WO2022030627A1 - 半導体ウエハ用処理液 - Google Patents

半導体ウエハ用処理液 Download PDF

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WO2022030627A1
WO2022030627A1 PCT/JP2021/029371 JP2021029371W WO2022030627A1 WO 2022030627 A1 WO2022030627 A1 WO 2022030627A1 JP 2021029371 W JP2021029371 W JP 2021029371W WO 2022030627 A1 WO2022030627 A1 WO 2022030627A1
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Prior art keywords
ion
bromide
treatment liquid
semiconductor wafer
acid
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PCT/JP2021/029371
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English (en)
French (fr)
Japanese (ja)
Inventor
由樹 吉川
伴光 佐藤
享史 下田
貴幸 根岸
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Tokuyama Corp
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Tokuyama Corp
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Priority to KR1020237003791A priority Critical patent/KR20230048318A/ko
Priority to JP2021551588A priority patent/JP7375032B2/ja
Priority to US17/636,539 priority patent/US12195658B2/en
Priority to CN202180058168.6A priority patent/CN116057208A/zh
Publication of WO2022030627A1 publication Critical patent/WO2022030627A1/ja
Priority to JP2022113534A priority patent/JP7735233B2/ja
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • 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
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/32—Alkaline compositions
    • C23F1/40—Alkaline 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
    • C23F1/10—Etching compositions
    • C23F1/14—Aqueous compositions
    • C23F1/32—Alkaline 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
    • 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
    • C23F11/141—Amines; Quaternary ammonium compounds
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P14/00—Formation of materials, e.g. in the shape of layers or pillars
    • H10P14/40—Formation of materials, e.g. in the shape of layers or pillars of conductive or resistive materials
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10P—GENERIC PROCESSES OR APPARATUS FOR THE MANUFACTURE OR TREATMENT OF DEVICES COVERED BY CLASS H10
    • H10P50/00—Etching of wafers, substrates or parts of devices
    • H10P50/60—Wet etching
    • H10P50/66—Wet etching of conductive or resistive materials
    • H10P50/663—Wet etching of conductive or resistive materials by chemical means only
    • H10P50/667—Wet etching of conductive or resistive materials by chemical means only by liquid etching only
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W20/00—Interconnections in chips, wafers or substrates
    • H10W20/01—Manufacture or treatment
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10W—GENERIC PACKAGES, INTERCONNECTIONS, CONNECTORS OR OTHER CONSTRUCTIONAL DETAILS OF DEVICES COVERED BY CLASS H10
    • H10W20/00—Interconnections in chips, wafers or substrates
    • H10W20/40—Interconnections external to wafers or substrates, e.g. back-end-of-line [BEOL] metallisations or vias connecting to gate electrodes
    • H10W20/45—Interconnections external to wafers or substrates, e.g. back-end-of-line [BEOL] metallisations or vias connecting to gate electrodes characterised by their insulating parts
    • H10W20/48—Insulating materials thereof

Definitions

  • the present invention relates to a novel treatment liquid for etching a transition metal existing on a semiconductor wafer, which is used in a semiconductor device manufacturing process.
  • the design rules for semiconductor devices have become finer, and wiring resistance tends to increase.
  • the increase in wiring resistance it has become remarkable that the high-speed operation of the semiconductor element is hindered, and countermeasures are required. Therefore, as the wiring material, a wiring material having improved electromigration resistance and a reduced resistance value is desired as compared with the conventional wiring material.
  • ruthenium or tungsten, molybdenum or chromium (hereinafter, tungsten, molybdenum and chromium may be collectively referred to as Group 6 metal) has higher electromigration resistance.
  • the design rule of a semiconductor element is attracting attention as a wiring material having a diameter of 10 nm or less because the resistance value of the wiring can be reduced.
  • ruthenium can prevent electromigration even when copper is used as the wiring material, so it is also being considered to use ruthenium as a barrier metal for copper wiring. ..
  • the wiring is formed by dry etching or wet etching as in the conventional wiring material.
  • dry etching these metals, in-plane non-uniformity due to plasma distribution occurs, and the etching rate increases or decreases depending on the reaction species and the flux or energy of the ions, so precision etching is difficult. There was a problem. Therefore, wet etching is attracting attention as a method capable of etching these metals more precisely.
  • ruthenium, tungsten, molybdenum, or chromium In order to microfabricate semiconductor devices, it is necessary to microfabricate ruthenium, tungsten, molybdenum, or chromium in wet etching. Precise control of the etching rate of these metals is required to achieve microfabrication of ruthenium, tungsten, molybdenum, or chromium. Further, in order to realize multi-layer wiring, the flatness of each metal layer is indispensable, and the flatness of the metal surface after etching is also desired.
  • Patent Document 1 as a method for etching a ruthenium film, pH 12 or higher and a standard redox potential of 300 mV vs.
  • Patent Document 2 proposes a method of oxidizing, dissolving and removing ruthenium with an aqueous solution having a pH of 11 or higher containing orthoperiodic acid.
  • Patent Document 3 proposes a treatment liquid for a ruthenium metal having a pH of 10 or more and less than 12 containing a bromine-containing compound, an oxidizing agent, a basic compound and water.
  • Patent Document 4 proposes a cleaning method for oxidizing, dissolving and removing ruthenium by using a removing solution in which a strong acid such as nitric acid is further added to cerium (IV) ammonium nitrate.
  • Patent Document 5 contains ruthenium and tungsten containing hypochlorite ion and a solvent and having a pH of more than 7 and less than 12.0 at 25 ° C.
  • a processing liquid for a wafer to be provided has been proposed. It has been shown that the treatment liquid contains hypochlorite ions and can remove ruthenium and tungsten adhering to the end face portion and the back surface portion of the semiconductor wafer.
  • Patent Document 6 proposes a solution for removing tungsten metal containing orthoperiodic acid and water. It has been shown that the removing liquid can stably remove unnecessary tungsten metal formed or adhered to the semiconductor substrate.
  • Patent Document 7 discloses a method of processing copper and molybdenum with a chemical solution containing an oxidizing agent and an acid to form wiring.
  • the oxidizing agent include hydrogen peroxide, persulfuric acid, nitric acid, hypochlorous acid, permanganate and dichromic acid.
  • a molybdenum film is etched using an aqueous solution containing hydrogen peroxide and a carboxylic acid as the chemical solution is shown.
  • the method for etching ruthenium described in Patent Documents 1 and 4 is a method for removing ruthenium residue adhering to the back surface of a semiconductor substrate or a bevel, and ruthenium can be dissolved and removed.
  • the precision etching of ruthenium was not disclosed and was difficult.
  • the treatment liquid described in Patent Document 2 is a treatment liquid for an etching residue containing ruthenium, as in Patent Document 1, and it is difficult to maintain the flatness of the ruthenium surface after the etching treatment. Moreover, since it is difficult to accurately control the etching rate of ruthenium, it is difficult to perform precise etching of ruthenium. Therefore, it has been difficult to use it in a wiring forming process that requires precise etching of ruthenium.
  • the processing liquid described in Patent Document 3 describes that ruthenium used in the manufacturing process of semiconductor elements, wirings, and barrier metals configured on a substrate such as a semiconductor wafer is etched.
  • the purpose is to clean a substrate such as a semiconductor wafer, not to precision etching. Therefore, when ruthenium is etched with the treatment liquid described in Patent Document 3, the flatness of the ruthenium surface after the etching treatment is not maintained, and it is difficult to accurately control the etching rate. Therefore, it is difficult to use the treatment liquid described in Patent Document 3 in the wiring forming process that requires precise etching of ruthenium, and there is room for further improvement.
  • the tungsten treatment liquid described in Patent Document 5 is intended to remove tungsten adhering to the end face portion and the back surface portion of the semiconductor wafer, and is not intended for precision etching.
  • the removal liquid described in Patent Document 6 is also intended to stably remove unnecessary tungsten metal formed or adhered to the semiconductor substrate, and is not intended for precision etching. Therefore, when tungsten is etched with the treatment liquid described in Patent Document 5 or Patent Document 6, the flatness of the surface of the tungsten after the etching treatment is not maintained, and it is difficult to accurately control the etching rate. Therefore, it is difficult to use the treatment liquid described in Patent Document 5 or Patent Document 6 in the wiring forming process that requires precise etching of tungsten, and further improvement is required.
  • the chemical solution for etching molybdenum described in Patent Document 7 is a chemical solution containing an oxidizing agent and an acid.
  • the only oxidizing agent disclosed in the examples of Patent Document 7 is hydrogen peroxide, which has a problem that the life of the liquid is short due to the autolysis reaction and the etching rate is not stable.
  • an object of the present invention is precision processing of a transition metal capable of etching a transition metal existing on a semiconductor wafer at an accurate etching rate and maintaining the flatness of the transition metal surface after the etching process.
  • the purpose is to provide a suitable treatment liquid.
  • the present inventors have conducted diligent studies to solve the above problems. With a treatment liquid containing only hypochlorous acid ions, it is difficult to accurately control the etching rate, and the flatness of the transition metal surface after the etching treatment cannot be maintained. Therefore, we proceeded with the study of the components to be added to the treatment liquid. As a result, they have found that by adding a specific alkylammonium salt, the flatness of the transition metal surface after the etching treatment can be maintained and the etching rate can be controlled, and the present invention has been completed.
  • the configuration of the present invention is as follows.
  • Item 1 A treatment liquid for etching transition metals on semiconductor wafers.
  • (B) A processing liquid for a semiconductor wafer containing an alkylammonium salt represented by the following formula (1).
  • a is an integer of 6 to 20
  • R 1 , R 2 , and R 3 are independently hydrogen atoms or alkyl groups having 1 to 20 carbon atoms
  • X - is a bromine-containing ion.
  • Item 2 The treatment liquid for a semiconductor wafer according to Item 1, wherein the (A) hypoiodide ion or periodic acid ion is a hypohaloic acid ion.
