WO2024061290A1 - Agent de nivellement, composition d'électroplacage et leur utilisation - Google Patents

Agent de nivellement, composition d'électroplacage et leur utilisation Download PDF

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WO2024061290A1
WO2024061290A1 PCT/CN2023/120181 CN2023120181W WO2024061290A1 WO 2024061290 A1 WO2024061290 A1 WO 2024061290A1 CN 2023120181 W CN2023120181 W CN 2023120181W WO 2024061290 A1 WO2024061290 A1 WO 2024061290A1
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Prior art keywords
electroplating
formula
electroplated
leveling agent
tertiary amine
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PCT/CN2023/120181
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English (en)
Chinese (zh)
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韩佐晏
肖斐
程元荣
王旭东
陈俊叶
屈新萍
孙谦丞
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华为技术有限公司
复旦大学
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Publication of WO2024061290A1 publication Critical patent/WO2024061290A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
    • 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
    • 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
    • C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
    • 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
    • C25D3/30—Electroplating: Baths therefor from solutions of tin
    • C25D3/32—Electroplating: Baths therefor from solutions of tin characterised by the organic bath constituents used
    • 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
    • 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
    • C25D3/46—Electroplating: Baths therefor from solutions of silver
    • 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
    • C25D3/48—Electroplating: Baths therefor from solutions of gold
    • 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
    • C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
    • C25D3/52—Electroplating: Baths therefor from solutions of platinum group metals characterised by the organic bath constituents used
    • 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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • 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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/58—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of copper
    • 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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
    • 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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/62—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of gold
    • 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
    • C25D3/56—Electroplating: Baths therefor from solutions of alloys
    • C25D3/64—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of silver
    • 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

Definitions

  • the embodiments of the present application relate to the technical field of metal electroplating, and in particular to a leveling agent, an electroplating composition and their applications.
  • copper metal is widely used as a metal interconnect material in integrated circuits, printed circuit boards and other fields due to its good conductivity, ductility and other characteristics.
  • metal copper filling of trenches, through holes and other holes of different sizes is completed through an electroplating process to build an interconnection structure.
  • additives include leveling agents, which can not only help to fill holes and other defects, but also reduce the thickness difference of the copper layer in the interconnection pattern area and the non-interconnection pattern area, ensuring that the surface of the copper plating layer is smooth. properties to facilitate smooth subsequent chemical mechanical polishing (CMP).
  • CMP chemical mechanical polishing
  • embodiments of the present application provide a leveling agent.
  • the electroplating composition using the leveling agent is used for filling interconnect structures in electronic substrates, and can realize defect-free metal filling of small-sized holes and grooves, ensuring that The surface flatness of the metal coating obtained on the interconnection areas with different distribution densities is high, which reduces the difficulty of chemical mechanical polishing and improves the reliability of the coating.
  • the first aspect of the embodiment of the present application provides a leveling agent for metal plating.
  • the leveling agent includes a polyamide substance, and the polyamide substance includes a repeating unit represented by formula (I). , or the protonated or N-quaternized product of the repeating unit represented by formula (I):
  • R is selected from a hydrogen atom, a substituted or unsubstituted alkyl group, and A 1 and A 2 independently contain a tertiary amine nitrogen atom located on the main chain of the amide repeating unit represented by formula (I).
  • the above-mentioned leveling agent provided in the embodiments of the present application is a polyamide substance containing tertiary amine nitrogen atoms in the main chain or a polyamide derivative obtained by protonation and N-quaternization.
  • the leveling agent is added to the electroplating composition.
  • the thickness difference of the electroplated metal layer in the area reduces the platform fluctuation on the surface of the coating, thereby obtaining a better planarization effect and facilitating the subsequent CMP process.
  • both A 1 and A 2 in the main chain of the leveling agent's repeating unit contain tertiary amine nitrogen atoms, which is beneficial to the leveling agent's balanced high and stable adsorption capacity and ensuring higher structural stability, so that the resulting coating contains The impurity content is low and the coating reliability is high.
  • a 1 and A 2 independently contain 1-5 tertiary amine structures as shown in formula (i):
  • R 1 and R 2 are independently selected from a direct single bond, an alkylene group, or an alkylene group containing at least one of an ether oxygen atom and a nitrogen atom connecting group;
  • R 3 is selected from an alkyl group, an aralkyl group. group, hydroxyalkyl group, or an alkyl group or hydroxyalkyl group containing an ether oxygen atom and/or a tertiary amine nitrogen atom;
  • the position marked * represents the connection position to the main chain of the amide repeating unit represented by formula (I).
  • A2 is represented by -R1 - NR3 - R2- or -R11 - NR31 - R21 - NR32 -R12 , wherein R1 , R2 , R11 , R12 are independently selected from alkylene groups, R21 is selected from alkylene groups or alkylene groups containing tertiary amine nitrogen atoms; R31 , R32 , R3 are independently selected from alkyl groups, hydroxyalkyl groups, or alkyl groups or hydroxyalkyl groups containing ether oxygen atoms and/or tertiary amine nitrogen atoms. In some embodiments, R1 , R2 , R11 , R12 , R21 are independently selected from linear C1 - C6 alkylene groups.
  • the A 1 represents -NR 3 - or -NR 3 '-R'-NR 3 '-, wherein R 3 and R 3 ' are independently selected from alkyl, aralkyl, hydroxyl Alkyl, or alkyl or hydroxyalkyl containing ether oxygen atoms and/or tertiary amine nitrogen atoms; R' is selected from alkylene or alkylene containing tertiary amine nitrogen atoms.
  • the alkylene group containing a tertiary amine nitrogen atom is expressed as -[D 1 -NR 3 ′′] c -D 2 -, where D 1 , D 2 , R 3 ” is independently selected from alkylene, c is an integer greater than or equal to 1, and when n is greater than 1, each D 1 or each R 3 ” is the same or different.
  • the polyamide material includes 2-200 repeating units represented by the formula (I) or its protonated or N-quaternized products.
  • the polyamide material also includes repeating units represented by formula (II), or protonated or N-quaternized products of repeating units represented by formula (II):
  • a 3 does not contain a tertiary amine nitrogen atom, and the A 3 includes a direct bond, an alkylene group, or an alkylene group containing an ether oxygen atom.
  • the alkylene group containing an ether oxygen atom is represented by -(R 4 -O) x -R 5 -, where R 4 and R 5 are the same or different Alkylene group, x is an integer greater than or equal to 1, and when x is greater than 1, each R 4 is the same or different alkylene group.
  • the polyamide material includes no more than 200 repeating units represented by the formula (II) or its protonated or N-quaternized products.
  • the second aspect of the embodiments of the present application provides a method for preparing a leveling agent, including:
  • the leveling agent includes polyamide substances, and the polyamide substances include repeating units represented by formula (I), or protonated or N-quaternized products of repeating units represented by formula (I),
  • a 1 contains a tertiary amine nitrogen atom located on the main chain of the dicarboxylate material represented by formula (A), and M is selected from a substituted or unsubstituted alkyl group; in formula (B), A 2 Containing tertiary amine nitrogen atoms located on the main chain of the aliphatic diamine represented by formula (B), A1 and A2 in formula (I) independently contain located on the main chain of the amide repeating unit represented by formula (I) The tertiary amine nitrogen atom, R in formula (B) and formula (I) is selected from hydrogen atoms, substituted or unsubstituted alkyl groups.
  • the amine substance in step (1), can be represented by R 3 -NH 2 , or R 3 '-NH-R'-NH-R 3 '.
  • the dicarboxylate material containing a tertiary amine nitrogen atom as shown in formula (A) can be obtained through the reaction of step (1).
  • the amine substance used is R 3 -NH 2
  • a 1 in the corresponding formula (A) is -NR 3 -
  • the amine substance used when the amine substance used is R 3 '-NH-R'-NH-R 3 '
  • a 1 in the corresponding formula (A) is -NR 3 '-R'-NR 3 '-.
  • the preparation method of the leveling agent provided in the embodiments of the present application has a simple process and is suitable for large-scale production.
  • the third aspect of the embodiments of the present application provides an electroplating composition.
  • the electroplating composition includes a metal ion source and an electroplating additive.
  • the electroplating additive includes the leveling agent described in the first aspect of the embodiments of the present application or the implementation of the present application.
  • the leveling agent prepared by the preparation method described in the second aspect.
  • the concentration of the leveling agent in the electroplating composition is 1 ppm-200 ppm. Controlling the concentration of the above-mentioned leveling agent in the electroplating composition within a suitable range is conducive to obtaining a moderate metal deposition speed and better achieving defect-free and high flatness of small-sized holes. Board filling, thus facilitating the production of fine circuits and improving the reliability of electronic products.
  • the electroplating composition further includes one or more of an accelerator and an inhibitor.
  • an accelerator and an inhibitor The synergistic cooperation of leveling agents, accelerators, inhibitors, etc. can effectively reduce the surface roughness of the copper layer. It can also achieve uniform surface copper thickness in areas with different wiring densities, and can better realize defect-free small-sized trenches. High flatness of the entire plate filling reduces the technical difficulty of subsequent polishing processes.
  • the electroplating additive also includes other leveling agents.
  • the electroplating composition further includes an acidic electrolyte and a halide ion source.
  • the halide ion source includes a chloride ion source;
  • the acidic electrolyte includes sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, perchloric acid, acetic acid, fluoroboric acid, alkyl sulfonic acid, arylsulfonic acid, sulfamate One or more acids.
