WO2014115758A1 - Solution de gravure - Google Patents

Solution de gravure Download PDF

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WO2014115758A1
WO2014115758A1 PCT/JP2014/051237 JP2014051237W WO2014115758A1 WO 2014115758 A1 WO2014115758 A1 WO 2014115758A1 JP 2014051237 W JP2014051237 W JP 2014051237W WO 2014115758 A1 WO2014115758 A1 WO 2014115758A1
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Prior art keywords
etching solution
acid
solution according
nickel
nickel platinum
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PCT/JP2014/051237
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English (en)
Japanese (ja)
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斉藤　康夫
冬樹 佐藤
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昭和電工株式会社
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Publication of WO2014115758A1 publication Critical patent/WO2014115758A1/fr

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    • 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
    • C23F1/30—Acidic compositions for etching other metallic material
    • 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
    • C23F1/44—Compositions for etching metallic material from a metallic material substrate of different composition
    • 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
    • H01L21/02—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
    • H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268

Definitions

  • the present invention relates to an etching solution. More particularly, the present invention relates to an etching solution that can selectively remove nickel platinum alloy-based metals without attacking silicon-based materials and other metals and metal compounds.
  • contact resistance is reduced by siliciding electrodes such as a gate, a source, and a drain for miniaturization, power saving, and speeding up of a MOS transistor.
  • siliciding electrodes such as a gate, a source, and a drain for miniaturization, power saving, and speeding up of a MOS transistor.
  • nickel, cobalt, titanium, or tungsten silicide has been used as a metal used for an electrode.
  • nickel platinum silicide is formed using, for example, an alloy obtained by adding several atomic percent to several tens atomic percent of platinum to nickel to further reduce the contact resistance of the electrode and control heat resistance, overgrowth, and the like. The way is done.
  • nickel silicide not containing platinum when nickel silicide not containing platinum is used, as an example, a nickel thin film is formed on a polysilicon surface, nickel silicide is formed in a self-aligning manner by heat treatment (salicide process), and SPM often used in RCA cleaning.
  • a method of removing excess nickel by treatment with (sulfuric acid / hydrogen peroxide (sulfuric acid / hydrogen peroxide)) or HPM (hydrochloric acid / hydrogen peroxide (hydrochloric acid / hydrogen peroxide)) has been used.
  • the above method is not sufficient for the production of a device using nickel platinum silicide.
  • Platinum is a metal with very strong corrosion resistance, and when it is treated with a chemical solution generally used for removing nickel or the like, or SPM or HPM, a residue mainly composed of platinum remains on the surface of the semiconductor device substrate. Such residues cause problems in the electrical characteristics, reliability, yield, and the like of the semiconductor device.
  • aqua regia having a general composition
  • the surface of the material that comes into contact with the liquid, such as silicide is likely to be rough or change in film thickness, which similarly adversely affects the characteristics of the semiconductor device. Therefore, a method of selectively removing the nickel platinum alloy without damaging silicide or other metals has been studied.
  • Patent Document 1 discloses a chemical containing a substance having a property of coordinating with nickel, such as an aqueous solution containing ammonia water or cyanide, in order to first remove most of nickel by SPM and then protect nickel platinum silicide. After the treatment, a method of dissolving and removing platinum with aqua regia having a general composition is disclosed. However, this method is difficult to handle because it uses aqua regia having a strong corrosive force, harmful cyanide and the like.
  • Patent Document 2 discloses a method in which a nickel platinum alloy (hereinafter also referred to as NiPt) is removed with a composition containing methanesulfonic acid, halogen ions, nitric acid, and water, and Al is not damaged.
  • NiPt nickel platinum alloy
  • methanesulfonic acid needs to be purified by distillation or the like for semiconductors, it has a drawback that the cost of the chemical solution is high because of its highly corrosive substance, resulting in high cost of the chemical solution.
  • Patent Document 3 discloses that Ni, Pd or a laminated film thereof functioning as a barrier metal film of a solder bump is removed with an etching solution containing acetic acid, hydrochloric acid, nitric acid and water.