  • Item 3 The treatment liquid for a semiconductor wafer according to Item 1 or 2, wherein the hypobromous acid ion is hypobromous acid ion, and the concentration of hypobromous acid ion is 0.0096 to 1.92% by mass.
  • hypochlorite ion is hypochlorite ion and hypobromous acid ion
  • concentration of hypochlorite ion is 0.05 to 20.0% by mass
  • concentration of hypobromous acid ion is Item 2.
  • Item 5 The treatment liquid for a semiconductor wafer according to any one of Items 1 to 4, wherein the concentration of the alkylammonium salt represented by the formula (B) (1) is 0.0001 to 10% by mass.
  • Item 6 Further, Item 1 to include (C) at least one ammonium ion selected from the group consisting of tetramethylammonium ion, ethyltrimethylammonium ion, tetraethylammonium ion, tetrapropylammonium ion, and tetrabutylammonium ion. 5. The treatment liquid for a semiconductor wafer according to any one of 5.
  • Item 7 Any one of Items 1 to 6, wherein the (A) hypochlorous acid ion or periodic acid ion is a hypochlorous acid ion, and the pH at 25 ° C. is more than 7 and less than 14.0.
  • Item 9. The processing liquid for a semiconductor wafer according to any one of Items 1 to 8, further comprising chloride ions.
  • Item 11. The processing liquid for semiconductor wafers according to any one of Items 1 to 10, wherein the concentration of the metal contained in the processing liquid for semiconductor wafer is 1 ppb or less on a mass basis.
  • Item 12 An etching method comprising a step of bringing the semiconductor wafer processing liquid according to any one of Items 1 to 10 into contact with the semiconductor wafer.
  • Item 13 A chemical solution for a semiconductor wafer, which comprises the following (A), (B) and (C).
  • Item 14 A chemical solution containing at least one ammonium salt selected from the group consisting of tetramethylammonium bromide, ethyltrimethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, and tetrabutylammonium bromide.
  • a method for producing a chemical solution for a semiconductor wafer which comprises a step of mixing an alkylammonium salt represented by the following formula (1).
  • Item 15 The method for producing a semiconductor wafer chemical solution according to Item 14, wherein the semiconductor wafer chemical solution contains a metal having a (C) concentration of 1 ppb or less on a mass basis.
  • Item 16 Bromine-containing gas that generates bromide ions when dissolved in a solution containing tetramethylammonium hydroxide, ethyltrimethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide or tetrabutylammonium hydroxide, or water.
  • Item 16 A method for producing a processing liquid for a semiconductor wafer, which comprises a step of mixing the chemical solution for a semiconductor wafer according to Item 13 with a solution containing hypochlorite ions.
  • the transition metal can be wet-etched in the process of forming the semiconductor element.
  • the flatness of the transition metal surface after etching is maintained (less surface roughness), and the etching rate of the transition metal is accurately controlled by the oxidant concentration, pH, type and / or concentration of alkylammonium salt. Is possible. Therefore, the processing liquid for semiconductor wafers of the present invention can be suitably used when forming a semiconductor element having a multilayer wiring structure in which flatness of each layer is required.
  • the surface of the transition metal after the etching treatment is excellent in flatness in the processing liquid for semiconductor wafers of the present invention, the surface of the transition metal in contact with the treatment liquid can be uniformly and uniformly etched.
  • it is suitable for semiconductor manufacturing that requires precise etching of ruthenium at a level of several nm, and can be suitably used, for example, in the formation of a semiconductor element having a wiring structure of 10 nm or less.
  • the mechanism by which the treatment liquid of the present invention maintains the flatness of the transition metal after the etching treatment, particularly ruthenium or the sixth group metal, is not always clear, but the following can be considered.
  • the case where the transition metal is ruthenium will be described as an example, but it is presumed that the flatness of the surface of other transition metals is maintained by the same mechanism. That is, the alkylammonium ions contained in the alkylammonium salt contained in the treatment liquid are preferentially adsorbed on the ruthenium surface where it is more easily etched to form a protective layer.
  • the protective layer prevents contact with the hypohalogenate ion that oxidizes and dissolves ruthenium, so that the etching rate of the easily etched portion decreases, and as a result, ruthenium is uniformly dissolved. Therefore, it is considered that the flatness of the ruthenium surface after the etching treatment can be maintained as compared with the etching treatment with the treatment liquid containing only hypochlorous acid ions.
  • the etching of ruthenium is partially suppressed by adsorbing the alkylammonium ion on the surface of ruthenium, the amount of ruthenium adsorbed can be controlled by adjusting the type and concentration of the alkylammonium ion. It is thought that accurate control of the etching rate of ruthenium will be possible.
  • the processing liquid for semiconductor wafers of the present invention can etch ruthenium at an etching rate of 10 ⁇ / min or more. Further, by controlling the oxidant concentration, pH, type and / or concentration of the alkylammonium salt, the etching rate of ruthenium can be arbitrarily adjusted and the etching amount can be controlled to a desired value. That is, the treatment liquid of the present invention is a treatment liquid that can be suitably used for precision etching of ruthenium.
  • the treatment liquid for semiconductor wafers of the present invention maintains the flatness of the surface of transition metals, especially ruthenium or Group 6 metal, after etching treatment, and transition metals, among others. It is a treatment liquid that can accurately control the etching rate of ruthenium or Group 6 metal. Therefore, it is a treatment liquid that can be suitably used in the semiconductor manufacturing process, and more preferably in the wiring forming process.
  • the transition metal to which the treatment liquid of the present invention is applied may be formed by any method, but for example, in the semiconductor manufacturing process, a semiconductor is used by a known method such as CVD, ALD, or sputtering method. Formed on a wafer. By etching the formed transition metal with a treatment liquid, wiring for a semiconductor is formed.
  • the transition metal contained in the wafer treated with the treatment liquid of the present invention is not particularly limited, and examples of the transition metal include Ru, Rh, Ti, Ta, Co, Cr, Hf, Os, and Pt. , Ni, Mn, Cu, Zr, La, Mo, W and the like. Among them, Ru, W, Mo, or Cr can be suitably used because, by treating with the treatment liquid of the present invention, precise etching can be achieved and a surface having excellent flatness can be obtained. ..
  • ruthenium is not limited to ruthenium metal, and may contain ruthenium element. That is, ruthenium metal, ruthenium alloy, ruthenium oxide, etc. are referred to as ruthenium.
  • tungsten also referred to as W
  • W is not limited to tungsten metal, and may contain a tungsten element. That is, tungsten metal, tungsten alloy, tungsten oxide, etc. are referred to as tungsten.
  • molybdenum also referred to as Mo
  • Mo is not limited to molybdenum metal, and may contain molybdenum element. That is, molybdenum metal, molybdenum alloy, molybdenum oxide, etc.
  • chromium also referred to as Cr
  • Cr is not limited to the chromium metal, and may contain a chromium element. That is, chromium metal, chromium alloy, chromium oxide, etc. are referred to as chromium.
  • the group 6 metal represents tungsten, molybdenum, and chromium.
  • the treatment liquid of the present invention is a treatment liquid capable of maintaining the flatness of the transition metal surface after etching.
  • the fact that the flatness of the transition metal surface is maintained after etching means that the flatness of the transition metal surface to be etched does not substantially change before and after etching, or even if it changes, it is a practical problem. It means that it is within the range that does not become.
  • the case where the flatness of the transition metal surface is not maintained is not only the case where pitting corrosion occurs in the transition metal film due to etching or the case where non-uniform etching (location unevenness) occurs, but also the case where the metal surface is not maintained. It also includes the case where the surface roughness increases.
  • the flatness of the transition metal surface can be easily confirmed by, for example, observing the transition metal surface with a scanning electron microscope (SEM) or observing / measuring with an atomic force microscope (AFM). Therefore, by observing, measuring, and comparing the surface of the wafer containing the transition metal to be etched before and after the etching process by the above evaluation method, whether or not the flatness of the metal surface after etching is maintained. Can be easily determined.
  • SEM scanning electron microscope
  • AFM atomic force microscope
  • Figures 1 and 2 show an example of the wiring formation process.
  • the wiring forming process will be described by taking the case where the transition metal is ruthenium or a metal of the sixth group as an example.
  • a substrate 1 made of a semiconductor (for example, Si) is prepared.
  • the prepared substrate is subjected to an oxidation treatment to form a silicon oxide film on the substrate.
  • an interlayer insulating film 2 made of a low dielectric constant (Low-k) film is formed, and via holes are formed at predetermined intervals.
  • the transition metal 3 is embedded in the via hole by thermal CVD, and a transition metal film is further formed (FIG. 1). This is wet-etched with a treatment liquid to etch a transition metal film, and a transition metal wiring is formed (FIG. 2).
  • the treatment liquid of the present invention contains (A) hypohalogenate ion or periodic acid ion, and (B) alkylammonium salt represented by the following formula (1).
  • A hypohalogenate ion or periodic acid ion
  • B alkylammonium salt represented by the following formula (1).
  • a is an integer of 6 to 20
  • R 1 , R 2 , and R 3 are independently hydrogen atoms or alkyl groups having 1 to 20 carbon atoms
  • X - is a bromine-containing ion. Is.
  • hypochlorous acid ion refers to hypochlorous acid ion, hypobromous acid ion, and hypoiodous acid ion. These may be used alone or in combination. Hypochlorous acid ions etch transition metals as an oxidant.
  • the hypohalogenate ion used in the present invention may be added to the treatment liquid by any method. For example, by dissolving the hypohalite in a solvent, the hypohalogenate is added to the treatment liquid. It is possible to generate acid ions.
  • hypobromous acid ion can be generated by dissolving hypochlorite in a solvent, and hypobromous acid ion can be generated by dissolving hypobromous acid in a solvent. Further, by blowing chlorine gas or bromine gas into the treatment liquid, hypochlorite ion and hypobromous acid ion can be generated, respectively. Hypochlorite ion or hypobromous acid ion can also be added to the treatment liquid of the present invention by adding chlorine water or bromine water to the solvent.