  • the acidic electrolyte can make the electroplating composition acidic, which facilitates the protonation of the above-mentioned leveling agent in the electroplating composition, so as to have better adsorption capacity for the substrate to be electroplated;
  • the halide ion source especially the chloride ion source, can make the crystallization of the coating denser, It can play a synergistic effect on the performance of inhibitors.
  • the fourth aspect of the embodiments of the present application provides the leveling agent as described in the first aspect or the leveling agent prepared by the preparation method as described in the second aspect, or the composition as described in the third aspect in electroplated metal. application.
  • the electroplated metal includes electroplated copper and copper alloy, electroplated nickel and nickel alloy, electroplated tin and tin alloy, electroplated cobalt and cobalt alloy, electroplated ruthenium and ruthenium alloy, electroplated silver and silver alloy, electroplated gold and Any of the gold alloys.
  • the electroplated metal includes electroplated metal in the printed circuit board preparation process, electroplated metal in the integrated circuit metal interconnection process, and electroplated metal in the electronic packaging process.
  • the electroplated metal can be electroplated metal in processes including hole filling (such as Damascus trench filling, through silicon hole filling, other via hole filling, etc.), metal bump deposition, substrate rewiring and other processes.
  • the electroplated metal includes full metal electroplating filling of hole slots on the electronic substrate.
  • the electronic substrate can be an ordinary substrate, a printed circuit board, a chip, a packaging substrate, etc.
  • the hole slot includes a trench and/or a via hole, and the via hole can include a through hole, a blind hole, and a buried hole.
  • the leveling agent provided by the embodiments of the present application can achieve defect-free filling of nano-scale small-sized holes and can reduce high-density interconnection pattern areas and low-density interconnection patterns.
  • the thickness difference of the regional copper interconnection layer makes the plating surface flatter and more uniform, reducing the difficulty of the subsequent CMP process.
  • the fifth aspect of the embodiment of the present application provides an electroplating device, including:
  • An electroplating tank the electroplating tank is filled with the electroplating composition described in the third aspect of the embodiment of the present application;
  • the cathode comprising a substrate to be electroplated at least partially immersed in the electroplating composition
  • An electroplating power supply the negative electrode of the electroplating power supply is electrically connected to the cathode, and the positive electrode of the electroplating power supply is electrically connected to the anode, so as to apply current to the substrate to be electroplated when the electroplating power supply is turned on.
  • the sixth aspect of the embodiment of the present application provides a method of electroplating metal, including the following steps:
  • the method of electroplating metal can be performed using the electroplating device provided in the fourth aspect of the embodiment of the present application.
  • the substrate to be electroplated is provided with a hole groove, and the hole groove includes one or more of a trench, a through hole, and a blind hole.
  • the lateral size of the hole groove is 10 nm-500 nm, and/or the aspect ratio of the hole groove is greater than or equal to 3.
  • the electroplating includes the first step of electroplating, the second step of electroplating and the third step of electroplating, wherein the current density of the first step of electroplating is 0.3ASD-0.8ASD, and the electroplating time is 3s-20s;
  • the current density of the second step of electroplating is 0.5ASD-1.5ASD, and the electroplating time is 30s-50s;
  • the current density of the third step of electroplating is 1ASD-10ASD, and the electroplating time is 30s-50s.
  • Step-by-step plating allows for better defect-free filling and a suitable surface metal layer thickness.
  • the metal layer includes an in-hole filling layer that fills the hole grooves and a surface deposition layer deposited around the hole grooves.
  • the substrate to be electroplated is provided with a high-density slot area and a low-density slot area with different slot densities, the average thickness of the surface deposition layer on the high-density slot area is different from that of the low-density slot area.
  • the ratio of the average thickness of the surface deposit may be less than or equal to 1.2.
  • the seventh aspect of the present application provides an electronic substrate, including a base layer and a metal layer disposed on the base layer.
  • the metal layer is formed by electroplating the composition described in the third aspect of the embodiment of the present application, or using the fifth aspect. The method described in this aspect is formed.
  • the metal layer includes copper or copper alloy layer, nickel or nickel alloy layer, tin or tin alloy layer, cobalt or cobalt alloy layer, ruthenium or ruthenium alloy layer, silver or silver alloy layer, electroplated gold and Any of the gold alloys.
  • the base layer includes a substrate and a dielectric layer, the dielectric layer is provided with holes, and the metal layer includes an in-hole filling layer that fills the holes.
  • An embodiment of the present application further provides an electronic device, which includes the electronic substrate described in the sixth aspect of the embodiment of the present application.
  • Figure 1 is a schematic diagram of the formation process of copper interconnection layers in semiconductor processes.
  • Figure 2 is a schematic structural diagram of a substrate with multiple copper interconnect layers.
  • Figure 3a is a schematic diagram of void defects formed by filling holes in conventional electroplating copper.
  • Figure 3b is a schematic diagram of pore defects formed by filling holes in conventional electroplating copper.
  • Figure 3c is a schematic diagram of existing electroplated copper filling holes to form an uneven copper layer.
  • Figure 4 is a schematic diagram of an electroplating device provided by an embodiment of the present application.
  • FIG. 5 is a schematic structural diagram of an electronic substrate provided by an embodiment of the present application.
  • Figures 6a and 6b are cross-sectional electron microscopy photos of the electroplated chip sample in Comparative Example 1 at different magnifications.
  • Figure 6c is an atomic force microscope photo of the surface of the light sheet after electroplating in Comparative Example 1.
  • Figures 7a and 7b are cross-sectional electron micrographs at different magnifications of the electroplated chip sample in Example 1 of the present application.
  • Figure 7c is an atomic force microscope photo of the surface of the light sheet after electroplating 1.
  • Figures 8a and 8b are cross-sectional electron microscopy photos at different magnifications of the electroplated chip sample in Example 2 of the present application.
  • Figures 9a and 9b are cross-sectional electron microscopy photos at different magnifications of the electroplated chip sample in Example 3 of the present application.
  • Figure 10 is a cross-sectional electron microscope photo of the chip sample after electroplating in Comparative Example 2.
  • FIG. 1 is a schematic diagram of the formation process of a copper interconnect layer in a semiconductor process.
  • 10 a is a patterned substrate.
  • the patterned substrate 10 a includes a base 10 and a patterned dielectric layer 201 .
  • the patterned dielectric layer 201 is provided with a plurality of trenches 2 .
  • the plurality of trenches 2 of the dielectric layer 201 are filled with copper to form a copper layer 202, and the electroplated substrate 10b is obtained.
  • the copper layer 202 includes a filling layer in the holes filled in the trenches 2 and a surface deposition layer covering the surface of the dielectric layer 201 .
  • the dielectric layer 201 and the copper layer 202 together form a copper interconnection layer 20' that has not been processed by CMP.
  • the electroplated substrate 10b is processed by CMP to remove the surface deposited layer of the copper layer 202, specifically, the copper interconnection layer 20' is transformed into the CMP-processed copper interconnection layer 20, thereby obtaining the CMP-processed substrate 10c.
  • the CMP-treated substrate 10c can also be further prepared for copper interconnection layers, for example, a copper interconnection layer 30 is formed on the copper interconnection layer 20 to obtain a substrate 10d with multiple copper interconnection layers.
  • the ideal situation of the copper interconnection layer 20 should be as shown in the electroplated substrate 10b in Figure 1, with the holes in trench 2 filled
  • the layer has no holes, gaps and other defects; in order to facilitate the CMP process, after electroplating and depositing copper, the surface deposition layer of the copper layer 202 formed should be as shown in 10b of Figure 1, the high-density interconnection pattern area and the low-density interconnection pattern area.
  • the thickness difference of the copper interconnection layers is small, and the surface of the entire copper layer 202 is relatively flat.
  • the "high-density interconnection pattern area” refers to the area where the density of interconnection patterns (such as holes and slots) of the interconnection layer (including the number of holes and slots or the area ratio of all holes and slots) is relatively high
  • the "low-density interconnection pattern area” It refers to the area where the density of interconnection patterns (such as holes and slots) in the interconnection layer is relatively low.
  • the current plating solution formula cannot ensure the formation of a copper interconnect layer with high surface flatness and no defects. It is prone to defects such as holes and gaps as shown in Figure 3a and Figure 3b below, or as shown in Figure 3a and 3b.
  • the problem shown in 3c is that the thickness of the copper interconnection layer is significantly different between the high-density interconnection pattern area and the low-density interconnection pattern area.
  • the problem shown in Figure 3c can be suppressed to a certain extent by leveling agents. Leveling agents can assist in inhibiting copper deposition. While achieving hole-free filling, the surface of the plating layer tends to be flat and uniform, and the areas with different density areas of interconnect patterns can be reduced.
  • Embodiments of the present application provide a leveling agent for electroplating solutions, which can facilitate high-flatness, defect-free filling of small-sized holes (including trenches and via holes).
  • the leveling agent provided in the embodiments of the present application can be added as an additive to the basic electroplating solution to form an electroplating composition for metal electroplating.
  • the leveling agent includes polyamide substances, and the polyamide substances include repeating units represented by formula (I), or protonated or N-quaternized products of repeating units represented by formula (I):
  • R is selected from a hydrogen atom, a substituted or unsubstituted alkyl group, and A 1 and A 2 independently contain a tertiary amine nitrogen atom located on the main chain of the repeating unit shown in formula (I).
  • the above-mentioned leveling agent provided in the embodiments of the present application can specifically be a polyamide material containing tertiary amine nitrogen atoms in the main chain of the repeating unit or a polyamide derivative obtained by partial or complete protonation or N-quaternization of the repeating unit.
