CN1290160C - Metallization method for producing integrated circuit copper interconnecting wire by separating bipolar acid chemical plating - Google Patents
Metallization method for producing integrated circuit copper interconnecting wire by separating bipolar acid chemical plating Download PDFInfo
- Publication number
- CN1290160C CN1290160C CN 200410080014 CN200410080014A CN1290160C CN 1290160 C CN1290160 C CN 1290160C CN 200410080014 CN200410080014 CN 200410080014 CN 200410080014 A CN200410080014 A CN 200410080014A CN 1290160 C CN1290160 C CN 1290160C
- Authority
- CN
- China
- Prior art keywords
- anode
- copper
- cathode
- silicon substrate
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 50
- 239000010949 copper Substances 0.000 title claims abstract description 50
- 238000007747 plating Methods 0.000 title claims abstract description 47
- 239000002253 acid Substances 0.000 title claims abstract description 42
- 239000000126 substance Substances 0.000 title claims abstract description 40
- 238000001465 metallisation Methods 0.000 title claims abstract description 11
- 238000004519 manufacturing process Methods 0.000 title abstract description 3
- 239000000758 substrate Substances 0.000 claims abstract description 50
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 48
- 239000010703 silicon Substances 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 42
- 239000010410 layer Substances 0.000 claims abstract description 38
- 239000003870 refractory metal Substances 0.000 claims abstract description 18
- 150000004767 nitrides Chemical class 0.000 claims abstract description 16
- 239000003292 glue Substances 0.000 claims abstract description 9
- 239000011241 protective layer Substances 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 55
- 230000004888 barrier function Effects 0.000 claims description 32
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 20
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 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 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 6
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- 238000006479 redox reaction Methods 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 239000003929 acidic solution Substances 0.000 claims 1
- 238000009792 diffusion process Methods 0.000 claims 1
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 abstract description 5
- 239000013078 crystal Substances 0.000 abstract description 5
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 abstract description 5
- 229940112669 cuprous oxide Drugs 0.000 abstract description 5
- 230000007797 corrosion Effects 0.000 abstract description 2
- 238000005260 corrosion Methods 0.000 abstract description 2
- 230000033116 oxidation-reduction process Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 25
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 10
- 229910001431 copper ion Inorganic materials 0.000 description 9
- 230000002378 acidificating effect Effects 0.000 description 8
- -1 fluorine ions Chemical class 0.000 description 8
- 238000000151 deposition Methods 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 230000008021 deposition Effects 0.000 description 6
- 229910000040 hydrogen fluoride Inorganic materials 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910052731 fluorine Inorganic materials 0.000 description 5
- 239000011737 fluorine Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 206010070834 Sensitisation Diseases 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000007772 electroless plating Methods 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000008313 sensitization Effects 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052715 tantalum Inorganic materials 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 229910000838 Al alloy Inorganic materials 0.000 description 2
- YXLXNENXOJSQEI-UHFFFAOYSA-L Oxine-copper Chemical compound [Cu+2].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 YXLXNENXOJSQEI-UHFFFAOYSA-L 0.000 description 2
- 238000007323 disproportionation reaction Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- 238000012369 In process control Methods 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010965 in-process control Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
Landscapes
- Electrodes Of Semiconductors (AREA)
- Electroplating Methods And Accessories (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
Abstract
The present invention relates to a metallization method for separating bipolar electrode acidity to prepare integrated circuit interconnecting lines by chemical plating, which belongs to the application field of chemical plating. In the method, a silicon base plate is used as a cathode, the silicon substrate is used as an anode, and one surface of the silicon substrate is coated with a refractory metal or nitride thereof. A layer of elargol or organic glue protective layer wraps a silicon surface which is exposed outside the anode base board to prevent corrosion in a chemical plating process, and the cathode and the anode are separated and put in an acid solution. The cathode and the anode react in the acid solution in the mode of oxidation reduction, and a layer of copper film is directly and chemically plated on the refractory metal and the silicon substrate of the refractory metal and the nitride. Copper film grains prepared by the process have the characteristics of uniformity, littleness, strong force of bonding with the base plate, preferred orientation of (3) crystal grains and no cuprous oxide. The method has the advantages of convenient solution configuration, good base plate protection, simple production step and low cost; the present invention is a good alternative scheme of a chemical copper plating method of basicity and single electrode acidity.
Description
Technical Field
The invention belongs to the field of chemical plating application, and particularly relates to a novel separated double-electrode acidic chemical plating method which is mainly applied to an interconnection line metallization process of an integrated circuit.