  • an etching solution containing acetic acid, hydrochloric acid, nitric acid and water.
  • aqua regia or a mixed solution of hydrochloric acid, nitric acid and acetic acid is used when Pd is etched. When such an etching solution is used, etching is performed. It is described that there is a problem that the metal for bump electrodes corrodes and lacks, and some of them are dissolved during etching.
  • etching solution diluted 20 to 25 times with acetic acid.
  • corrosion of solder bumps occurs when the reverse aqua regia is diluted 11 times or 51 times.
  • Patent Document 3 does not describe that NiPt can be etched with the above etching solution, or damage to Al, nickel silicide, nickel platinum silicide (hereinafter also referred to as NiPtSi), W, Ti, and the like.
  • JP 2009-176818 A US Patent Application Publication No. 2012/0231632 JP-A-9-213700
  • An object of the present invention is to provide silicon-based materials (Si, SiO 2 , Si 3 N 4 , nickel silicide, NiPtSi, etc.) and nickel platinum alloy-based metals without damaging Al, W, Ti, TiN and TaN. It is an object of the present invention to provide an etching solution that can selectively remove the.
  • an etching solution containing carboxylic acid, an oxidizing halogen compound, and water can contain Si, SiO 2, Si 3 N 4 .
  • nickel platinum alloys can be selectively removed without damaging silicon-based materials such as nickel silicide and nickel platinum silicide, and Al, W, Ti, TiN and TaN, and have completed the present invention. That is, the present invention includes the following matters.
  • An etchant that is 4-55 mmol / kg.
  • the etching solution according to [1] which is for removing nickel platinum alloy-based metals.
  • the halogen compound having oxidizing properties is selected from the group consisting of hypochlorous acid, chloric acid, hypobromous acid, bromic acid, iodic acid, hypoiodous acid, chlorine, bromine, iodine and nitrosyl halide.
  • the halogen compound having oxidizing properties includes a compound produced by mixing a halogen source and an oxidizing agent, and the halogen source is hydrochloric acid, hydrobromic acid, ammonium chloride, ammonium bromide, bromine, chlorine, and 1,
  • the etching solution according to [6], wherein the oxidizing agent is nitric acid.
  • the etching solution according to any one of [1] to [7] further comprising an anionic surfactant.
  • a first liquid containing a halogen source and a second liquid containing an oxidizing agent, wherein at least one of the first liquid and the second liquid contains a carboxylic acid, and the first liquid An etching solution kit in which at least one of the liquid and the second liquid contains water, and the first liquid and the second liquid are mixed immediately before use, according to any one of [1] to [10]
  • An etchant kit that produces an etchant.
  • a method of selectively removing using the etching solution according to any one of [10] to [10].
  • the etching solution of the present invention can selectively remove nickel platinum alloy without damaging silicon-based materials (Si, SiO 2 , Si 3 N 4 , nickel silicide, NiPtSi, etc.). Therefore, it is extremely effective for manufacturing semiconductor devices such as MOS transistors.
  • Example No. of the present invention An Si substrate with a SiO 2 film was formed as Example No. of the present invention.
  • 4 is a SEM image of the surface of SiO 2 after being treated at 50 ° C. for 3 minutes using an etching solution having a composition of 4.
  • the Si substrate with the Si 3 N 4 film is referred to as Example No. 1 of the present invention.
  • 4 is an SEM image of the surface of Si 3 N 4 after being treated at 50 ° C. for 3 minutes using an etching solution having a composition of 4 .
  • the etching solution of the present invention includes a carboxylic acid, an oxidizing halogen compound, and water, and can selectively remove nickel platinum alloy-based metals with respect to silicon-based materials and Al, W, Ti, TiN, and TaN. It is possible to do.