  • the leveling agent When the leveling agent is added to the electroplating composition and used for electroplating metal filling of holes in semiconductor manufacturing processes such as integrated circuit manufacturing, it can use the positive charge generated by the protonation of its tertiary amine nitrogen atoms in the acidic electroplating composition.
  • the leveling agent has a high electrochemical adsorption capacity for the electroplating cathode and the substrate to be electroplated, inhibits excessive deposition of metal to a certain extent, and can ensure defect-free filling of metal in smaller holes. Under such circumstances, it is easier to preferentially adsorb on the raised positions on the plating surface and better suppress the deposition of electroplated metal, which slows down the plating rate at the raised positions, reduces the thickness difference of the electroplated metal layer in wiring areas with different densities, and effectively reduces the plating layer
  • the platform on the surface is undulating, thereby achieving better planarization effect, which is beneficial to the subsequent CMP process and ensures the electrical connection reliability of the coating after CMP treatment.
  • A1 and A2 on the main chain of the repeating unit of the polyamide substance both contain tertiary amine nitrogen atoms, which is more conducive to ensuring that the leveling agent is in the electroplating composition.
  • the charge distribution is more uniform, which facilitates the balance of high and stable electrochemical adsorption capacity, and the leveling agent has high structural stability, which can reduce the impurity content in the resulting coating and improve the reliability of the coating.
  • the polyamide material when the above-mentioned polyamide material includes the protonated or N-quaternized product of the repeating unit represented by formula (I), it specifically refers to the complete or partial protonated or N-quaternized product of the repeating unit represented by formula (I).
  • the product obtained by quaternization, the polyamide material at this time is also a polyamide derivative.
  • the derivative specifically refers to the tertiary amine nitrogen atoms (i.e., the tertiary amine nitrogen atoms of A 1 and A 2 ) in the amide repeating unit represented by formula (I), and is not limited to the tertiary amine nitrogen atoms located in the amide represented by formula (I).
  • the substituted or unsubstituted alkyl group may be a substituted or unsubstituted C 1 -C 20 alkyl group, that is, the number of carbon atoms of the substituted or unsubstituted alkyl group may be 1-20, for example, specifically 1, 2 , 3, 4, 5, 6, 7, 8, 9, 10, 12, 15, 17, 18 or 19, etc. In some embodiments, the number of carbon atoms of the substituted or unsubstituted alkyl group may be 1-10 , further it can be 1-6.
  • the substituents in the substituted alkyl group include one or more of aryl, hydroxyl, alkoxy, etc., and generally do not include substituents containing nitrogen atoms.
  • R can be hydrogen (H), methyl (-CH 3 ), ethyl (-CH 2 CH 3 ), benzyl (-CH 2 Ph, where Ph represents a benzene ring) or hydroxyethyl group (-CH 2 CH 2 OH), etc.
  • a 1 and A 2 may independently contain 1-5 tertiary amine structures as shown in formula (i):
  • R 1 and R 2 are independently selected from a direct single bond, an alkylene group, or an alkylene group containing at least one of an ether oxygen atom (-O-) and a connecting group with a nitrogen atom;
  • R 3 is selected from Alkyl, aralkyl, hydroxyalkyl, or alkyl or hydroxyalkyl containing ether oxygen atoms and/or tertiary amine nitrogen atoms; the position marked * represents the connection to the main chain of the repeating unit represented by formula (I) Location.
  • formula (i) when R 1 and R 2 are directly connected single bonds, formula (i) is specifically -NR 3 -.
  • R 1 and R 2 are independently selected from an alkylene group, or an alkylene group containing at least one of an ether oxygen atom and a linking group with a nitrogen atom
  • the number of carbon atoms in the alkylene group may be 1-20, for example 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20.
  • R 1 and R 2 can be Straight chain or branched chain.
  • R 1 and R 2 are independently selected from a C 1 -C 10 alkylene group, or a C 1 -C 10 alkylene group containing at least one of an ether oxygen atom and a nitrogen atom-bearing connecting group; In other embodiments, R 1 and R 2 are independently selected from C 1 -C 6 alkylene, or C 1 -C 6 alkylene containing at least one of an ether oxygen atom and a nitrogen atom connecting group. . Wherein, the alkylene group may contain at least one ether oxygen atom, or at least one connecting group with nitrogen atom, or at least one ether oxygen atom and at least one connecting group with nitrogen atom.
  • the linking group with nitrogen atom can specifically be -NR"-, R" is a hydrogen atom, or a substituted or unsubstituted alkyl group, wherein, when R" is a substituted or unsubstituted alkyl group, the linking group is specifically A linking group containing a tertiary amine nitrogen atom.
  • R” is a hydrogen atom
  • the linking group is a linking group containing a secondary amine nitrogen atom (-NH-).
  • the alkylene group, the alkylene group containing at least one of the ether oxygen atom and the nitrogen atom connecting group can be substituted or unsubstituted.
  • the substituent on it can be an alkoxy group, One or more of hydroxyl group, tertiary amino group, etc.
  • the number of carbon atoms of the alkyl group may be 1-20, for example, specifically 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19 or 20. In some embodiments, the number of carbon atoms of the alkyl group may be 1-10, and further may be 1-6.
  • the alkyl group can be linear, branched or cyclic, and is preferably linear or branched, so that the above-mentioned leveling agent has good solubility in the electroplating solution.
  • Exemplary alkyl groups may be linear -CH 2 CH 3 , branched -CH(CH 3 )(CH 3 ), or cyclic cyclohexyl.
  • the number of carbon atoms of the hydroxyalkyl group may be 1-20, 1-10 or 1-6, etc., and may be linear or branched.
  • Exemplary hydroxyalkyl groups may be -CH2CH2OH , -CH2CH (OH) -CH3 , etc.
  • An alkyl group or hydroxyalkyl group with a smaller number of carbon atoms can help improve the solubility of the above-mentioned leveler in aqueous solutions.
  • Aralkyl refers to an alkyl group substituted by a substituted or unsubstituted aryl group, where the number of carbon atoms of the aryl group can be 6-30, such as 6-15, or even 6-10, and the carbon atoms of the substituted alkyl group , as mentioned above, it can be 1-20, for example, 1-10, etc.
  • An exemplary aralkyl group may be benzyl ( -CH2 -Ph).
  • the alkyl or hydroxyalkyl group containing ether oxygen atoms and/or tertiary amine nitrogen atoms may specifically contain one or more ether oxygen atoms, or one or more tertiary amine nitrogen atoms, or one or Multiple ether oxygen atoms and one or more tertiary amine nitrogen atoms.
  • Ether oxygen atoms and tertiary amine nitrogen atoms can exist in chain form or cyclic form in the alkyl group. Specifically, they can be embedded in the molecular chain of the alkyl group as a connecting group, or they can be substituted by forming a heterocyclic substituent. alkyl.
  • an alkyl group containing one tertiary amine nitrogen atom can be chain -CH 2 CH 2 -N(CH 3 )(CH 3 ), or Alkyl groups containing one ether oxygen atom can be chain-CH 2 CH 2 -O-CH 2 CH 3 or
  • the number of carbon atoms of the alkyl group containing an ether oxygen atom and the hydroxyalkyl group containing an ether oxygen atom may be 1-20, 1-10, 1-6, etc.
  • the above-mentioned A 2 can be expressed as -R 1 -NR 3 -R 2 -or -R 1 1 -NR 3 1 -R 2 1 -NR 3 2 -R 1 2 , where, R 1 , R 2 , R 1 1 , and R 1 2 are independently selected from alkylene groups, such as linear or branched C 1 -C 6 alkylene groups; R 2 1 can be selected from alkylene groups or tertiary amine nitrogen-containing groups.
  • Atom alkylene such as linear or branched C 1 -C 6 alkylene or chain C 1 -C 6 alkylene containing tertiary amine nitrogen atoms, in some embodiments, R 2 1 It is a linear C 1 -C 6 alkylene group, preferably a linear C 2 -C 6 alkylene group.
  • R 1 , R 2 , R 1 1 , and R 1 2 are alkylene groups with appropriate carbon chains, amines with A 2 are easier to obtain and are easier to adsorb on the substrate to be electroplated;
  • the alkyl group within an appropriately long range is beneficial to -NR 3 1 - and -NR 3 2 - maintaining structural stability, and the flatness of the electroplated metal layer in relatively higher-density wiring areas will be improved.
  • R 3 1 and R 3 2 can refer to the previous description of R 3 .
  • a 2 contains a tertiary amine nitrogen atom located on the main chain of the repeating unit, which can help the above-mentioned leveler have higher electrochemical adsorption capacity and help balance its
  • the charge distribution in the acidic plating solution can better inhibit excessive metal deposition, reduce the thickness difference of the electroplated metal layer in wiring areas with different densities, and achieve better planarization effect.
  • a 2 can be represented as -(CH 2 ) a -NR 3 -(CH 2 ) a - or -(CH 2 ) a -NR 3 1 -(CH 2 ) b -NR 3 2 -( CH 2 ) a -, wherein a and b are independently an integer greater than or equal to 1, such as an integer from 1 to 6; R 3 , R 3 1 , R 3 2 are independently selected from alkyl, hydroxyalkyl, Or an alkyl or hydroxyalkyl group containing ether oxygen atoms and/or tertiary amine nitrogen atoms, and C 1 -C 6 alkylene or C 1 -C 6 hydroxyalkyl groups are more common.
  • a is 1 or 2
  • b is 2 or 3.
