WO2022124246A1 - リセスエッチング液、リセスエッチング方法および表面処理された半導体基板の製造方法 - Google Patents
リセスエッチング液、リセスエッチング方法および表面処理された半導体基板の製造方法 Download PDFInfo
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- WO2022124246A1 WO2022124246A1 PCT/JP2021/044614 JP2021044614W WO2022124246A1 WO 2022124246 A1 WO2022124246 A1 WO 2022124246A1 JP 2021044614 W JP2021044614 W JP 2021044614W WO 2022124246 A1 WO2022124246 A1 WO 2022124246A1
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- WO
- WIPO (PCT)
- Prior art keywords
- recess etching
- acid
- cobalt
- etching solution
- metal layer
- Prior art date
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- 238000005530 etching Methods 0.000 title claims abstract description 209
- 239000004065 semiconductor Substances 0.000 title claims abstract description 62
- 239000000758 substrate Substances 0.000 title claims abstract description 54
- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 123
- 239000002184 metal Substances 0.000 claims abstract description 123
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 121
- 239000010941 cobalt Substances 0.000 claims abstract description 121
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 121
- -1 nitrogen-containing heterocyclic compound Chemical class 0.000 claims abstract description 20
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Images
Classifications
-
- 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
- C23F1/00—Etching metallic material by chemical means
- C23F1/10—Etching compositions
- C23F1/14—Aqueous compositions
- C23F1/16—Acidic compositions
- C23F1/28—Acidic compositions for etching iron group metals
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K13/00—Etching, surface-brightening or pickling compositions
-
- 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
- C23F1/00—Etching metallic material by chemical means
- C23F1/02—Local etching
-
- 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
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76877—Filling of holes, grooves or trenches, e.g. vias, with conductive material
- H01L21/76883—Post-treatment or after-treatment of the conductive material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76886—Modifying permanently or temporarily the pattern or the conductivity of conductive members, e.g. formation of alloys, reduction of contact resistances
Definitions
- the present invention relates to a recess etching solution, a recess etching method, a method for manufacturing a surface-treated semiconductor substrate, and a method for manufacturing a semiconductor element.
- Non-Patent Document 1 as an example of recess etching using a chemical solution, a method of treating a cobalt metal layer with a mixture containing hydrogen peroxide and either hydrofluoric acid or acetic acid in one step and peroxidation are performed. As a result of comparing the methods of repeatedly performing the oxidation treatment with hydrogen and the etching treatment with acetic acid, it is disclosed that the latter is more suitable in that the recess etching amount can be easily controlled. Patent Document 1 also describes a method of repeatedly performing an oxidation treatment of a metal layer on a substrate surface with an oxidizing fluid and an etching treatment of the metal oxide layer with an etching solution.
- Patent Document 1 and Non-Patent Document 1 has a problem that, for example, recess etching takes a long time or the process is complicated. Further, in order to obtain highly reliable wiring in which electromigration is unlikely to occur, the smoothness of the etching surface when performing recess etching on the via or the metal embedded in the trench, which is the conductor layer, is important. .. Under such circumstances, it is desirable to be able to provide a recess etching solution for uniformly performing recess etching on metal wiring in a shorter time and a recess etching method using the same.
- the present invention relates to a recess etching solution, a recess etching method, a semiconductor substrate manufacturing method, and a semiconductor element manufacturing method shown below.
- the recess etching solution containing (A) an organic acid, (B) a nitrogen-containing heterocyclic compound and / or both of (C) an organic solvent, and (D) water.
- the recess etching solution according to the above [1] which comprises (A) an organic acid, (B) a nitrogen-containing heterocyclic compound, (C) an organic solvent, and (D) water.
- Triazole 4-amino-1,2,4-triazole, 3-mercapto-4-methyl-4H-1,2,4-triazole, 1H-benzotriazole, 1H-benzotriazole-1-methanol, 4-methyl- 1H-benzotriazole, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 5-methyl-1H-benzotriazole, 3-chloro-1H-benzotriazole, 5-chloro-1H-benzotriazole, 1,2 , 4-Triazole-3-carboxylate methyl, 2- (5-chloro-2-benzotriazolyl) -6-tertbutyl-p-cresol, and 3-amino-1H-triazole selected from the group 1
- the recess etching solution according to any one of the above [1] to [6], which is more than a seed.
- component (C) is at least one selected from the group consisting of organic solvents having an HLB (Hydrophile-Lipophile Balance) value of 3 to 15. Recess etching solution described in. [9]
- the component (C) is 1-propanol, 2-propanol, 1-butanol, 2-butanol, 2-methyl-1-propanol, 2-methyl-2-propanol, cyclohexanol, ethylene glycol, propylene glycol.
- the cobalt-containing metal layer embedded in the via or trench formed in the semiconductor substrate is brought into contact with the recess etching solution according to any one of [1] to [11] to bring the cobalt into contact with the surface of the cobalt-containing metal layer.
- a recess etching method comprising a recess etching step of performing recess etching on the surface of a contained metal layer.
- the cobalt-containing metal layer embedded in the via or trench formed in the semiconductor substrate is brought into contact with the recess etching solution according to any one of the above [1] to [11] to bring the cobalt into contact with the surface of the cobalt-containing metal layer.
- a method for manufacturing a surface-treated semiconductor substrate which comprises a recess etching step of applying recess etching to the surface of the contained metal layer.
- the cobalt-containing metal layer embedded in a via or a trench formed in a semiconductor substrate is brought into contact with the recess etching solution according to any one of the above [1] to [11] to bring the cobalt into contact with the surface of the cobalt-containing metal layer.
- a recess etching process that performs recess etching on the surface of the contained metal layer A step of obtaining a semiconductor substrate in which a wiring circuit is constructed by stacking a metal wiring layer on the surface of a cobalt-containing metal layer in the surface-treated semiconductor substrate obtained in the above step.
- a method for manufacturing a semiconductor device which comprises a step of obtaining a semiconductor device by cutting a semiconductor substrate on which a wiring circuit obtained in the above step is constructed into a predetermined shape.
- recess etching can be performed on the metal wiring including the cobalt-containing metal layer more efficiently in a shorter time.
- the recess etching amount can be controlled, and a more uniform recess etching surface having excellent smoothness can be formed.
- the recess etching solution according to the present invention is a recess etching solution for performing recess etching on the surface of a cobalt-containing metal layer embedded in a via or a trench formed in a semiconductor substrate. It is characterized by containing (A) an organic acid, (B) a nitrogen-containing heterocyclic compound and / or both of (C) an organic solvent, and (D) water.
- the recess etching solution according to the present invention performs recess etching on the surface of a cobalt-containing metal layer embedded in a via or a trench formed in a semiconductor substrate in one step without performing an oxidation treatment and an etching treatment in separate steps.
- component (A) an organic acid is referred to as “component (A)
- component (B) a nitrogen-containing heterocyclic compound is referred to as “component (B)”
- component (C) an organic solvent is referred to as “component (C)”.
- component (D) water may be referred to as” component (D) ".