  • the action mechanism of the etching of the nickel platinum alloy by the etching solution of the present invention is estimated as follows. That is, the nickel in the nickel platinum alloy is dissolved by the acid in the etching solution. Platinum is oxidized by a halogen compound having an oxidizing property, and platinum oxide and halogen are further formed into a complex, whereby the compound is easily dissolved in the etching solution. Carboxylic acid improves the wettability of the etching solution with the nickel platinum alloy, and the halogen compound having an oxidizing property easily attacks the surface of the nickel platinum alloy.
  • the carboxylic acid also has a role of controlling the oxidizing halogen compound so as not to corrode materials such as Al, W, Ti, and NiPtSi.
  • the etching solution of the present invention it is possible to provide a processing means effective for a semiconductor device forming method using a salicide process. Furthermore, by optimizing the composition of the etching solution of the present invention, the surface of the substrate treated with this etching solution can be brought into a state where there are very few nickel and platinum residues.
  • the carboxylic acid used in the etching solution of the present invention is preferably a liquid at room temperature.
  • examples thereof include formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, lactic acid as hydroxy acid, and oxalic acid as dicarboxylic acid, which are saturated monocarboxylic acids having 1 to 6 carbon atoms.
  • a saturated monocarboxylic acid having 1 to 6 carbon atoms is preferable, and acetic acid or propionic acid is more preferable because a high-purity product suitable for a semiconductor manufacturing process is easily available and inexpensive.
  • the carboxylic acid is blended in the etching solution in an amount of 75 to 99% by mass, preferably 80 to 95% by mass, more preferably 85 to 95% by mass.
  • carboxylic acid concentration is lower than 75% by mass, the etching rate of NiPt decreases, and NiPt cannot be efficiently removed.
  • carboxylic acid concentration exceeds 99% by mass and approaches 100% by mass, the concentration of the halogen compound having oxidizing properties decreases, and the etching rate of NiPt decreases.
  • a plurality of the above carboxylic acids may be used in combination. Other saturated carboxylic acids, unsaturated carboxylic acids, aromatic carboxylic acids, dicarboxylic acids, hydroxy acids, carboxylic acid derivatives, etc.
  • these acids or derivatives thereof include succinic acid, malonic acid, malic acid, citric acid, tartaric acid, benzoic acid, phthalic acid, and gallic acid.
  • ascorbic acid may be added.
  • halogen compounds having oxidative properties include halogen alone, hypohalous acid, halogen acid, nitrosyl halide, etc., hypochlorous acid, chloric acid, hypobromite, bromic acid, iodic acid, hypoiodine Acid, chlorine (Cl 2 ), bromine (Br 2 ), iodine and nitrosyl halide are preferred.
  • the halogen alone, the halogen acid, and the hypohalous acid can be included in the etching solution by blowing fluorine or chlorine as a gas into an etching solution containing water, for example. Bromine (liquid) or iodine (solid) may be introduced into the etching solution.
  • a halogen compound having oxidizing properties can be generated in the etching solution.
  • the halogen source fluorine, hydrofluoric acid, chlorine (Cl 2 ), hydrochloric acid, bromine (Br 2 ), hydrobromic acid, iodine, iodic acid, ammonium fluoride, ammonium chloride, ammonium bromide, 1, 3
  • organic compounds that release halogen (in the liquid) such as dichloro-5,5-dimethylhydantoin.
  • the oxidizing agent include nitric acid, hydrogen peroxide, and ammonium persulfate.
  • halogen source and the oxidizing agent may be used alone or in combination.
  • Most halogenated compounds that are oxidizable are unstable and decompose over time, and it is difficult to obtain high-purity products for semiconductors. Therefore, in consideration of safety and quality, a halogen source and an oxidizing agent are practically used. It is preferable to produce by mixing.
  • combinations of halogen sources and oxidizing agents include the group consisting of hydrochloric acid, hydrobromic acid, ammonium chloride, ammonium bromide, bromine, chlorine, and 1,3-dichloro-5,5-dimethylhydantoin as the halogen source.
  • a combination of at least one selected from nitric acid and nitric acid as an oxidizing agent is mentioned, but considering safety, availability of high-purity products suitable for semiconductor manufacturing processes, nitric acid and hydrochloric acid, and nitric acid and chloride A combination of ammonium is preferred.
