CN104465507A - Copper interconnection forming method - Google Patents
Copper interconnection forming method Download PDFInfo
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- CN104465507A CN104465507A CN201410849545.XA CN201410849545A CN104465507A CN 104465507 A CN104465507 A CN 104465507A CN 201410849545 A CN201410849545 A CN 201410849545A CN 104465507 A CN104465507 A CN 104465507A
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- copper
- adhesion layer
- layer
- formation method
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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
- H01L21/76877—Filling of holes, grooves or trenches, e.g. vias, with conductive material
- H01L21/76879—Filling of holes, grooves or trenches, e.g. vias, with conductive material by selective deposition of conductive material in the vias, e.g. selective C.V.D. on semiconductor material, plating
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
- H01L21/76871—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers
- H01L21/76873—Layers specifically deposited to enhance or enable the nucleation of further layers, i.e. seed layers for electroplating
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
The invention provides a copper interconnection forming method. The copper interconnection forming method includes the following steps that firstly, a semiconductor substrate is provided, and the processes of photoetching and etching are conducted on the semiconductor substrate, so that a groove is formed; secondly, a diffusion impervious layer and an adhesion layer are deposited in the groove; thirdly, an electrochemical reduction process is conducted on the adhesion layer, so that metallic oxide on the surface of the adhesion layer is reduced; fourthly, a copper seed crystal layer is formed on the surface of the reduced adhesion layer; fifthly, the groove is filled with metallic copper; finally, a planarization process is adopted for removing a redundant diffusion impervious layer, a redundant adhesion layer, a redundant copper seed crystal layer and redundant metallic copper outside the groove. According to the copper interconnection forming method, the metallic oxide on the surface of the adhesion layer is removed through the electrochemical reduction process, so that the electrical resistivity of the surface of the adhesion layer is reduced, and the uniform copper seed crystal layer is easily formed through a follow-up electroplating process; meanwhile, the nucleation rate of the copper seed crystal layer on the surface of the adhesion layer is increased, the copper seed crystal layer which is dense and low in electrical resistivity is easily formed, and the adhesivity between the copper seed crystal layer and the adhesion layer is better.
Description
Technical field
The present invention relates to semiconductor integrated circuit manufacturing technology field, more specifically, relate to a kind of formation method of copper-connection.
Background technology
Copper interconnection technology refers to the novel semi-conductor manufacturing process adopting copper metal material replacement conventional aluminum interconnect materials in the making of semiconductor integrated circuit interconnection layer.Due to the thickness adopting copper interconnecting line can reduce interconnection layer, the distributed capacitance between interconnection layer is reduced, thus make frequency raising become possibility.But along with wafer size is increasing, technology generation is more and more less, and integrated level is more and more higher, strict all the more to the reliability requirement of device, higher requirement be it is also proposed to existing copper interconnection process.
But, along with the raising of chip integration, the size of interconnecting line also becomes less, meanwhile, under the effect of larger current density, the Cu atom in copper interconnecting line is easily along with electron motion direction is moved, produce ELECTROMIGRATION PHENOMENON, so-called ELECTROMIGRATION PHENOMENON is the metal migration phenomena that metal wire produces under electric current and temperature action, and it may make metal wire rupture, thus affects the normal work of chip.
In current copper wiring technique, the interface between copper and diffusion impervious layer can adopt adhesion layer to solve the problem of copper metal electro-migration.General adhesion layer adopts inert metal as Ru, Mo, Co, Os etc., wherein, because the resistivity of Co metal is lower, and minimum with the lattice surface mismatch of Cu, adhesiveness is best, and Co has been considered to the adhesive layer material of 20nm technology node and following most possible application.
But Co is a kind of very active metal, when it exposes in atmosphere, easily form the oxide of cobalt on surface.Co is as the adhesion layer in copper-connection, and thickness only has several nanometer usually, and the existence of oxide on surface can increase the resistivity of adhesion layer, cause the overpotential of the edge of sample in deposition process and centre inconsistent, so, the sample after electroplating technology just there will be adhesion layer intermediate thin, and both sides are thick.In addition, the nucleation of Cu on Co is a heterogeneous nucleation, and the existence of oxide can reduce the nucleation density of Cu on Co greatly, and then impact adhesiveness between the two, thus causes ELECTROMIGRATION PHENOMENON.Therefore, those skilled in the art need a kind of formation method providing copper-connection badly, there is the problem of metal oxide to solve adhesion layer surface in prior art.
Summary of the invention
For above problem, for overcoming the deficiencies in the prior art, the object of the present invention is to provide a kind of formation method of copper-connection, there is the problem of metal oxide to solve adhesion layer surface in prior art.