- the recess etching solution according to the present invention is used to perform recess etching on the surface of a cobalt-containing metal layer embedded in a via or a trench formed on a semiconductor substrate.
- the cobalt-containing metal layer to be recess-etched is a cobalt-containing metal layer.
- the cobalt content is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 90% by mass or more, particularly preferably 95% by mass or more, and may be 99% by mass or more.
- the cobalt-containing metal layer may contain a component other than cobalt, and may contain, for example, another metal component as long as it is in the range of less than 50% by mass.
- cobalt has crystal regions having various crystal orientations and grain sizes, and that there are amorphous regions and gaps in the crystal grain boundaries. Due to this, the cobalt-containing metal layer embedded in the vias or trenches formed in the semiconductor substrate is caused by corrosion due to the oxidation (aging) of cobalt over time and the corrosion potential difference between crystal orientations. It is presumed that there are two types of partial corrosion, galvanic corrosion (Co ⁇ Co 2+ + 2e- ). Cobalt in the amorphous region and near the gap is easily oxidized by aging, and the oxidized cobalt is rapidly etched by the acid-based chemical solution.
- any one of the component (B) and the component (C) is added to the component (A) having an etching action.
- recess etching is performed on the surface of the cobalt-containing metal layer embedded in the via or trench formed in the semiconductor substrate in one step while suppressing the partial corrosion of cobalt with one liquid. I found that I could do it.
- an etched surface having excellent smoothness can be obtained by suppressing partial corrosion of cobalt in this way.
- the component (B) has an anticorrosion effect on cobalt.
- the corrosion potentials of all crystal orientations are shifted to noble, and it is presumed that this effect reduces the corrosion potential difference between the crystal orientations, thereby galvanic corrosion. Is considered to be able to be suppressed.
- the component (C) has an action of destabilizing cobalt ions (Co 2+ ) generated by galvanic corrosion as compared with water. Therefore, it is presumed that the component (C) has an effect of reducing galvanic corrosion of cobalt.
- the etching of cobalt is caused by oxidation and dissolution as expressed by the following equation, but the cobalt ion (Co 2+ ) is destabilized by the component (C), so that the dissolution of cobalt oxide is delayed.
- the etching of cobalt oxide generated by aging can be moderated, so that partial corrosion of cobalt can be suppressed.
- organic solvents are generally more hydrophobic than water, they have a higher dissolved oxygen concentration than water. Therefore, the oxidation rate of cobalt increases due to the effect of the component (C).
- the etching rate of cobalt is balanced because the oxidation rate is increased by the component (C) but the dissolution rate is decreased, and the etching rate of cobalt is significantly impaired by the component (C). It is presumed that there is no such thing.
- the component (B) and the component (C) each have an action of suppressing partial corrosion of cobalt.
- only one of the component (B) and the component (C) may be used, or both the component (B) and the component (C) may be used.
- the component (A) has an etching action on the cobalt-containing metal layer.
- the organic acid of the component (A) is not particularly limited as long as it is an organic compound having a carboxyl group.
- the component (A) include aliphatic carboxylic acids, aromatic carboxylic acids and amino acids. Among them, an aliphatic carboxylic acid and an aromatic carboxylic acid are preferable, and one or more selected from the group consisting of an aliphatic carboxylic acid having 1 to 12 carbon atoms and an aromatic carboxylic acid having 6 to 16 carbon atoms is more preferable. ..
- Examples of the aliphatic carboxylic acid include formic acid, acetic acid, propionic acid, lactic acid, glycolic acid, diglycolic acid, pyruvate, oxaloacetate, oxalic acid, malonic acid, butyric acid, hydroxybutyric acid, tartaric acid, succinic acid, and malic acid.
- aromatic carboxylic acid examples include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, mandelic acid, 2-methylbenzoic acid, 3-methylbenzoic acid, 4-methylbenzoic acid, 2-ethylbenzoic acid, 3-.
- aromatic carboxylic acid benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, 3-hydroxybenzoic acid, 4-hydroxybenzoic acid, and combinations thereof are preferable.
- component (A) either only an aliphatic carboxylic acid or an aromatic carboxylic acid may be used, or both an aliphatic carboxylic acid and an aromatic carboxylic acid may be used.
- the content of the component (A) is preferably 0.001 to 10% by mass, more preferably 0.01 to 3% by mass, and further preferably 0.03 to 1 by mass based on the mass of the recess etching solution. It is by mass, particularly preferably 0.06 to 0.5% by mass.
- the upper limit value and the lower limit value can be appropriately combined, and the numerical range obtained by the combination is also disclosed.
- the component (B) has an action of suppressing partial corrosion of cobalt contained in the cobalt-containing metal layer.
- the nitrogen-containing heterocyclic compound of the component (B) is not particularly limited as long as it is a compound containing a nitrogen atom as a hetero atom constituting the ring.
- triazoles, tetrazole, thiazoles, pyrazoles, imidazoles, nucleobases and the like can be mentioned.
- triazoles examples include 1,2,3-triazole, 1,2,4-triazole, 3,5-dimethyl-1,2,4-triazole, 3-amino-1,2,4-triazole, 4 -Amino-1,2,4-triazole, 3-mercapto-4-methyl-4H-1,2,4-triazole, 1H-benzotriazole, 1H-benzotriazole-1-methanol, 4-methyl-1H-benzo Triazole, 2- (2-hydroxy-5-methylphenyl) benzotriazole, 5-methyl-1H-benzotriazole, 3-chloro-1H-benzotriazole, 5-chloro-1H-benzotriazole, 1,2,4- Examples include methyl triazole-3-carboxylate, 2- (5-chloro-2-benzotriazolyl) -6-tertbutyl-p-cresol, and 3-amino-1H-triazole.
- Examples of the tetrazole include 1H-tetrazole, 5-methyl-1H-tetrazole, 5-phenyl-1H-tetrazole, 5-mercapto-1-methyl-1H-tetrazole, 5-mercapto-1-phenyl-1H-tetrazole. , 5-Benzyl-1H-tetrazole, and 5-amino-1H-tetrazole.
- Examples of thiazoles include 1,3-thiazole and 4-methylthiazole.
- Examples of pyrazoles include pyrazole and 3,5-dimethylpyrazole.
- imidazoles examples include imidazole, 2-methylimidazole, 1-propyl imidazole, 1-isopropyl imidazole, 2-undecyl imidazole, 2-phenyl imidazole, benz imidazole, 2-methyl benz imidazole, and 2-hydroxybenz imidazole.
- Nucleobases include, for example, purines, adenines, guanines, pyrimidines, uracils, thymines, and cytosines. These can be used alone or in combination of two or more. Among these, triazoles are preferable, and among them, 1,2,4-triazole, 1H-benzotriazole, and 5-methyl-1H-benzotriazole are preferable.
- the content of the component (B) is preferably 0.001 to 5% by mass, more preferably 0.01 to 1% by mass, still more preferably 0.025 to 0, based on the mass of the recess etching solution. It is .4% by mass, particularly preferably 0.025 to 0.1% by mass.
- the component (C) has an action of suppressing partial corrosion of cobalt contained in the cobalt-containing metal layer.