  • a 2 can specifically be -CH 2 -N(CH 3 )-CH 2 -, -(CH 2 ) 2 -N(CH 3 )-(CH 2 ) 2 -, -CH 2 -N (CH 2 CH 3 )-CH 2 -, -CH 2 -N(CH 2 CH 2 OH)-CH 2 -, -CH 2 -N(CH 3 )-(CH 2 ) 2 ⁇ 3 -N(CH 3 )-CH 2 -, -(CH 2 ) 2 -N(CH 3 )-(CH 2 ) 2 ⁇ 3 -N(CH 3 )-(CH 2 ) 2 -.
  • 2 to 3 represent 2 or 3.
  • the above-mentioned A 1 can be expressed as -NR 3 - or -NR 3 '-R'-NR 3 '-, wherein R' is selected from an alkylene group or an alkylene group containing a tertiary amine nitrogen atom. group; the two R 3 's in -NR 3 '-R'-NR 3 '- can be the same group to make the above polyamide materials easier to obtain.
  • the selection range of R 3 ' can be found in the previous discussion of R 3 description of.
  • R 3 and R 3 ' are independently selected from alkyl, aralkyl, hydroxyalkyl, or alkyl or hydroxyalkyl containing ether oxygen atoms and/or tertiary amine nitrogen atoms.
  • R 3 is selected from an alkyl group, a hydroxyalkyl group, an alkyl group containing an ether oxygen atom, an alkyl group containing a tertiary amine nitrogen atom, or a hydroxyalkyl group containing an ether oxygen atom, etc.
  • R 3 ' is selected from an alkyl group. base or aralkyl group.
  • a 1 is -NR 3 -, that is, A 1 contains a tertiary amine structure represented by formula (i) that can be connected to the main chain of the amide repeating unit represented by formula (I).
  • R 3 may also contain at least one tertiary amine nitrogen atom, but such tertiary amine nitrogen atom is not located on the main chain of the amide repeating unit shown in formula (I).
  • R 3 can be methyl, ethyl, n-propyl, isopropyl (-CH(CH 3 )CH 3 )), cycloalkyl, hydroxyethyl (-CH 2 CH 2 OH), hydroxy-n-propyl Propyl (-CH 2 CH 2 CH 2 OH), -CH 2 -CH(OH)CH 3 , -CH 2 CH 2 -O-CH 2 CH 2 OH, -CH 2 CH 2 -O-CH 2 CH 3 , -(CH 2 ) 2 -N(CH 3 ) 2 , -(CH 2 ) 2 -N(CH 2 CH 3 ) 2 , -(CH 2 ) 3 -N(CH 3 ) 2 ,
  • R 3 here is preferably a linear or branched alkyl group, a linear or branched hydroxyalkyl group, a linear or branched chain containing an ether oxygen atom al
  • R' is an alkylene group containing a tertiary amine nitrogen atom in between, which can be represented as -[D 1 -NR 3 ′′] c -D 2 -, wherein D 1 , D 2 , R 3 ′′ are independently selected from alkylene, such as C 1 -C 6 alkylene; c is an integer greater than or equal to 1, and c is greater than When 1, each D 1 or each R 3 ′′ is the same or different.
  • a 1 in this case can be -N(CH 3 )-(CH 2 ) 2 -N(CH 3 )-(CH 2 ) 2 -N(CH 3 )-(CH 2 ) 2 -N(CH 3 )-, -N(CH 3 )-(CH 2 ) 2 -N(CH 3 )-(CH 2 ) 2 -N(CH 3 )-or-N(CH 3 )-(CH 2 ) 3 -N(CH 3 )-(CH 2 ) 3 -N(CH 3 )-.
  • a 1 which can be expressed as -NR 3 '-R'-NR 3 '-, when R' is an alkylene group, it can specifically be a C 1 -C 6 alkylene group, such as a C 2 -C 4 alkylene group. alkyl.
  • a 1 in this case can be specifically -N(CH 3 )-(CH 2 ) 2 ⁇ 3 -N(CH 3 )-, -N(CH 2 CH 3 )-(CH 2 ) 2 ⁇ 3 -N (CH 2 CH 3 )-, -N(CH 2 Ph)-(CH 2 ) 2 -N(CH 2 Ph)-, etc.
  • the above-mentioned polyamide substances may include 2-200 amide repeating units as shown in the above formula (I) or their complete or partial protonation or N-quaternization products. In some embodiments may include 2 to 50 amide repeating units as shown in the above formula (I) or their complete or partial protonation or N-quaternization products. Among them, controlling the number of repeating units represented by formula (I) or their protonated or N-quaternized products within an appropriate range helps the polyamide material to achieve both good solubility and leveling effect in the electroplating solution. It can be understood that, in the case of polyamide, it may include one repeating unit as shown in formula (I), or may include repeating units with multiple different structures as shown in formula (I).
  • the amide repeating unit represented by the above formula (I) can correspond to an aliphatic diamine containing a tertiary amine nitrogen atom in the molecular structure (as shown in formula (A)) and an aliphatic diamine containing a tertiary amine nitrogen atom in the molecular structure.
  • the amide repeating unit of the dicarboxylic acid ester of the atom shown in formula (B)).
  • the polyamide material also includes amide repeating units represented by formula (II), or all or part of the protonated or N-quaternized products of the amide repeating units represented by formula (II) :
  • a 3 is different from the aforementioned A 2 in that A 3 does not contain a tertiary amine nitrogen atom, and A 3 may include a direct bond, an alkylene group, or an alkylene group containing an ether oxygen atom.
  • the amide repeating unit represented by formula (II) can correspond to another diamine (shown in the following formula (C)) that does not contain a tertiary amine nitrogen atom in the molecular structure and a dicarboxylic acid containing a tertiary amine nitrogen atom in the molecular structure.
  • Amide repeating units of esters shown in formula (B)).
  • the preparation equation of the above polyamide material can be expressed as:
  • a 3 is an alkylene group
  • its carbon number may be 1-20, 1-10 or 1-6, etc., for example, specifically 1, 2, 3, 4 or 5, etc.
  • a 3 is an alkylene group containing an ether oxygen atom, specifically, it may be an alkylene group containing one or more ether oxygen atoms.
  • the alkylene group containing ether oxygen atoms can be expressed as -(R 4 -O) x -R 5 -, R 4 and R 5 are the same or different alkylene groups, x is an integer greater than or equal to 1, and When x is greater than 1, each R 4 is the same or different alkylene group.
  • Each R 4 or R 5 can specifically be an alkylene group with 1 to 10 carbon atoms, such as an alkylene group with 1 to 60 carbon atoms, such as methylene, ethylene, propylene, isoethylene.
  • x is an integer from 1 to 10, such as 1, 2, 3, 4, 5, 6, 7, 8, 9 or 10.
  • the above-mentioned polyamide substances may include no more than 200 amide repeating units represented by formula (II) or their protonated or N-quaternized products. In some embodiments, they may include no more than 50 amide repeating units represented by formula (II) or their protonated or N-quaternized products.
  • the number of repeating units shown in the formula (II) is controlled not to be too large, so as to prevent the polyamide material from having a good solubility in the electroplating solution from being too low.
  • the number of moles of the amide repeating unit represented by formula (II) is 1/5-5 of the amide repeating unit represented by formula (I).
  • the embodiments of the present application also provide a method for preparing a leveling agent, including:
  • the polyamide materials include repeating units represented by formula (I), or protonated or N-quaternized products of repeating units represented by formula (I),
  • a 1 contains a tertiary amine nitrogen atom located on the main chain of the dicarboxylate material represented by formula (A), and M is selected from a substituted or unsubstituted alkyl group; in formula (B), A 2 Containing tertiary amine nitrogen atoms located on the main chain of the aliphatic diamine represented by formula (B), A1 and A2 in formula (I) independently contain located on the main chain of the amide repeating unit represented by formula (I) The tertiary amine nitrogen atom, R in formula (B) and formula (I) is selected from hydrogen atoms, substituted or unsubstituted alkyl groups.
  • a 1 in formula (A) is the same as A 1 in formula (I)
  • a 2 and R in formula (B) are the same as A 2 and R in formula (I), where These groups will not be described again.
  • the above-mentioned M may be selected from substituted or unsubstituted C 1 -C 20 alkyl groups, or substituted or unsubstituted C 1 -C 6 alkyl groups.
  • M may be methyl, ethyl, n-propyl, etc.
  • M when M is methyl, the acrylate is specifically methyl acrylate; when M is ethyl, the acrylate is specifically ethyl acrylate.
  • an amine substance containing a -NH 2 or -NH structure is reacted with an acrylic ester to synthesize a dicarboxylate substance with a tertiary amine structure, and then The dicarboxylate material and the diamine material with different structures are subjected to transesterification and polycondensation reaction to prepare a polyamide material in which the repeating units A1 and A2 both have tertiary amine structures.
  • the structure, position and quantity of the tertiary amine in the resulting polyamide material can be designed more flexibly, thereby better controlling the leveling agent according to different application scenarios. adsorption capacity of molecules.
  • the preparation method of the leveling agent is simple in process and easy to operate, and can obtain polyamide substances with higher purity and high yield.
  • the molecular structure of the amine substance contains at least one primary amino group (-NH 2 ) or at least two imino groups (-NH-, Containing secondary ammonia nitrogen atoms) is to facilitate at least two Michael additions with acrylates containing unsaturated double bonds to obtain dicarboxylate materials containing at least one tertiary amine nitrogen atom on the main chain of the molecular structure.
  • a tertiary amine nitrogen atom will be introduced into the main chain of the dicarboxylate substance obtained by formula (A).
