CN103579101A - Method using pulse electrocoppering mode to achieve copper interconnection - Google Patents
Method using pulse electrocoppering mode to achieve copper interconnection Download PDFInfo
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- CN103579101A CN103579101A CN201310540962.1A CN201310540962A CN103579101A CN 103579101 A CN103579101 A CN 103579101A CN 201310540962 A CN201310540962 A CN 201310540962A CN 103579101 A CN103579101 A CN 103579101A
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/38—Electroplating: Baths therefor from solutions of copper
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D7/00—Electroplating characterised by the article coated
- C25D7/12—Semiconductors
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Abstract
The invention belongs to the technical field of copper interconnection structures and in particular relates to a method using a pulse electrocoppering mode to achieve copper interconnection. The method comprises the following steps of using a plasma physical sputtering method to deposit a dielectric layer on a semiconductor substrate, using a physical sputtering method to sputter TaN to serve as a diffusion blocking layer and then to sputter Ta to serve as an adhesion promoting layer, using a physical sputtering method to sputter a copper seed crystal layer, slicing a substrate of the obtained copper seed crystal layer into small rectangular pieces and using the small rectangular pieces as negative poles and high-purity copper bars as positive poles to carry out pulse electrocoppering. The method has the advantages of reducing concentration polarization, improving the cathode-current density and the electroplating efficiency, reducing hydrogen brittleness and coating holes, improving purity and improving physical performance of coatings. In addition, the obtained coatings have better protection performance, can obtain compact low-specific-resistance metal settled layers and have lower specific resistance and electromigration resistance.
Description
Technical field
The invention belongs to copper interconnection structure technical field, be specifically related to a kind of method that mode that adopts Pulse Electric copper facing realizes copper-connection.
Background technology
Along with improving constantly of chip integration, copper has replaced aluminium gradually becomes the main flow interconnection technique in very lagre scale integrated circuit (VLSIC) interconnection.In current chip manufacturing, the wiring of chip and interconnection are all almost to adopt the method for direct current electrode position to obtain copper coating.Direct current electrode position only has variable element of current/voltage, and pulse plating has three main variable elements between current/voltage, pulsewidth, arteries and veins in, but also can change the waveform of pulse signal.By contrast, pulse plating has stronger control ability to electroplating process.
About the theory of pulse plating, in eighties of last century, just just someone proposes.In recent years, some researchs in integrated circuit copper interconnecting application about pulse plating had been delivered successively abroad.But at present at home, for the research of Pulse Electric copper facing, mainly concentrate on metallurgical grade and electroplate and printed circuit board (PCB) (PCB) wiring aspect, almost less than be applied to the bibliographical information of integrated circuit copper interconnecting about pulse plating.In PCB, the characteristic size of circuit is about tens microns, and in chip, the characteristic size of copper-connection is 1 micron, therefore the performance of submicron order thickness copper coating has been determined the performance of whole integrated circuit.
Summary of the invention
For above-mentioned problems of the prior art, the invention provides a kind of method that mode that is applicable to the employing Pulse Electric copper facing of very lagre scale integrated circuit (VLSIC) production realizes copper-connection, to solve the deficiencies in the prior art.
The mode of employing Pulse Electric provided by the invention copper facing realizes the method for copper-connection, and concrete steps are:
Steps A. in Semiconductor substrate, using plasma physics sputtering method deposition thickness is the silicon dioxide of 800 ~ 1000 nm, as dielectric layer;
It is the TaN of 10 ~ 20 nm that step B. is used physical sputtering method sputter thickness, as diffusion impervious layer; Sputter thickness is the Ta of 10 ~ 20 nm again, as adhesion promoting layer;
It is the copper seed layer of 30 ~ 100 nm that step C. is used physical sputtering method sputter thickness;
Step D. is sliced into little rectangular sheet by the Semiconductor substrate that obtains copper seed layer;
Step e. using described little rectangular sheet as negative electrode, the highly purified copper rod of parcel one deck filter membrane, as anode, carries out Pulse Electric copper facing.