  • the periodic acid ion refers to orthoperiodic acid ion, metaperiodic acid ion and the like. Periodic acid ions etch transition metals as an oxidant.
  • the periodic acid ion used in the present invention may be added to the treatment liquid by any method. These may be used alone or in combination.
  • the counter ion (cation) in the hypohalogenate ion and the periodium acid ion is an alkali metal ion, an alkaline earth metal ion, and an organic cation. When alkali metal ions and alkaline earth metal ions remain on the semiconductor wafer, they have an adverse effect on the semiconductor wafer (adverse effects such as a decrease in the yield of the semiconductor wafer).
  • organic cations are preferred as counterions.
  • the organic cation at least one ammonium ion selected from any of tetramethylammonium ion, tetraethylammonium ion, tetrapropylammonium ion, tetrabutylammonium ion, and ethyltrimethylammonium ion in consideration of industrial production. Is preferable, and tetramethylammonium ion or ethyltrimethylammonium ion is particularly preferable.
  • tetramethylammonium ion or ethyltrimethylammonium ion as the counter ion, sodium ion or calcium ion in the treatment liquid can be reduced, so that tetramethylammonium ion or ethyltrimethylammonium ion can be used in the treatment liquid. It preferably contains ions.
  • the range of the concentration of hypochlorite ion or the range of the concentration of periodic acid ion when the hypochlorite ion is hypochlorite ion or hypoiodous acid ion is relative to the total amount of the treatment liquid. , 0.05 to 20% by mass, preferably. If it is within the above range, the decrease in concentration due to the decomposition of hypochlorous acid ion or periodic acid ion in the treatment liquid is suppressed (hereinafter, the decomposition reaction of hypochlorous acid ion or periodate ion in the treatment liquid is suppressed.
  • the effect of suppressing the decrease in the concentration of hypochlorous acid ion or periodic acid ion may be said to have good "storage stability"), and the transition metal can be etched at a high etching rate. .. If the concentration of hypochlorite ion, hypoiodous acid ion or periodate ion is larger than 20% by mass, the storage stability may be deteriorated. Further, when the concentration of hypochlorite ion or periodic acid ion is smaller than 0.05% by mass, the etching rate of the transition metal tends to be slow, and the production efficiency tends to decrease.
  • the concentration of hypoiodous acid ion, hypoiodous acid ion or periodic acid ion is 0.05 to 20% by mass from the viewpoint of the etching rate of the transition metal and the storage stability of the treatment liquid. It is preferably 0.1 to 15% by mass, more preferably 0.3 to 10% by mass, still more preferably 0.5 to 6% by mass, and particularly preferably 0.5 to 0.5% by mass. 4% by mass.
  • the concentration range is preferably 0.0096 to 1.92% by mass with respect to the total amount of the treatment liquid.
  • the transition metal can be etched at a high etching rate by suppressing a decrease in concentration due to decomposition of hypobromous acid ions in the treatment liquid. If the hypobromous acid ion concentration is greater than 1.92% by mass, the storage stability may deteriorate. Further, when the hypobromous acid ion concentration is smaller than 0.0096% by mass, the etching rate of the transition metal tends to be slow, and the production efficiency tends to decrease.
  • the hypobromous acid ion concentration is preferably 0.0096 to 1.92% by mass, more preferably 0, from the viewpoint of the etching rate of the transition metal and the storage stability of the treatment liquid. It is .048 to 1.92% by mass, more preferably 0.096 to 0.96% by mass.
  • the concentration of hypochlorous acid ion or periodic acid ion in the treatment liquid of the present invention can be obtained by calculation at the time of manufacturing the treatment liquid, or can be confirmed by directly analyzing the treatment liquid.
  • the concentration of hypohalogenate ion or periodate ion can be determined from the absorption spectrum of hypohalogenate ion or periodate ion measured by iodine titration method or a spectrophotometer. The method of finding it can be mentioned.
  • the treatment liquid of the present invention containing hypochlorous acid ion preferably has a pH of more than 7 and less than 14.0.
  • the pH of the treatment liquid is preferably more than 7 and preferably less than 14.0. It is more preferably 8 or more and less than 14.0, further preferably the pH is 8 or more and less than 13, and most preferably the pH is 9 or more and 12.5 or less.
  • Hypochlorite ion is hypochlorous acid ion or hypobromous acid ion from the viewpoint that it exists stably in the above pH range, the etching rate of the transition metal is high, and a high-purity product suitable for semiconductor production can be easily produced. It is preferably an acid ion. For example, if it is within the above range, the hypochlorite ion concentration is unlikely to decrease during storage. For example, the etching performance of the transition metal is high even after storage for 15 days in a dark place at 23 ° C. and an inert gas atmosphere. It can be a treatment liquid that is fully exhibited. In the case of a treatment liquid containing periodic acid ions, the pH is preferably 1 or more and 14.0 or less.
  • the preferable pH range of the treatment liquid containing periotide ion varies depending on the transition metal to be treated.
  • the pH is preferably 1 or more and 9 or less, and when the transition metal is tungsten.
  • the pH is preferably 4 or more and 14 or less, when the transition metal is molybdenum, the pH is preferably 6 or more and 14 or less, and when the transition metal is chromium, the pH is 4 or more and 14 or less. Is preferable.
  • pH is a value at 25 ° C.
  • the treatment liquid of the present invention contains an alkylammonium salt.
  • the following can be considered as the mechanism by which the treatment liquid of the present invention can maintain the flatness of the transition metal surface after the etching treatment. That is, it is considered that the cation (alkylammonium ion) of the alkylammonium salt contained in the treatment liquid is adsorbed on the surface of the transition metal at the portion of the polar group centered on the nitrogen atom.
  • the alkyl group which is a non-polar group of the adsorbed cation, is located in a direction away from the surface of the transition metal, and a hydrophobic protective layer is formed on the surface of the transition metal.
  • the formed protective layer inhibits the contact between the hypohalite ion or periodium acid ion contained in the treatment liquid and the transition metal, and as a result, the transition metal is uniformly and uniformly etched. Therefore, it is considered that the flatness of the transition metal surface after the etching treatment is maintained.
  • the alkylammonium salt contained in the treatment liquid of the present invention is an alkylammonium salt represented by the following formula (1).
  • a is an integer of 6 to 20
  • R 1 , R 2 , and R 3 are independently hydrogen atoms or alkyl groups having 1 to 20 carbon atoms
  • X - is a bromine-containing ion. Is.
  • the integer a in the above formula (1) represents the number of methylene groups, and if the integer a is 6 to 20, it can be used without particular limitation, but the integer a is 6 to 15. Is more preferable, and it is further preferable that the integer a is 8 to 15.
  • Any alkylammonium salt having a methylene group within the above-mentioned range can be suitably used because it is adsorbed on the surface of the transition metal and forms an appropriate protective layer. Further, as the integer a of the alkylammonium salt is larger, the adsorption amount of the alkylammonium ion of the alkylammonium salt on the surface of the transition metal increases, so that the etching rate of the transition metal tends to decrease.
  • the integer a of the alkylammonium salt when the integer a of the alkylammonium salt is large, the water solubility of the alkylammonium salt is lowered, which causes particles to be generated in the treatment liquid, which is a factor of lowering the yield of the semiconductor element.
  • the integer a of the alkylammonium salt becomes smaller, the amount adsorbed on the transition metal surface decreases, an appropriate protective layer is not formed on the transition metal surface, and the flatness of the transition metal surface after etching tends to be unmaintainable. It is in.
  • R 1 , R 2 , and R 3 in the above formula (1) are independently hydrogen atoms or alkyl groups having 1 to 20 carbon atoms, and may be the same or different from each other.
  • R 1 , R 2 , and R 3 are preferably alkyl groups having 1 to 20 carbon atoms.
  • the carbon number of R 1 , R 2 , and R 3 is preferably the same as or smaller than the integer a, respectively, and the group of any one of R 1 , R 2 , and R 3 is more likely to be a methyl group. preferable.
  • the alkylammonium salt represented by the above formula (1) contains bromine-containing ions.
  • the bromine-containing ion is an ion containing bromine, and examples thereof include a bromate ion, a bromate ion, a perbromate ion, a hypobromous acid ion, and a bromide ion.
  • the inclusion of an alkylammonium salt containing bromine-containing ions in the treatment liquid improves the flatness of the transition metal surface after etching. The reason for this is not always clear, but it can be considered as follows. Since the alkylammonium salt is partially or wholly dissociated in the treatment liquid, bromine-containing ions are present in the treatment liquid.
  • the etching rate of the transition metal by hypohalogenate ion or periodate ion should be controlled to some extent. Is presumed to be possible. It is presumed that the surface roughness due to etching can be suppressed by reducing the etching rate of the transition metal.
  • Alkylammonium salts containing bromine-containing ions are more stable and easier to synthesize than alkylammonium salts containing chlorine-containing ions or fluorine-containing ions, so high-purity products can be obtained industrially at low cost. Further, the alkylammonium salt containing bromine-containing ions has an advantage that the amount of alkylammonium ions per unit weight is higher than that containing iodine-containing ions. Therefore, the alkylammonium salt contained in the treatment liquid of the present invention contains bromine-containing ions.
  • alkylammonium salt represented by the formula (1) that can be preferably used in the present invention are n-octyltrimethylammonium bromide, decyltrimethylammonium bromide, dodecyltrimethylammonium bromide, and tetradecyltrimethylammonium bromide.
