WO2002000965A1 - Agent anticorrosion - Google Patents

Agent anticorrosion Download PDF

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Publication number
WO2002000965A1
WO2002000965A1 PCT/JP2001/005504 JP0105504W WO0200965A1 WO 2002000965 A1 WO2002000965 A1 WO 2002000965A1 JP 0105504 W JP0105504 W JP 0105504W WO 0200965 A1 WO0200965 A1 WO 0200965A1
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WO
WIPO (PCT)
Prior art keywords
anticorrosion
copper
metal film
anticorrosive
film
Prior art date
Application number
PCT/JP2001/005504
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English (en)
Japanese (ja)
Inventor
Corporation Nec
Original Assignee
Koito, Tatsuya
Hirano, Keiji
Aoki, Hidemitsu
Tomimori, Hiroaki
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Application filed by Koito, Tatsuya, Hirano, Keiji, Aoki, Hidemitsu, Tomimori, Hiroaki filed Critical Koito, Tatsuya
Publication of WO2002000965A1 publication Critical patent/WO2002000965A1/fr

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Classifications

    • 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
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
    • H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
    • H01L21/321—After treatment
    • H01L21/32115—Planarisation
    • H01L21/3212—Planarisation by chemical mechanical polishing [CMP]
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
    • C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
    • C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
    • C23F11/14—Nitrogen-containing compounds
    • C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom

Definitions

  • the present invention relates to an anticorrosion agent for preventing corrosion of a metal film formed on a semiconductor wafer, and more particularly to an anticorrosion agent for preventing corrosion of corrosive metals such as copper formed on a semiconductor wafer. .
  • a metal film that has been patterned into a predetermined shape is formed on a semiconductor wafer, and wirings and connection plugs are formed.
  • anticorrosion technology for preventing corrosion of the metal film and preventing an increase in interconnect resistance is important.
  • copper has been widely used as a constituent material of wiring and connection plugs from the viewpoint of achieving high-speed operation of devices, and the demand for corrosion prevention of metal films has become more severe than ever. I have. This is because copper has excellent properties such as excellent electrification-migration resistance and low resistance, but easily oxidizes and etches, and is easily corroded.
  • An example of a process in which corrosion prevention of a metal film is important is a stripping process using a resist stripper.
  • a resist stripper When forming through-holes on metal wiring, it is necessary to form a hole by dry etching, and then remove and remove the resist residue and etching residue. Is an important issue. For this reason, it is widely practiced to add an anticorrosive to the resist stripping solution to prevent corrosion of metal wiring.
  • aromatic hydroxy compounds such as hydroxybenzoic acid, organic compounds containing a carboxyl group such as acetic acid, cunic acid, and succinic acid, and benzotriazole (BTA) have been used.
  • Japanese Unexamined Patent Publication No. Hei 8-333495) Japanese Unexamined Patent Publication No. Hei 8-333495.
  • the damascene method In the damascene method, first, a wiring groove is formed in the insulating film 3 (FIG. 3 (a)), and then a non-metal film 4 is formed on the entire surface. Next, after a copper film 5 is formed on the entire surface so as to fill the wiring groove (FIG.
  • Dating is a phenomenon in which the center of the surface of the copper film 5 is dented as shown in FIG. This is caused by the fact that the polishing rate of the copper film 5 is much higher than the polishing rate of the non-metal film 4.
  • various problems such as a decrease in the cross-sectional area of the wiring and a local increase in the resistance are caused.
  • Erosion is a phenomenon in which the CMP progresses excessively in the dense wiring area, and the surface of the dense wiring area is dented as shown in Fig. 3 (d).
  • the slit between the copper film and the barrier metal film refers to a slit as shown in FIG. 4 generated in the CMP by a kind of battery effect. The occurrence of such a slit increases the wiring resistance and causes a subsequent film formation failure.
  • the adhesion of copper polished by CMP to wafers, etc. means that copper ions generated during CMP accumulate on the polishing pad and re-adhere on the A-side, deteriorating the flatness of the A-side. Or cause an electrical short circuit. This problem is described in, for example, JP-A-10-116804.
  • CMP requires not only metal quality degradation due to corrosion but also metal corrosion protection for process reasons.
  • traditional CMP mainly W
  • BTA and its derivatives are difficult to be decomposed by living organisms, and there is a problem that it is difficult to treat wastewater containing them.
  • biological treatment Organic wastewater generated from semiconductor manufacturing plants is usually subjected to biological treatment (hereinafter referred to as “biological treatment”), decomposed, and released.
  • biological treatment for substances that cannot be treated by biological treatment, other It is desirable to treat by means or to replace with other biodegradable chemicals.
  • the above-mentioned BTA and its derivatives are extremely difficult to decompose by biological treatment. For the above reasons, factories that use chemicals containing BTAs not only pose environmental risks to the treatment of their waste liquids and wastewater, but also have to rely on treatment methods other than biodegradation treatment, which are costly and laborious. It was not possible to get it.
  • an aromatic hydroxy compound or an organic conjugate containing a ruboxyl group was sometimes used as an anticorrosive agent.
  • it is more biodegradable than BTAs.
  • BTAs are mainly for the purpose of preventing corrosion of wiring materials made of aluminum-copper alloy, they do not have sufficient anticorrosion action against easily corrosive metals such as copper, and are subject to severe conditions such as CMP. It was difficult to use it as an anticorrosive for use in steels.
  • Japanese Patent Application Laid-Open No. 9-291381 discloses a water-soluble antibacterial agent.
  • urea condensates isocyanuric acid, hydantoin, uric acid, triscarboxymethyl isocyanuric acid, and triscarboxyethyl isocyanuric acid are exemplified.