Further, in the present invention, described Semiconductor substrate is monocrystalline substrate or III-V compound substrate.
Further, in the present invention, described little rectangular sheet is of a size of 2.5 cm to 10 cm * 4, cm * 1 cm.
Further, in the present invention, while carrying out Pulse Electric copper facing, at bottom of electrolytic tank, near negative electrode place, place a magnetic stir bar, speed setting is 300 ~ 500 revs/min.
Further, in the present invention, while carrying out Pulse Electric copper facing, between the pulsewidth of pulse and arteries and veins, at 2 ~ 10 ms, current density is 2 ~ 8 A/dm
2, temperature is 25 ~ 40 ℃, and voltage is 30 ~ 50 V, and pH value is 8 ~ 10 to electroplate.
Further, in the present invention, while carrying out Pulse Electric copper facing, electroplating bath components comprises: Cu ion concentration 15 ~ 20 g/L, H
2sO
4content 100 ~ 200 g/L, Cl ion concentration 30 ~ 50 mg/L, accelerator 1 ~ 5 ml/L, inhibitor 2 ~ 10 ml/L and leveling agent 3 ~ 6 ml/L.
Wherein, described accelerator, inhibitor, leveling agent are the conventional composition of common electroplate liquid, for example, can adopt the ViaForm series of products of Enthone company.
Effect of the present invention
According to the mode of employing Pulse Electric provided by the invention copper facing, realize the method for copper-connection, the electrochemical principle of Pulse Electric copper facing institute foundation is to utilize pulse tension and relaxation to increase the activation polarization of negative electrode, reduce the concentration polarization of negative electrode, thereby improve the physical and chemical performance of coating.In direct current electrode position, because metal ion convergence negative electrode is constantly deposited, thereby inevitably cause concentration polarization.And pulse plating is when current lead-through, the metal ion that approaches negative electrode is deposited fully; When electric current turn-offs, negative electrode discharge ion around returns to initial concentration again.Concentration of metal ions in cathode surface diffusion layer has just obtained supplementing in time like this, and diffusion layer periodic intervals formula forms, thus attenuate the actual (real) thickness of diffusion layer.If use short pulse, will occur very large current strength, this deposits metal ion is under the high overpotential that direct current electrode position do not realize, degree of polarization strengthens, dispersibility is better, thereby improves coating performance, and its effect is with to add the effect of additive in electroplate liquid similar.Near the existence of the turn-off time not only concentration of target recovers beneficial, but also can produce some to phenomenons such as the favourable recrystallization of sedimentary deposit, adsorption desorptions.
The method major advantage that the mode of employing Pulse Electric provided by the invention copper facing realizes copper-connection has:
(1) reduce concentration polarization, improved cathode-current density and electroplating efficiency;
(2) reduce hydrogen embrittlement and coating hole, improve purity, improve coating physical property;
(3) gained coating has good protective;
(4) can obtain fine and close low resistivity metal sedimentary deposit;
(5) compare conventional aluminum interconnection, copper-connection has lower resistivity, deelectric transferred ability;
(6) adopt pulse plating method to realize logical interconnection, cost is lower than conventional P VD method, and efficiency is higher.The size that is embodied in little rectangular sheet can further expand the required size of commercial Application to, and can guarantee the effect of its plating.And large-sized application means the rising of output and the decline of unit cost.The electroplating effect the present invention relates to is better than general electroplating effect, is embodied in the resistivity (Fig. 2) of accompanying drawing explanation, the crystal orientation (Fig. 3) of copper, the surface topography (Fig. 5) that AFM records.The raising of these effects has benefited from design, electroplate liquid, the SiO of negative electrode
2/ TaN/Cu seed crystal lamination and pulse arrange the comprehensive of these factors.
Accompanying drawing explanation
Fig. 1 is the method flow diagram that the mode of employing Pulse Electric provided by the invention copper facing realizes copper-connection.
Fig. 2 is the method acquisition resistivity of electro-coppering and the relation of current density that the mode of employing Pulse Electric provided by the invention copper facing realizes copper-connection.
