low solubility in water and is not mixed with the composition for gold plating, and therefore, it is not practical.
From the above results, it is considered that the use of acetonitrile reduces the rate of gold deposition on the surface of the silicon semiconductor, and facilitates the control of the structure of the gold plating layer on the surface of the silicon semiconductor.
Example 3 Effect of suppressing extrapattern deposition Using hexafluorosilicic acid and/or tetrafluoroboric acid
A silicon substrate (n-Si (100) Low < 0.02. omega. cm, Niake corporation) on which a resist pattern (OFPR-800LB, film thickness of about 1.8 μm, Tokyo Kasei) having an L/S of 1 μm/1 μm was formed was cut into a size of 0.5cm × 1 cm. The silicon substrate was immersed in each composition (0.1L) of example 6 (3 mM of tetrachloroauric (III) acid, 1M of hexafluorosilicic acid, pH < 1), example 7 (3 mM of tetrachloroauric (III) acid, 1M of tetrafluoroboric acid, pH < 1), example 8 (3 mM of tetrachloroauric (III) acid, 1M of hexafluorosilicic acid, 1M of tetrafluoroboric acid, pH < 1), and comparative examples (3 mM of tetrachloroauric (III) acid, 1M of hydrofluoric acid, pH 2-3) for 1 minute while stirring (100rpm) at room temperature (25 ℃) to precipitate gold. Then, the silicon substrate was showered for 10 seconds (overflow with pure water) and dried with a nitrogen flow. The surface of the silicon substrate was observed with a field emission scanning electron microscope (Regulus 8230, hitachi high-tech co.) to confirm the presence or absence of the off-pattern deposition.
As a result, although a large amount of the off-pattern deposition was observed in the comparative example, only a small amount was observed in example 6, not in example 7, and only a small amount was observed in example 8. In addition, in examples 6 and 7 and comparative example, it was confirmed that a large amount of gold was precipitated on the silicon substrate, and precipitation of gold was not hindered, but in example 7, a small amount of gold was precipitated on the silicon substrate. The above results are summarized in Table 3.
[ Table 3]
TABLE 3 inhibition effect of extrapattern precipitation based on hexafluorosilicic acid and/or tetrafluoroboric acid
It is thus found that the use of hexafluorosilicic acid or tetrafluoroboric acid as the fluorine compound, rather than hydrofluoric acid, can suppress the deposition of the plating composition outside the pattern. Further, it is also found that the use of a combination of hexafluorosilicic acid and tetrafluoroboric acid instead of hydrofluoric acid as the fluorine compound can suppress the deposition of the plating composition outside the pattern.
From the above results, it is considered that the use of hexafluorosilicic acid and/or tetrafluoroboric acid as the fluorine compound reduces the rate of dissolution of the oxide film on the surface of the silicon semiconductor and reduces the rate of deposition of gold on the surface of the silicon semiconductor, thereby facilitating the control of the structure of the gold plating layer on the surface of the silicon semiconductor.
Various combinations of the features of the present invention described in the present specification may be made, and the forms obtained by such combinations also include combinations not specifically described in the present specification, and are within the scope of the present invention. In addition, it will be understood by those skilled in the art that a variety of changes may be made without departing from the spirit of the invention, and equivalents including the changes are also included in the scope of the invention. Therefore, it should be understood that the forms described in the present specification are only examples, and they are not described to limit the scope of the present invention.
Claims (7)
1. A composition for electroless gold plating of a surface of a silicon semiconductor comprising a source of gold ions, a fluorine compound and acetonitrile.
2. The composition according to claim 1, wherein the fluorine compound is 1 or more fluorine compounds selected from the group consisting of hydrofluoric acid, ammonium fluoride, ammonium bifluoride, hexafluorosilicic acid and tetrafluoroboric acid.
3. A composition for electroless gold plating of a surface of a silicon semiconductor comprising a source of gold ions and hexafluorosilicic acid and/or tetrafluoroboric acid.
4. The composition of claim 3, further comprising acetonitrile.
5. The composition of any one of claims 1 to 4, wherein the silicon semiconductor is silicon, silicon oxide, and/or silicon carbide.
6. The composition according to any one of claims 1 to 5, wherein the pH is 7 or below.
7. A method for depositing gold, comprising a step of applying the composition according to any one of claims 1 to 6 to the surface of a silicon semiconductor.
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| US20100098863A1 (en) | 2003-03-12 | 2010-04-22 | University Of Missouri | Process for spontaneous deposition from an organic solution |
| JP5281847B2 (en) | 2008-08-19 | 2013-09-04 | 独立行政法人科学技術振興機構 | COMPOSITE MATERIAL, ITS MANUFACTURING METHOD, AND ITS MANUFACTURING DEVICE |
| US10358725B2 (en) | 2017-06-14 | 2019-07-23 | Eastman Kodak Company | Compositions and methods for forming articles having silver metal |
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2020
- 2020-03-06 JP JP2020038971A patent/JP7457537B2/en active Active
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- 2021-03-04 CN CN202110240282.2A patent/CN113355665A/en active Pending
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|---|---|---|---|---|
| US4474838A (en) * | 1982-12-01 | 1984-10-02 | Omi International Corporation | Electroless direct deposition of gold on metallized ceramics |
| DE3917867A1 (en) * | 1989-06-01 | 1990-12-06 | Hoechst Ceram Tec Ag | Electroless gold plating - of tungsten or molybdenum metallisations esp. on electronic ceramic components |
| US6593221B1 (en) * | 2002-08-13 | 2003-07-15 | Micron Technology, Inc. | Selective passivation of exposed silicon |
| JP2005336600A (en) * | 2004-04-30 | 2005-12-08 | Alps Electric Co Ltd | Electroless plating method for silicon substrate and method for forming metallic layer on silicon substrate |
| WO2011109878A1 (en) * | 2010-03-12 | 2011-09-15 | Katholieke Universiteit Leuven | Liquid metal salts |
| CN102443801A (en) * | 2010-10-08 | 2012-05-09 | 华康半导体股份有限公司 | Method for forming micropore structure or groove structure on surface of silicon crystal substrate |
| CN108350575A (en) * | 2015-12-18 | 2018-07-31 | 罗门哈斯电子材料有限责任公司 | Golden electroplating solution |
| US20180327908A1 (en) * | 2015-12-18 | 2018-11-15 | Dow Global Technologies Llc | Gold plating solution |
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| JP7457537B2 (en) | 2024-03-28 |
| JP2021139015A (en) | 2021-09-16 |
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