Background
In an integrated circuit, a thin metal film is deposited on a silicon substrate of the integrated circuit, and metal wires are formed by photolithography to connect separated elements isolated from each other as required to form a desired circuit, and such metal wires are called integrated circuit interconnection lines. The process of depositing a metal film on an integrated circuit silicon substrate is referred to as a metallization process.
With the advent of very large scale integrated circuits, aluminum and aluminum alloys have poor electromigration resistance due to high resistivity, and the deposition of aluminum and aluminum alloy films on integrated circuit silicon substrates has no longer been compatible with the requirements of very large scale integrated circuits. Because copper has the advantages of low resistivity, high electromigration resistance, high stress damage resistance, high thermal conductivity coefficient and the like, the copper replaces aluminum to become a new generation of interconnection line material. However, since copper is very easy to diffuse in the silicon substrate, which causes the silicon substrate to fail, a layer of refractory metal such as Ta, Ti, W, etc. or nitride thereof is introduced between the copper metal thin film and the silicon substrate in the copper metallization process as a barrier layer for preventing copper from diffusing into the silicon substrate. Therefore, in the metallization process of copper interconnection lines, the copper film is plated on the barrier layer made of refractory metal such as Ta, Ti, W, etc. or its nitride.
The copper metal film can be prepared by physical vapor deposition, chemical vapor deposition and electrochemical deposition. Electroless plating is one of electrochemical deposition, and is a promising copper interconnection line preparation technology due to its good characteristics of simple preparation, excellent film properties, good step coverage capability and low cost.
Conventional electroless copper plating utilizes the redox reaction of a solution to reduce copper ions on the deposition surface under alkaline conditions. Copper salt in the solution provides copper ions, formaldehyde is used as a reducing agent, tetramethylammonium hydroxide is used as a pH value regulator, and EDTA and the copper ions form a complex compound to improve the stability of the solution. Meanwhile, a surfactant and a leveling agent are added into the solution to improve the quality of the plated copper film. However, since barrier layers of refractory metals such as Ta, Ti, W, etc. or nitrides thereof do not have catalytic activity against copper ions, and copper ions cannot be directly deposited on the surfaces thereof, catalytic sensitization of the deposition surfaces is required before electroless plating. The main catalytic sensitization process today is catalyzed by Pd atoms: pd ions are reduced into Pd atoms in an acid solution, and Pd atomic groups are pinned on the deposition surface by utilizing the etching effect of the acid solution on refractory metals, wherein the Pd atomic groups are the deposition backrest of copper ions. The alkaline chemical plating method has various process steps and great difficulty in process control, and simultaneously, because Pd belongs to noble metal, the production cost is increased. Nowadays, studies on direct electroless copper plating on barrier layers are being conducted in taiwan, japan and the like. The taiwan design of the acid electroless copper plating process has been the more successful example. Since both the oxidation reaction of the cathode and the reduction reaction of the anode are performed on one substrate in this acid copper plating method, it is called a single-electrode acid electroless plating method.
The method comprises the following steps: placing a silicon substrate with one surface plated with a refractory metal nitride barrier layer into an acid solution consisting of copper chloride and hydrofluoric acid for reaction, wherein the hydrofluoric acid oxidizes the exposed silicon surface of the silicon substrate, and the reaction formula is as follows:
the released electrons are transported to the surface of the barrier layer by fluorine ions and chlorine ions, are reduced into copper by copper ions and are deposited on the surface of the barrier layer, and direct chemical plating is realized, wherein the reaction formula is as follows:
although the acid electroless plating method achieves direct electroless copper plating on the barrier layer, the copper film is deposited on the barrier layer surface while the silicon surface of the silicon substrate exposed to the solution is corroded, the substrate is damaged and cannot be used, and the method is not suitable for industrial application.
Disclosure of Invention
The invention aims to provide a metallization method for preparing an integrated circuit copper interconnection wire by separating double-electrode acid chemical plating. The copper film prepared by the method has the advantages of fine and uniform crystal grains, strong bonding force with the barrier layer and the like, and is a powerful alternative scheme of the alkaline chemical plating and single-electrode acidic chemical plating methods.
The invention provides a metallization method for preparing integrated circuit copper interconnection wires by separating double-electrode acid chemical plating, which is characterized in that a silicon substrate is used as a cathode, a silicon substrate plated with refractory metal or nitride thereof is used as an anode, and a silver glue or organic glue protective layer is coated on the exposed silicon surface of the anode substrate to prevent the anode substrate from being corroded in the chemical plating process; and separating the cathode and the anode in an acid solution, carrying out oxidation-reduction reaction on the cathode and the anode in the acid solution, and directly and chemically plating a copper film on a silicon substrate made of refractory metal or nitride.