Fig. 3 is Cu (200) crystal orientation and (111) crystal orientation intensity ratio that the mode of employing Pulse Electric provided by the invention copper facing realizes the method acquisition electro-coppering of copper-connection.
Fig. 4 is the grain size that the mode of employing Pulse Electric provided by the invention copper facing realizes the method acquisition electro-coppering of copper-connection.
Fig. 5 is the three-dimensional AFM schematic diagram that method that the mode of employing Pulse Electric provided by the invention copper facing realizes copper-connection obtains the surface topography of electro-coppering.
Fig. 6 is the SEM schematic diagram that method that the mode of employing Pulse Electric provided by the invention copper facing realizes copper-connection obtains the surface topography of electro-coppering.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention will be further described.
Embodiment 1
The method that the mode of employing Pulse Electric copper facing realizes copper-connection is as follows:
Steps A. adopt monocrystalline substrate, first use the silicon dioxide SiO of plasma physics sputtering method (PECVD) deposit 800nm
2as dielectric layer.
The TaN that step B. is used physical sputtering method (Physical Vapor Deposition, PVD) sputter 10nm is as diffusion impervious layer, the Ta adhesion promoting layer of sputter 10 nm again.
Step C. is used the copper seed layer of physical sputtering method (Physical Vapor Deposition, PVD) sputter 30nm, and copper seed layer provides a conductive layer for pulse plating below.
Step D. is sliced into the substrate that obtains copper seed layer to be of a size of the little rectangular sheet of 2.5 cm * 1 cm.
Step e. using described little rectangular sheet as negative electrode, the highly purified copper rod of parcel one deck filter membrane is as anode for carrying out Pulse Electric copper facing, and the effect of the filter membrane outside anode copper rod stops impurity to enter copper coating while being plating, affects coating performance.
During Pulse Electric copper facing, at bottom of electrolytic tank, near negative electrode place, place a magnetic stir bar.During plating, the magnetic agitation instrument being placed in below electrolysis tank produces magnetic field, drives stirrer uniform rotation, and speed setting is 300 revs/min.
During Pulse Electric copper facing, between the pulsewidth of pulse and arteries and veins, at 2 ms, current density is 2 A/dm
2, temperature is 25 ℃, and voltage is 30V, and pH value is 8 to electroplate.
During Pulse Electric copper facing, electroplating bath components comprises:
ion concentration 15 g/L, H
2sO
4content 100g/L, Cl ion concentration 30 mg/L, accelerator 1 ml/L, inhibitor 2 ml/L and leveling agent 3ml/L.Wherein, accelerator, inhibitor, leveling agent adopt the ViaForm series of products of Enthone company.
The method that the mode of employing Pulse Electric copper facing realizes copper-connection is as follows:
Steps A. adopt III-V compound substrate, first use the silicon dioxide of plasma physics sputtering method deposit 900 nm as dielectric layer.
The TaN that step B. is used physical sputtering method sputter 15nm is as diffusion impervious layer, the Ta adhesion promoting layer of sputter 15nm again.
Step C. is used the copper seed layer of physical sputtering method sputter 65 nm, and copper seed layer provides a conductive layer for pulse plating below.
Step D. is sliced into the substrate that obtains copper seed layer to be of a size of the little rectangular sheet of 5 cm * 2 cm.
Step e. using described little rectangular sheet as negative electrode, the highly purified copper rod of parcel one deck filter membrane is as anode for carrying out Pulse Electric copper facing, and the effect of the filter membrane outside anode copper rod stops impurity to enter copper coating while being plating, affects coating performance.
During Pulse Electric copper facing, at bottom of electrolytic tank, near negative electrode place, place a magnetic stir bar.During plating, the magnetic agitation instrument being placed in below electrolysis tank produces magnetic field, drives stirrer uniform rotation, and speed setting is 400 revs/min.
During Pulse Electric copper facing, between the pulsewidth of pulse and arteries and veins, at 6 ms, current density is 5 A/dm
2, temperature is 33 ℃, and voltage is 40 V, and pH value is 9 to electroplate.