  • the temperature of the Michael addition reaction can be -20°C to 50°C, such as 0°C, 5°C, 10°C, 20°C, 30°C, 35°C or 40°C, etc.; the reaction time can be It is 1-24 hours.
  • the reaction in step (1) can be carried out under solvent-free conditions or in the presence of a solvent.
  • Exemplary solvents can be low-boiling point solvents such as diethyl ether, methanol, and tetrahydrofuran.
  • the amine substance in step (1) can be selected from one or more of the following substances, but is not limited thereto: methylamine (CH 3 NH 2 ), ethylamine (CH 3 -CH 2 -NH 2 ), propylamine (CH 3 -CH 2 -CH 2 -NH 2 ), isopropylamine (CH 3 -CH(NH 2 )-CH 3 ), ethanolamine (OH-CH 2 -CH 2 -NH 2 ), 2-hydroxypropylamine (also known as "isopropanolamine", CH 3 -CH(OH)-CH 2 -NH 2 ), 3-hydroxypropylamine (OH-CH 2 CH 2 CH 2 -NH 2 ), diglycolamine (NH 2 -CH 2 -CH 2 -O-CH 2 -CH 2 -OH), 2-ethoxyethylamine (NH 2 -CH 2 -CH 2 -O-CH 2 - CH 3 ), cyclohexylamine, 2-t
  • step (2) the dicarboxylate material containing a tertiary amine nitrogen atom represented by the formula (A) and the aliphatic aliphatic ester material containing a tertiary amine nitrogen atom represented by the formula (B)
  • the diamine undergoes transesterification and polycondensation reaction to form polyamide.
  • the reaction temperature of the transesterification polycondensation reaction can be 30 to 120°C, and the reaction can be carried out without a catalyst or in the presence of an alkaline catalyst.
  • Alkaline catalysts may include, but are not limited to, triethylamine, 1,8-diazabicycloundec-7-ene, sodium hydroxide, potassium hydroxide, sodium methoxide, sodium ethoxide, sodium carbonate, potassium carbonate, etc. one or more of them.
  • the progress of the reaction can be improved by reducing pressure or passing nitrogen gas.
  • a 2 in formula (B) contains a tertiary amine nitrogen atom located on the main chain of the molecular structure of formula (B).
  • the aliphatic diamine conforming to the structure of formula (B) can be exemplified as follows: N,N-bis(3-aminoethyl)methylamine (NH 2 -CH 2 CH 2 -N(CH 3 )-CH 2 CH 2 -NH 2 ), N,N-bis(3-aminoethyl)ethylamine (NH 2 -CH 2 CH 2 -N(CH 2 CH 3 )-CH 2 CH 2 -NH 2 ), N,N-bis (3-Aminopropyl)methylamine (NH 2 -CH 2 CH 2 CH 2 -N(CH 3 )-CH 2 CH 2 CH 2 -NH 2 ), N,N-bis(3-aminoethyl)ethanolamine (NH 2 -CH 2 CH 2 -N(CH 2 CH 2 OH)-CH 2 CH 2 -NH 2 ), N,N'-bis(aminoethyl)-N,N'-dimethyl-1, 2-Ethy
  • step (2) during the transesterification polycondensation reaction, the reaction raw materials used may not be limited to the aliphatic diamine containing tertiary amine nitrogen atoms represented by formula (B), and may also include other diamines. amine.
  • a diamine substance including an aliphatic diamine containing a tertiary amine nitrogen atom represented by the formula (B) and a dicarboxylic acid containing a tertiary amine nitrogen atom represented by the formula (A) are combined. Acid ester substances undergo transesterification and polycondensation reactions.
  • the diamine substance can be only an aliphatic diamine represented by formula (B), or include an aliphatic diamine represented by formula (B) and other diamines (for example, aliphatic diamine represented by formula (C) without tertiary amine nitrogen. atoms of diamine).
  • the ratio of the total molar amount of the diamine substance to the molar amount of the dicarboxylic acid ester substance represented by formula (A) may be (0.9-1.1):1.
  • other diamines conforming to the structure of formula (C) may include one or more of the following substances: ethylenediamine (NH 2 -(CH 2 ) 2 -NH 2 ), 1,3- Propylenediamine (NH 2 -(CH 2 ) 3 -NH 2 ), 1,4-butanediamine (NH 2 -(CH 2 ) 4 -NH 2 ), aminopropyl ether (NH 2 -(CH 2 ) 3 -O-(CH 2 ) 3 -NH 2 ), 3-oxa-1,5-pentanediamine (NH 2 -(CH 2 ) 2 -O-(CH 2 ) 2 -NH 2 ), 1, 8-Diamino-3,6-dioxaoctane (NH 2 -(CH 2 ) 2 O-(CH 2 ) 2 O-(CH 2 ) 2 -NH 2 ), 1,11-diamino-3 ,6,9-Trioxaundecane (NH
  • the embodiment of the present application also provides a composition, which is an electroplating composition.
  • the electroplating composition includes a metal ion source and an electroplating additive, wherein the electroplating additive includes the above-mentioned leveling agent of the embodiment of the application or adopts the method of the present application.
  • the electroplating composition can be used as a plating solution for electroplating the deposited metal layer.
  • the concentration of the above-mentioned leveling agent in the embodiment of the present application is 1-200 ppm. In some embodiments, the concentration of the above-mentioned leveling agent is 1-50 ppm. Controlling the concentration of the above-mentioned leveling agent in the electroplating composition within a suitable range is conducive to obtaining a moderate metal deposition speed and better achieving defect-free and high-flatness filling of the entire board in small-sized holes, thereby conducive to the production of fine circuits. It is helpful to improve the reliability of electronic products.
  • the electroplating additive may also include other leveling agents.
  • Other leveling agents are different from the leveling agents described above in the embodiments of this application.
  • the other leveling agents may be substances containing nitrogen heterocycles (such as pyridine ring, imidazole ring, quinoline ring), or polymers that do not contain nitrogen functional groups (such as epoxy rings and/or ether oxygen bonds).
  • Other leveling agents can work with the above-mentioned leveling agents in the embodiments of the present application to inhibit excessive deposition of electroplated metal, ensuring that smaller-sized graphics will not be filled in early, and reducing the platform undulations on the surface of the plating layer.
  • the electroplating additive further includes one or more of an accelerator and an inhibitor.
  • an accelerator and an inhibitor The synergistic cooperation of the above-mentioned leveling agents, accelerators, inhibitors, etc. can make the surface of the electroplated metal layer tend to be flat while achieving defect-free filling of smaller-sized holes, and can also be used in areas with different wiring densities. Achieve uniform thickness of surface coating, thereby reducing the technical difficulty of subsequent polishing processes.
  • the plating additive includes both an accelerator and an inhibitor.
  • an accelerator refers to an additive that can increase the plating rate of the electroplating composition.
  • the molecular weight of the accelerator is generally small and can be adsorbed on the metal surface and the bottom of the trench.
  • the accelerator speeds up the deposition rate on the surface and the bottom of the trench by reducing the electrochemical potential and cathodic polarization of the electroplating reaction, which is especially beneficial to accelerating the bottom of the trench.
  • metal deposition thereby achieving overfilling of the trench, and at the same time, it can also play a role in refining the grains of the metal layer.
  • accelerators may include, but are not limited to, organic substances containing sulfur atoms and/or sulfur-containing functional groups and/or their salts, such as disulfide bond-containing organic substances and their salts, thiol substances (containing -SH ), thiourea substances, compounds with sulfonic acid groups and their salts, etc.
  • the accelerator may include thiourea, allylthiourea, acetylthiourea, 2-morpholinoethanesulfonic acid, sodium polydisulfidepropanesulfonate (SPS), 2-mercaptoethanesulfonate sodium salt (MES), sodium 3-mercapto-1-propanesulfonate (MPS), potassium 3-mercapto-1-propanesulfonate, 3-mercapto-propanesulfonate-(3-sulfopropyl) ester (the structure is as follows (shown in a-9)), N,N-dimethyl-dithiocarbamic acid-(3-sulfopropyl) ester (also known as "N,N-dimethyl-dithiocarbonylpropane sulfonic acid Sodium"), sodium N,N-dimethyldithiocarboxamide propane sulfonate (DPS), sodium N,N-dimethyldithiocarboxamide
  • the accelerator can be used in various amounts, which can be adjusted according to the specific formula of the above-mentioned electroplating composition, electroplating process parameters, etc.
  • the amount of the accelerator used is 0.05ppm-3000ppm, such as 0.1ppm-3000ppm.
  • the concentration of the accelerator therein can be 1-1000ppm.
  • the concentration of the accelerator in the electroplating composition, can be 1ppm-500ppm, such as 2ppm-500ppm.
  • the concentration of the accelerator in the electroplating composition, can be 1ppm-50ppm, such as 2ppm, 5ppm, 10ppm, 20ppm, 25ppm, 30ppm, 35ppm or 40ppm, etc. In some embodiments, the concentration of the accelerator in the electroplating composition is 1ppm-30ppm, and further can be 5-30ppm.
  • the accelerator includes one or more of SPS and MPS; the concentration of the accelerator in the electroplating composition is 1 ppm-50 ppm, preferably 1-30 ppm.
  • inhibitors refer to additives that can inhibit the metal plating rate.
  • Inhibitors are generally electrically neutral in the electroplating composition.
  • the inhibitor has a moderate molecular weight and is generally adsorbed at the openings and side walls of the pores. By inhibiting the deposition rate of metal cations there, it can avoid premature sealing of the pores and the occurrence of holes and gaps inside the pores.
  • the inhibitor may include, but is not limited to, a polymer containing at least one heteroatom substitution and more particularly oxygen substitution, such as a polyether.