- the component (C) for example, an organic solvent having an HLB (Hydrophile-Lipophile Balance) value of 3 to 15 is preferable.
- the HLB value is more preferably 3 to 13, more preferably 3 to 11, and even more preferably 3 to 9. The smaller the HLB value and the higher the hydrophobicity, the higher the effect of destabilizing the cobalt ion (Co 2+ ) and the higher the effect of controlling etching.
- component (C) examples include methanol, ethanol, 1-propanol, 2-propanol (isopropyl alcohol), 1-butanol, 2-butanol, 2-methyl-1-propanol and 2-methyl-2-.
- the content of the component (C) is preferably 1 to 99% by mass, more preferably 5 to 80% by mass, still more preferably 10 to 60% by mass, and particularly preferably 30 to 50% by mass based on the mass of the recess etching solution. %.
- the recess etching solution according to the present invention contains water as a diluent.
- Water is preferably water from which metal ions, organic impurities, particle particles and the like have been removed by distillation, ion exchange treatment, filter treatment, various adsorption treatments and the like, and pure water or ultrapure water is particularly preferable.
- the content of the component (D) is the remainder of the recess etching solution, and is preferably 1% by mass or more, more preferably 5 to 99.9% by mass, based on the mass of the recess etching solution. It is more preferably 20 to 99% by mass, still more preferably 30 to 95% by mass, and particularly preferably 35 to 90% by mass.
- the recess etching solution according to the present invention has an oxidation generally used for etching a cobalt-containing metal layer in addition to the above components (A), component (B), component (C), and component (D).
- Additives such as agents, reducing agents, surfactants, chelating agents, inorganic acids, and alkalis may be contained within a range that does not impair the effects of the present invention.
- the recess etching solution according to the present invention does not contain an oxidizing agent because the etching rate of cobalt becomes remarkably high due to the inclusion of an oxidizing agent and it may be difficult to control the recess etching amount. ..
- the recess etching solution according to the present invention does not contain the sulfonium compound.
- an inorganic acid including, for example, sulfuric acid, nitric acid, hydrochloric acid, phosphoric acid, sulfamic acid, etc.
- the content of the inorganic acid is preferably less than 0.1% by mass based on the mass of the recess etching solution, or is preferably not substantially contained.
- the content of the inorganic acid is more preferably less than 0.1% by mass, still more preferably less than 0.01% by mass, and particularly preferably less than 0.001% by mass, based on the mass of the etching solution.
- the total content of the component (A), the component (B), the component (C), and the component (D) is preferably 95% by mass or more based on the mass of the recess etching solution. , 96 to 100% by mass, more preferably 97 to 100% by mass, still more preferably 98 to 100% by mass, and particularly preferably 99 to 100% by mass.
- the recess etching solution according to the present invention is the above. It is preferable to include the component (A) 0.001 to 10% by mass, the component (B) 0.001 to 5% by mass, the component (C) 1 to 99% by mass, and the balance of the component (D), as described above.
- a recess etching solution in which a more preferable range of the contents of the component (A), the component (B), and the component (C) is combined is more preferable.
- the recess etching solution according to the present invention contains 0.001 to 10% by mass of the component (A), 0.01 to 1% by mass of the component (B), and 89 to 99.989% by mass of the component (D).
- the component (A) is preferably 0.001 to 10% by mass
- the component (B) is 0.025 to 0.4% by mass
- the component (D) is 89.6 to 99.974% by mass. More preferably, it contains 0.001 to 10% by mass of the component (A), 0.025 to 0.1% by mass of the component (B), and 89.9 to 99.974% by mass of the component (D). Is more preferable.
- the recess etching solution according to the present invention contains 0.001 to 10% by mass of the component (A), 5 to 80% by mass of the component (C), and 10 to 94.999% by mass of the component (D). It is more preferable to contain 0.001 to 10% by mass of the component (A), 10 to 60% by mass of the component (C), and 30 to 89.999% by mass of the component (D). A) It is more preferable to contain 0.001 to 10% by mass, the component (C) 30 to 50% by mass, and the component (D) 40 to 69.999% by mass.
- the pH value of the recess etching solution is not particularly limited, but is preferably in the range of 1.0 to 6.0, more preferably 1.5 to 4.5, and further preferably 2.3 to 3. It is 8.8, and particularly preferably 2.3 to 3.6.
- a pH adjusting agent may be added as necessary to adjust the pH range.
- the pH adjuster for example, potassium hydroxide, lithium hydroxide, cesium hydroxide, triethylamine, ammonia, tetramethylammonium hydroxide, ethanolamine, 1-amino-2-propanol and the like can be used.
- the pH adjuster one kind or two or more kinds can be used.
- the recess etching solution according to the present invention can be prepared by uniformly stirring the above components (A) to (D) and, if necessary, other components (E). In addition, a part or all of the water of the component (D) may be added later. Further, after preparing and storing a liquid containing the components (A) to (C), a part of the component (D), and further, if necessary, the other component (E) in advance, the component (D) can be used. You may use it after diluting with the balance.
- the above-mentioned recess etching solution is brought into contact with the surface of a cobalt-containing metal layer embedded in a via or a trench formed in a semiconductor substrate to bring the surface of the cobalt-containing metal layer into contact with the surface of the cobalt-containing metal layer. It is characterized by including a recess etching step of performing recess etching.
- FIG. 1 is a process explanatory view of the recess etching method according to the present invention. Note that FIG. 1 schematically shows only the structure necessary for explaining the process of the recess etching method.
- the substrate 100 is prepared.
- a barrier metal layer 40 such as a titanium layer or a titanium nitride layer may be formed on the inner wall of the via or the trench.
- the semiconductor substrate 100 can be manufactured by a method generally used in the art. For example, it can be manufactured as follows. First, the interlayer insulating film 20 is formed on the substrate 10. Next, vias or trenches are formed in the interlayer insulating film 20 by dry etching or the like.
- a barrier metal layer 40 is formed on the inner wall of the via or the trench, if necessary.
- the cobalt-containing metal layer 30 is formed so as to fill the vias or trenches formed in the interlayer insulating film 20.
- CMP chemical mechanical polishing
- the recess etching solution 50 is brought into contact with the surface of the cobalt-containing metal layer 30 exposed on the upper part of the semiconductor substrate 100.
- the method of bringing the recess etching solution 50 into contact with the surface of the cobalt-containing metal layer 30 is not particularly limited.
- a method of bringing the recess etching solution into contact with the surface of the cobalt-containing metal layer by a form such as dropping (single-leaf spin treatment) or spraying, or a method of immersing the surface of the cobalt-containing metal layer in the recess etching solution is adopted. Can be done.
- the temperature of the recess etching solution when the recess etching solution 50 is brought into contact with the cobalt-containing metal layer 30 is not particularly limited, but is, for example, 0 to 70 ° C, preferably 25 to 65 ° C, and more preferably 25 to. It is 60 ° C., more preferably 30 to 60 ° C.
- the temperature of the recess etching solution is 25 ° C. or higher, the recess etching can be performed in a shorter time.