  • this technology is aimed at preventing metal buckling during metal processing such as cutting, polishing, and plastic processing, and in the storage of such metal.
  • Anti-corrosion is to prevent the progress of metal oxidation
  • anti-corrosion in the present invention is to prevent corrosion of the metal film formed on the semiconductor layer. Specifically, it is intended to prevent a metal such as copper from being dissolved by a resist stripping solution, various cleaning solutions, a CMP slurry, or the like, or from being altered by forming a complex or the like.
  • the treatment with the P-matrix agent is usually performed in the air to form a protective layer made of a protective agent on an oxide film present on the metal surface
  • the present invention provides "Corrosion protection” is to form a protective layer by applying an anticorrosive agent to a clean metal surface that has not been oxidized. Even if the surface of the metal is slightly oxidized (when the surface is slightly oxidized), the metal B-diameter formed on the semiconductor wafer has various problems such as increased resistance and poor adhesion to the film formed thereon. Problems arise.
  • the anticorrosive agent of the present invention forms a dense protective film on the surface of the metal film, substantially completely suppresses oxidation of the metal film, and dissolves the metal film in a resist stripping solution or various cleaning solutions. It is necessary to effectively prevent the formation of That is, “corrosion protection” in the present invention requires a higher level of metal film protection than protection. Furthermore, as will be described later, anticorrosives used for preventing corrosion of a metal film formed on a semiconductor wafer need to have various characteristics, unlike anticorrosives for general metal members. . As described above, in designing the anticorrosive agent of the present invention used in the manufacturing process of a semiconductor device, it is necessary to study from a viewpoint different from that of general metal. Disclosure of the invention
  • the present invention has been made in view of the above circumstances, has an excellent anticorrosion performance for effectively preventing corrosion of easily corrodable metals such as copper, has excellent product safety, and further has a decomposition treatment by living organisms. It is an object of the present invention to provide an anticorrosive agent that has good decomposability and that can be used.
  • an anticorrosion agent for preventing corrosion of a metal film formed on a semiconductor wafer, which contains a heterocyclic compound having a six-membered ring containing a nitrogen atom as an anticorrosion component.
  • An anticorrosive is provided.
  • an anticorrosion agent for preventing corrosion of a metal film formed on a semiconductor wafer, wherein
  • the present invention provides an anticorrosive comprising a heterocyclic compound having a 5- or 6-membered heterocyclic ring containing the following atomic group.
  • an anticorrosion agent for preventing corrosion of a metal film formed on a semiconductor element comprising purine or a derivative thereof as an anticorrosion component. Is provided.
  • an anticorrosion solution obtained by dissolving the anticorrosion agent in water or a water-soluble organic solvent.
  • an anticorrosion treatment solution for use in a semiconductor way, wherein the anticorrosion treatment solution is a corrosion-resistant treatment solution for a metal film formed thereon, the anticorrosion treatment solution comprising the anticorrosive agent.
  • a storage solution for storing a semiconductor wafer having a metal film formed on a surface thereof, wherein the storage solution contains the anticorrosive agent.
  • a metal film is formed on a semiconductor wafer, a part of the metal film is chemically and mechanically polished, and the surface of the semiconductor wafer is cleaned using a cleaning liquid.
  • the present invention provides an anticorrosion treatment method comprising performing an anticorrosion treatment on the metal film by using the method.
  • the present invention uses a heterocyclic compound having a specific structure as described above as an anticorrosive Since it is used, a dense protective layer is formed on the surface of the metal film, and the surface of the metal film can be kept moderately hydrophobic, and exhibits excellent anticorrosion performance. In addition to being excellent in safety, it is possible to decompose by living organisms and easily perform wastewater treatment.
  • the anticorrosive in the present invention is used for the purpose of preventing the corrosion of a metal film formed on a semiconductor wafer, it is necessary to have various properties unlike the anticorrosive for general metal members.
  • the post-corrosion treatment be not adversely affected.
  • an anticorrosive is left on the surface of a metal film and an insulating film or other metal film is formed thereon, the device performance may be adversely affected, such as an increase in resistance and film peeling. Therefore, select an anticorrosion agent that does not adversely affect the element performance even if it remains, or select an anticorrosion agent that desorbs from the metal film surface at the stage after the anticorrosion treatment and before moving to the next process It is desirable to do so.
  • the anticorrosive of the present invention has the above properties. That is, the anticorrosive contained in the release agent composition of the present invention exhibits strong release performance even in the presence of other chemical substances. It does not damage the substrate or other films. In addition, the anticorrosive attached to the metal film is quickly eliminated by preheating for film formation. Furthermore, it is excellent in safety and biodegradability. Therefore, the configuration is particularly suitable for preventing corrosion of the metal film formed on the semiconductor wafer.
  • FIG. 1 is a process sectional view for explaining a copper wiring forming process by a damascene method.
  • FIG. 2 is a schematic configuration diagram of a chemical mechanical polishing apparatus.
  • FIG. 4 is a diagram showing a cross section of a copper wiring in which dishing and slit have occurred.
  • FIG. 5 is a view for explaining a step after CMP.
  • FIG. 6 is a view for explaining a process after the CMP.
  • FIG. 7 is a diagram for explaining a process using the anticorrosive agent according to the present invention.
  • FIG. 8 is a diagram for explaining a process using the anticorrosive agent according to the present invention.
  • FIG. 9 is a process cross-sectional view for explaining the through-hole forming process.
  • FIG. 10 is a process cross-sectional view for explaining the through-hole forming process.
  • FIG. 11 is a graph showing the effect of uric acid concentration on the etching rate of a copper film.
  • FIG. 12 is a diagram showing a change in the electron migration lifetime due to the difference in the anticorrosion treatment.