  • Bromide such as ammonium, hexadecyltrimethylammonium bromide, octadecyltrimethylammonium bromide, didecyldimethylammonium bromide, didodecyldimethylammonium bromide, ethyltrimethylammonium bromide ion, n-octyltrimethylammonium hypobromine, next Decyltrimethylammonium bromine, dodecyltrimethylammonium hypobromite, tetradecyltrimethylammonium hypobromite, hexadecyltrimethylammonium hypobromite, octadecyltrimethylammonium hypobromite, dodecyldimethylammonium hypobromite, Hypobromite, such as didodecyldimethylammonium hypobromite, N-octyltrimethylammonium bromate, decyltrimethylammonium
  • the amount of the alkylammonium salt added is preferably in the range of 0.0001 to 10% by mass with respect to the entire treatment liquid.
  • the amount of the alkylammonium salt added is within this range, the amount of alkylammonium ion adsorbed can be controlled by adjusting the type and concentration of the alkylammonium ion, and the etching rate of the transition metal can be accurately controlled. Furthermore, by adjusting the type and concentration of alkylammonium ions, a sufficient protective layer can be formed on the surface of the transition metal, and the flatness of the surface of the transition metal after the etching treatment can be maintained.
  • adding an alkylammonium salt only one kind may be added, or two or more kinds may be added.
  • the treatment liquid of the present invention is derived from the addition of an alkylammonium salt and contains a metal (or a metal ion, hereinafter referred to as a metal including the case of a metal ion) in the production of the treatment liquid.
  • a metal or a metal ion, hereinafter referred to as a metal including the case of a metal ion
  • the contained metals include lithium, sodium, potassium, aluminum, magnesium, calcium, chromium, manganese, iron, nickel, cobalt, copper, silver, cadmium, barium, zinc, and lead, and their ions. Be done.
  • the metal acts as a catalyst for the decomposition of the alkyl group in alkali and promotes the decomposition reaction.
  • the content of the metal in the treatment liquid should be small, but the inclusion of a small amount of metal makes it possible to maintain the flatness of the metal surface after the etching treatment (prevent surface roughness). Therefore, the metal content is selected from lithium, sodium, potassium, aluminum, magnesium, calcium, chromium, manganese, iron, nickel, cobalt, copper, silver, cadmium, barium, zinc, and lead.
  • one metal is 0.01 ppt or more and 1 ppb or less, more preferably 1 ppt or more and 1 ppb or less, further preferably 10 ppt or more and 500 ppt or less, and most preferably 100 ppt or more and 200 ppt or less. .. Further, when these metals remain on the semiconductor wafer, they have an adverse effect on the semiconductor wafer (adverse effects such as a decrease in the yield of the semiconductor wafer). When the metal content exceeds 1 ppb, the metal content can be suppressed to 1 ppb or less by filtration, distillation, ion exchange, or the like.
  • the treatment liquid of the present invention (A) hypohalogenate ion or periodate ion, (B) alkylammonium salt represented by the formula (1), (C) ammonium ion described in detail below, and other additions.
  • the rest other than the agent is water.
  • the water contained in the treatment liquid of the present invention is preferably water from which metal ions, organic impurities, particle particles, etc. have been removed by distillation, ion exchange treatment, filter treatment, various adsorption treatments, etc., more preferably pure water, and ultrapure water. Pure water is most preferable. As such water, those produced by a method widely known in semiconductor production can be preferably used.
  • (C) Ammonium ion In the treatment solution of the present invention, when hypohalite ion is added to the treatment solution by dissolving hypohalite in water or the like, the hypohalite contained in the hypohalite is contained in the treatment solution. The counter ion of the hypohalite ion will be contained in the treatment liquid.
  • hypohalite when the hypohalite is sodium hypochlorite, sodium ions are contained in the treatment liquid, and when it is calcium hypochlorite or the like, calcium ions are contained as counterions in the treatment liquid.
  • the alkali metal ions such as sodium ion and calcium ion and the alkaline earth metal ion remain on the semiconductor wafer, they have an adverse effect on the semiconductor wafer (adverse effect such as a decrease in the yield of the semiconductor wafer). It is preferable that the abundance in the liquid is small, and it is actually preferable that the abundance is infinitely absent.
  • an organic ion is preferable as the counterion of the hypohalogenate ion
  • the (C) ammonium ion which may be contained in the treatment liquid of the present invention may be tetramethylammonium ion or ethyl in consideration of industrial production. It is preferably at least one ammonium ion selected from the group consisting of trimethylammonium ion, tetraethylammonium ion, tetrapropylammonium ion, and tetrabutylammonium ion.
  • tetramethylammonium ion and ethyltrimethylammonium ion are more preferable as the ammonium ion, and tetramethylammonium ion is particularly preferable because a high-purity product is industrially easily available. Therefore, by selecting tetramethylammonium ion as the counter ion, sodium ion and calcium ion in the treatment liquid can be reduced, so that it is preferable that the treatment liquid contains tetramethylammonium ion. Further, it may be separately contained as tetramethylammonium hydroxyside.
  • ammonium ion is preferably tetramethylammonium ion or ethyltrimethylammonium ion, but ethyltrimethylammonium ion is preferable in terms of handling safety.
  • the (C) ammonium ion may be a counterion of an organic alkali added to the treatment liquid of the present invention.
  • the organic alkali is tetramethylammonium hydroxide, ethyltrimethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide
  • the (C) ammonium ion is the organic alkali.
  • the concentration range of the ammonium ion is preferably 0.001 to 30% by mass with respect to the entire treatment liquid.
  • the concentration of ammonium ions satisfies this range, a treatment liquid having excellent long-term storage stability can be obtained.
  • the concentration of ammonium ion is more preferably 0.005 to 20% by mass, further preferably 0.01 to 15% by mass, and particularly preferably 0.05 to 8%. It is mass%.
  • tetramethylammonium ion contains a hypochlorite ion after passing an aqueous solution of tetramethylammonium hydroxide through an ion exchange resin to prepare an ion exchange resin exchanged for a tetramethylammonium ion type. It is possible to include tetramethylammonium ions in the treatment liquid by bringing the solution into contact with the ion exchange resin and ionizing the cations contained in the solution with tetramethylammonium ions.
  • the treatment liquid of the present invention may contain at least one anion species selected from halogenate ions, subhalosates ions, and halide ions.
  • anion species selected from halogenate ions, subhalosates ions, and halide ions.
  • halogenate ions such as ClO 3- , BrO 3- , IO 3- , etc .
  • hypochlorite ions such as ClO 2- , BrO 2-, IO 2- , etc .
  • Cl- , Br- examples thereof include halide ions such as I- .
  • One of these anion species may be contained in the treatment liquid, or two or more kinds of anion species may be contained.
  • anion species for example, when ions having the same oxidation number of halogen atoms are contained such that two kinds among halogenate ions are contained, or when one kind of subhalochloride ion and a halide are contained. It is possible to include ions having different oxidation numbers of halogen atoms so that one kind of ion is included.
  • an anionic species in the treatment liquid, the stability of the alkylammonium bromide contained in the treatment liquid can be improved. The reason for this is not clear, but when the alkylammonium bromide is dissolved, the bromide ion exists as a counterion of the alkylammonium ion.
  • alkylammonium bromide may precipitate during storage. Therefore, it is considered effective to add an anion species that counterion-exchanges with the bromide ion in order to stabilize it as an alkylammonium ion in the treatment liquid.
  • halogenate ions and / or halide ions are preferably contained as the anion species, and chlorate ions and / or It is more preferable that chloride ions are contained.
  • the anion species used in the present invention can be generated by dissolving an acid, a salt or the like containing the anion species in a treatment liquid.
  • Acids containing anionic species include halogen acids such as chloric acid, bromic acid and iodic acid; chlorous acids such as chlorous acid, bromine acid and iodic acid; hydrogen chloride, hydrogen bromide, hydrogen iodide and the like. Examples include hydrogen halide.
  • the salt containing anionic species include alkali metal salts, alkaline earth metal salts, organic salts and the like.
  • the alkali metal salt includes potassium chloride, sodium chlorite, potassium bromide, sodium bromine, potassium iodide, sodium iodate and the like
  • the organic salt includes tetramethylammonium chloride and odor.
  • examples thereof include organic salts containing onium ions such as quaternary alkylammonium salts such as tetramethylammonium chloride and tetramethylammonium iodide.
  • the hydrogen halide can also be generated by dissolving a halogen gas such as chlorine gas, bromine gas, or iodine gas in water.
  • acids containing anionic species and organic salts because they do not contain metals that cause a decrease in yield in semiconductor production, and considering the ease of industrial acquisition and handling.
  • it is more preferable that it is an organic salt containing onium ions such as a quaternary alkylammonium salt.
  • organic salts those that can be particularly preferably used in terms of stability, purity and cost are tetramethylammonium chloride, tetramethylammonium bromide, tetramethylammonium iodide, ethyltrimethylammonium chloride, and bromide.
  • Examples thereof include ethyltrimethylammonium, ethyltrimethylammonium iodide, tetraethylammonium chloride, tetraethylammonium bromide, tetraethylammonium iodide, tetrapropylammonium chloride, tetrapropylammonium bromide, tetrapropylammonium iodide and the like.
  • the acid or salt containing the anion species used to generate the anion species in the treatment liquid an industrially available salt may be used or may be prepared by a known method.
  • the quaternary alkylammonium salt containing the anion species can be prepared by preparing an aqueous solution of tetramethylammonium hydroxide and injecting chlorine, bromine or the like. Further, a tetramethylammonium hydroxide solution is brought into contact with a cation exchange type ion exchange resin to convert the cations in the ion exchange resin into tetramethylammonium ions, and then halogen acids such as hydrochloric acid, bromic acid and iodic acid are circulated.
  • a solution containing a quaternary alkylammonium salt of the anion species can also be prepared by a method of exchanging ions.
  • the content of at least one anion species among the above anion species is 1% by mass to 20% by mass.
  • the anion species needs to be contained in the treatment liquid in an amount of 1% by mass to 20% by mass.