For solving the problem, the invention provides a kind of formation method of copper-connection, comprising the following steps:
Step S01: provide semi-conductive substrate, carries out photoetching and etching technics to described Semiconductor substrate, to form groove;
Step S02: deposit diffusion barriers and adhesion layer in described groove;
Step S03: carry out Process of Electrochemical Reduction to described adhesion layer, to reduce the metal oxide on described adhesion layer surface;
Step S04: the surface of the adhesion layer after reduction forms copper seed layer;
Step S05: be full of metallic copper and cover the surface of described copper seed layer in described groove;
Step S06: adopt flatening process to remove described groove outer unnecessary diffusion impervious layer, adhesion layer, copper seed layer and metallic copper.
Preferably, in described step S03, described Process of Electrochemical Reduction comprises the following steps:
Step S031: putting in electrolyte solution by described adhesion layer take adhesion layer as negative electrode, and it is applied to the negative potential of 5 ~ 10V, the duration is more than 600s;
Step S032: cleaning is carried out and drying to described adhesion layer.
Preferably, in described step S031, described electrolyte solution comprises the tetramethyl oxyammonia that deionized water and concentration are 0.03 ~ 0.05mol/L.
Preferably, the pH value of described electrolyte solution is 10 ~ 12.
Preferably, in described step S032, by washed with de-ionized water, nitrogen drying is passed through to described adhesion layer.
Preferably, in step S04, described copper seed layer adopts electroplating technology deposition to be formed.
Preferably, the ethylenediamine complexing agent that the electroplate liquid adopted in described electroplating technology comprises copper sulphate that concentration is 0.03 ~ 0.06mol/L, concentration is 0.06 ~ 0.12mol/L and concentration are the triethanolamine complexing agent of 0.03 ~ 0.05mol/L; Wherein, the proportioning of described ethylenediamine complexing agent is greater than described triethanolamine complexing agent.
Preferably, in described electroplating technology, current density is 1mA/cm
2to 5mA/cm
2.
Preferably, the pH value of described electroplate liquid is 9 ~ 11.
Preferably, the material of described adhesion layer is Co.
As can be seen from technique scheme, the formation method of a kind of copper-connection provided by the invention, by adopting Process of Electrochemical Reduction to remove the metal oxide on its surface to adhesion layer in electrolyte solution, reduce the resistivity on adhesion layer surface on the one hand, be conducive to subsequent electroplating process and form uniform copper seed layer, the removal of metal oxide can improve the nucleation rate of copper seed layer on adhesion layer surface effectively on the other hand, be conducive to forming fine and close and that resistivity is lower copper seed layer, adhesiveness is between the two better simultaneously.
Accompanying drawing explanation
By reference to the accompanying drawings, and by reference to detailed description below, will more easily there is more complete understanding to the present invention and more easily understand its adjoint advantage and feature, wherein:
Fig. 1 is the schematic flow sheet of the preferred embodiment of the formation method of a kind of copper-connection provided by the invention;
Fig. 2-Fig. 6 is the structural representation of the preferred embodiment of the formation method of a kind of copper-connection provided by the invention.
Embodiment
For making content of the present invention clearly understandable, below in conjunction with Figure of description, content of the present invention is described further.Certain the present invention is not limited to this specific embodiment, and the general replacement known by those skilled in the art is also encompassed in protection scope of the present invention.Secondly, the present invention's detailed statement that utilized schematic diagram to carry out, when describing example of the present invention in detail, for convenience of explanation, schematic diagram, should in this, as limitation of the invention not according to general ratio partial enlargement.
Be described in further detail below in conjunction with the formation method of the drawings and specific embodiments to a kind of copper-connection provided by the invention, it should be noted that, accompanying drawing all adopts the form that simplifies very much and all uses non-ratio accurately, only in order to object that is convenient, the aid illustration embodiment of the present invention lucidly.
Refer to Fig. 1, Fig. 1 is the schematic flow sheet of the preferred embodiment of the formation method of a kind of copper-connection provided by the invention; Meanwhile, please control reference Fig. 2-Fig. 6, Fig. 2-Fig. 6 be the structural representation of the preferred embodiment of the formation method of a kind of copper-connection provided by the invention.
Refer to Fig. 1, the invention provides a kind of formation method of copper-connection, comprise the following steps:
As shown in Figure 2, step S01: provide semi-conductive substrate 10, carries out photoetching and etching technics to Semiconductor substrate 10, to form groove 20.
Concrete, in the present embodiment, the material of described Semiconductor substrate 10 can be the one in monocrystalline silicon, polysilicon, amorphous silicon, the material of described Semiconductor substrate 10 can also be silicon-on-insulator (SOI, Silicon On Insulator), or epitaxial structure on other semi-conducting materials or silicon.In addition, the width of groove 20 is preferably 40nm ~ 50nm.
As shown in Figure 3, step S02: deposit diffusion barriers 30 and adhesion layer 40 in groove 20.