- the temperature is 60 ° C. or lower, changes in the liquid composition can be suppressed and the treatment conditions can be kept constant.
- the time (treatment time) for bringing the recess etching solution 50 into contact with the cobalt-containing metal layer 30 is not particularly limited, but is usually preferably 15 seconds or more and 10 minutes or less, and more preferably 30 seconds or more, 7 .5 minutes or less, more preferably 30 seconds or more and 5 minutes or less.
- the optimum treatment time may be appropriately selected according to the contact method between the cobalt-containing metal layer and the recess etching solution, the temperature of the recess etching solution, and the like.
- the etching rate of the cobalt-containing metal layer is preferably 0.5 to 20 nm / min, more preferably 0.9 to 15 nm / min, still more preferably 0.9 to 10 nm / min. Particularly preferably, it is 0.9 to 7.5 nm / min.
- recess etching By bringing the recess etching solution 50 into contact with the surface of the cobalt-containing metal layer 30 as described above, recess etching can be performed on the surface of the cobalt-containing metal layer 30 as shown in FIG. 1 (c).
- the barrier metal layer 40 of the portion subjected to the recess etching may be separately removed by etching in the step after the recess etching, or may proceed to the next step without going through the etching step.
- the above-mentioned recess etching solution is brought into contact with the cobalt-containing metal layer to perform recess etching, and then appropriately washed with water, isopropyl alcohol, an aqueous ammonia solution, an aqueous solution of tetramethylammonium hydroxide, or the like, if necessary. You may. Further, the rust preventive treatment may be performed with an aqueous solution containing a rust preventive agent.
- the above-mentioned recess etching is performed on the surface of a cobalt-containing metal layer embedded in a via or a trench formed in the semiconductor substrate. It is characterized by including a recess etching step of contacting a liquid to perform recess etching on the surface of the cobalt-containing metal layer.
- the "surface-treated semiconductor substrate” means the cobalt-containing metal by contacting the surface of the cobalt-containing metal layer embedded in the via or trench formed in the semiconductor substrate with the recess etching solution.
- a semiconductor substrate with recess etching on the surface of the layer is characterized by including a recess etching step of contacting a liquid to perform recess etching on the surface of the cobalt-containing metal layer.
- the method of bringing the recess etching solution into contact with the surface of the cobalt-containing metal layer, the temperature of the recess etching solution at the time of contact, and the contact time are as described in "2. Recess etching method” above. Further, it is also possible to perform cleaning as appropriate after the recess etching step, as described in "2. Recess etching method” above.
- a surface-treated semiconductor substrate in which the surface of a cobalt-containing metal layer embedded in a via or a trench formed in a semiconductor substrate is subjected to recess etching.
- a wiring circuit can be constructed by further stacking metal wiring layers containing cobalt or copper in the above-mentioned step after recess etching. can.
- the amount of recess etching applied to the cobalt-containing metal layer by the recess etching according to the present invention is not particularly limited, but the metal. From the viewpoint of preventing a short circuit in the metal wiring due to misalignment during formation of the wiring pattern, the thickness is preferably 2.5 to 20 nm, more preferably 5 to 15 nm, and even more preferably 7.5 to 12.5 nm.
- the surface roughness (Ra) of the recess etching surface applied to the cobalt-containing metal layer by the recess etching according to the present invention is preferably 8.5 nm or less, more preferably 5 nm or less, still more preferably 3 nm or less, and even more so. It is preferably 2.5 nm or less, and particularly preferably 1 nm or less.
- the surface roughness (Ra) of the recess etched surface means the roughness correction value of the cobalt-containing metal layer. The roughness correction value can be measured by the method described in Examples described later.
- the metal wiring can be uniformly recess-etched in the recess etching step, a short circuit of the metal wiring is unlikely to occur, and a semiconductor element having excellent electrical characteristics can be obtained.
- the metal wiring layer that can be stacked on the surface of the cobalt-containing metal layer is not particularly limited as long as it can be electrically connected to the cobalt-containing metal layer, such as those containing cobalt or copper.
- the metal wiring layer that can be stacked on the surface of the cobalt-containing metal layer may be one layer or two or more layers.
- Examples 1-18 (1) Preparation of recess etching solution Each component was mixed at the composition ratio shown in Table 1 and stirred to prepare a recess etching solution in a uniform state.
- the treatment temperature in each example is shown in Table 1 for the time shown in Table 1.
- the etching treatment was performed by immersing the cobalt metal layer in a recess etching solution.
- FIG. 2 shows a cross-sectional SEM image of the evaluation sample after the etching treatment of Example 11 (magnification: 100,000 times, observing a range of 2070 nm in the lateral direction).
- etching rate of the cobalt-containing metal layer was calculated by defining the value obtained by dividing the difference in film thickness of the cobalt metal layer before and after the etching treatment by the treatment time (5 minutes) as the etching rate. An etching rate of 0.5 (nm / min) or higher was regarded as acceptable.
- ⁇ Roughness correction value of cobalt-containing metal layer (Co roughness correction value)>
- the roughness value of the cobalt-containing metal layer after the etching treatment was obtained by the method described in "(3) Calculation of roughness value".
- SEM images were acquired at four different locations, and the average value of the four roughness values obtained from each SEM image was defined as "roughness value A”.
- the roughness value (roughness value B;) of the cobalt-containing metal layer after being contacted with an acetic acid aqueous solution (0.01% by mass) at 30 ° C. for 5 minutes without being immersed in the recess etching solution. 6.7 nm) was calculated.
- a value obtained by subtracting the roughness value B from the roughness value A is defined as a “roughness correction value”, and a roughness correction value of 8.5 (nm) or less is regarded as a pass.
- Comparative Examples 1-9 A recess etching solution was prepared in the same manner as in Examples except that the composition ratios and treatment times shown in Table 2 were used, and the cobalt-containing metal layer was etched using the evaluation sample. The etching rate and roughness correction value of the cobalt-containing metal layer were calculated in the same manner as in the examples.
- hydrofluoric acid shows the mass% in terms of hydrogen fluoride.
- the roughness correction value of the cobalt-containing metal layer can be suppressed to a low level, and smooth etching can be performed by one-step treatment. A surface can be obtained (Examples 1 to 18).
- Table 2 when only the organic acid is used and the nitrogen-containing heterocyclic compound and the organic solvent are not used (Comparative Examples 1 to 3), or when only the inorganic acid is used (Comparative Examples 4 and 5).
- the roughness correction value of the cobalt-containing metal layer was also significantly increased.
- the smooth etching surface of the cobalt-containing metal layer can be efficiently obtained in a shorter time by performing the treatment in one step using the recess etching solution according to the present invention. Since the recess etching solution according to the present invention is excellent in obtaining a smooth etching surface in the treatment of the cobalt-containing metal layer, it can be suitably used as a recess etching solution in which the smoothness of the etching surface is important.