  • the anion species contained in the treatment liquid are contained, at least one of the contained anion species needs to be contained in the treatment liquid in an amount of 1% by mass to 20% by mass. ..
  • the stability of the alkylammonium bromide contained in the treatment liquid can be improved.
  • the concentration may be sufficient to exchange with bromide ions to stabilize alkylammonium ions in the treatment liquid, and the concentration of the anion species is preferably 1% by mass to 20% by mass. It is more preferably 10% by mass to 10% by mass, further preferably 0.1% by mass to 10% by mass, and most preferably 1% by mass to 10% by mass.
  • the concentration is 1% by mass to 20% by mass from the viewpoint of achieving both sufficient etching rate and smoothness and stability of alkylammonium ions in the treatment liquid.
  • the anion species contained in the above is preferably a halide ion or a halide ion.
  • the content of other anion species other than the anion species in the above concentration range is not particularly limited, and depends on the type of the metal species to be etched and the etching site. It may be set as appropriate, and the content of other anion species may be 1% by mass to 20% by mass. If the content of the anion species is too high, the etching rate tends to decrease and the effect of improving stability tends to decrease. Therefore, when two or more anion species are contained, the content of the anion species tends to decrease.
  • the total of is preferably 20% by mass or less, more preferably 10% by mass or less, and most preferably 5% by mass or less.
  • the content of anionic species in the treatment liquid can be measured by using an ion chromatograph method. By using this method, it is possible to identify and quantify anion species by appropriately setting the column type and conditions.
  • additives Conventional additives
  • other additives conventionally used in the semiconductor treatment liquid may be added to the treatment liquid of the present invention as long as the object of the present invention is not impaired.
  • acids, alkalis, metal anticorrosive agents, water-soluble organic solvents, fluorine compounds, oxidizing agents, reducing agents, complexing agents, chelating agents, surfactants, defoaming agents, pH adjusters, etc. can be added.
  • the treatment liquid of the present invention containing hypohalite ion can be produced by adding and mixing an alkylammonium salt to a hypohalite solution containing hypohalite ion or an aqueous hypohalite solution.
  • Aqueous hypobromous acid solution can be prepared by dissolving commercially available hypochlorites such as sodium hypochlorite, calcium hypochlorite, and sodium hypobromous acid in water, sodium hydroxide solution, and tetramethyl hydroxide. It can be produced by blowing chlorine or bromine gas into an alkaline aqueous solution such as an ammonium aqueous solution.
  • hypochlorous acid ion may be exchanged for tetramethylammonium ion by contacting an aqueous solution of sodium hypochlorite or an aqueous solution of sodium hypobromous acid with an ion exchange resin having a tetramethylammonium type. Can be done.
  • the treatment liquid of the present invention containing periodic acid ions can be produced by adding and mixing an alkylammonium salt to a periodic acid solution containing periodic acid ions or a periodic acid aqueous solution.
  • the aqueous peroxide solution can be produced by dissolving commercially available periodic acid such as ortho-periodic acid, sodium ortho-periodic acid, potassium ortho-periodic acid, and sodium meta-periodic acid in water.
  • the method for producing the treatment liquid of the present invention will be described in detail by taking as an example a treatment liquid containing a hypochlorite aqueous solution in which the counterion of hypochlorite ion is exchanged using an ion exchange resin.
  • a method for producing the treatment liquid of the present invention by converting an aqueous solution of sodium hypochlorite into an aqueous solution of tetramethylammonium hypochlorite by ion exchange.
  • an aqueous solution containing tetramethylammonium ions specifically, an aqueous solution of tetramethylammonium hydroxide is brought into contact with an ion exchange resin to prepare an ion exchange resin in the form of tetramethylammonium.
  • the ion exchange resin to be used is not particularly limited as long as it is a known cation exchange resin.
  • a hydrogen type ion exchange resin or a sodium type ion exchange resin can be used.
  • a hydrogen type ion exchange resin having a low possibility of being mixed with sodium is preferable.
  • a weakly acidic or strongly acidic ion exchange resin can be used without particular limitation.
  • the hypochlorite aqueous solution for example, sodium hypochlorite aqueous solution is brought into contact with the ion exchange resin to obtain a tetramethylammonium hypochlorite aqueous solution.
  • An aqueous solution of sodium hypochlorite can be prepared by dissolving sodium hypochlorite in water.
  • sodium hypochlorite was used here because of its good storage stability and handling, but it may be commercially available and easily available, and calcium hypochlorite or the like can also be used. ..
  • sodium hypochlorite having a low sodium chloride content.
  • Such sodium hypochlorite is generally marketed as low-salt sodium hypochlorite.
  • the step of ion exchange may be repeated.
  • metal ions such as sodium and calcium, which are counterions of hypochlorite ions contained in the aqueous solution of tetramethylammonium hypochlorite, can be reduced.
  • the treatment solution of the present invention containing tetramethylammonium ion can be produced by mixing and dissolving an alkylammonium salt and, if necessary, other additives in the obtained tetramethylammonium hypochlorite aqueous solution.
  • the hypobromous acid ion contained in the treatment liquid of the present invention may be generated in the treatment liquid.
  • a method of producing hypobromous acid ion in the treatment liquid there is a method of oxidizing a bromine-containing compound with an oxidizing agent.
  • the amount ratio of the bromine-containing compound and the oxidant contained in the treatment liquid is the chemical quantitative ratio and reaction rate when the bromine-containing compound reacts with the oxidant to generate hypobromous acid ion, and the treatment liquid. It is preferable to determine by considering the chemical ratio and reaction rate when the contained Br- reacts with the oxidant to generate hypobromous acid ion, but in reality, there are multiple factors in these reactions.
  • the ratio of the value obtained by dividing the concentration of the bromine-containing compound by the chemical equivalent (molar equivalent) of the bromine-containing compound to the value obtained by dividing the concentration of the oxidant by the chemical equivalent (molar equivalent) of the oxidant is 0.
  • the etching rate of the transition metal is stabilized.
  • the reaction equivalent (molar equivalent) of the bromine-containing compound and the chemical equivalent (molar equivalent) of the oxidizing agent may be in the range of 0.001 to 100.
  • the amount ratio of hypobromous acid ion to hypochlorite ion contained in the treatment solution is Br - by the rate of decrease of hypobromous acid ion, more accurately, the reduction reaction and / or decomposition reaction of hypobromous acid ion. It is preferable to consider the rate of formation of hypobromous acid and the rate of the oxidation reaction from Br- to BrO- by hypobromous acid ion, but in reality, multiple factors are complicated in these reactions. It is difficult to determine an appropriate amount ratio of hypobromous acid ion and hypochlorite ion because they affect each other.
  • the ratio of the molar concentration of hypobromous acid ion to the molar concentration of hypobromous acid ion is in the range of 0.001 to 100. If there is, Br - generated by the reduction reaction or decomposition reaction of BrO - can be reoxidized to BrO - by hypobromous acid ion, and the etching rate of the transition metal is stabilized.
  • the bromine-containing compound used in the treatment liquid of the present invention contains a bromine atom and is oxidized by an oxidizing agent described later to bromine, hypobromous acid, hypobromous acid ion, bromic acid, bromic acid ion, bromic acid.
  • Bromic acid, perbromic acid, perbromate ion, bromide ion may be any compound as long as it is produced.
  • the hydrogen bromide referred to here may be hydrogen bromide gas or hydrobromic acid, which is an aqueous solution of hydrogen bromide.
  • bromine salt examples include lithium bromide, sodium bromide, potassium bromide, rubidium bromide, cesium bromide, ammonium bromide, and onium bromide.
  • the onium bromide here is a compound formed from onium ions and bromide ions.
  • Onium ions are compounds of polyatomic cations formed by adding excess protons (hydrogen cations) to monoatomic anions.
  • a compound that produces hypobromous acid or hypobromous acid ion in the treatment liquid can also be suitably used as the bromine-containing compound.
  • examples of such compounds include, but are not limited to, bromohydantoins, bromoisocyanuric acids, bromsulfamic acids, bromchloramines and the like. More specific examples of the compound include 1-bromo-3-chloro-5,5-dimethylhydantoin, 1,3-dibromo-5,5-dimethylhydantoin, tribromoisocyanuric acid and the like.
  • the bromine-containing compound may be added to the treatment liquid as hydrogen bromide or a bromine salt, may be added to the treatment liquid as a solution containing a bromine salt, or may be added to the treatment liquid as a bromine gas. good. Since the bromine-containing compound is easy to handle in the semiconductor manufacturing process, it is preferable to mix the bromine-containing compound as a bromine salt or a solution containing a bromine salt or hydrogen bromide with another treatment liquid.
  • the bromine-containing compound contained in the treatment liquid may be used alone or in combination of two or more. In semiconductor manufacturing, it is desirable that the bromine-containing compound does not contain a metal because the mixing of a metal or a metal ion causes a decrease in yield.
  • onium bromide contains substantially no metal, and thus can be suitably used as the bromine-containing compound of the present invention.
  • the onium bromides the quaternary onium bromide, the tertiary onium bromide, and hydrogen bromide are industrially easily available and easy to handle, and thus, as the bromine-containing compound of the present invention. It is more suitable.
  • Quaternary onium bromide is a bromate consisting of ammonium ion or phosphonium ion that can be stably present in the treatment liquid.
  • quaternary onium bromide tetramethylammonium bromide, ethyltrimethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetrapentylammonium bromide, tetra bromide Hexylammonium, methyltriethylammonium bromide, diethyldimethylammonium bromide, trimethylpropylammonium bromide, butyltrimethylammonium bromide, trimethylnonylammonium bromide, decyltrimethylammonium bromide, tetradecyltrimethylammonium, hexadecyl
  • a compound in which a proton is added to a tertiary amine, a secondary amine, or a primary amine can also be used.