  • the concentration of the halogen atom of the oxidizing halogen compound in the etching solution is 1.4 to 55 mmol / kg, and is 2, 5, or 10 mmol depending on the type of the oxidizing halogen compound, or the halogen source and the oxidizing agent. / Kg or more, 50, 45 or 40 mmol / kg or less.
  • the etching rate with respect to Al of the etching solution of the present disclosure may be 5 nm / min or less at 50 ° C., preferably 2 nm / min or less, more preferably 1 nm / min or less.
  • the etching rate for Al can be calculated by the following procedure. An Al thin film with a film thickness of 50 nm (L0) is formed on the Si substrate by sputtering. A substrate having an Al thin film is cut into a 2 ⁇ 2 cm square to obtain a sample piece. Using a sheet resistance meter, the sheet resistance value on the Al thin film side of an unused substrate with a known film thickness is measured, and the sheet resistance value (x) with respect to the film thickness of 50 nm (L0) is measured.
  • the sample piece is treated at 50 ° C. for 3 minutes, and the first sheet resistance value (y) on the Al thin film side is measured.
  • the sample piece is again treated with the same etching solution at 50 ° C. for 3 minutes, and then the second sheet resistance value (z) on the Al thin film side is measured.
  • the sample piece is rinsed with secondary distilled water and air-dried, and then the sheet resistance value is measured.
  • Each sheet resistance value measurement is an average of 6 times, and the film thickness and the etching rate are calculated using the following equations.
  • Film thickness after first treatment (L1) L0 ⁇ (x / y)
  • Film thickness after the second treatment (L2) L0 ⁇ (x / z)
  • Etching rate (L1-L2) / 3 [nm / min]
  • the most common method for producing oxidative halogen compounds is described below.
  • nitric acid is most preferable from the viewpoint of stability.
  • the most common halogen source is hydrochloric acid.
  • the concentration in the case of hydrochloric acid is 0.005 to 0.2% by mass. If it is lower than 0.005% by mass, the concentration of active species that dissolve NiPt is low, and the etching rate of NiPt is low. On the other hand, if it exceeds 0.2% by mass, the damage to Al increases.
  • 0.005 mass% and 0.2 mass% are converted into the chlorine atom concentration of the etching solution, they are 1.4 mmol / kg and 55 mmol / kg, respectively.
  • surfactant In the etching solution of the present invention, if necessary, surfactant, acetonitrile, acetone, methanol, etc. for improving NiPt removability, protecting other materials of devices such as Al, NiPtSi, and improving liquid permeability to patterns.
  • An organic solvent miscible with water such as ethanol, isopropanol, and N-methylpyrrolidone can also be added.
  • Surfactants include cationic, nonionic, or anionic surfactants. Among these, anionic surfactants are used for the purpose of removing metals and other residues and protecting Al, silicon-based materials and the like.
  • anionic surfactant examples include sulfuric acid ester, sulfonic acid, carboxylic acid, phosphoric acid ester, and derivatives and salts thereof having a linear alkyl group having 8 to 20 carbon atoms.
  • anionic surfactant has a linear alkyl group having 12 carbon atoms
  • anionic surfactant ammonium dodecyl sulfate, triethanolamine dodecyl sulfate, dodecylbenzenesulfonic acid, dodecylsulfonic acid , Dodecyl diphenyl ether disulfonic acid, and derivatives and salts thereof, but the type of the anionic surfactant is not particularly limited.
  • anionic surfactants may be added in the form of a salt.
  • nonionic surfactants such as a polyoxyalkylene alkyl ether derivative which shows a defoaming effect
  • the etching solution of the present invention needs to be mixed with a carboxylic acid, an oxidizing halogen compound such as hypohalous acid or halogen acid, and water at the time of use.
  • hypohalous acid and halogen acid are easily decomposed in the prepared etching solution, when transporting, the halogen source and the oxidizing agent are divided into two or more liquids, and these liquids are mixed immediately before use.