- Substrate 20 Interlayer insulating film 30 Cobalt-containing metal layer 40 Barrier metal layer 50 Recess etching solution 60 Recess etching amount 100 Semiconductor substrate
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Abstract
Description
この問題を改善する技術として、フルセルフアラインビア(Fully Self Aligned Via、 以下「FSAV」ともいう。)プロセスが提唱されている。FSAVプロセスを用いたアプローチの一つとして、下部導体層であるビアまたはトレンチ内に埋め込まれた金属に対して、予めリセスエッチングを行うことが考えられる。
非特許文献1では、薬液を用いたリセスエッチングの例として、コバルト金属層に対して、過酸化水素とフッ酸または酢酸のいずれかを含む混合物を用いて一段階で処理する方法と、過酸化水素による酸化処理と酢酸によるエッチング処理を繰り返し行う方法を比較した結果、後者がリセスエッチング量を制御し易いなどの点で、より適していたことが開示されている。
特許文献1においても、酸化流体による基板表面の金属層の酸化処理と、エッチング液による酸化金属層のエッチング処理を繰り返し行う方法が記載されている。
また、エレクトロマイグレーションなどが起こりにくい信頼性の高い配線を得るためには、導体層であるビアまたはトレンチ内に埋め込まれた金属に対してリセスエッチングを施す際のエッチング面の平滑性が重要となる。
このような状況下、より短時間でかつ均一に金属配線にリセスエッチングを施すためのリセスエッチング液およびそれを用いたリセスエッチング方法を提供できることが望ましい。
[1]半導体基板に形成されたビアまたはトレンチ内に埋め込まれたコバルト含有金属層の表面にリセスエッチングを施すためのリセスエッチング液であって、
(A)有機酸と、(B)含窒素複素環式化合物および(C)有機溶剤のいずれかまたは両方と、(D)水とを含む、前記リセスエッチング液。
[2](A)有機酸、(B)含窒素複素環式化合物、(C)有機溶剤、および(D)水を含む、前記[1]に記載のリセスエッチング液。
[3]前記成分(A)が、炭素数1~12の脂肪族カルボン酸および炭素数6~16の芳香族カルボン酸からなる群より選ばれる1種以上である、前記[1]または[2]に記載のリセスエッチング液。
[4]前記芳香族カルボン酸が、安息香酸、フタル酸、イソフタル酸、テレフタル酸、3-ヒドロキシ安息香酸、および4-ヒドロキシ安息香酸からなる群より選ばれる1種以上である、前記[3]に記載のリセスエッチング液。
[5]前記脂肪族カルボン酸が、酢酸およびクエン酸からなる群より選ばれる1種以上である、前記[3]または[4]に記載のリセスエッチング液。
[6]前記成分(B)が、トリアゾール類、テトラゾール類、チアゾール類、ピラゾール類、イミダゾール類、および核酸塩基からなる群より選ばれる1種以上である、前記[1]から[5]のいずれか一項に記載のリセスエッチング液。
[7]前記成分(B)が、1,2,3-トリアゾール、1,2,4-トリアゾール、3、5-ジメチル-1,2,4-トリアゾール、3-アミノ-1,2,4-トリアゾール、4-アミノ-1,2,4-トリアゾール、3-メルカプト-4-メチル-4H-1,2,4-トリアゾール、1H-ベンゾトリアゾール、1H-ベンゾトリアゾール-1-メタノール、4-メチル-1H-ベンゾトリアゾール、2-(2-ヒドロキシ-5-メチルフェニル)ベンゾトリアゾール、5-メチル-1H-ベンゾトリアゾール、3-クロロ-1H-ベンゾトリアゾール、5-クロロ-1H-ベンゾトリアゾール、1,2,4-トリアゾール-3-カルボン酸メチル、2-(5-クロロ-2-ベンゾトリアゾリル)-6-tertブチル-p-クレゾール、および3-アミノ-1H-トリアゾールからなる群より選ばれる1種以上である、前記[1]から[6]のいずれか一項に記載のリセスエッチング液。
[8]前記成分(C)が、HLB(Hydrophile-Lipophile Balance)値3~15を有する有機溶剤からなる群より選ばれる1種以上である、前記[1]から[7]のいずれか一項に記載のリセスエッチング液。
[9]前記成分(C)が、1-プロパノール、2-プロパノール、1-ブタノール、2-ブタノール、2-メチル-1-プロパノール、2-メチル-2-プロパノール、シクロヘキサノール、エチレングリコール、プロピレングリコール、1,2-ブタンジオール、1,3-ブタンジオール、1,4-ブタンジオール、2,3-ブタンジオール、1,2-ペンタンジオール、1,5-ペンタンジオール、2,4-ペンタンジオール、ジエチレングリコール、ジプロピレングリコール、ジブチレングリコール、トリエチレングリコール、トリプロピレングリコール、1,2-ヘキサンジオール、1,6-ヘキサンジオール、ネオペンチルグリコール、グリセリン、ジメチルスルホキシド、ジメチルホルムアミド、ジメチルアセトアミド、アセトン、およびメチルエチルケトンからなる群より選ばれる1種以上である、前記[1]から[8]のいずれか一項に記載のリセスエッチング液。
[10](A)有機酸0.001~10質量%、(B)含窒素複素環式化合物0.001~5質量%、および(C)有機溶剤1~99質量%を含む、前記[1]から[9]のいずれか一項に記載のリセスエッチング液。
[11]pH値が1.0から6.0の範囲である、前記[1]から[10]のいずれか一項に記載のリセスエッチング液。
[12]半導体基板に形成されたビアまたはトレンチ内に埋め込まれたコバルト含有金属層の表面に、前記[1]から[11]のいずれか一項に記載のリセスエッチング液を接触させて前記コバルト含有金属層の表面にリセスエッチングを施すリセスエッチング工程を含む、リセスエッチング方法。
[13]半導体基板に形成されたビアまたはトレンチ内に埋め込まれたコバルト含有金属層の表面に、前記[1]から[11]のいずれか一項に記載のリセスエッチング液を接触させて前記コバルト含有金属層の表面にリセスエッチングを施すリセスエッチング工程を含む、表面処理された半導体基板の製造方法。
[14]半導体基板に形成されたビアまたはトレンチ内に埋め込まれたコバルト含有金属層の表面に、前記[1]から[11]のいずれか一項に記載のリセスエッチング液を接触させて前記コバルト含有金属層の表面にリセスエッチングを施すリセスエッチング工程と、
前記工程で得られた表面処理された半導体基板におけるコバルト含有金属層の表面に、金属配線層を積み重ねていくことで配線回路を構築した半導体基板を得る工程と、
前記工程で得られた配線回路を構築した半導体基板を所定の形状に切り分けることで半導体素子を得る工程を含む、半導体素子の製造方法。
本発明にかかるリセスエッチング液は、半導体基板に形成されたビアまたはトレンチ内に埋め込まれたコバルト含有金属層の表面にリセスエッチングを施すためのリセスエッチング液であって、
(A)有機酸と、(B)含窒素複素環式化合物および(C)有機溶剤のいずれかまたは両方と、(D)水とを含むことを特徴とする。