  • phosphonium bromide tetramethylphosphonium bromide, tetraethylphosphonium bromide, tetrapropylphosphonium bromide, tetrabutylphosphonium bromide, tetraphenylphosphonium bromide, methyltriphenylphosphonium bromide, bromide Phenyltrimethylphosphonium, methoxycarbonylmethyl bromide (triphenyl) phosphonium.
  • Tertiary onium bromide is a bromate consisting of sulfonium ions that can be stably present in the treatment liquid.
  • tertiary sulfonium bromide trimethylsulfonium bromide, triethylsulfonium bromide, tripropylsulfonium bromide, tributylsulfonium bromide, triphenylsulfonium bromide,- (2carboxyethyl) dimethylsulfonium, etc.
  • quaternary onium bromide which is a bromate consisting of ammonium ions, is preferable because of its high stability, industrial availability, and low cost.
  • the quaternary onium bromide is preferably tetraalkylammonium bromide, which has particularly excellent stability and can be easily synthesized.
  • the carbon number of the alkyl group is not particularly limited, and the carbon number of the four alkyl groups may be the same or different.
  • tetraalkylammonium bromide having 1 to 20 carbon atoms per alkyl group can be preferably used.
  • tetraalkylammonium bromide which has a small number of carbon atoms in the alkyl group, can be more preferably used because the number of bromine atoms per weight is large.
  • Examples include tetramethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetrapentylammonium bromide, tetrahexylammonium bromide, and tetramethylammonium bromide, among others. Tetraethylammonium bromide, tetrapropylammonium bromide, and tetrabutylammonium bromide are preferred, with tetramethylammonium bromide being the most preferred.
  • the number of bromine-containing compounds contained in the treatment liquid may be one or a plurality.
  • tetraalkylammonium bromide used in the present invention commercially available tetraalkylammonium bromide may be used, or tetraalkylammonium bromide produced from tetraalkylammonium and bromide ion may be used. I do not care.
  • a method for producing tetraalkylammonium bromide it can be produced by mixing an aqueous solution containing tetraalkylammonium hydroxide with an aqueous solution containing bromide ions or a bromine-containing gas that generates bromide ions when dissolved in water.
  • tetraalkylammonium hydroxide used for producing tetraalkylammonium bromide examples include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, and tetrabutylammonium hydroxide. Among them, tetramethylammonium hydroxide is more preferable because the number of hydroxide ions per unit weight is large and a high-purity product is easily available.
  • Bromine ion sources used to produce tetraalkylammonium bromide that generate bromide ions include hydrogen bromide, lithium bromide, sodium bromide, potassium bromide, rubidium bromide, cesium bromide, and ammonium bromide. And so on. Among them, hydrogen bromide is preferable because it contains substantially no metal, is easily available industrially, and a high-purity product is easily available. Examples of the bromine-containing gas that generates bromide ions when dissolved in water include hydrogen bromide gas.
  • the amount of the bromine-containing compound added is not particularly limited, and may be determined in consideration of the etching rate of the transition metal, the stability of the treatment solution, the solubility of the bromine-containing compound, the cost, and the like.
  • the bromine-containing compound added to the treatment liquid is oxidized by an oxidizing agent described later, and is a chemical species effective for etching transition metals, specifically, bromine, hypobromous acid (HBrO), and hypobromous acid ion.
  • the treatment liquid containing HBrO, BrO ⁇ , HBrO 2 , BrO 2 ⁇ , HBrO 3 and BrO 3 ⁇ has a high etching rate of the transition metal. It preferably contains a chemical species.
  • a treatment liquid containing a large amount of HBrO and BrO ⁇ (hereinafter, also referred to as BrO ⁇ or the like) is more preferable in that the etching rate of the transition metal is particularly high and the treatment time can be shortened. Therefore, when the bromine-containing compound is oxidized by an oxidizing agent, the bromine atom contained in the bromine-containing compound may be oxidized to HBrO, BrO- , HBrO2 , BrO2- , HBrO3 , BrO3-. It is preferable to oxidize it to BrO ⁇ or the like.
  • the treatment liquid of the present invention contains a bromine-containing compound, an oxidizing agent, a base compound and water
  • the treatment liquid may be one liquid, or a treatment liquid obtained by mixing two or more treatment liquids or chemical solutions. May be.
  • the treatment liquid is one liquid, it becomes a solution containing all of the bromine-containing compound, the oxidizing agent, the basic compound and the alkylammonium salt represented by the above formula (1).
  • a treatment liquid may be produced by mixing two or more treatment liquids or chemicals.
  • the treatment liquid or the chemical liquid is two or more liquids
  • the treatment liquid or the chemical liquid contains at least one or more of a bromine-containing compound, an oxidizing agent, a base compound, and water. Further, other components described later may be contained.
  • the treatment liquid is one liquid or a mixture of two or more treatment liquids or chemicals
  • the presence of the bromine-containing compound, the oxidizing agent, and the base compound in the treatment liquid at the same time causes bromine.
  • the contained compound is oxidized by the oxidant, producing a chemical species that etches the transition metal.
  • the oxidation of the bromine-containing compound and the alkylammonium salt by the oxidizing agent can be prevented, and the treatment liquid of the present invention can be stably stored.
  • a widely known method can be used as a method for mixing the semiconductor chemical solution.
  • a method using a mixing tank, a method of mixing in the piping of a semiconductor manufacturing apparatus (in-line mixing), a method of mixing by simultaneously applying a plurality of liquids on a wafer, and the like can be preferably used.
  • the chemical solution and the treatment solution are mixed to produce the treatment solution, the chemical solution and the treatment solution may be mixed at any time.
  • it takes time to oxidize the bromine-containing compound it is possible to provide a time to generate a chemical species for etching the transition metal by mixing the chemical solution and the treatment solution before etching the transition metal.
  • the time required for oxidation is preferably short, and preferably 1 hour or less.
  • the time required for oxidation of the bromine-containing compound can be controlled by appropriately selecting the oxidant concentration, the bromine-containing compound concentration, the pH of the treatment liquid, the temperature of the treatment liquid, the stirring method of the treatment liquid, and the like. Further, when the concentration of the chemical species that etch the transition metal is low, the lifetime of the treatment liquid may be short and it may be difficult to control the manufacturing process. In such a case, it is preferable to perform mixing immediately before performing the transition metal etching.
  • the solution containing the oxidizing agent and the basic compound (treatment solution) with the chemical solution containing the bromine-containing compound and the alkylammonium salt, and it is preferable to mix the hypochlorite ion and the base. It is more preferable to mix the solution containing the compound (treatment solution) with the chemical solution containing the bromine-containing compound and the alkylammonium salt.
  • the solution (treatment liquid) containing the hypochlorite ion and the basic compound is preferably alkaline. In the mixing of the chemical solution and the treatment solution of the present invention, it is preferable that the pH of the treatment solution after mixing is alkaline.
  • the pH of the treatment liquid exceeds 7 and is less than 14.
  • the basic compound and / or water so that the treatment solution after mixing (including bromine-containing compound, oxidizing agent, basic compound and water) exceeds pH 7 and is less than 14. Adjust the concentration of. In this way, by keeping the pH of the treatment liquid after mixing above 7 and below 14, the bromine-containing compound is rapidly changed to a chemical species that etches the transition metal by the oxidizing agent, and the etching of the transition metal film is stable. It is possible to do it at a sufficient speed.
  • the pH of the mixed chemical solution and the treatment solution may be the same or different.
  • the pH of the treatment solution after mixing does not change significantly, and the solution can be suitably used as an etching solution for a transition metal.
  • the composition after mixing bromine-containing compound concentration, oxidizing agent concentration, basic compound concentration, pH
  • the mixing method such as the mixing ratio and the mixing order of the chemical solution and the treatment solution to be mixed is not particularly limited.
  • the decomposition of the hypochlorite compound may proceed locally.
  • the chemical species that etch the transition metal generated by the oxidation of the bromine-containing compound by the oxidizing agent varies depending on the pH of the treatment liquid, redox potential (ORP), etc., but mainly bromine, or bromide ion, hypobromous acid. Brobroic acid, bromous acid, bromic acid, perbromic acid and their ions.
  • the oxidizing agent used in the treatment liquid of the present invention has a function of oxidizing a bromine-containing compound and producing a chemical species effective for etching a transition metal. Specifically, nitrate, sulfuric acid, persulfate, peroxodisulfate, hypochloric acid, chloric acid, chloric acid, perchloric acid, hypobromic acid, bromine acid, bromic acid, perbromic acid, hypobromic acid.
  • oxidizing agents may be used alone or in combination of two or more. When adding these oxidizing agents to the treatment liquid of the present invention, any suitable solid, liquid, or gas may be selected according to the properties of the oxidizing agent to be used.
  • hypochlorous acid, chloronic acid, chloric acid, perchloric acid, hypobromic acid, bromine acid, bromic acid, perbromic acid, hypochlorous acid can be stably present even in alkaline conditions.
  • Acids, hypobromic acid, bromine acid, bromine acid, perbromic acid, and salts thereof, and the dissociated ions, ozone or hydrogen peroxide of these salts are more preferred, hypochlorite ions or ozone.
  • hypochlorite ion is most preferable.
  • hypochlorous acid, its salt, tetraalkylammonium hypochlorous acid, or ozone is used as the oxidizing agent, it is possible to substantially prevent the mixing of metals, and thus it is suitable as a treatment liquid for semiconductor production. .. Among them, tetraalkylammonium hypochlorous acid is particularly suitable because it exists stably even in an alkali and can efficiently oxidize the bromine-containing compound.
  • the concentration of the oxidizing agent is not particularly limited, and an amount capable of oxidizing the bromine-containing compound to a chemical species effective for etching a transition metal may be added.
  • the amount of the oxidizing agent added is preferably 0.1% by mass or more and 10% by mass or less. If the amount of the oxidizing agent added is less than 0.1% by mass, the bromine-containing compound cannot be efficiently oxidized, and the etching rate of the transition metal decreases. That is, the etching rate is low in the composition in which the oxidizing agent is not mixed. On the other hand, if the amount of the oxidizing agent added is larger than 10% by mass, the stability of the oxidizing agent is lowered, which is not appropriate.