During Pulse Electric copper facing, electroplating bath components comprises: Cu ion concentration 17g/L, H
2sO
4content 150g/L, Cl ion concentration 40 mg/L, accelerator 3 ml/L, inhibitor 6 ml/L and leveling agent 4 ml/L.Wherein, accelerator, inhibitor, leveling agent adopt the ViaForm series of products of Enthone company.
Embodiment 3
The method that the mode of employing Pulse Electric copper facing realizes copper-connection is as follows:
Steps A. adopt monocrystalline substrate, first use the silicon dioxide of plasma physics sputtering method deposit 1000 nm as dielectric layer.
The TaN that step B. is used physical sputtering method sputter 20 nm is as diffusion impervious layer, the Ta adhesion promoting layer of sputter 20 nm again.
Step C. is used the copper seed layer of physical sputtering method sputter 100 nm, and copper seed layer provides a conductive layer for pulse plating below.
Step D. is sliced into the substrate that obtains copper seed layer to be of a size of the little rectangular sheet of 10 cm * 4 cm.
Step e. using described little rectangular sheet as negative electrode, the highly purified copper rod of parcel one deck filter membrane is as anode for carrying out Pulse Electric copper facing, and the effect of the filter membrane outside anode copper rod stops impurity to enter copper coating while being plating, affects coating performance.
During Pulse Electric copper facing, at bottom of electrolytic tank, near negative electrode place, place a magnetic stir bar.During plating, the magnetic agitation instrument being placed in below electrolysis tank produces magnetic field, drives stirrer uniform rotation, and speed setting is 500 revs/min.
During Pulse Electric copper facing, between the pulsewidth of pulse and arteries and veins, at 10 ms, current density is 8 A/dm
2, temperature is 40 ℃, and voltage is ~ 50 V, and pH value is 10 to electroplate.
During Pulse Electric copper facing, electroplating bath components comprises: Cu ion concentration 20 g/L, H
2sO
4content 200 g/L, Cl ion concentration 50 mg/L, accelerator 5 ml/L, inhibitor 10 ml/L and leveling agent 6 ml/L.Wherein, accelerator, inhibitor, leveling agent adopt the ViaForm series of products of Enthone company.
experiment test
The electro-coppering that the method for using the mode of employing Pulse Electric provided by the invention copper facing to realize copper-connection obtains is tested as follows:
After completing pulse plating, at the thickness that guarantees copper under the prerequisite of 1 μ m, measured resistivity, X-ray diffraction spectrum (X-Ray Diffraction, XRD), scanning electron microscopy (Scanning Electron Microscopy, SEM) and atomic force microscope (Atomic Force Microscopy, AFM).
1, the resistivity of electro-coppering and the relation of current density, as shown in Figure 2.
2, the Cu of electro-coppering (200) crystal orientation and (111) crystal orientation intensity ratio, as shown in Figure 3.
3, the grain size test result of electro-coppering, as shown in Figure 4.
4, the three-dimensional AFM test result of the surface topography of electro-coppering, as shown in Figure 5.
5, the SEM test result of the surface topography of electro-coppering, as shown in Figure 6.
Claims (6)
1. adopt Pulse Electric copper facing mode to realize a method for copper-connection, it is characterized in that concrete steps are:
Steps A. in Semiconductor substrate, using plasma physics sputtering method deposition thickness is the silicon dioxide of 800 ~ 1000 nm, as dielectric layer;
It is the TaN of 10 ~ 20 nm that step B. is used physical sputtering method sputter thickness, as diffusion impervious layer; Sputter thickness is the Ta of 10 ~ 20 nm again, as adhesion promoting layer;
It is the copper seed layer of 30 ~ 100 nm that step C. is used physical sputtering method sputter thickness;
Step D. is sliced into little rectangular sheet by the Semiconductor substrate that obtains copper seed layer;
Step e. using described little rectangular sheet as negative electrode, the highly purified copper rod of parcel one deck filter membrane, as anode, carries out Pulse Electric copper facing.