本発明にかかるリセスエッチング液は、酸化処理とエッチング処理を別工程で行うことなく、一段階で半導体基板に形成されたビアまたはトレンチ内に埋め込まれたコバルト含有金属層の表面にリセスエッチングを施すことを可能にするため、より短時間で効率よくリセスエッチングを行うことができる。
以下、本明細書では、(A)有機酸を「成分(A)」と、(B)含窒素複素環式化合物を「成分(B)」と、(C)有機溶剤を「成分(C)」と、(D)水を「成分(D)」ということがある。
アモルファス領域や隙間付近のコバルトは、エイジングにより酸化されやすく、酸化されたコバルトは酸系の薬液により速やかにエッチングされる。また、結晶方位間の腐食電位差が存在する場合、特定の結晶方位にガルバニック腐食が生じやすく、局所的に薬液による腐食が進行しやすいと考えられる。
また、特に微細な配線パターンにおいては、グレインサイズが小さくなりやすく、結晶粒界が占める割合が増すために、平滑なエッチング面を得ることが難しい。
これらのことから、半導体基板に形成されたビアまたはトレンチ内に埋め込まれたコバルト含有金属層に平滑なエッチング面を形成するためには、コバルト含有金属層におけるコバルトの部分腐食を抑制する必要がある。
前記成分(C)は、水と比べて、ガルバニック腐食によって生じるコバルトイオン(Co2+)を不安定化する作用を有している。このため、前記成分(C)はコバルトのガルバニック腐食を低減する作用を持つと推測される。また、コバルトのエッチングは、次式で表されるとおり酸化および溶解によって生じるが、前記成分(C)によってコバルトイオン(Co2+)は不安定化するため、酸化コバルトの溶解が遅くなる。これにより、エイジングで生じた酸化コバルトのエッチングを緩やかにできるため、コバルトの部分腐食を抑制できる。また、一般的に有機溶剤は水よりも疎水性が高いため、水よりも溶存酸素濃度が高い。そのため、前記成分(C)の効果でコバルトの酸化速度は高くなる。すなわち、前記成分(C)により、酸化速度は高くなるが、溶解速度は低下するため、コバルトのエッチングレートがバランスするものと考えられ、前記成分(C)によってコバルトのエッチングレートが大きく損なわれることはないと推測される。
前述したとおり、本発明にかかるリセスエッチング液において、前記成分(A)はコバルト含有金属層に対するエッチング作用を有している。
前記成分(A)の有機酸としては、カルボキシル基を有する有機化合物であれば特に限定されない。成分(A)としては、例えば、脂肪族カルボン酸、芳香族カルボン酸およびアミノ酸などが挙げられる。中でも、脂肪族カルボン酸および芳香族カルボン酸が好ましく、炭素数1~12の脂肪族カルボン酸および炭素数6~16の芳香族カルボン酸からなる群より選ばれる1種以上であることがより好ましい。
これらは1種または2種以上を組み合わせて用いることができる。
これらの中でも、脂肪族カルボン酸としては、酢酸、クエン酸、およびこれらの組み合わせが好ましい。
これらは1種または2種以上を組み合わせて用いることができる。
これらの中でも、前記芳香族カルボン酸としては、安息香酸、フタル酸、イソフタル酸、テレフタル酸、3-ヒドロキシ安息香酸、4-ヒドロキシ安息香酸、およびこれらの組み合わせが好ましい。
なお、本明細書において数値範囲を示したときは、上限値および下限値を適宜組み合わせることができ、それによって得られる数値範囲も開示されているものとする。
本発明にかかるリセスエッチング液において、前記成分(B)はコバルト含有金属層に含有されるコバルトの部分腐食を抑制する作用を有している。
前記成分(B)の含窒素複素環式化合物としては、環を構成するヘテロ原子として窒素原子を含む化合物であれば特に限定されない。例えば、トリアゾール類、テトラゾール類、チアゾール類、ピラゾール類、イミダゾール類、および核酸塩基などが挙げられる。
テトラゾール類としては、例えば、1H-テトラゾール、5-メチル-1H-テトラゾール、5-フェニル-1H-テトラゾール、5-メルカプト-1-メチル-1H-テトラゾール、5-メルカプト-1-フェニル-1H-テトラゾール、5-ベンジル-1H-テトラゾール、および5-アミノ-1H-テトラゾールが挙げられる。
チアゾール類としては、例えば、1,3-チアゾール、および4-メチルチアゾールが挙げられる。
ピラゾール類としては、例えば、ピラゾールおよび3,5-ジメチルピラゾールが挙げられる。
イミダゾール類としては、例えば、イミダゾール、2-メチルイミダゾール、1-プロピルイミダゾール、1-イソプロピルイミダゾール、2-ウンデシルイミダゾール、2-フェニルイミダゾール、ベンズイミダゾール、2-メチルベンズイミダゾール、および2-ヒドロキシベンズイミダゾールが挙げられる。
核酸塩基としては、例えば、プリン、アデニン、グアニン、ピリミジン、ウラシル、チミン、およびシトシンが挙げられる。これらは1種または2種以上を組み合わせて用いることができる。
これらの中でも、トリアゾール類が好ましく、中でも、1,2,4-トリアゾール、1H-ベンゾトリアゾール、5-メチル-1H-ベンゾトリアゾールが好ましい。
本発明にかかるリセスエッチング液において、前記成分(C)はコバルト含有金属層に含有されるコバルトの部分腐食を抑制する作用を有している。
前記成分(C)としては、例えば、HLB(Hydrophile-Lipophile Balance)値3~15を有する有機溶剤が好ましい。HLB値は、3~13がより好ましく、さらに好ましくは3~11であり、ことさら好ましくは3~9である。HLB値が小さく疎水性が高いほど、コバルトイオン(Co2+)を不安定化する効果が高く、エッチングを制御する効果が高い。
本発明にかかるリセスエッチング液においては、希釈剤として水を含む。水は蒸留、イオン交換処理、フィルター処理、各種吸着処理などによって、金属イオン、有機不純物およびパーティクル粒子などが除去されたものが好ましく、特に純水または超純水が好ましい。
前記成分(D)の含有量は、リセスエッチング液の残部であり、前記リセスエッチング液の質量基準で、1質量%以上が好ましく、5~99.9質量%の範囲であることがより好ましく、さらに好ましくは20~99質量%、なお好ましくは30~95質量%、特に好ましくは35~90質量%である。
本発明にかかるリセスエッチング液は、前記成分(A)、成分(B)、成分(C)、および成分(D)以外に、コバルト含有金属層のエッチングに一般に用いられる酸化剤、還元剤、界面活性剤、キレート剤、無機酸、およびアルカリ等の添加剤を本発明の効果を阻害しない範囲で含有してもよい。
ただし、酸化剤を含有することで、コバルトのエッチングレートが顕著に高くなり、リセスエッチング量の制御が難しくなる場合があるため、本発明にかかるリセスエッチング液は、酸化剤を含有しないことが好ましい。また、スルホニウム化合物はコバルト表面に吸着し半導体素子の電気特性に影響する可能性もあるため、本発明にかかるリセスエッチング液は、スルホニウム化合物を含有しないことが好ましい。