  • the concentration of the oxidizing agent is more preferably 1 % by mass or more and 5% by mass or less, more preferably 0. Most preferably, it is 5% by mass or more and 4% by mass or less.
  • the pH of the solution containing the oxidizing agent is not particularly limited, but the pH is preferably more than 7 and less than 14, and more preferably 10 or more and 13 or less. With a solution in this pH range, the pH drop that occurs when the solution containing the bromine-containing compound and the solution containing the oxidizing agent are mixed can be reduced, and the treatment solution of the present invention can be stably produced and stored. And it becomes possible to use it.
  • the pH of the treated solution after mixing becomes alkaline when the solution containing the bromine-containing compound and the solution containing the oxidant are mixed.
  • the pH and amount of the solution containing the oxidizing agent may be adjusted.
  • the alkylammonium salt is added to an aqueous solution containing tetramethylammonium bromide, ethyltrimethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, or tetrabutylammonium bromide. It can be manufactured by adding and mixing.
  • An aqueous solution containing tetramethylammonium bromide, ethyltrimethylammonium bromide, tetraethylammonium bromide, tetrapropylammonium bromide, or tetrabutylammonium bromide is commercially available tetramethylammonium bromide, tetraethylammonium bromide, tetra bromide.
  • the conditions for using the treatment liquid of the present invention may be appropriately determined according to the etching conditions of the etching apparatus or the like to be used.
  • the treatment temperature can be 10 to 80 ° C, more preferably 20 to 70 ° C.
  • the etching rate of the transition metal changes depending on the temperature. Therefore, in order to improve the etching rate of the transition metal, 40 to 70 ° C. may be selected even within the above temperature range. If the temperature is in the temperature range of 40 to 70 ° C., the etching rate can be increased, and even a simple device can perform processing with good operability.
  • the time for using the treatment liquid of the present invention is in the range of 0.1 to 120 minutes, preferably 0.5 to 60 minutes, and may be appropriately selected depending on the etching conditions and the semiconductor element used.
  • an organic solvent such as alcohol can be used, but rinsing with deionized water is sufficient.
  • an acid such as hydrochloric acid, formic acid, acetic acid, sulfuric acid, nitric acid, hydrofluoric acid, citric acid, or oxalic acid, or a mixed solution of aqueous ammonia and hydrogen peroxide
  • an acid such as hydrochloric acid, formic acid, acetic acid, sulfuric acid, nitric acid, hydrofluoric acid, citric acid, or oxalic acid, or a mixed solution of aqueous ammonia and hydrogen peroxide
  • hydrochloric acid-hydrogenated water ozone water, sulfuric acid-hydrogenated water mixed solution, hydrofluoric acid-ammonium fluoride mixed solution, or the like.
  • these cleanings may be used in combination.
  • the wafer can be removed by heating it to a temperature at which the alkylammonium salt evaporates.
  • the treatment liquid of the present invention can set the etching rate of the transition metal to 10 ⁇ / min or more, preferably 30 ⁇ / min or more, and is excellent in the flatness of the transition metal surface after etching.
  • the treatment liquid of the present invention can be suitably used when a transition metal, particularly ruthenium, tungsten, molybdenum, or chromium, is used in the semiconductor device forming step.
  • PH measurement method The pH of 30 mL of the treatment liquid prepared in Examples and Comparative Examples was measured using a tabletop pH meter (LAQUA F-73, manufactured by HORIBA, Ltd.). The pH measurement was carried out after the treatment liquid was prepared and stabilized at 25 ° C.
  • the hypohalogenate ion concentration or the periodic acid ion concentration was measured using an ultraviolet-visible spectrophotometer (UV-2600, manufactured by Shimadzu Corporation).
  • UV-2600 ultraviolet-visible spectrophotometer
  • a calibration line was prepared using a hypohydranoic acid ion aqueous solution or a periodic acid ion aqueous solution having a known concentration, and the hypohydranoic acid ion or periodic acid ion concentration in the produced treatment liquid was determined.
  • the tetramethylammonium ion concentration in the treatment liquids of Examples and Comparative Examples was calculated from pH, hypochlorite ion concentration, and sodium ion concentration.
  • the sheet resistance was measured with a four-probe resistance measuring device (Loresta-GP, manufactured by Mitsubishi Chemical Analytech Co., Ltd.) and converted into a film thickness. After the etching treatment, the sheet resistance was similarly measured with a four-probe resistance measuring device and converted into a film thickness, which was used as the film thickness of the transition metal after the etching treatment. The difference between the film thickness of the transition metal after the etching treatment and the film thickness of the transition metal before the etching treatment was taken as the amount of change in the film thickness before and after the etching treatment.
  • the transition metal surface is subjected to an electric field radiation scanning electron microscope (100,000 times).
  • FE-SEM Field Emission Scanning Electron Microscope
  • Example 1> Manufacturing of treatment liquid
  • Preparation of hydrogen type ion exchange resin 200 mL of a sodium-type strong acid ion exchange resin (Amberlite IR-120BNa manufactured by Organo Corporation) was charged into a glass column (Biocolumn CF-50TK manufactured by AsOne Co., Ltd.) having an inner diameter of about 45 mm. After that, 1 L of hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd., for volumetric analysis) is passed through the ion exchange resin column to replace it with a hydrogen type, and 1 L of ultrapure water is passed to wash the ion exchange resin with water. Liquid.
  • hydrochloric acid manufactured by Wako Pure Chemical Industries, Ltd., for volumetric analysis
  • ⁇ (B) step> After putting 69 g of sodium hypochlorite pentahydrate (manufactured by Wako Pure Chemical Industries, Ltd., reagent special grade) in a 2 L fluororesin container, 931 g of ultrapure water is added, and 3.11% by mass of hypochlorite is added. An aqueous sodium acid solution was prepared. The prepared sodium hypochlorite aqueous solution was passed through an ion exchange resin exchanged for a tetramethylammonium type to obtain 1000 g of a tetramethylammonium hypochlorite aqueous solution.
  • Example 2 In Example 1, the amount of the ion exchange resin in the step (a) was 564 mL, the flow volume of the 10 mass% tetramethylammonium hydroxide solution was 2 L, and the concentration of the sodium hypochlorite aqueous solution in the step (b) was 8. An aqueous solution of tetramethylammonium hypochlorite was obtained at a concentration of .39% by mass. Further, as a pH adjusting step (c), a 25 mass% tetramethylammonium hydroxide (TMAH) solution was added to the tetramethylammonium hypochlorite aqueous solution until the pH reached 11.
  • TMAH tetramethylammonium hydroxide
  • Example 3 has the composition shown in Table 1 except that dodecyltrimethylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd., purity> 98%) is used as the alkylammonium salt represented by the formula (1).
  • a treatment liquid was prepared in the same manner as in Example 1, and evaluation was performed using the ruthenium membrane (sample piece) prepared in the same manner as in Example 1.
  • Example 4 has the composition shown in Table 1 except that octadecyltrimethylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd., purity> 98%) is used as the alkylammonium salt represented by the formula (1).
  • a treatment liquid was prepared in the same manner as in Example 1, and evaluation was performed using the ruthenium membrane (sample piece) prepared in the same manner as in Example 1.
  • Example 5 has the composition shown in Table 1 except that n-octyltrimethylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd., purity> 98%) is used as the alkylammonium salt represented by the formula (1).
  • a treatment liquid was prepared by the same method as in Example 1, and evaluation was performed using the ruthenium film (sample piece) prepared in the same manner as in Example 2.
  • Example 6 The same operation as in Example 1 was carried out to obtain an aqueous solution of tetramethylammonium hypochlorite, and then, as a pH adjustment step (c), a sodium-type strong acid ion exchange resin (manufactured by Organo Co., Ltd.) was exchanged for a hydrogen type.
  • the aqueous solution of tetramethylammonium hypochlorite was passed through a glass column filled with 50 mL of amberlite IR-120BNa).
  • Example 7 was carried out so as to have the composition shown in Table 1 except that hexadecyltrimethylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd., purity> 98%) was used as the alkylammonium salt represented by the formula (1).
  • a treatment liquid was prepared by the same method as in Example 2, and evaluation was performed using the ruthenium membrane (sample piece) prepared in the same manner as in Example 1.
  • Example 8 water and 25% by mass tetrahydroxyammonium hydroxide were added to sodium hypochlorite pentahydrate (manufactured by Wako Pure Chemical Industries, Ltd., special grade reagent) so that the amount of hypochlorite ion was 2.15% by mass. Methylammonium was added. 1 g of tetradecyltrimethylammonium bromide was added to 999 g of the obtained sodium hypochlorite aqueous solution to obtain a treatment liquid having the composition shown in Table 1. The evaluation results are shown in Table 2.
  • Example 9 was carried out so as to have the composition shown in Table 1 except that didecyldimethylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd., purity> 98%) was used as the alkylammonium salt represented by the formula (1).
  • a treatment liquid was prepared by the same method as in Example 1, and evaluation was performed using the ruthenium membrane (sample piece) prepared in the same manner as in Example 1.
  • Example 10 was carried out so as to have the composition shown in Table 1 except that didodecyldimethylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd., purity> 98%) was used as the alkylammonium salt represented by the formula (1).
  • a treatment liquid was prepared by the same method as in Example 1, and evaluation was performed using the ruthenium membrane (sample piece) prepared in the same manner as in Example 1.
  • Example 11 Hexadecyltrimethylammonium bromate aqueous solution and sodium bromate aqueous solution were mixed to precipitate hexadecyltrimethylammonium bromate. The mixed solution was filtered to separate the precipitated hexadecyltrimethylammonium bromate, and then washed with ultrapure water three times. A treatment solution having the composition shown in Table 1 was obtained in the same manner as in Example 1 except that tetradecyltrimethylammonium bromide was used as hexadecyltrimethylammonium bromate. Evaluation was performed using a ruthenium film (sample piece) prepared in the same manner as in Example 1.