  • the inhibitor may include polyethylene glycol substances, such as polyethylene glycol (PEG), polypropylene glycol (PPG), copolymers of polyethylene glycol and polypropylene glycol, connected by nitrogen atoms.
  • polyethylene glycol and polyglycerol such as Te701
  • amines such as ethoxylated amines
  • polyoxyalkylene amines such as alkanolamines, amides, alkyl polyether sulfonates, etc. one or more.
  • the copolymer of polyethylene glycol and polypropylene glycol can be block or random, for example, specifically an ethylene oxide-propylene oxide (EO/PO) diblock copolymer (ie, polyethylene glycol and polypropylene glycol).
  • the number average molecular weight of the inhibitor is 2,000-15,000, for example, 2,000-10,000.
  • the amount of inhibitor used can be adjusted according to the specific formula of the above-mentioned electroplating composition, electroplating process parameters, etc. Under normal circumstances, the amount of inhibitor used is 0.1ppm-3000ppm.
  • the concentration of the inhibitor in the electroplating composition may be 1-2000 ppm, such as 1-1000 ppm or 50-2000 ppm. In some embodiments, the concentration of the inhibitor in the electroplating composition may be 2 ppm-500 ppm, and further may be 50 ppm-500 ppm. In some specific embodiments, the concentration may be 100-300 ppm.
  • the inhibitor includes polyethylene glycol (PEG), polypropylene glycol (PPG), ethylene oxide-propylene oxide copolymer, ethylene oxide-propylene oxide-ethylene oxide copolymer
  • PEG polyethylene glycol
  • PPG polypropylene glycol
  • ethylene oxide-propylene oxide copolymer ethylene oxide-propylene oxide-ethylene oxide copolymer
  • concentration of the inhibitor in the electroplating composition is 50-500 ppm, preferably 100-300 ppm.
  • the electroplating composition further includes an acidic electrolyte and a halide ion source. That is, the electroplating composition at this time includes a metal ion source, an acidic electrolyte, a halide ion source and an electroplating additive.
  • the acidic electrolyte can make the electroplating composition acidic, which is beneficial to the protonation of the above-mentioned leveling agent in the electroplating composition.
  • the halide ion source can make the crystallization of the coating denser, finer and less rough, and can work synergistically with the inhibitor, so that the inhibitor can better inhibit early sealing when electroplating fills the hole slot.
  • the source of halide ions is a source of chloride ions.
  • the chloride ion source may be one or more of copper chloride, tin chloride, sodium chloride, potassium chloride and hydrochloric acid.
  • the concentration of chloride ions derived from the chloride ion source in the electroplating composition may be 1 ppm to 100 ppm, such as 10 ppm, 20 ppm, 30 ppm, 40 ppm, 50 ppm, 60 ppm, 70 ppm or 80 ppm, etc.
  • the acidic electrolyte includes but is not limited to sulfuric acid, phosphoric acid, nitric acid, hydrochloric acid, perchloric acid, acetic acid, fluoroboric acid, alkyl sulfonic acid (such as methyl sulfonic acid, ethyl sulfonic acid, propyl sulfonic acid). acid, trifluoromethanesulfonic acid, etc.), arylsulfonic acid (such as benzenesulfonic acid, phenolsulfonic acid, etc.), sulfamic acid, etc.
  • the acidic electrolyte includes one or more of sulfuric acid and methylsulfonic acid.
  • the total concentration of the acidic electrolyte in the electroplating composition can be 1g/L-100g/L, such as 1g/L, 10g/L, 20g/L, 30g/L, 40g/L, 50g /L, 55g/L, 60g/L, 70g/L, 80g/L, 90g/L, 100g/L.
  • Suitable acidic electrolyte and its concentration are beneficial to obtain suitable electroplating deposition rate.
  • the metal ion source includes a copper ion source, a nickel ion source, a tin ion source, a cobalt ion source, a ruthenium ion source, and a silver ion source. Either ion source or gold ion source. It can be understood that, depending on which metal layer is pre-deposited, the metal ion source in the electroplating composition will accordingly contain the corresponding metal element in the pre-deposited metal layer. For example, if a metal copper layer is pre-deposited, the metal ion source includes a copper ion source.
  • the metal ion source includes a copper ion source.
  • the copper ion source may include one or more of copper sulfate, copper nitrate, copper halide, copper acetate, copper methane sulfonate, and the like.
  • the acid system of copper ion source is used for electroplating, which has high electroplating efficiency, is environmentally friendly, and can better fill blind holes through the combination of various additives.
  • the concentration of the copper ion source in the electroplating composition is 1g/L-400g/L, for example, it can be 10g/L, 20g/L, 50g/L, 60g/L, 80g /L, 100g/L, 150g/L, 200g/L or 300g/L, etc. Controlling the copper ion source within a suitable content range is beneficial to balancing the deposition speed and the brightness and flatness of the resulting copper coating.
  • the new leveling agent provided in the embodiment of the present application is applied to metal plating liquids such as copper plating liquid. During the hole filling process, a sample with uniform surface metal thickness and good board appearance can be obtained, which is suitable for precision machining. Moreover, the leveling agent of the embodiment of the present application is particularly suitable for electroplating small holes with a lateral size between 10nm and 500nm. It can achieve defect-free and high surface flatness filling of all holes and grooves, which is beneficial to improving the reliability of the final product. .
  • the embodiments of the present application also provide the application of the above-mentioned leveling agent of the embodiments of the present application or the leveling agent prepared by the above-mentioned preparation method of the embodiments of the present application or the above-mentioned electroplating composition of the embodiments of the present application in metal electroplating.
  • the electroplated metal may include electroplated copper and copper alloys, electroplated nickel and nickel alloys, electroplated tin and tin alloys, electroplated cobalt and cobalt alloys, electroplated ruthenium and ruthenium alloys, electroplated silver and silver alloys, electroplated gold and gold alloys. any of them.
  • electroplated metal includes electroplated metal in the printed circuit board preparation process, electroplated metal in the integrated circuit metal interconnection process, or electroplated metal in the electronic packaging process.
  • electroplated metal can be specifically used for filling holes and slots on electronic substrates, depositing metal bumps, rewiring substrates, etc.
  • the slots may include trenches and/or via holes, and the via holes may include one or more of through holes, blind vias, and buried vias.
  • Electronic substrates can be wafer chips (such as copper Damascus process), through silicon via (TSV) adapter boards, printed circuit boards, packaging substrates, etc.
  • the electroplated metal may be electroplated metal in Damascus chip trench filling, through silicon hole filling, via hole filling, metal bump deposition, substrate rewiring and other processes.
  • electroplating metal includes full metal electroplating filling of hole slots on the electronic substrate.
  • Full metal filling can be electroplated copper and copper alloy, electroplated nickel and nickel alloy, electroplated tin and tin alloy, electroplated cobalt and cobalt alloy, electroplated ruthenium and ruthenium alloy, or electroplated silver and silver alloy, electroplated gold and gold alloy filling.
  • the above-mentioned leveling agent provided by the embodiments of the present application for all-metal plating filling of holes on electronic substrates can achieve defect-free filling of nano-scale small-sized holes, and at the same time can reduce the high-density interconnection pattern area and low-density
  • the thickness difference of the metal interconnect coating in the interconnect pattern area makes the coating surface flatter and more uniform, improves the uniformity of the entire plate plating of the electronic substrate, and reduces the difficulty of subsequent CMP processes; it is also conducive to the production of fine circuits, improving the reliability of electronic products, thereby making it more It is a good way to meet the manufacturing needs of high-density interconnection products through simple processes and low cost.
  • Embodiments of the present application also provide a method for electroplating metal, including the following steps:
  • the substrate to be electroplated is usually used as a cathode, which can be partially or completely placed in an electroplating tank filled with an electroplating composition, and an anode can be placed in the electroplating tank, which can be soluble or insoluble during the electroplating process.
  • the cathode and the anode can be electrically connected to the electroplating power supply through wiring, and the cathode and the anode together form a conductive circuit with the help of the electroplating composition as an electrolyte, thereby achieving metal deposition on the substrate to be electroplated.
  • the electroplating device 200 includes:
  • the electroplating tank 20 is filled with the electroplating composition 21 described in the embodiment of the present application,
  • the cathode 22 and the anode 23 are arranged in the electroplating tank 20, the cathode 22 includes a substrate to be electroplated that is at least partially immersed in the electroplating composition 21,
  • the electroplating power supply 24 has a negative electrode electrically connected to the cathode 22 and a positive electrode electrically connected to the anode 23 to apply current to the substrate to be plated when the electroplating power supply 24 is turned on.
  • the cathode 22 and the anode 23 are generally placed opposite each other, and they are generally placed apart, for example, separated by a separator 25 .
  • the cathode 22 and the anode 23 are placed vertically in the electroplating tank 20 in Figure 4, it can be understood that the cathode 22 and the anode 23 can also be placed horizontally in the electroplating tank 20. Specifically, it can be determined according to the position of the substrate to be electroplated. The details will depend on the plating location.
  • a potential is usually applied to the cathode, so that when the electroplating power supply is turned on, current is also applied to the substrate to be plated.
  • electroplating copper Cu ions in the electroplating composition are reduced at the cathode, thereby forming plated metal Cu on the substrate to be electroplated.
  • the oxidation reaction proceeds at the anode, and the anode may dissolve or become inactive during the electroplating process. Dissolution occurs.
  • the applied current may be a direct current, a pulse current, or other suitable current.