また、無機酸(例えば硫酸、硝酸、塩酸、リン酸、スルファミン酸などを含む)を含有すると、エッチング処理後の表面が荒れてしまい、平滑な表面を得ることが困難である場合があるため、無機酸の含有量は、リセスエッチング液の質量基準で0.1質量%未満とするか、実質的に含有しないことが好ましい。無機酸の含有量は、エッチング液の質量基準で、より好ましくは0.1質量%未満、さらに好ましくは0.01質量%未満、特に好ましくは0.001質量%未満である。
本発明にかかるリセスエッチング液においては、pH範囲を調整するために必要に応じてpH調整剤を添加してもよい。pH調整剤としては、例えば、水酸化カリウム、水酸化リチウム、水酸化セシウム、トリエチルアミン、アンモニア、水酸化テトラメチルアンモニウム、エタノールアミン、1-アミノ-2-プロパノールなどが使用できる。pH調整剤は、1種または2種以上を用いることができる。
本発明にかかるリセスエッチング方法は、半導体基板に形成されたビアまたはトレンチ内に埋め込まれたコバルト含有金属層の表面に、上述したリセスエッチング液を接触させて前記コバルト含有金属層の表面にリセスエッチングを施すリセスエッチング工程を含むことを特徴とする。
図1は、本発明にかかるリセスエッチング方法の工程説明図である。なお、図1では、リセスエッチング方法の工程を説明するために必要な構造のみを模式的に表している。
ビアまたはトレンチの内壁には、チタン層、窒化チタン層などのバリアメタル層40が形成されていてもよい。
半導体基板100は、当業界で一般的に用いられている方法で製造することができる。例えば、以下のようにして製造することができる。
まず、基板10上に層間絶縁膜20を形成する。
次に、層間絶縁膜20にドライエッチング等によりビアまたはトレンチを形成する。さらに、ビアまたはトレンチの内壁には、必要に応じてバリアメタル層40を形成する。
続いて、層間絶縁膜20に形成されたビアまたはトレンチ内を充填するようにコバルト含有金属層30を形成する。
最後に、必要に応じてCMP(化学機械研磨)を行うことにより、上部が平滑な半導体基板100を得ることができる。
本発明にかかる表面処理された半導体基板の製造方法は、半導体基板に形成されたビアまたはトレンチ内に埋め込まれたコバルト含有金属層の表面に、上述したリセスエッチング液を接触させて前記コバルト含有金属層の表面にリセスエッチングを施すリセスエッチング工程を含むことを特徴とする。ここで、「表面処理された半導体基板」とは、半導体基板に形成されたビアまたはトレンチ内に埋め込まれたコバルト含有金属層の表面に、前記リセスエッチング液を接触させることによって、前記コバルト含有金属層の表面にリセスエッチングが施された半導体基板のことをいう。
本発明にかかる半導体素子の製造方法は、
半導体基板に形成されたビアまたはトレンチ内に埋め込まれたコバルト含有金属層の表面に、上述したリセスエッチング液を接触させて前記コバルト含有金属層の表面にリセスエッチングを施すリセスエッチング工程と、
前記工程で得られた表面処理された半導体基板におけるコバルト含有金属層の表面に、金属配線層を積み重ねていくことで配線回路を構築した半導体基板を得る工程と、
前記工程で得られた配線回路を構築した半導体基板を所定の形状に切り分けることで半導体素子を得る工程を含むことを特徴とする。
本発明によれば、リセスエッチング工程において、均一に金属配線にリセスエッチングを施すことができるため、金属配線のショートが生じにくく、電気特性に優れた半導体素子を得ることができる。
コバルト含有金属層の表面に積み重ねることができる金属配線層は、コバルトや銅を含むものなど、コバルト含有金属層と電気的に接続できるものであれば特に制限されない。コバルト含有金属層の表面に積み重ねることができる金属配線層は、1層であっても2層以上であってもよい。
(1)リセスエッチング液の調製
表1に記載の組成比で各成分を混合し、撹拌して均一な状態としてリセスエッチング液を調製した。
リセスエッチング液の評価用サンプルとして、基板表面にコバルト金属層(厚み:90nm)を有する、株式会社フィルテック製「CVDコバルト膜付きウェハ」を用いた。
前処理として、前記評価用サンプル表面に酢酸水溶液(0.01質量%)を30℃にて5分接触させ、コバルト金属層の表面に存在する酸化物を除去した。
次に、前処理した前記評価用サンプル表面に、前記(1)で調製したリセスエッチング液を50℃または20℃(各実施例における処理温度を表1に示した)で、表1記載の時間(後述のコバルト含有金属層のエッチングレートから算出される、コバルト金属層膜厚50nmのエッチングに必要な時間)リセスエッチング液に浸漬させて、エッチング処理を施した。
エッチング処理後の評価用サンプルに対して、FIB加工(装置:Thermo scientific社製Helios G4 UX)を施して、エッチング処理後の評価用サンプルの平滑な断面を取得した。
次に、得られた評価用サンプルの断面をSEM(装置:Thermo scientific社製Helios G4 UX)で観察し、Image J(開発元;Wayne Rasband アメリカ国立衛生研究所)を用いて、SEM画像からラフネスのXY座標をエクセルデータに変換した。
エクセルデータを用いてY座標の標準偏差を算出することにより、コバルト含有金属層のラフネス値を得た。
なお、エッチング処理後の評価用サンプルの断面の一例として、実施例11のエッチング処理後の評価用サンプルの断面SEM画像(倍率100000倍、横方向2070nmの範囲を観察)を図2に示す。
コバルト含有金属層のエッチングレートは、エッチング処理前後のコバルト金属層膜厚差を処理時間(5分間)で除した値をエッチングレートと定義して算出した。エッチングレート0.5(nm/min)以上を合格とした。
前記「(3)ラフネス値の算出」に記載の方法にて、エッチング処理後のコバルト含有金属層のラフネス値を得た。FIB加工で得られた1つの断面において、SEM画像を異なる4か所で取得し、各SEM画像から得られたラフネス値4点の平均値を「ラフネス値A」と定義した。
また、前記方法にて、リセスエッチング液への浸漬を行わず、酢酸水溶液(0.01質量%)を30℃にて5分接触させた後のコバルト含有金属層のラフネス値(ラフネス値B;6.7nm)を算出した。
ラフネス値Aからラフネス値Bを減じた値を「ラフネス補正値」と定義し、ラフネス補正値8.5(nm)以下を合格とした。
表2に記載の組成比および処理時間としたこと以外は、実施例と同様にしてリセスエッチング液を調製し、評価用サンプルを用いてコバルト含有金属層にエッチング処理を行なった。実施例と同様にコバルト含有金属層のエッチングレートおよびラフネス補正値を算出した。
一方、表2に示されるとおり、有機酸のみで、含窒素複素環化合物および有機溶剤を用いなかった場合(比較例1~3)、あるいは無機酸のみを用いた場合(比較例4、5)や、無機酸に含窒素複素環化合物および有機溶剤のいずれかまたは両方を組み合わせた場合(比較例6~9)、コバルト含有金属層のラフネス補正値も顕著に増加した。
以上の結果に示されるとおり、本発明にかかるリセスエッチング液を用いて一段階で処理することで、コバルト含有金属層の平滑なエッチング面をより短時間で効率的に得ることができる。本発明にかかるリセスエッチング液は、コバルト含有金属層の処理において平滑なエッチング面を得ることに優れているため、エッチング面の平滑性が重要となるリセスエッチング液として好適に用いることができる。