The invention has the characteristics and effects that:
the chemical plating method of the invention is characterizedin that the anode and the cathode are separated under open circuit. The fluorine ions in the solution oxidize the silicon substrate serving as a cathode under an acidic condition, electrons released by oxidation are combined with the fluorine ions to form complex ions, and the complex ions are diffused and transmitted to an anode in the solution; the silicon surface of the anode substrate except the barrier layer formed by refractory metal or nitride thereof is protected by silver glue or organic glue, thereby ensuring that the silicon substrate cannot lose efficacy due to corrosion. Copper ions receive electrons transported by fluorine ions on the surface of the barrier layer of the anode and are directly deposited on the surface of the barrier layer.
The fluoride ions and the nitrate ions contained in the acidic chemical plating solution have the effects of cleaning and etching refractory metals and nitrides thereof, on one hand, an oxide layer on the surface of a precipitate is removed, the effect of catalytic sensitization is achieved, and the premise is created for direct chemical plating of copper ions; on the other hand, the etching effect of fluorine ions on the precipitation substrate increases the backrest of copper ion deposition, and improves the binding force of the copper film and the precipitation substrate.
And because the two electrodes are separately arranged, the distance between the two electrodes can be changed along with the configuration of the solution and the reaction temperature. When the distance between the cathode and the anode is changed between 0mm and 5mm, the particle size, shape, copper film covering capacity and the bonding force between the copper film and the barrier layer of the deposited copper film are correspondingly changed. The cathode can also be placed opposite to the surface of the barrier layer, the prepared copper film is also related to the distance between the two electrodes, and the copper film prepared when the cathode and the barrier layer are placed opposite to each other is also different in particle size, shape, coverage rate and binding force.
The copper film plated by the separated double-electrode acidic chemical plating method has fine and uniform crystal particles and better bonding force with a substrate, and a solid silicon electrode needs to be introduced in an oxidation-reduction reaction, so that the stability of the solution is better than that of an alkaline solution, and the solution cannot lose efficacy due to the disproportionation reaction. Meanwhile, the copper film plated by the method has (111) preferred orientation, and can meet the requirement of the integrated circuit on the grain orientation of the copper metal layer. And the formation of cuprous oxide is suppressed since the redox reaction takes place on two separate electrodes. The copper film prepared by the separated double-electrode acidic chemical plating method is subjected to substance analysis by adopting an X-ray analysis method, and cuprous oxide is not found on the plated copper film. In alkaline chemical plating, cuprous oxide is easily formed on the surface of the plated copper film due to disproportionation reaction, the resistivity of the copper film is increased, and the problem can be successfully solved by adopting the copper film prepared by the method. Therefore, the method for preparing the integrated circuit copper interconnection line by separating the double-electrode acidic chemical plating realizes the direct chemical plating on the refractory metal and the nitride thereof, the prepared copper film has fine and uniform particles, good binding force and preferred (111) crystal grain orientation, and the generation of cuprous oxide is effectively inhibited; the components and the preparation process of the solution are simple and easy to implement, and the cost is low.
The chemical plating method of the inventioncan be directly applied to the preparation of copper interconnection lines in deep submicron integrated circuits of integrated circuits, can also be used in the early stage catalytic sensitization step of alkaline chemical plating, or the preparation of electroplated copper seed crystal layers.
Detailed Description
The invention discloses a metallization method for preparing integrated circuit copper interconnection lines by separating double-electrode acidic chemical plating, which comprises the steps of taking a silicon substrate as a cathode, taking the silicon substrate plated with refractory metal or nitride thereof on one surface as an anode, and wrapping a silver glue or organic glue protective layer on the exposed silicon surface of the anode substrate to prevent the anode substrate from being corroded in the chemical plating process; and separating the cathode and the anode in an acid solution, carrying out oxidation-reduction reaction on the cathode and the anode in the acid solution, and directly and chemically plating a copper film on a silicon substrate made of refractory metal and nitride.
The chemical plating solution adopted by the invention can be prepared by adding at least one of 0.1-1 mol/l copper salt, 0-16 g/l ammonium fluoride and 0-20 wt% hydrofluoric acid dropwise, and adjusting the pH value of the solution to 0.1-5.
When the cathode of the silicon substrate is arranged opposite to the surface of the anode barrier layer, the distance between the cathode and the anode barrier layer can be 0-5 mm; when the silicon substrate cathode is disposed on the back side of the anode barrier layer, the distance between the anode barrier layer and the silicon substrate cathode can be 0-5 mm.