  • the component (a) in the present invention may contain a heterocyclic compound having a six-membered ring containing a nitrogen atom in the molecule.
  • a heterocyclic compound exhibits a good anticorrosive action and a good biodegradability due to the chelating action of the nitrogen atom in the complex.
  • each atom of C, N, 0, and H is on the same plane
  • Lactam type Lactim type In the above formula, a conjugate system spreads over each of the N, C, and 0 atoms, and electrons are delocalized in this region. The electrons in this conjugated system are liable to interact with the free orbitals on the metal surface, and are considered to form stable chelate bonds.
  • the above-mentioned atomic group is contained in the cyclic portion of the 5- or 6-membered heterocyclic ring, the steric hindrance is low, and the above-mentioned atomic group is easily accessible to metal atoms. Conceivable.
  • heterocyclic compound having a 5- or 6-membered heterocyclic ring containing an amide unit or an iminohydrin unit in the molecule has a remarkable anticorrosive action for the above-mentioned reason.
  • the reason for the good biodegradability is presumed to be related to the high biocompatibility of the amide bond.
  • Azaguanine such as 8-azaguanine and derivatives thereof
  • Pteridine such as pteridine, pterin, 2-amino-4,6-dihydroxypteridine, 2-amino-1,4,7-dihydroxypteridine, 2-amino-4,6,7-trihydroxypteridine, and derivatives thereof;
  • Cyanuric acid isocyanuric acid, triscarboxymethylcyanuric acid, triscarboxycylcyanuric acid, triscarboxymethylisocyanuric acid, triscarboxyxyl isocyanuric acid, etc.
  • Conductor ;
  • Hydantoin allantoin and derivatives thereof, such as hydantoin, dimethylhydantoin, and allantoin (5-ureidohydantoin);
  • Nicotinic acid such as isonicotinic acid and citrazinic acid and derivatives thereof; and the like, and these can be used alone or in combination of two or more.
  • purine and its derivatives, and nicotinic acid and their derivatives are preferred and used. It is not only excellent in biodegradability, but also has an excellent anticorrosion effect on metals such as copper.
  • pudding and its derivatives exhibit an excellent anticorrosion effect, do not damage the semiconductor substrate and various films formed thereon, and do not adversely affect the processes after the peeling treatment. Therefore, it is preferably used.
  • the compound represented by the following general formula (1) particularly uric acid, is a highly safe substance that is widely distributed in nature, is particularly excellent in biodegradability, and is extremely excellent in anticorrosion. Used.
  • (,,. ⁇ 2 and ⁇ 3 are each independently a hydrogen atom, a hydroxyl group, a carbon atom. Represents a alkyl group or an amino group. )
  • At least one of A 2 and A 3 is a hydroxyl group (in this case, a structure having an amide bond in the heterocyclic ring is obtained, and the anticorrosive action and the biodegradability are particularly improved.
  • uric acid has the following resonance structure.
  • the anticorrosive of the present invention can be used by dispersing it in water or a water-soluble organic solvent described below. In this case, if the alkanolamines are further added, the solubility of the anticorrosive can be improved. If an alkanolamine having good biodegradability is selected, an anticorrosive solution having particularly excellent safety and biodegradability can be obtained.
  • alkanolamines include monoethanolamine, jetanolamine, N-ethylaminoethanol, N-methylaminoethanol, N-methylethylethanol, dimethylaminoethanol, 2- (2-aminoethoxyamine).
  • Ethanol, 1-amino-12-propanol, triethanolamine, monopropanolamine, dibutanolamine and the like are exemplified. Of these, monoethanolamine and N-methylaminoethanol are particularly preferred. These compounds may be used alone or in combination of two or more.
  • the mixing ratio of the anticorrosive component (hereinafter, referred to as component (a)) and the alkanolamines (hereinafter, referred to as component (b)) in the anticorrosive agent can be set arbitrarily.
  • the amount of the component (b) relative to 100% by mass of the component is preferably 0.1 to 1000% by mass, and more preferably 1 to 100% by mass. With such a mixing ratio, it is possible to exhibit higher anticorrosion performance.
  • a copper alloy containing copper as a main component is an alloy containing 90% by mass or more of copper, such as Mg, Sc, Zr, Hf, Nb, Ta, Cr, or Mo.
  • a copper alloy containing a different element improve the high-speed operability of the device with low resistance, but are liable to cause corrosion such as dissolution and alteration by a chemical solution, so that the application effects of the present invention are remarkable.
  • the anticorrosion solution according to the present invention is obtained by dissolving the anticorrosion agent in water and / or a water-soluble organic solvent.
  • water-soluble organic solvent examples include sulfoxides such as dimethyl sulfoxide; sulfones such as dimethyl sulfone, getyl sulfone, bis (2-hydroxyethyl) sulfone and tetramethylene sulfone; N, N-dimethylformamide; Amides such as N-methylformamide, N, N-dimethylacetamide, N-methylacetamide, N, N-getylacetamide; N-methyl-2-pyrrolidone, N-ethyl-12-pyrrolidone Lactams such as N-propyl-12-pyrrolidone, N-hydroxymethyl-12-pyrrolidone, N-hydroxyethyl-12-pyridone; 1,3-dimethyl-2-imidazolidinone; Imidazolidinones such as, 3-Jethyl-2-imidazolidinone and 1,3-diisopropyl-l2-imidazolidinone; r-
  • Alkanolamines may be added to the anticorrosive liquid according to the present invention.
  • the solubility of the anticorrosion component (component (a)) can be increased, and the anticorrosion effect is more remarkably exhibited.
  • the concentration of the components (a) and (b) in the anticorrosive solution according to the present invention is appropriately set according to the intended use and purpose. For example, the following is preferable. That is, the amount of the component (a) is W
  • the lower limit is preferably 0.0001% by mass, particularly preferably 0.01% by mass.