  • the electroplating composition 21 contained in the electroplating tank 20 can be stirred.
  • the The stirring device 26 is placed in the electroplating tank 20 to increase the fluidity of the electroplating composition 21.
  • the suitable stirring device 26 may be a stirring mechanism or a gas purge assembly, or other suitable devices.
  • the gas purge assembly generally has a ventilation pipeline inserted into the electroplating composition. Several holes can be provided on the wall of the portion of the ventilation pipeline immersed in the electroplating composition to allow purge gas (such as air, inert gas) to pass through the holes flow out.
  • the substrate to be electroplated may be a substrate without holes, for example, a patternless silicon substrate with a silicon dioxide layer/tantalum layer/tantalum nitride layer deposited on the surface.
  • holes are provided on the substrate to be electroplated, and the metal layer includes an in-hole filling layer that fills the holes and a surface deposition layer deposited around the holes.
  • the via slot includes a trench and/or a via hole, and the via hole may include one or more of a through hole, a blind hole, and a buried hole.
  • the substrate to be electroplated may be provided with areas with different hole and groove distribution densities, such as a high-density hole and groove distribution area and a low-density hole and groove distribution area.
  • the substrate to be electroplated can have holes with different lateral sizes and depths at the same time.
  • the lateral size of the hole groove may be 10nm-500nm, specifically 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm, 90nm, 100nm, 110nm, 120nm, 125nm, 130nm, 150nm, 200nm , 300nm, 400nm, 450nm, etc.
  • its lateral dimension refers to the width of the trench
  • its lateral dimension refers to the diameter of the through hole.
  • the lateral dimensions of the pores may range from 10 nm to 120 nm.
  • the electroplating composition provided by the embodiment of the present application is still good for electroplating and filling holes with smaller lateral dimensions.
  • the lateral dimension of the hole groove is 60 nm-120 nm.
  • the aspect ratio of the hole groove is greater than or equal to 3.
  • the depth ratio refers to the ratio of the depth of the slot to its lateral dimensions.
  • defects such as holes and gaps are more likely to occur, and the electroplated surface is relatively uneven.
  • using the electroplating composition provided in the embodiments of the present application can achieve this for holes with a large depth-to-width ratio. Defect-free filling with high surface flatness.
  • the depth of the hole groove can be 100nm-300nm, for example, it can be 100nm, 150nm, 200nm, 280nm or 300nm, etc. In some embodiments, the depth of the pore grooves may be 120-250 nm.
  • the inner wall of the hole is usually metallized.
  • a metal seed layer such as a copper seed layer, is formed on the inner wall of the hole to achieve a good connection between the hole to be plated and the anode during electroplating. Electrical connection.
  • the electroplating process conditions are: the electroplating temperature is 10°C-65°C, for example, 20-30°C; the current density is 0.3ASD-106ASD, and the total electroplating time is 10s-200s.
  • the above-mentioned electroplating composition can be stirred so that the concentration of the electroplating composition in each place in the electroplating tank remains substantially consistent.
  • the electroplating includes the first step of electroplating, the second step of electroplating and the third step of electroplating.
  • the current density of the first step of electroplating is 0.3ASD-0.8ASD, such as 0.5 or 0.65ASD; the electroplating time is 3s-20s, such as 5s-12s.
  • the current density of the second step of electroplating is 0.5ASD-1.5ASD, such as 1ASD or 1.2ASD; the electroplating time is 30s-50s, such as 35s or 40s.
  • the current density of the third step of electroplating is 1ASD-10ASD, such as 2ASD, 5ASD, 6ASD or 8ASD, etc.; the electroplating time is 30s-50s, such as 45s.
  • the temperatures of each electroplating step can be the same or different.
  • defect-free filling can be better obtained through step-by-step electroplating, and a suitable surface metal layer thickness can be obtained.
  • the first step of electroplating can better repair the copper seed layer; the second step of electroplating can better achieve pore filling; and the third step of electroplating can thicken the surface to facilitate subsequent polishing and grinding.
  • an embodiment of the present application also provides an electronic substrate 100, including a base layer 101 and a metal layer 102 disposed on the base layer.
  • the metal layer 102 is formed by electroplating with the electroplating composition described above in the embodiment of the present application, or by using the present invention.
  • the application embodiment is formed by the method of electroplating metal described above.
  • the metal layer 102 includes a copper or copper alloy layer, nickel or nickel alloy layer, tin or tin alloy layer, cobalt or cobalt alloy layer, ruthenium or ruthenium alloy layer, silver or silver alloy layer, gold or gold alloy any of the layers.
  • the base layer 101 includes a substrate 1011 and a dielectric layer 1012.
  • the dielectric layer 1012 on the base layer 101 is provided with a hole groove 103.
  • the metal layer 102 includes an in-hole filling layer 1021 that fills the hole groove 103 and a hole filling layer 1021 deposited on the base layer 101.
  • a layer 1022 is deposited on the surface around the hole 103 .
  • regions with different densities are provided in the holes 103 , and the thickness difference of the surface deposition layer 1022 is small. Overall, the surface of the surface deposition layer 1022 is flat and has low roughness. It can be understood that in some embodiments, after the surface deposition layer 1022 is removed by the CMP process, the metal layer 102 only includes the in-hole filling layer 1021 that fills the hole trench 103.
  • a metal seed layer such as a copper seed layer, formed by metallizing the hole groove 103 between the base layer 101 and the metal layer 102 .
  • the lateral size of the hole groove 103 may be 10 nm-500 nm, and the aspect ratio may be greater than or equal to 3.
  • a plurality of holes 103 may be provided on the base layer 101, and the plurality of holes 103 may have different lateral dimensions and depths, or may have the same lateral dimensions and depths.
  • the thickness of the surface deposition layer 1022 is less than 2 ⁇ m. In some embodiments, the thickness is less than or equal to 1 ⁇ m. In the embodiment of the present application, the ratio of the average thickness H1 of the surface deposition layer 1022 in the high-density interconnection pattern area to the average thickness H2 of the surface deposition layer 1022 in the low-density interconnection pattern area is less than or equal to 1.2. In some embodiments, the ratio of H1 to H2 is less than or equal to 1.10. In some embodiments, the ratio of H1 to H2 is less than or equal to 1.05, such as 1.03, 1.02 or 1.01. This ratio is very close to the super-flattening effect (ratio value is 1.0). In some embodiments, the ratio of H1 to H2 is equal to 1.0.
  • the electronic substrate 100 shown in FIG. 5 is a schematic structural diagram that has not been processed by CMP.
  • the surface deposition layer 1022 can be removed through a polishing process.
  • An embodiment of the present application also provides an electronic device.
  • the electronic device adopts the electronic substrate 100 described in the embodiment of the present application.
  • At least one refers to one or more
  • plural items refers to two or more.
  • At least one of the following” or similar expressions thereof refers to any combination of these items, including any combination of single items (items) or plural items (items).
  • at least one of a, b, or c or “at least one of a, b, and c” can mean: a, b, c, a-b (that is, a and b), a-c, b-c, or a-b-c, where a, b, and c can be single or multiple respectively.
  • a polyamide L1 whose structure is shown in Formula 1:
  • the preparation method of polyamide L1 includes the following steps:
  • a copper electroplating solution includes components in the following mass proportions:
  • Copper sulfate (calculated as copper ions): 100g/L,
  • Leveling agent (specifically polyamide L1): 5ppm,
  • Accelerator specifically sodium polydisulfide propane sulfonate (SPS): 25ppm
  • Inhibitor specifically polyether L64, ethylene oxide-propylene oxide-ethylene oxide copolymer: 250 ppm.
  • Comparative Example 1 a copper electroplating solution without adding leveling agent is used as Comparative Example 1.
  • the only difference between the copper electroplating solution in Comparative Example 1 and Example 1 is that polyamide L1 is not added.
  • the copper electroplating solution of Example 1 and the copper electroplating solution of the comparative example were used to electroplate copper filling on a substrate to be electroplated with a groove or through-hole structure with a width of 60nm-120nm and a depth of 120nm-250nm.
  • the substrate to be electroplated was a Damascus graphic chip with a copper seed layer in the groove or through-hole.
  • the electroplating temperature was room temperature electroplating (temperature was 20-30° C.).
  • the electroplating process adopted a three-step current method.
  • the current density of the first electroplating step was 0.65ASD, and the electroplating time was 6 seconds.
  • the current density of the second electroplating step was 1ASD, and the electroplating time was 40 seconds.
  • the current density of the third electroplating step was 6ASD, and the electroplating time was 45 seconds.
  • a non-patterned silicon wafer (referred to as a light wafer) with a copper middle layer deposited on the surface was electroplated with copper using the copper electroplating solutions of Example 1 and the comparative example 1 according to the above electroplating process.
  • Figures 6a and 6b are cross-sectional electron microscope photos of the electroplated chip sample of Comparative Example 1 at different magnifications.
  • Figure 6b is a partial enlarged view of Figure 6a.
  • Figure 6c is an atomic force microscope photo of the light sheet surface after electroplating of Comparative Example 1. . It can be seen from Figure 6a and Figure 6b that without adding leveling agent, after the grooves, through holes and other hole structures in the chip are filled by electroplating, hole defects still exist (see Figure 6b), and the grooves Or the thickness of the copper plating layer above the high-density area and the low-density area of the through hole is quite different.
  • the average thickness of the copper layer in the high-density area (approximately 0.830 ⁇ m) and the average thickness of the copper layer in the low-density area (approximately 0.660 ⁇ m)
  • the ratio is as high as 1.26, making it difficult to perform subsequent CMP operations.