In the present embodiment, diffusion impervious layer 30 and adhesion layer 40 can adopt atomic layer deposition or chemical vapor deposition method to be formed; Wherein, adhesion layer 40 material is preferably the inert metals such as Co, Ta or Ru, the material of diffusion impervious layer 30 is preferably as tantalum nitride, titanium nitride or nitrogenize ruthenium, and the material of diffusion impervious layer 30 also can be comprise Ta, TaN, Ru, Co or Mn, and its oxide, nitrogen oxide.The thickness of diffusion impervious layer 30 and adhesion layer 40 is preferably 1 ~ 2 nanometer.
Concrete, first deposit diffusion barriers 30 in groove 20, diffusion impervious layer 30 covers sidewall and the bottom of groove 20, covers the surface of substrate 10 simultaneously; Diffusion impervious layer 30 can be individual layer or laminated construction, and in the present embodiment, the material of adhesion layer 40 is preferably Co.
Step S03: carry out Process of Electrochemical Reduction to adhesion layer 40, to reduce the metal oxide on adhesion layer 40 surface.
Concrete, Process of Electrochemical Reduction comprises the following steps: step S031: putting in electrolyte solution by adhesion layer 40, take adhesion layer as negative electrode, and it is applied to the negative potential of 5 ~ 10V, the duration is more than 600s; Step S032: cleaning is carried out and drying to adhesion layer 40.
In the present embodiment, in step S031, electrolyte solution comprises the tetramethyl oxyammonia that deionized water and concentration are 0.03 ~ 0.05mol/L, and the pH value of electrolyte solution is preferably 10 ~ 12.In step S032, by washed with de-ionized water, nitrogen drying is passed through to adhesion layer 40.The whole process of Process of Electrochemical Reduction is carried out at normal temperatures.
As shown in Figure 4, step S04: the surface of the adhesion layer 40 after reduction forms copper seed layer 50.
Concrete, copper seed layer 50 adopts electroplating technology to deposit and is formed, and the ethylenediamine complexing agent that the electroplate liquid adopted in electroplating technology comprises copper sulphate that concentration is 0.03 ~ 0.06mol/L, concentration is 0.06 ~ 0.12mol/L and concentration are the triethanolamine complexing agent of 0.03 ~ 0.05mol/L; Wherein, the proportioning of described ethylenediamine complexing agent is greater than described triethanolamine complexing agent.Wherein, the pH value of electroplate liquid is preferably 9 ~ 11; In electroplating technology, current density is 1mA/cm
2to 5mA/cm
2.
As shown in Figure 5, step S05: the surface being full of metallic copper 60 covering copper inculating crystal layer 50 in groove 20.
Concrete, metallic copper 60 adopts electroplating technology deposition to be formed, and adopt conventional acid electroplate liquid to continue to fill in copper seed layer 50, the current density of filling metallic copper 60 employing is 20mA/cm
2to 50mA/cm
2.
As shown in Figure 6, step S06: adopt flatening process to remove groove 20 outer unnecessary diffusion impervious layer 30, adhesion layer 40, copper seed layer 50 and metallic copper 60.
Concrete, chemical and mechanical grinding method (chemical mechanical planarization, CMP) can be adopted to remove outer unnecessary diffusion impervious layer 30, adhesion layer 40, copper seed layer 50 and the metallic copper 60 of groove 20.In the present embodiment, Cu polishing fluid first can be adopted to remove a large amount of Cu in surface, then with barrier polishing solution, polishing is carried out to barrier layer, finally obtain even curface.
In sum, the formation method of a kind of copper-connection provided by the invention, by adopting Process of Electrochemical Reduction to remove the metal oxide on its surface to adhesion layer in electrolyte solution, reduce the resistivity on adhesion layer surface on the one hand, be conducive to subsequent electroplating process and form uniform copper seed layer, the removal of metal oxide can improve the nucleation rate of copper seed layer on adhesion layer surface effectively on the other hand, be conducive to forming fine and close and that resistivity is lower copper seed layer, adhesiveness is between the two better simultaneously.
Be understandable that, although the present invention with preferred embodiment disclose as above, but above-described embodiment and be not used to limit the present invention.For any those of ordinary skill in the art, do not departing under technical solution of the present invention ambit, the technology contents of above-mentioned announcement all can be utilized to make many possible variations and modification to technical solution of the present invention, or be revised as the Equivalent embodiments of equivalent variations.Therefore, every content not departing from technical solution of the present invention, according to technical spirit of the present invention to any simple modification made for any of the above embodiments, equivalent variations and modification, all still belongs in the scope of technical solution of the present invention protection.