  • the upper limit is not particularly limited, but is, for example, about 20% by mass due to solubility.
  • the upper limit of the amount of component (b) is preferably 20% by mass / 0 , particularly preferably 10% by mass / 0 .
  • the lower limit is preferably 0.0001% by mass, and particularly preferably 0.001% by mass. With such a blending amount, the anticorrosion performance can be further improved.
  • the anticorrosive agent of the present invention is used for anticorrosion of metal films (particularly copper films) formed on semiconductor wafers.
  • anticorrosion treatment solutions used for CMP slurry or after CMP, and storage of wafers liquid, or, c present invention can be applied to the stripping solution of Regis Bok, etc., a metal film, particularly when applied to a semiconductor ⁇ E eighteen of CM P processes with an exposed surface of the copper film, more effective It is.
  • the metal corrosive slurry is used, so that the corrosion of the metal is apt to progress, (i) dishing erosion occurs, and (ii) the slit between the metal film and the barrier metal film.
  • the steel wiring forming process using CMP is performed through the steps shown in FIG.
  • a silicon oxide film 1, a silicon nitride film 2 and a silicon oxide film 3 are formed in this order on a silicon wafer (not shown), and then dry etching is performed.
  • a plurality of wiring grooves patterned into a predetermined shape are formed.
  • a barrier metal film 4 is deposited on the entire surface by a sputtering method.
  • the material of Roh 1 barrier metal film Ta, TaN, T i, Ding i N, W, WN, can be used WS i N, etc., the thickness is usually about 10 to 100 nm.
  • a copper film 5 is formed on the barrier metal film 4 (FIG. 1 (b)).
  • the copper film 5 can be formed by a plating method, a CVD method, a sputtering method, or the like.
  • the surface of the copper film 5 is polished by the CMP method.
  • CMP usually uses a slurry consisting mainly of an oxidizing agent and abrasive grains, and etches the copper surface by the chemical action of the oxidizing agent.
  • the surface of the oxide film is mechanically removed by abrasive grains.
  • a single slurry for CMP may be used, but two or more slurries may be used from the viewpoint of preventing dicing and erosion. Two types of slurries for polishing can be used.
  • the anticorrosive agent of the present invention When applied to a slurry for CMP, it may be used in any stage of the slurry.However, as shown in Fig. It is effective. This is because the effect of preventing corrosion of the copper film 5 constituting the wiring portion and the effect of suppressing dating / erosion are further remarkable.
  • CMP ends when the barrier metal film 4 is removed and the torque changes (FIG. 1 (d)). Thereafter, post-cleaning is performed as necessary, and then rinsing is performed with a rinsing liquid containing pure water as a main component. Then, the copper wiring forming process is completed.
  • CMP can be performed using, for example, a chemical mechanical polishing apparatus as shown in FIG.
  • the wafer 21 on which an insulating film, a copper-based metal film, or the like is formed is placed on a wafer carrier 22 of a spindle.
  • the surface of the wafer 21 is brought into contact with a polishing pad 24 stuck on a rotating plate (platen) 23, and the slurry for CMP is supplied to the surface of the polishing pad 24 from a slurry supply port 25 for CMP.
  • the pad conditioner 26 is brought into contact with the surface of the polishing pad 24 to condition the polishing pad surface.
  • the slurry for CMP may be supplied from the rotating plate 23 to the surface of the polishing pad 24.
  • the present invention can be applied in post-processing after CMP.
  • Figure 5 shows an example of post-processing after CMP.
  • CMP once store the wafer in the storage solution, perform post-CMP cleaning to remove abrasive particles and the like. Then, if necessary, add an anticorrosive Perform anti-corrosion treatment, and finally rinse with a rinsing liquid containing pure water as a main component.
  • the anticorrosive agent according to the present invention is added to the above-mentioned storage solution, anticorrosion treatment solution, and rinsing solution, there is no risk of waste liquid treatment, and there is a risk of working on the safety of chemical substances. Therefore, it is possible to suitably prevent corrosion of the copper film formed on the substrate.
  • the slurry for chemical mechanical polishing of the present invention contains the anticorrosive agent according to the present invention described above.
  • the content of the anticorrosive is preferably 0.01% by mass or more, more preferably 0.1% by mass or more based on the total amount of the slurry, from the viewpoint of obtaining a sufficient anticorrosive effect. From the viewpoint of adjusting the polishing rate to an appropriate value, the content is preferably 30% by mass or less, more preferably 20% by mass or less. If the content is too large, the anticorrosion effect becomes too large, and the polishing rate of copper is too low, so that it may take time for CMP.
  • the slurry for chemical mechanical polishing of the present invention preferably contains a polishing material, an oxidizing agent, and water in addition to the above anticorrosive agent, and may further contain an organic acid or the like as appropriate. .
  • abrasives examples include alumina such as mono-alumina, 0-alumina, and 5-alumina, silica such as fumed silica and colloidal silica, titania, zirconia, germania, ceria, and abrasive grains of these metal oxides.
  • alumina such as mono-alumina, 0-alumina, and 5-alumina
  • silica such as fumed silica and colloidal silica
  • titania, zirconia, germania, ceria examples of abrasives.
  • abrasives include alumina such as mono-alumina, 0-alumina, and 5-alumina, silica such as fumed silica and colloidal silica, titania, zirconia, germania, ceria, and abrasive grains of these metal oxides.
  • abrasives include alumina such as mono-alumina, 0-alumina, and 5-alumina, silica such as fumed silica and coll
  • the content of the abrasive in the CMP slurry is appropriately set in consideration of the polishing efficiency, the polishing accuracy, and the like, and is preferably 0.1 to 50% by mass, and more preferably ⁇ 2%, based on the total amount of the slurry composition. To 30% by mass.