  • the roughness Rq of the surface of the light sheet after electroplating in Comparative Example 1 is only 12.7nm, which is relatively rough and the surface flatness is poor.
  • Figures 7a and 7b are respectively cross-sectional scanning electron microscope photographs at different magnifications of the electroplated chip sample in Example 1 of the present application.
  • Figure 7b is a partial enlargement of Figure 7a. It can be seen that when polyamide L1 is added as a leveling agent in the plating solution, defect-free filling of small-sized trenches and through-holes is achieved (see Figure 7b), and high-density groove areas and low-density holes are filled The surface of the copper layer in the groove area has small fluctuations.
  • the ratio of the average thickness of the copper layer in the high-density hole and groove area (about 0.816 ⁇ m) to the average thickness of the copper layer in the low-density hole and groove area (about 0.806 ⁇ m) is only 1.01, which is smooth. The degree is greatly improved, and the result is very close to the ideal leveling effect of 1.0, which can greatly reduce the burden of the subsequent CMP polishing process.
  • the thickness fluctuation of the surface of the light sheet after adding polyamide L1 as a leveling agent is also significantly reduced compared with the light sheet obtained in Comparative Example 1.
  • the surface roughness Rq of the light sheet after electroplating is only 5.28nm.
  • polyamide L1 as a leveling agent in the electroplating solution formula can have a significant leveling effect.
  • a polyamide L2 whose structure is shown in formula (2):
  • the preparation method of polyamide L2 includes the following steps:
  • a copper electroplating solution the formula of which is different from that of the copper electroplating solution in Example 1 only in that the leveling agent is polyamide L2.
  • the copper electroplating solution of Example 2 is used for electroplating copper filling.
  • the substrate to be electroplated has grooves or through-holes. Damascus graphics chip with copper seed layer, the electroplating process is the same as in Example 1.
  • Figures 8a and 8b are cross-sectional SEM photos of the chip samples after electroplating in Example 2 of the present application at different magnifications, and Figure 8b is a partial enlarged view of Figure 8a.
  • Figures 8a and 8b that when polyamide L2 is added as a leveling agent, small-sized grooves, through holes and other hole structures are all filled without defects, and the thickness difference of the copper plating layer above the high-density hole groove area and the low-density hole groove area is small, among which the ratio of the average thickness of the copper layer in the high-density hole groove area to the average thickness of the copper layer in the low-density hole groove area is only 1.03, which is very close to the ideal leveling effect of 1.0, thereby greatly reducing the burden of the subsequent CMP polishing process.
  • polyamide L2 as a leveling agent in the electroplating solution formula achieves defect-free filling of small-sized holes and slots, and high-flatness simultaneous filling of different-sized and different
  • the preparation method of polyamide L3 includes the following steps:
  • the hydrogen nuclear magnetic resonance spectrum results of the polyamide L3 are: 1 H NMR (400MHz, CDCl 3 ) ⁇ (ppm): 3.28 (s, 2H), 2.88 (s, 2H), 2.69 (s, 2H), 2.36 (s ,4H),2.22(s,3H),2.19(s,3H),1.65(s,2H).
  • a copper electroplating solution the formula of which is different from that of the copper electroplating solution in Example 1 only in that the leveling agent is polyamide L3.
  • the copper electroplating solution of Example 3 is used to perform electroplating copper filling.
  • the substrate to be electroplated has grooves or through-holes. Damascus graphics chip with copper seed layer, the electroplating process is the same as in Example 1.
  • Figures 9a and 9b are cross-sectional scanning electron microscope photographs of the electroplated chip sample at different magnifications in Example 3 of the present application, and Figure 9b is a diagram Magnified view of part of 9a. It can be seen from Figure 9a and Figure 9b that when polyamide L3 is added as a leveling agent, small-sized trenches, through-holes and other hole structures can be filled without defects, and the high-density hole area is closely related to the low-density hole structure. The difference in thickness of the copper plating layer above the high-density hole and groove area is small.
  • the average thickness of the copper layer in the high-density hole and groove area (approximately 0.744 ⁇ m) and the average thickness of the copper layer in the low-density hole and groove area (approximately 0.715 ⁇ m)
  • the ratio is only 1.04, which is closer to the ideal leveling effect of 1.0, which can greatly reduce the burden of the subsequent CMP polishing process.
  • polyamide L3 is used as a leveling agent in the electroplating solution formula to achieve defect-free filling of small-sized holes and grooves, as well as high-flatness simultaneous filling of areas with different sizes and hole setting densities, and has a significant leveling effect.
  • step (2) the reaction raw material 1,8-diamino-3,6-dioxaoctane is also added.
  • the preparation method of polyamide L4 includes the following steps:
  • a copper electroplating solution the formula of which is different from the copper electroplating solution in Embodiment 1 only in that the leveling agent is polyamide L4.
  • Example 4 Take the same Damascus graphics chip as in Example 1, and use the copper electroplating solution of Example 4 to electroplat and fill it with copper.
  • polyamide L4 as a leveling agent in the electroplating solution formula has good leveling effect.
  • step (2) N,N'-bis(aminopropyl)-N,N'-dimethyl-1,2- Ethylenediamine replaces N,N-bis(3-aminopropyl)methylamine.
  • a copper electroplating solution the formula of which is different from the copper electroplating solution in Embodiment 1 only in that the leveling agent is polyamide L5.
  • Example 2 Take the same Damascus graphics chip as in Example 1, and use the copper electroplating solution of Example 5 to electroplat and fill it with copper.
  • polyamide L5 as a leveling agent in the electroplating solution formula has good leveling effect.
  • step (2) N,N',N"-trimethyldiethylenetriamine is used to replace N,N-bis(3-amino Propyl)methylamine.
  • a copper electroplating solution the formula of which is different from the copper electroplating solution in Embodiment 1 only in that the leveling agent is polyamide L6.
  • Example 2 Take the same Damascus graphics chip as in Example 1, and use the copper electroplating solution of Example 6 to electroplat and fill it with copper.
  • polyamide L6 as a leveling agent in the electroplating solution formula has good leveling effect.
  • the preparation method of polyamide D2 includes the following steps:
  • the hydrogen nuclear magnetic resonance spectrum results of the polyamide D2 are: 1 H NMR (400MHz, Chloroform-d) ⁇ (ppm): 3.09 (s, 2H), 2.43 (s, 2H), 2.32 (s, 2H), 2.11(s,3H),1.59(s,2H).
  • a copper electroplating solution the formula of which is different from the copper electroplating solution in Embodiment 1 only in that the leveling agent is polyamide D2.
  • the copper electroplating solution of Comparative Example 2 is used for electroplating copper filling.
  • the substrate to be electroplated has grooves or through-holes. Damascus graphics chip with copper seed layer, the electroplating process is the same as in Example 1.
  • FIG10 is a scanning electron microscope photo of the cross section of the chip sample after electroplating in Comparative Example 2.
  • the thickness of the copper plating layer above the high-density hole slot area and the low-density hole slot area is quite different, and the ratio of the average thickness of the copper layer in the high-density hole slot area to the low-density hole slot area is about 1.18, that is, the copper layer thickness in the high-density hole slot area is about 18% higher than that in the low-density hole slot area, while the copper layer thickness in the high-density hole slot area in Example 1 is only 1% higher than that in the low-density hole slot area.
  • the new leveling agent of the embodiment of the present application is added to the electroplating composition and used for electroplating copper filling, which can ensure that the metal copper in the micro-sodium sized trench is filled without pores, and the leveling agent inhibits the passage of Excessive deposition of copper will eventually achieve a better planarization effect, effectively reducing the plateau undulations of the coating surface, thereby obtaining samples with uniform copper thickness and good board appearance, reducing the difficulty of subsequent polishing processes and improving the reliability of the final product.

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Abstract

Les modes de réalisation de la présente invention concernent un agent de nivellement comprenant une substance polyamide. La substance polyamide comprend un motif répétitif représenté par la formule (I) ou un produit protoné ou N-quaternisé du motif répétitif représenté par la formule (I). Dans la formule (I), R est choisi parmi un atome d'hydrogène et un alkyle substitué ou non substitué, et A1 et A2 comprennent indépendamment un atome d'azote d'amine tertiaire situé sur le squelette du motif répétitif d'amide représenté par la formule (I). L'agent de nivellement est avantageux pour obtenir un remplissage à haute planéité sans défaut des trous et des fentes. Les modes de réalisation de la présente invention concernent en outre un procédé de préparation de l'agent de nivellement et son utilisation.
PCT/CN2023/120181 2022-09-23 2023-09-20 Agent de nivellement, composition d'électroplacage et leur utilisation WO2024061290A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3951789A (en) * 1973-10-11 1976-04-20 Allied Chemical Corporation Novel high diffusivity membranes
CN1553927A (zh) * 2001-08-10 2004-12-08 �����ɷ� 季铵化聚酰胺型胺、其制备、对应的组合物及其用途
CN103547631A (zh) * 2011-06-01 2014-01-29 巴斯夫欧洲公司 包含用于自下向上填充硅穿孔和互联件特征的添加剂的金属电镀用组合物

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3951789A (en) * 1973-10-11 1976-04-20 Allied Chemical Corporation Novel high diffusivity membranes
CN1553927A (zh) * 2001-08-10 2004-12-08 �����ɷ� 季铵化聚酰胺型胺、其制备、对应的组合物及其用途
CN103547631A (zh) * 2011-06-01 2014-01-29 巴斯夫欧洲公司 包含用于自下向上填充硅穿孔和互联件特征的添加剂的金属电镀用组合物

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