The examples of the invention are as follows:
the first embodiment is as follows:
the acid solution is 1mol/l copper sulfate and 20 wt% hydrofluoric acid, and nitric acid and deionized water are added dropwise to adjust the pH value of the solution to 0.2. The cathode of the silicon substrate is arranged opposite to the surface of the barrier layer of the anode, the distance is 5mm, and the temperature of the acid solution is 50 ℃ during chemical plating.
Example two:
0.45mol/l of copper nitrate and 10 wt% of hydrofluoric acid in the acid solution, adding deionized water to adjust the pH of the solution to 5, placing the cathode of the silicon substrate opposite to the surface of the barrier layer of the anode at a distance of 0mm, and controlling the temperature of the acid solution to be 70 ℃ during chemical plating.
Example three:
the acid solution is 0.45mol/l copper sulfate and 8 wt% hydrofluoric acid, deionized water is added to adjust the pH value of the solution to 3, the cathode of the silicon substrate is placed opposite to the surface of the barrier layer of the anode at a distance of 1mm, and the temperature of the acid solution is 50 ℃ during chemical plating.
Example four:
the acid solution is 0.45mol/l of copper nitrate and 8 wt% of hydrogen fluoride, deionized water is added to adjust the pH value of the solution to 1, the distance between the cathode of the silicon substrate and the surface of the barrier layer of the anode is 0.5mm, and the temperature of the acid solution is 50 ℃ during chemical plating.
Example five:
the acid solution is 0.30mol/l of copper chloride and 16g/l of ammonium fluoride, hydrochloric acid and deionized water are dripped to adjust the pH value of the solution to0.1, the cathode of the silicon substrate is placed at a distance of 5mm opposite to the surface of the barrier layer of the anode, and the temperature of the acid solution is 80 ℃ during chemical plating.
Example six:
the acid solution is 0.1mol/l of copper nitrate, 4 wt% of hydrogen fluoride and 2g/l of ammonium fluoride, nitric acid and deionized water are dripped to adjust the pH value of the solution to 2, the cathode of the silicon substrate is placed opposite to the surface of the barrier layer of the anode at a distance of 2mm, and the temperature of the acid solution is 40 ℃ during chemical plating.
Example seven:
0.1mol/l copper sulfate and 5 wt% hydrogen fluoride in acid solution, dropwise adding sulfuric acid and deionized water to adjust the pH value of the solution to about 1, placing the cathode of the silicon substrate opposite to the surface of the barrier layer of the anode at a distance of 0mm, and controlling the temperature of the acid solution to be 60 ℃ during chemical plating.
Example eight:
the acid solution is 0.5mol/l copper sulfate, 10 wt% hydrogen fluoride and 6g/l ammonium fluoride, nitric acid and deionized water are dripped to adjust the pH value of the solution to 1, the cathode of the silicon substrate is placed opposite to the surface of the barrier layer of the anode at a distance of 2mm, and the temperature of the acid solution is 65 ℃ during chemical plating.
Example nine:
the acid solution is 0.45mol/l of copper chloride, 4 wt% of hydrogen fluoride and 10g/l of ammonium fluoride, nitric acid and deionized water are dripped to adjust the pH value of the solution to 2, the cathode of the silicon substrate is placed opposite to the surface of the barrier layer of the anode at a distance of 2mm, and thetemperature of the acid solution is 55 ℃ during chemical plating.
Example ten:
the acid solution is 0.40mol/l copper sulfate, 8 wt% hydrogen fluoride and 3g/l ammonium fluoride, nitric acid and deionized water are dripped to adjust the pH value of the solution to 1, the cathode of the silicon substrate is arranged opposite to the surface of the barrier layer of the anode at a distance of 1mm, and the temperature of the acid solution is 60 ℃ during chemical plating.
Claims (5)
1. A metallization method for preparing integrated circuit copper interconnection wires by separating double-electrode acid chemical plating is characterized in that a silicon substrate is used as a cathode, a silicon substrate plated with refractory metal or nitride thereof on one surface is used as an anode, and a silver glue or organic glue protective layer is coated on the exposed silicon surface of the anode substrate; and separating the cathode and the anode in an acid solution, carrying out oxidation-reduction reaction on the cathode and the anode in the acid solution, and directly and chemically plating a copper film on a silicon substrate made of refractory metal or nitride.
2. The method of claim 1, wherein the acidic solution is prepared by adding 0.1-1 mol/l copper salt, 0-16 g/l ammonium fluoride and 0-20 wt% hydrofluoric acid, and adding dropwise acid and deionized water to adjust the pH of the solution to 0.1-5.