  • the oxidizing agent can be appropriately selected from known water-soluble oxidizing agents in consideration of the type of the conductive metal film, polishing accuracy, and polishing efficiency.
  • hydrogen peroxide H 2 ⁇ 2
  • do not cause heavy metal ion contamination H 2 ⁇ 2
  • hypochlorous acid HC 10
  • perchloric acid examples include nitric acid, ozone water, and organic peroxides such as peracetic acid and nitrobenzene. Among them, it does not contain a metal component, not generate a harmful byproduct H 2 0 2 is preferred arbitrariness.
  • the amount of the oxidizing agent is preferably at least 0.01% by mass, more preferably at least 0.05% by mass, based on the total amount of the CMP slurry, from the viewpoint of obtaining a sufficient effect of addition. From the viewpoint of suppressing dating and adjusting the polishing rate to an appropriate level, the amount is preferably 15% by mass or less, more preferably 10% by mass or less.
  • a solution containing an oxidizing agent having a predetermined concentration and a solution containing an abrasive are separately adjusted, and immediately before use. May be mixed.
  • the organic acid is added to promote the oxidation of the oxidizing agent and perform stable polishing.
  • the organic acid one having a function as a proton donor is used, and diamino carboxylic acid is preferably used.
  • carboxylic acids include citric acid, formic acid, acetic acid, propyl acetic acid, butyric acid, valeric acid, acrylic acid, lactic acid, succinic acid, nicotinic acid, oxalic acid, malonic acid, tartaric acid, malic acid, Examples include glutaric acid, cunic acid, maleic acid, and salts thereof. '
  • amino acids include, for example, L-glucamic acid, D-glucamic acid, L-glucamic acid monohydrochloride, L-glucamic acid sodium monohydrate, L-glutamine, glutathione, glycylglycine, DL-alanine, L-alanine, -alanine, D-alanine, ⁇ -peranine, 7 "-aminobutyric acid, etc.-aminocaproic acid, L-arginine monohydrochloride Salt, L-aspartic acid, L-aspartic acid monohydrate, L-aspartic acid potassium, L-aspartate calcium trihydrate, D-aspartic acid, L-titrulline, L-tryptophan, L-threonine, L-arginine, glycine, L-cystine, L-cystine, L-cystine hydrochloride [7] hydrate, L-proximal xyproline, shi-isol
  • the content of the organic acid is preferably at least 0.01% by mass, more preferably at least 0.05% by mass, based on the total amount of the slurry for CMP, from the viewpoint of obtaining a sufficient effect of addition as a proton donor.
  • the content is preferably 5% by mass or less, more preferably 3% by mass or less.
  • the CMP slurry of the present invention may contain various additives such as a dispersant, a buffer, a viscosity modifier and the like, which are widely and generally added to the CMP slurry, as long as the properties are not impaired. .
  • the slurry for CMP according to the present invention can be produced by using a general method for producing a free abrasive polishing slurry composition. That is, an appropriate amount of abrasive particles is mixed with the dispersion medium. If necessary, mix the appropriate amount of protective agent. In this state, air is strongly adsorbed on the surface of the abrasive particles, so that the abrasive particles have poor wettability and exist in an aggregated state. Therefore, in order to make the aggregated abrasive particles into primary particles, the particles are dispersed.
  • a general dispersing method and dispersing apparatus can be used. Specifically, it can be carried out by a known method using, for example, an ultrasonic disperser, various types of bead mill dispersers, kneaders, ball mills and the like.
  • the storage solution of the present invention is preferably an aqueous solution in which the anticorrosive agent of the present invention is dissolved in water.
  • the lower limit of the concentration of the anticorrosive agent relative to the whole storage solution is preferably ⁇ 0.01% by mass, more preferably 0.01% by mass or more. If the concentration of the anticorrosive is too low, a sufficient anticorrosive effect may not be obtained. Although there is no particular upper limit on the concentration of the anticorrosive agent, a sufficient anticorrosive effect can be obtained, for example, at 20% by mass or less. However, in some cases, the anticorrosive agent of the present invention does not have sufficient anticorrosive properties simply by adding it to water.c Therefore, by adding alkanolamine and adjusting the pH to alkaline. Therefore, it is necessary to increase the solubility of purines and purine derivatives, and adjust the concentration to obtain sufficient anticorrosion performance.
  • the storage solution according to the present invention can be used not only for storage after CMP but also for various processes.
  • the anticorrosion treatment liquid of the present invention is preferably an aqueous solution in which the anticorrosive agent of the present invention is dissolved in water, like the above-mentioned storage solution. Other additives, water-soluble organic solvents, and the like may be appropriately added to this aqueous solution.
  • the lower limit of the concentration of the anticorrosive in the whole storage solution is preferably 0.001% by mass, more preferably 0.01% by mass or more.
  • Anticorrosive concentration If it is too low, a sufficient anticorrosion effect may not be obtained. Although there is no particular upper limit on the concentration of the anticorrosive, a sufficient anticorrosive effect can be obtained, for example, at 20 mass% or less.
  • the anticorrosion treatment solution of the present invention can be applied to the anticorrosion treatment step shown in FIG. 5 or to a pure water rinsing step.
  • the anticorrosion treatment liquid preferably has a configuration in which the anticorrosion agent of the present invention is dissolved in pure water in the above concentration range.
  • the anticorrosion treatment solution of the present invention can be used not only in the anticorrosion treatment after CMP but also in various steps.
  • the above-mentioned slurry for chemical mechanical polishing, anticorrosion treatment solution, and storage solution are used for treating semiconductors A having a metal film-exposed surface, and the metal film contains a copper film or copper as a main component.