Claims (10)
1. a formation method for copper-connection, is characterized in that, comprise the following steps:
Step S01: provide semi-conductive substrate, carries out photoetching and etching technics to described Semiconductor substrate, to form groove;
Step S02: deposit diffusion barriers and adhesion layer in described groove;
Step S03: carry out Process of Electrochemical Reduction to described adhesion layer, to reduce the metal oxide on described adhesion layer surface;
Step S04: the surface of the adhesion layer after reduction forms copper seed layer;
Step S05: be full of metallic copper and cover the surface of described copper seed layer in described groove;
Step S06: adopt flatening process to remove described groove outer unnecessary diffusion impervious layer, adhesion layer, copper seed layer and metallic copper.
2. the formation method of copper-connection according to claim 1, is characterized in that, in described step S03, described Process of Electrochemical Reduction comprises the following steps:
Step S031: putting in electrolyte solution by described adhesion layer take adhesion layer as negative electrode, and it is applied to the negative potential of 5 ~ 10V, the duration is more than 600s;
Step S032: cleaning is carried out and drying to described adhesion layer.
3. the formation method of copper-connection according to claim 2, is characterized in that, in described step S031, described electrolyte solution comprises the tetramethyl oxyammonia that deionized water and concentration are 0.03 ~ 0.05mol/L.
4. the formation method of copper-connection according to claim 3, is characterized in that, the pH value of described electrolyte solution is 10 ~ 12.
5. the formation method of copper-connection according to claim 2, is characterized in that, in described step S032, passes through nitrogen drying to described adhesion layer by washed with de-ionized water.
6. the formation method of copper-connection according to claim 1, is characterized in that, in step S04, described copper seed layer adopts electroplating technology deposition to be formed.
7. the formation method of copper-connection according to claim 6, it is characterized in that, the ethylenediamine complexing agent that the electroplate liquid adopted in described electroplating technology comprises copper sulphate that concentration is 0.03 ~ 0.06mol/L, concentration is 0.06 ~ 0.12mol/L and concentration are the triethanolamine complexing agent of 0.03 ~ 0.05mol/L; Wherein, the proportioning of described ethylenediamine complexing agent is greater than described triethanolamine complexing agent.
8. the formation method of copper-connection according to claim 7, is characterized in that, in described electroplating technology, current density is 1mA/cm
2to 5mA/cm
2.
9. the formation method of copper-connection according to claim 7, is characterized in that, the pH value of described electroplate liquid is 9 ~ 11.
10. the formation method of copper-connection according to claim 1, is characterized in that, the material of described adhesion layer is Co.
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| CN201410849545.XA CN104465507A (en) | 2014-12-26 | 2014-12-26 | Copper interconnection forming method |
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| CN201410849545.XA CN104465507A (en) | 2014-12-26 | 2014-12-26 | Copper interconnection forming method |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105679784A (en) * | 2015-06-26 | 2016-06-15 | 上海磁宇信息科技有限公司 | Method for preparing peripheral conductive path of magnetic random access memory |
| CN108987376A (en) * | 2018-06-25 | 2018-12-11 | 复旦大学 | A kind of anti-Cu diffusion barrier material of low-resistivity manganese oxygen nitrogen |
| CN110473828A (en) * | 2019-08-22 | 2019-11-19 | 上海华力集成电路制造有限公司 | Electro-coppering fill process method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6713373B1 (en) * | 2002-02-05 | 2004-03-30 | Novellus Systems, Inc. | Method for obtaining adhesion for device manufacture |
| CN103003939A (en) * | 2010-07-19 | 2013-03-27 | 国际商业机器公司 | Method and structure to improve the conductivity of narrow copper filled vias |
| CN103855082A (en) * | 2012-11-30 | 2014-06-11 | 朗姆研究公司 | Wet activation of ruthenium containing liner/barrier |
-
2014
- 2014-12-26 CN CN201410849545.XA patent/CN104465507A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6713373B1 (en) * | 2002-02-05 | 2004-03-30 | Novellus Systems, Inc. | Method for obtaining adhesion for device manufacture |
| CN103003939A (en) * | 2010-07-19 | 2013-03-27 | 国际商业机器公司 | Method and structure to improve the conductivity of narrow copper filled vias |
| CN103855082A (en) * | 2012-11-30 | 2014-06-11 | 朗姆研究公司 | Wet activation of ruthenium containing liner/barrier |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105679784A (en) * | 2015-06-26 | 2016-06-15 | 上海磁宇信息科技有限公司 | Method for preparing peripheral conductive path of magnetic random access memory |
| CN108987376A (en) * | 2018-06-25 | 2018-12-11 | 复旦大学 | A kind of anti-Cu diffusion barrier material of low-resistivity manganese oxygen nitrogen |
| CN110473828A (en) * | 2019-08-22 | 2019-11-19 | 上海华力集成电路制造有限公司 | Electro-coppering fill process method |
| US11728213B2 (en) | 2019-08-22 | 2023-08-15 | Shanghai Huali Integrated Circuit Corporation | Method of copper plating filling |
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