20 層間絶縁膜
30 コバルト含有金属層
40 バリアメタル層
50 リセスエッチング液
60 リセスエッチング量
100 半導体基板
Claims (14)
- 半導体基板に形成されたビアまたはトレンチ内に埋め込まれたコバルト含有金属層の表面にリセスエッチングを施すためのリセスエッチング液であって、
(A)有機酸と、(B)含窒素複素環式化合物および(C)有機溶剤のいずれかまたは両方と、(D)水とを含む、前記リセスエッチング液。 - (A)有機酸、(B)含窒素複素環式化合物、(C)有機溶剤、および(D)水を含む、請求項1に記載のリセスエッチング液。
- 前記成分(A)が、炭素数1~12の脂肪族カルボン酸および炭素数6~16の芳香族カルボン酸からなる群より選ばれる1種以上である、請求項1または2に記載のリセスエッチング液。
- 前記芳香族カルボン酸が、安息香酸、フタル酸、イソフタル酸、テレフタル酸、3-ヒドロキシ安息香酸、および4-ヒドロキシ安息香酸からなる群より選ばれる1種以上である、請求項3に記載のリセスエッチング液。
- 前記脂肪族カルボン酸が、酢酸およびクエン酸からなる群より選ばれる1種以上である、請求項3または4に記載のリセスエッチング液。
- 前記成分(B)が、トリアゾール類、テトラゾール類、チアゾール類、ピラゾール類、イミダゾール類、および核酸塩基からなる群より選ばれる1種以上である、請求項1から5のいずれか一項に記載のリセスエッチング液。
- 前記成分(B)が、1,2,3-トリアゾール、1,2,4-トリアゾール、3、5-ジメチル-1,2,4-トリアゾール、3-アミノ-1,2,4-トリアゾール、4-アミノ-1,2,4-トリアゾール、3-メルカプト-4-メチル-4H-1,2,4-トリアゾール、1H-ベンゾトリアゾール、1H-ベンゾトリアゾール-1-メタノール、4-メチル-1H-ベンゾトリアゾール、2-(2-ヒドロキシ-5-メチルフェニル)ベンゾトリアゾール、5-メチル-1H-ベンゾトリアゾール、3-クロロ-1H-ベンゾトリアゾール、5-クロロ-1H-ベンゾトリアゾール、1,2,4-トリアゾール-3-カルボン酸メチル、2-(5-クロロ-2-ベンゾトリアゾリル)-6-tertブチル-p-クレゾール、および3-アミノ-1H-トリアゾールからなる群より選ばれる1種以上である、請求項1から6のいずれか一項に記載のリセスエッチング液。
- 前記成分(C)が、HLB(Hydrophile-Lipophile Balance)値3~15を有する有機溶剤からなる群より選ばれる1種以上である、請求項1から7のいずれか一項に記載のリセスエッチング液。
- 前記成分(C)が、1-プロパノール、2-プロパノール、1-ブタノール、2-ブタノール、2-メチル-1-プロパノール、2-メチル-2-プロパノール、シクロヘキサノール、エチレングリコール、プロピレングリコール、1,2-ブタンジオール、1,3-ブタンジオール、1,4-ブタンジオール、2,3-ブタンジオール、1,2-ペンタンジオール、1,5-ペンタンジオール、2,4-ペンタンジオール、ジエチレングリコール、ジプロピレングリコール、ジブチレングリコール、トリエチレングリコール、トリプロピレングリコール、1,2-ヘキサンジオール、1,6-ヘキサンジオール、ネオペンチルグリコール、グリセリン、ジメチルスルホキシド、ジメチルホルムアミド、ジメチルアセトアミド、アセトン、およびメチルエチルケトンからなる群より選ばれる1種以上である、請求項1から8のいずれか一項に記載のリセスエッチング液。
- (A)有機酸0.001~10質量%、(B)含窒素複素環式化合物0.001~5質量%、および(C)有機溶剤1~99質量%を含む、請求項1から9のいずれか一項に記載のリセスエッチング液。
- pH値が1.0から6.0の範囲である、請求項1から10のいずれか一項に記載のリセスエッチング液。
- 半導体基板に形成されたビアまたはトレンチ内に埋め込まれたコバルト含有金属層の表面に、請求項1から11のいずれか一項に記載のリセスエッチング液を接触させて前記コバルト含有金属層の表面にリセスエッチングを施すリセスエッチング工程を含む、リセスエッチング方法。
- 半導体基板に形成されたビアまたはトレンチ内に埋め込まれたコバルト含有金属層の表面に、請求項1から11のいずれか一項に記載のリセスエッチング液を接触させて前記コバルト含有金属層の表面にリセスエッチングを施すリセスエッチング工程を含む、表面処理された半導体基板の製造方法。
- 半導体基板に形成されたビアまたはトレンチ内に埋め込まれたコバルト含有金属層の表面に、請求項1から11のいずれか一項に記載のリセスエッチング液を接触させて前記コバルト含有金属層の表面にリセスエッチングを施すリセスエッチング工程と、
前記工程で得られた表面処理された半導体基板におけるコバルト含有金属層の表面に、金属配線層を積み重ねていくことで配線回路を構築した半導体基板を得る工程と、
前記工程で得られた配線回路を構築した半導体基板を所定の形状に切り分けることで半導体素子を得る工程を含む、半導体素子の製造方法。
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CN202180081678.5A CN116547411A (zh) | 2020-12-07 | 2021-12-06 | 凹部蚀刻液、凹部蚀刻方法及表面处理过的半导体基板的制造方法 |
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JP2019061978A (ja) | 2017-09-22 | 2019-04-18 | 株式会社Screenホールディングス | 基板処理方法および基板処理装置 |
WO2019150990A1 (ja) * | 2018-02-05 | 2019-08-08 | 富士フイルム株式会社 | 薬液、薬液の製造方法、基板の処理方法 |
JP2020107757A (ja) * | 2018-12-27 | 2020-07-09 | 富士フイルム株式会社 | 薬液、被処理物の処理方法 |
WO2021049208A1 (ja) * | 2019-09-09 | 2021-03-18 | 富士フイルム株式会社 | 処理液、キット、処理液の製造方法、基板の洗浄方法、基板の処理方法 |
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JP2019061978A (ja) | 2017-09-22 | 2019-04-18 | 株式会社Screenホールディングス | 基板処理方法および基板処理装置 |
WO2019150990A1 (ja) * | 2018-02-05 | 2019-08-08 | 富士フイルム株式会社 | 薬液、薬液の製造方法、基板の処理方法 |
JP2020107757A (ja) * | 2018-12-27 | 2020-07-09 | 富士フイルム株式会社 | 薬液、被処理物の処理方法 |
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