  • the effect of the present invention is more remarkably exhibited when the copper alloy film is
  • the storage solution and anticorrosion solution of the present invention may optionally contain additives, organic solvents and the like.
  • additives organic solvents and the like.
  • an acid or base for adjusting the pH may be added to improve the solubility of the anticorrosive, and a water-soluble organic compound miscible with water or other compounding components may be added to further improve the anticorrosion performance.
  • Solvents can be used.
  • the anticorrosive according to the present invention can also be applied to a stripping solution such as a resist.
  • a stripping solution such as a resist.
  • alkanoamine examples include monoethanolamine, jetano-lamine, N-ethylaminoethanol, N-methylaminoethanol, N-methylgenolamine, dimethylaminoethanol, and 2- (2-aminoethylamine.
  • Toxi Ethanol, 1-amino-2-propanol, triethanolamine, monopropanolamine, dibutanolamine and the like are exemplified. Of these, monoethanolamine and N-methylaminoethanol are particularly preferred.
  • hydrofluoric acid salt can be used as the release component. Specifically, fluoride ammonium or the like is preferably used. When hydrofluoric acid is used, deposits and the like adhering to the resist side wall can be removed.
  • the upper limit of the release component in the release solution is preferably 95% by mass, and particularly preferably 85% by mass.
  • the lower limit is preferably 1% by mass, and particularly preferably 10% by mass.
  • the upper limit of the proportion of water in the stripping solution is preferably 90% by mass, particularly 80% by mass. / 0 is preferred.
  • the lower limit is preferably 1% by mass, and particularly preferably 5% by mass.
  • the stripping solution using the anticorrosive of the present invention may contain a water-soluble organic solvent.
  • a water-soluble organic solvent the same ones as described above can be used.
  • the upper limit of the amount of the water-soluble raw organic solvent is preferably 80% by mass, particularly preferably 70% by mass.
  • the lower limit is preferably 5% by mass, particularly preferably 10% by mass.
  • the above-mentioned stripping liquid is used to turn an unnecessary object on the semiconductor substrate into an object to be stripped.
  • the unnecessary substances on the semiconductor substrate refer to various unnecessary substances generated during a semiconductor device manufacturing process, and include a resist film, an etching residue after dry etching, and a chemically modified resist film. In particular, it is more effective when the object to be peeled is a resist film and / or an etching residue on the semiconductor substrate including the metal film exposed surface. Further, when the metal film is a copper film, the anticorrosive action of the anticorrosive agent of the present invention is more effectively exhibited.o
  • the above-mentioned stripping solution can be used for stripping various resists, and should be applied to KrF resists made of aromatic compounds and ArF resists such as alicyclic acryl polymers.
  • a positive resist containing a naphthoquinonediazide compound and a novolak resin (ii) a compound that generates an acid upon exposure, a compound that is decomposed by an acid to increase the solubility in an aqueous solution of an aqueous solution, and (Iiii) a compound capable of generating an acid upon exposure, and a positive resist containing a soluble resin having a group which is decomposed by the acid and increases the solubility in an aqueous solution of an aqueous solution.
  • an interlayer connection plug on a copper wiring is formed by a process.
  • a silicon oxide film 1, a silicon nitride film 2, and a silicon oxide film 3 are formed on a semiconductor substrate (not shown) on which elements such as transistors are formed.
  • a copper interconnect composed of a barrier metal film 4 and a copper film 5 is formed by a known damascene process using chemical polishing (CMP), and a silicon nitride film 6 having a thickness of about 50 to 100 nm is formed thereon.
  • CMP chemical polishing
  • an interlayer insulating film (silicon oxide film or low dielectric constant film) 7 having a thickness of about 600 to 1 OOO nm is formed.
  • the thickness of the copper film 5 is arbitrarily selected, but is preferably, for example, 350 nm or less from the viewpoint of reducing the parasitic capacitance between adjacent wirings.
  • the thickness of the copper wiring is reduced, the thickness of the corroded layer relative to the entire copper wiring layer becomes relatively large, and an increase in wiring resistance due to corrosion of the copper surface becomes a particular problem.
  • the use of the stripping solution can reduce the film thickness while solving such a problem.
  • the thickness of the silicon nitride film 6 is set to about 50 to 100 nm, but it may be made thicker to enhance the function as an etching stopper film.
  • a resist film 8 patterned into a predetermined shape is provided on the interlayer insulating film 7 (FIG. 9 (b)).
  • the interlayer insulating film 7 is dry-etched using the resist film 8 as a mask until the silicon nitride film 6 is exposed, thereby forming a through hole 10 (FIG. 9 (c)).
  • the etching residue 11 adheres to the inner wall of the through hole 10.
  • the opening diameter of the through hole is, for example, about 0.2 m.
  • As an etching gas it is preferable to use a gas that can etch an interlayer insulating film faster than a silicon nitride film.
  • the silicon nitride film 6 also has a function of preventing diffusion of copper and a function as an etching stop film. However, as shown in FIG.
  • the silicon nitride film 6 is controlled on the silicon nitride film 6.
  • dry etching cannot be stopped well. This is for the following reasons.
  • various through holes are generally formed on the semiconductor wafer.
  • etching proceeds slowly in a hole with a small opening diameter due to the micro-loading effect. For this reason, it is necessary to provide a certain amount of etching time for the etching for forming the through-hole, and as a result, the silicon nitride film 6 is etched in some of the through-holes and the copper film 5 The part will be exposed.
  • the silicon nitride film 6 is formed thick in the step shown in FIG. 9 (a), it is possible to prevent the copper film 5 from being exposed.However, in this case, the capacitance between adjacent copper wirings increases, and the semiconductor element The disadvantage is that the high-speed operation is hindered.