  • An etchant may be prepared and hypohalous acid or halogen acid may be generated in the etchant.
  • the first liquid containing a halogen source and the second liquid containing an oxidizing agent are included, at least one of the first liquid and the second liquid containing a carboxylic acid, and the first liquid
  • An etchant kit in which at least one of the second liquid and the second liquid contains water can be used.
  • the first liquid may be a mixed liquid of carboxylic acid, water, and nitric acid
  • the second liquid may be a carboxylic acid, water, and a halogen source.
  • the first liquid may be carboxylic acid, water, and nitric acid
  • the second liquid may be a halogen source.
  • nickel platinum alloy-based metal is an alloy containing nickel and platinum as main components, and typically, nickel is 80 to 99.5 atomic%, and platinum is 0.5 to 20 atoms. % Alloy.
  • metals other than platinum for example, noble metals such as gold, palladium, iridium, ruthenium and rhodium, corrosion resistant metals such as tantalum and hafnium, germanium, other general metals, and those Metals that can be treated with the etching solution of the present invention also contain impurity components, such as carbon, which are inevitable to be mixed during metal nitrides and oxides, metal processing, refining, and film formation, such as carbon. Included in the range.
  • the etching solution of the present invention can be used for removing a nickel platinum alloy-based metal formed on a substrate, for example, a nickel platinum alloy-based metal film.
  • the etching solution of the present invention does not attack silicon-based materials such as Si, SiO 2 , Si 3 N 4 , nickel silicide, and Al, W, Ti, TiN, and TaN.
  • the formed nickel platinum alloy metal can be suitably removed.
  • the method for forming a nickel platinum alloy-based metal on the substrate is not particularly limited, and any method such as sputtering, CVD (Chemical Vapor Deposition), ALD (Atomic Layer Deposition), vacuum deposition, plating, etc. is used.
  • film forming conditions and heat treatment conditions are not limited.
  • Si, SiO 2 and Si 3 N 4 are mixed with germanium, boron, nitrogen, phosphorus, arsenic, gallium, antimony, carbon, etc. It may be doped.
  • Nickel silicide in a broad sense includes nickel silicide (nickel silicide), nickel platinum silicide (nickel platinum silicide), etc., and these are formed on the surface of the semiconductor device by heat treatment when manufacturing the semiconductor device. Since the composition and distribution of atoms change, they are also included in those treated with the etching solution of the present invention.
  • the amount of solution used, the number of treatments, the treatment temperature, etc. may be arbitrarily set in order to optimize selectivity and removability according to the formation conditions, film thickness, etc. of the metal thin film. .
  • a liquid temperature preferably 1 to 100 ° C., more preferably 15 to 80 ° C.
  • excellent metal removal property, metal selectivity and liquid life can be obtained.
  • the metal removability may be lowered.
  • it is desirable to heat paying attention to a change in concentration due to decomposition of components and volatilization of components of liquid.
  • NiPt removability was judged by the fact that there was no remaining nickel platinum alloy metal film on the substrate surface and no floating matter was generated in the etching solution.
  • the processing time may be extended and the processing temperature may be increased so as not to damage the silicon-based material.
  • the processing can be usually performed by supplying the etching solution to the surface of the semiconductor wafer with a single wafer cleaning device. Moreover, the process of immersing a semiconductor wafer in etching liquid may be sufficient. These treatments can also be performed using stirring, rocking and / or ultrasonic application. In addition, any device using nickel platinum alloy as a material can be used for electronic devices other than MOS transistors.
  • One embodiment of a method for manufacturing a semiconductor device using the etching solution of the present invention includes the following steps. That is, a step of forming a nickel platinum alloy metal film on at least a part of a substrate made of a silicon material, and etching at least a part of the nickel platinum alloy metal film without damaging the silicon material And selectively removing using a liquid.