3. The method of claim 2, wherein the copper salt is selected from the group consisting of copper sulfate, copper nitrate, and copper chloride, and the acid used to adjust the pH of the solution is selected from the group consisting of nitric acid, sulfuric acid, and hydrochloric acid.
4. The method according to claim 1, wherein the distance between the cathode and the anode is kept in the range of 0 to 5 mm.
5. The method of claim 1, wherein the refractory metal or nitride thereof acts as a barrier layer to prevent diffusion of copper into the silicon substrate, and wherein the silicon substrate cathode is disposed opposite to or opposite to the barrier layer surface of the anode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410080014 CN1290160C (en) | 2004-09-24 | 2004-09-24 | Metallization method for producing integrated circuit copper interconnecting wire by separating bipolar acid chemical plating |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200410080014 CN1290160C (en) | 2004-09-24 | 2004-09-24 | Metallization method for producing integrated circuit copper interconnecting wire by separating bipolar acid chemical plating |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1610066A CN1610066A (en) | 2005-04-27 |
| CN1290160C true CN1290160C (en) | 2006-12-13 |
Family
ID=34765576
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200410080014 Expired - Fee Related CN1290160C (en) | 2004-09-24 | 2004-09-24 | Metallization method for producing integrated circuit copper interconnecting wire by separating bipolar acid chemical plating |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1290160C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7776741B2 (en) * | 2008-08-18 | 2010-08-17 | Novellus Systems, Inc. | Process for through silicon via filing |
| US10472730B2 (en) | 2009-10-12 | 2019-11-12 | Novellus Systems, Inc. | Electrolyte concentration control system for high rate electroplating |
| SG10201710532WA (en) * | 2013-06-17 | 2018-02-27 | Applied Materials Inc | Method for copper plating through silicon vias using wet wafer back contact |
| JP6713809B2 (en) * | 2016-03-31 | 2020-06-24 | 株式会社荏原製作所 | Substrate manufacturing method and substrate |
| US10692735B2 (en) | 2017-07-28 | 2020-06-23 | Lam Research Corporation | Electro-oxidative metal removal in through mask interconnect fabrication |
-
2004
- 2004-09-24 CN CN 200410080014 patent/CN1290160C/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN1610066A (en) | 2005-04-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US6503375B1 (en) | Electroplating apparatus using a perforated phosphorus doped consumable anode | |
| EP1887106B1 (en) | Metal coating, Forming Method Thereof and Metal Wiring | |
| KR101110447B1 (en) | Plated article having metal thin film formed by electroless plating, and manufacturing method thereof | |
| EP1783783A1 (en) | Conductive fine particle, method for producing conductive fine particle and electroless silver plating liquid | |
| US20140318414A1 (en) | Nano-metal solution and nano-metal complex grains | |
| TW200403808A (en) | Semiconductor device and manufacturing method thereof | |
| US7064065B2 (en) | Silver under-layers for electroless cobalt alloys | |
| JPH08316233A (en) | Manufacture of semiconductor device | |
| CN1290160C (en) | Metallization method for producing integrated circuit copper interconnecting wire by separating bipolar acid chemical plating | |
| CN1867411A (en) | Compositions and methods for the electroless deposition of NiFe on a work piece | |
| US20100170800A1 (en) | Composite material and method of manufacturing the same | |
| KR100807948B1 (en) | Method of preparing low resistance metal pattern, patterned metal wire structure, and display devices using the same | |
| JP4217271B2 (en) | Conductive fine particles and anisotropic conductive materials | |
| JP4891919B2 (en) | Improved stabilization and performance of autocatalytic electroless process | |
| JP3482402B2 (en) | Replacement gold plating solution | |
| US20140034370A1 (en) | Metallization mixtures and electronic devices | |
| TWI509104B (en) | Plating solutions for electroless deposition of ruthenium | |
| KR100788310B1 (en) | Method of Ag electroless plating on ITO electrode | |
| US6875260B2 (en) | Copper activator solution and method for semiconductor seed layer enhancement | |
| US10648096B2 (en) | Electrolyte, method of forming a copper layer and method of forming a chip | |
| CN1784507A (en) | Compositions for the currentless deposition of ternary materials for use in the semiconductor industry | |
| WO2008130081A1 (en) | Manufacturing method of conductive ball using eletroless plating | |
| US7780772B2 (en) | Electroless deposition chemical system limiting strongly adsorbed species | |
| EP4310221A1 (en) | Electroless copper plating by means of a catalytic reaction | |
| CN100346454C (en) | A metallized contact layer structure of silicon based device and method for making same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20061213 Termination date: 20100924 |