  • FIG. 10 (a) shows a state in which the resist film and the etching residue 11 can be effectively removed without damaging the copper film 5 by using the liquid.
  • the etching of the silicon nitride film 6 is performed by changing the above-mentioned etching and etching gas.
  • the etching residue 12 adheres to the inner wall of the through hole 10 (FIG. 10 (b)).
  • a stripping treatment is performed again using the stripping solution described above.
  • the copper film 5 is exposed at the bottom of the through hole 10.
  • the stripping solution containing the anticorrosive agent of the present invention the copper film 5 is etched without damaging the copper film 5.
  • the residue 12 can be removed (Fig. 10 (c)).
  • the amount of each component is based on the total amount of the anticorrosive solution and the stripping solution unless otherwise specified.
  • FIG. 7 The state corresponding to this step is shown in FIGS. 8 (a) and 8 (b).
  • a silicon nitride film 80 and a silicon oxide film 82 were formed in this order on a silicon wafer, and then patterned into a predetermined shape by dry etching. A plurality of wiring grooves were formed.
  • a barrier metal film 84 of TaN was deposited on the entire surface by a sputtering method, a seed Cu 85 and a plating Cu 86 were formed. Subsequently, the wafer surface was polished by the CMP method to form a copper wiring as shown in FIG. 8 (b).
  • the scrub cleaning step 72 was performed c, that is, the brush was moved while applying a cleaning liquid composed of electrolytic ionized water to the rotating brush to remove particle contamination.
  • a spin cleaning step 74 was performed. In this process, an aqueous solution of oxalic acid was sprayed as a cleaning solution while rotating the semiconductor wafer to remove metal contamination, that is, copper oxide on the surface, and rinsed with pure water.
  • an anticorrosion treatment step 75 was performed. This step is performed continuously after the spin cleaning step 74 so that the wafer surface does not come into contact with air. That is, the anticorrosion treatment is performed by spraying the anticorrosion treatment liquid without drying the surface of the wafer. As a result, oxidation of the metal film (copper film) on the wafer surface can be prevented, and an anticorrosive can be attached to a clean metal surface that has not been oxidized.
  • the anticorrosion treatment was performed by spraying the treatment liquid onto the surface of the phenol while rotating the phenol at a predetermined number of rotations, similarly to the spin cleaning.
  • anticorrosive treating solution used c using an anticorrosive treatment liquid containing an anticorrosive agent of the present invention in anticorrosion treatment step 7 5 has the following composition.
  • the anticorrosion solution was sprayed on the wafer surface at a flow rate of 1 liter / min for 10 seconds while rotating the semiconductor wafer to prevent corrosion of the Cu film.
  • a spin rinse-drying step 76 the substrate was rinsed with pure water for 15 seconds, and then dried.
  • a film forming step 78 FIG. 7
  • a silicon nitride film 88 was formed as shown in FIG. 8C, and a silicon oxide film 89 was formed thereon.
  • an upper layer wiring was formed to complete the semiconductor device.
  • the obtained semiconductor device showed the designed performance.
  • the adhesion at the Cu / silicon nitride film interface was evaluated to evaluate the degree of deterioration of the Cu surface.
  • the evaluation was performed by laying out lines in a grid pattern at a pitch of 1 mm on the silicon nitride film, then attaching an adhesive tape on the silicon nitride film, peeling it off, and peeling it out of the 100 grids. This was done by counting the number of grids. Excessive peeling ⁇ If the interface adhesion is poor, the Cu surface It is considered that the corrosion is progressing. Table 2 shows the evaluation results.
  • the copper wiring was formed by forming a copper film by plating and then performing CMP. Next, steps from scrub cleaning 72 to interlayer film formation 79 were performed according to the procedure shown in FIG. Except for the composition of the anticorrosion treatment solution, the same procedure was performed as in Example 1. Next, holes were formed in the Si 3 N 4 film and interlayer film, a plug metal was buried inside, and a pad was formed to connect to this plug.Conducting portions were formed at both ends of the wiring. .
  • the biodegradability of the test substances shown in Table 3 was evaluated by a biodegradability test method based on the MITI method. Activated sludge was inoculated with the test substance in an inorganic medium so that the concentration of the test substance became 1 OOmgZl.], Cultured at 25 ° C, and the oxygen consumption was measured using a closed system oxygen consumption measuring device. In addition, the residual amount of the test substance was measured, the decomposition rate was determined from the oxygen consumption, and the biodegradability was determined according to the following evaluation criteria.
  • ⁇ ... Decomposition rate is 40% or more and less than 60%
  • ⁇ ⁇ -'Decomposition rate is 10% or more and less than 40%
  • Table 4 shows the evaluation results.
  • the release agent composition according to the present invention was applied to a process of forming a through hole on a copper wiring, and the releasability and corrosion resistance were evaluated.
  • the samples to be evaluated were prepared according to the same processes as those shown in Figs. 9 to 10 (c).
  • As the resist film material PEX4 (manufactured by Tokyo Ohka Kogyo Co., Ltd.), which is a positive resist material for KrF, was used.
  • the resist film was exposed through a mask pattern, and developed using an aqueous solution of tetramethylammonium hydroxide to obtain a resist pattern.
  • the interlayer insulating film was dry-etched until the silicon nitride film was exposed to form a through hole having an opening diameter of 0.2 ⁇ m.
  • an etching gas a full-year carbon-based gas was used. After the etching was completed, a part of the resist film was removed by oxygen plasma ashes, and then a release treatment was performed using a release agent composition shown in Table 5.1 of NO.
  • the etching gas was changed and the silicon nitride film was etched to expose the copper wiring at the bottom of the through hole.