2. employing Pulse Electric copper facing mode according to claim 1 realizes the method for copper-connection, it is characterized in that: described Semiconductor substrate is monocrystalline substrate or III-V compound substrate.
3. the mode of employing Pulse Electric according to claim 1 copper facing realizes the method for copper-connection, it is characterized in that: described little rectangular sheet is of a size of 2.5 cm to 10 cm * 4, cm * 1 cm.
4. according to the employing Pulse Electric copper facing mode described in any one in claims 1 to 3, realize the method for copper-connection, it is characterized in that: while carrying out Pulse Electric copper facing, at bottom of electrolytic tank, near negative electrode place, place a magnetic stir bar, speed setting is 300 ~ 500 revs/min.
5. employing Pulse Electric copper facing mode according to claim 4 realizes the method for copper-connection, it is characterized in that: while carrying out Pulse Electric copper facing, between the pulsewidth of pulse and arteries and veins, at 2 ~ 10 ms, current density is 2 ~ 8 A/dm
2, temperature is 25 ~ 40 ℃, and voltage is 30 ~ 50 V, and pH value is 8 ~ 10 to electroplate.
6. employing Pulse Electric copper facing mode according to claim 4 realizes the method for copper-connection, it is characterized in that: while carrying out Pulse Electric copper facing, and in electroplating bath components, Cu ion 15 ~ 20 g/L, H
2sO
4100 ~ 200 g/L, Cl ion 30 ~ 50 mg/L, accelerator 1 ~ 5 ml/L, inhibitor 2 ~ 10 ml/L and leveling agent 3 ~ 6 ml/L.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110055389A (en) * | 2019-04-18 | 2019-07-26 | 北京科技大学 | A kind of method that continuous electric pulse room temperature quickly eliminates hydrogen in solid metal |
| CN111211094A (en) * | 2020-01-10 | 2020-05-29 | 四川豪威尔信息科技有限公司 | Method for manufacturing copper interconnection structure of integrated circuit |
| CN113930807A (en) * | 2021-11-11 | 2022-01-14 | 中南大学 | Method for preparing copper-arsenic alloy by pulse electrodeposition |
| CN114481240A (en) * | 2020-10-23 | 2022-05-13 | 应用材料公司 | Electroplating seed layer build-up and repair |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070272560A1 (en) * | 2006-02-21 | 2007-11-29 | Alchimer | Method and compositions for direct copper plating and filing to form interconnects in the fabrication of semiconductor devices |
| US20130062214A1 (en) * | 2011-09-13 | 2013-03-14 | Semiconductor Manufacturing International (Beijing) Corporation | Method for manufacturing semiconductor device |
| CN102995076A (en) * | 2012-12-05 | 2013-03-27 | 陕西师范大学 | Electrocoppering solution for filling blind microvia |
-
2013
- 2013-11-05 CN CN201310540962.1A patent/CN103579101A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070272560A1 (en) * | 2006-02-21 | 2007-11-29 | Alchimer | Method and compositions for direct copper plating and filing to form interconnects in the fabrication of semiconductor devices |
| US20130062214A1 (en) * | 2011-09-13 | 2013-03-14 | Semiconductor Manufacturing International (Beijing) Corporation | Method for manufacturing semiconductor device |
| CN102995076A (en) * | 2012-12-05 | 2013-03-27 | 陕西师范大学 | Electrocoppering solution for filling blind microvia |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110055389A (en) * | 2019-04-18 | 2019-07-26 | 北京科技大学 | A kind of method that continuous electric pulse room temperature quickly eliminates hydrogen in solid metal |
| CN111211094A (en) * | 2020-01-10 | 2020-05-29 | 四川豪威尔信息科技有限公司 | Method for manufacturing copper interconnection structure of integrated circuit |
| CN114481240A (en) * | 2020-10-23 | 2022-05-13 | 应用材料公司 | Electroplating seed layer build-up and repair |
| CN113930807A (en) * | 2021-11-11 | 2022-01-14 | 中南大学 | Method for preparing copper-arsenic alloy by pulse electrodeposition |
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Application publication date: 20140212 |