  • This method includes, for example, a step of sequentially forming polysilicon and a nickel platinum alloy thin film as electrode materials on at least a part of a substrate made of a silicon-based material, and a step of forming nickel platinum silicide in a self-aligning manner by heat treatment (salicide) And a step of selectively removing unreacted nickel platinum alloy using the etching solution of the present invention.
  • the balance other than the components listed in Tables 1 and 2 is water. Secondary distilled water was used as the water. Acetic acid was used for electronic materials manufactured by Showa Denko KK, and 35 mass% hydrochloric acid and 60 mass% nitric acid were used for electronic materials manufactured by Kishida Chemical Co., Ltd.
  • the water in the etching solution is composed of secondary distilled water and moisture contained in the reagent. The sample piece was put into the etching solution and allowed to stand, and the etching solution was kept at 50 ° C. using a thermostatic bath.
  • the sample piece was treated at 50 ° C. for 3 minutes, and the sheet resistance value (y) on the first thin film side was measured.
  • the sample piece was again treated with the same etching solution at 50 ° C. for 3 minutes, and then the sheet resistance value (z) on the second thin film side was measured.
  • the sample piece was rinsed with secondary distilled water and air-dried, and then the sheet resistance value was measured. Each sheet resistance value measurement was an average of 6 times.
  • the calculation of the specific film thickness and etching rate was performed according to the following formula.
  • Tables 1 and 2 collectively show the etching rates when the Al, W, or Ti film-coated substrates are each immersed in an etching solution.
  • damage evaluation for TaN and TiN was conducted using a sample piece formed by sputtering TaN and TiN with a thickness of 50 nm on a Si substrate. The same procedure was performed using an etching solution having a composition of 4. In both cases, the etching rate was less than 2 nm / min, and good results were obtained.
  • the sheet resistance value was measured after water rinsing and drying. Then, the 2nd etching process was implemented similarly to the 1st etching process, the sheet resistance value was measured after water rinse and drying. The increase rate of the sheet resistance value ⁇ (second sheet resistance value-1st sheet resistance value) / first sheet resistance value ⁇ ⁇ 100 was 1.4%. From this result, it can be seen that the damage of NiPtSi is very small.
  • Damage of SiO 2 and Si 3 N 4 is immersed film coated substrate was formed by sputtering 50nm film thickness of the respective Si substrate of SiO 2 and Si 3 N 4 in 3 minutes etchant 50 ° C., water rinsing Evaluation was made by observing the surface with an electron microscope (SEM) after drying. The results are shown in FIG. 1a (SiO 2 ) and FIG. 1b (Si 3 N 4 ), respectively. No damage was observed on the surfaces of SiO 2 and Si 3 N 4 .
  • the etching solution of the present invention can efficiently remove the nickel platinum alloy without damaging the silicon-based material and the substrate containing Al, W, Ti, TiN, and TaN, it is useful in manufacturing a semiconductor device. .

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Abstract

　L'invention concerne une solution de gravure qui peut détacher sélectivement des métaux d'alliage de platine de nickel sans endommager les matériaux à base de silicium ou Al, W, Ti, TiN et TaN. Cette solution de gravure contient de l'acide carboxylique, un composé halogéné oxydant et de l'eau. La concentration de l'acide carboxylique est de 75 à 99 % en masse, et la concentration d'atomes d'halogène du composé halogéné oxydant dans la solution de gravure est de 1,4 à 55 mmol/kg.
PCT/JP2014/051237 2013-01-24 2014-01-22 Solution de gravure WO2014115758A1 (fr)

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US10204789B2 (en) 2016-03-15 2019-02-12 Renesas Electronics Corporation Manufacturing method of semiconductor device and semiconductor device
CN112259455A (zh) * 2020-10-19 2021-01-22 扬州扬杰电子科技股份有限公司 一种改善带钝化层结构的Ag面产品金属残留的方法
WO2021176913A1 (fr) * 2020-03-04 2021-09-10 富士フイルム株式会社 Solution de traitement et récipient de solution de traitement

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CN104962921B (zh) * 2015-05-22 2017-06-27 江苏大学 一种镍钛合金表面无镍层的制备方法
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