  • the etching residue generated by this etching is For removal, the same release agent composition (N 0.1 in Table 5) as used in the above-described release treatment was used, and the release treatment was performed again.
  • the state of corrosion of the copper film surface was observed and evaluated according to the following four levels.
  • the state of the surface of the HSQ film when HSQ (hydrogensilsesquioxane) was used as the low dielectric constant film was observed, and evaluated according to the following four grades.
  • MSQ methyl silsesquioxane
  • the release agent composition of the present invention has excellent release performance and anticorrosion performance.
  • the present invention is applied to a single damascene process. W
  • the present invention can be applied to a so-called dual damascene process.
  • a silicon wafer having a copper film formed on the entire surface of the substrate was immersed in a predetermined stripper at 80 for 10 minutes.
  • the copper etching rate was measured from the thickness of the copper film before and after immersion.
  • the stripping solution used was of the following composition. In order to eliminate the effect of pH fluctuation due to the difference in the amount of uric acid added, 2N — Aqueous ammonia was added to control the pH to 11.
  • NMAE N-methylaminoethanol
  • the present embodiment is an example in which the release agent composition according to the present invention is applied to a process of forming a through hole on a copper wiring.
  • a peeling component ammonium fluoride having a strong peeling action was used. The process was almost the same as that in Example 5, but the thickness of the nitride film and the type of etching gas were slightly different, and the c evaluation results in which the deposit to be stripped was different from Example 5 are shown in the following table. The evaluation criteria for peelability and anticorrosion were the same as in Example 5. It was confirmed that those using uric acid exhibited the same peeling properties and anticorrosion properties as BTA derivatives. Table 6
  • the anticorrosive agent of the present invention contains specific components, so that corrosion of easily corrosive metals such as copper can be effectively prevented, and since it is highly safe, it is easy to handle. Since biological treatment is possible, wastewater treatment is also easy. Therefore, it can be suitably used for a manufacturing process of a semiconductor device provided with copper wiring.

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Abstract

L'invention concerne un agent anticorrosion permettant de protéger une couche métallique formée sur une tranche de semiconducteur contre la corrosion. Cet agent est caractérisé en ce qu'il comprend un composé hétérocyclique qui comporte un noyau à six chaînons contenant un atome d'azote.
PCT/JP2001/005504 2000-06-28 2001-06-27 Agent anticorrosion WO2002000965A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102150263A (zh) * 2008-11-06 2011-08-10 松下电器产业株式会社 引线、布线部件、封装部件、带有树脂的金属部件和树脂封装半导体装置以及它们的制造方法
US10190222B2 (en) 2015-05-28 2019-01-29 Ecolab Usa Inc. Corrosion inhibitors
US10202694B2 (en) 2015-05-28 2019-02-12 Ecolab Usa Inc. 2-substituted imidazole and benzimidazole corrosion inhibitors
US10519116B2 (en) 2015-05-28 2019-12-31 Ecolab Usa Inc. Water-soluble pyrazole derivatives as corrosion inhibitors
US10669637B2 (en) 2015-05-28 2020-06-02 Ecolab Usa Inc. Purine-based corrosion inhibitors

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Publication number Priority date Publication date Assignee Title
JPS57149474A (en) * 1981-03-11 1982-09-16 Chiyoda Kagaku Kenkyusho:Kk Corrosion inhibitor for cuppric metal
WO1996020295A1 (fr) * 1994-12-23 1996-07-04 Cookson Group Plc Procede de protection du cuivre ou d'alliages de cuivre contre la corrosion
JP2000008185A (ja) * 1998-06-22 2000-01-11 Mec Kk 銅および銅合金の防錆剤
JP2000183003A (ja) * 1998-10-07 2000-06-30 Toshiba Corp 銅系金属用研磨組成物および半導体装置の製造方法
JP2001055559A (ja) * 1999-08-18 2001-02-27 Jsr Corp 化学機械研磨用水系分散体

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS57149474A (en) * 1981-03-11 1982-09-16 Chiyoda Kagaku Kenkyusho:Kk Corrosion inhibitor for cuppric metal
WO1996020295A1 (fr) * 1994-12-23 1996-07-04 Cookson Group Plc Procede de protection du cuivre ou d'alliages de cuivre contre la corrosion
JP2000008185A (ja) * 1998-06-22 2000-01-11 Mec Kk 銅および銅合金の防錆剤
JP2000183003A (ja) * 1998-10-07 2000-06-30 Toshiba Corp 銅系金属用研磨組成物および半導体装置の製造方法
JP2001055559A (ja) * 1999-08-18 2001-02-27 Jsr Corp 化学機械研磨用水系分散体

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102150263A (zh) * 2008-11-06 2011-08-10 松下电器产业株式会社 引线、布线部件、封装部件、带有树脂的金属部件和树脂封装半导体装置以及它们的制造方法
US8723298B2 (en) 2008-11-06 2014-05-13 Panasonic Corporation Lead, wiring member, package component, metal component with resin, resin-encapsulated semiconductor device, and methods for producing the same
US10190222B2 (en) 2015-05-28 2019-01-29 Ecolab Usa Inc. Corrosion inhibitors
US10202694B2 (en) 2015-05-28 2019-02-12 Ecolab Usa Inc. 2-substituted imidazole and benzimidazole corrosion inhibitors
US10519116B2 (en) 2015-05-28 2019-12-31 Ecolab Usa Inc. Water-soluble pyrazole derivatives as corrosion inhibitors
US10669637B2 (en) 2015-05-28 2020-06-02 Ecolab Usa Inc. Purine-based corrosion inhibitors
US11306400B2 (en) 2015-05-28 2022-04-19 Ecolab Usa Inc. 2-substituted imidazole and benzimidazole corrosion inhibitors

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