  • Example 12 a treatment liquid was prepared in the same manner as in Example 6 so as to have the composition shown in Table 1 except that ruthenium bromide trimethylammonium was used as the alkylammonium salt represented by the formula (1). Evaluation was performed using a ruthenium film (sample piece) prepared in the same manner as in Example 1.
  • ruthenium film sample piece prepared in the same manner as in Example 1.
  • a treatment liquid was prepared in the same manner as in Example 1 except that the alkylammonium salt represented by the formula (1) was not added, and the same evaluation as in Example 1 was performed.
  • Comparative Example 2 has the composition shown in Table 1 except that tetrapropylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd., purity> 98%) was used as the alkylammonium salt represented by the formula (1).
  • a treatment liquid was prepared in the same manner as in Example 1, and evaluation was performed using the ruthenium membrane (sample piece) prepared in the same manner as in Example 1.
  • Example 13 > 25% by mass of tetramethylammonium hydroxide aqueous solution, ultrapure water, and tetradecyltrimethylammonium bromide were added to orthoperiodic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., content> 98.5%), and Table 1 shows.
  • a treatment solution having the described composition was obtained. Evaluation was performed using a ruthenium film (sample piece) prepared in the same manner as in Example 1.
  • Example 14 a treatment liquid was prepared in the same manner as in Example 6 so as to have the composition shown in Table 1 except that n-octyltrimethylammonium bromide was used as the alkylammonium salt represented by the formula (1). did.
  • the etching rate was evaluated by the above-mentioned "method for calculating the etching rate of a transition metal". The time for etching 50 ⁇ ⁇ 10 ⁇ of ruthenium oxide was calculated from the calculated etching rate, and the ruthenium oxide film treated with the time for etching 50 ⁇ ⁇ 10 ⁇ was prepared and used as a ruthenium oxide film for surface observation. The surface of the ruthenium oxide film for surface observation was observed with an electron microscope at 100,000 times.
  • Comparative Example 3 a treatment liquid was prepared in the same manner as in Example 14 except that the alkylammonium salt represented by the formula (1) was not added, and the same evaluation as in Example 14 was performed.
  • Example 15 a treatment liquid was prepared in the same manner as in Example 6 so as to have the composition shown in Table 1 except that decyltrimethylammonium bromide was used as the alkylammonium salt represented by the formula (1).
  • the etching rate was evaluated by the above-mentioned "method for calculating the etching rate of a transition metal" using a wafer on which tungsten was formed.
  • the time for etching 50 ⁇ ⁇ 10 ⁇ of tungsten was calculated from the calculated etching rate, and a tungsten film treated with the time for etching 50 ⁇ ⁇ 10 ⁇ was prepared and used as a tungsten film for surface observation.
  • the surface of the tungsten film for surface observation was observed with an electron microscope at 100,000 times.
  • Comparative Example 4 a treatment liquid was prepared in the same manner as in Example 15 except that the alkylammonium salt represented by the formula (1) was not added, and the same evaluation as in Example 15 was performed.
  • Example 16 a treatment liquid was prepared in the same manner as in Example 2 so as to have the composition shown in Table 1 except that dodecyltrimethylammonium bromide was used as the alkylammonium salt represented by the formula (1).
  • the etching rate was evaluated by the above-mentioned "method for calculating the etching rate of a transition metal".
  • the time for etching 50 ⁇ ⁇ 10 ⁇ of molybdenum was calculated from the calculated etching rate, and a molybdenum film treated with the time for etching 50 ⁇ ⁇ 10 ⁇ was prepared and used as a molybdenum film for surface observation.
  • the surface of the molybdenum film for surface observation was observed with an electron microscope at 100,000 times.
  • Comparative Example 5 a treatment liquid was prepared in the same manner as in Example 16 except that the alkylammonium salt represented by the formula (1) was not added, and the same evaluation as in Example 16 was performed.
  • Example 17 a treatment liquid was prepared in the same manner as in Example 1 so as to have the composition shown in Table 1 except that decyltrimethylammonium bromide was used as the alkylammonium salt represented by the formula (1).
  • the etching rate was evaluated by the above-mentioned "method for calculating the etching rate of a transition metal".
  • the time for etching 50 ⁇ ⁇ 10 ⁇ of chromium was calculated from the calculated etching rate, and a chromium film treated with the time for etching 50 ⁇ ⁇ 10 ⁇ was prepared and used as a chromium film for surface observation.
  • the surface of the chromium film for surface observation was observed with an electron microscope at 100,000 times.
  • Comparative Example 6 a treatment liquid was prepared in the same manner as in Example 17 except that the alkylammonium salt represented by the formula (1) was not added, and the same evaluation as in Example 17 was performed. As described above, the compositions of the treatment liquids prepared in Examples and Comparative Examples are shown in Table 1, and the obtained results are shown in Table 2.
  • Example 18 An aqueous solution of tetramethylammonium hypochlorous acid having a pH of 12.0 and 0.1 mol / L was prepared in the same manner as in Example 2. Tetramethylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd., purity> 97%) is added with a 25% by mass aqueous solution of tetramethylammonium hydroxide and ultrapure water to pH 12.0 and 0.1 mL / L. An aqueous solution was prepared.
  • Example 19 An aqueous solution of tetramethylammonium hypochlorous acid having a pH of 13.0 and 0.2 mL / L was prepared in the same manner as in Example 2. Further, a tetramethylammonium bromide aqueous solution having a pH of 13.0 and 0.2 mL / L was prepared by the same method as in Example 18. 200 mg of dimethyldioctylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd., purity> 97%) was added to 999.8 g of the obtained tetramethylammonium bromide aqueous solution to prepare a chemical solution containing a bromine-containing compound.
  • Example piece 500 g of the above 0.2 mL / L tetramethylammonium hypochlorous acid aqueous solution and 500 g of a chemical solution containing a bromine-containing compound were mixed to obtain a treatment solution having the composition shown in Table 4. Evaluation was performed using a ruthenium film (sample piece) prepared in the same manner as in Example 1.
  • Example 20 An aqueous solution of tetramethylammonium hypochlorous acid having a pH of 12.0 and 0.1 mol / L was prepared in the same manner as in Example 2. Tetrapropylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd., purity> 97%) is added with a 25 mass% aqueous solution of tetramethylammonium hydroxide and ultrapure water to pH 12.0, 0.1 mol / L tetrapropylammonium bromide. An aqueous solution was prepared.
  • Example 21 An aqueous solution of tetramethylammonium hypochlorous acid having a pH of 13.5 and 0.4 mL / L was prepared in the same manner as in Example 2. Further, a tetramethylammonium bromide aqueous solution having a pH of 13.5 and 0.4 mL / L was prepared by the same method as in Example 18. To 999.998 g of the obtained tetramethylammonium bromide aqueous solution, 2 mg of tetraheptylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd., purity> 98%) was added, and a chemical solution containing the bromine-containing compound having the composition shown in Table 3 was added. Prepared.
  • Example piece 500 g of the above 0.4 mol / L tetramethylammonium hypochlorous acid aqueous solution and 500 g of a chemical solution containing a bromine-containing compound were mixed to obtain a treatment solution having the composition shown in Table 4. Evaluation was performed using a ruthenium film (sample piece) prepared in the same manner as in Example 1.
  • Example 22 An aqueous solution of tetramethylammonium hypochlorous acid having a pH of 11.0 and 0.002 mL / L was prepared in the same manner as in Example 2. Further, a tetramethylammonium bromide aqueous solution having a pH of 11.0 and 0.002 mL / L was prepared by the same method as in Example 18.
  • Example 23 An aqueous solution of tetramethylammonium hypochlorous acid having a pH of 12.0 and 0.19 mL / L was prepared in the same manner as in Example 2. Further, a tetramethylammonium bromide aqueous solution having a pH of 12.0 and 0.1 mol / L was prepared by the same method as in Example 18. To 998 g of the obtained tetramethylammonium bromide aqueous solution, 2 g of dodecyltrimethylammonium bromide was added to prepare a chemical solution containing a bromine-containing compound having the composition shown in Table 3.
  • Example piece 500 g of the above 0.19 mL / L tetramethylammonium hypochlorous acid aqueous solution and 500 g of a chemical solution containing a bromine-containing compound were mixed to obtain a treatment solution having the composition shown in Table 4. Evaluation was performed using a ruthenium film (sample piece) prepared in the same manner as in Example 1.
  • Example 24 an aqueous solution of tetramethylammonium hypochlorous acid having a pH of 12.0 and 0.1 mol / L was prepared in the same manner as in Example 2. Further, n-octyltrimethylammonium bromide is mixed with an aqueous solution obtained by mixing an aqueous solution of ethyltrimethylammonium hydroxide and an aqueous solution of hydrobromic acid so as to have the composition shown in Table 3, to prepare a chemical solution containing a bromine-containing compound. did.
  • Example piece 500 g of the above 0.1 mol / L tetramethylammonium hypochlorous acid aqueous solution and 500 g of a chemical solution containing a bromine-containing compound were mixed to obtain a treatment solution having the composition shown in Table 4. Evaluation was performed using a ruthenium film (sample piece) prepared in the same manner as in Example 1.
  • Example 25 an aqueous solution of tetramethylammonium hypochlorous acid having a pH of 11.0 and 0.1 mol / L was prepared in the same manner as in Example 2. Further, a tetramethylammonium bromide aqueous solution having a pH of 11.0 and 0.1 mol / L was prepared by the same method as in Example 18. 20 mg of hexadecyltrimethylammonium bromide was added to 999.98 g of the obtained tetramethylammonium bromide aqueous solution to prepare a chemical solution containing a bromine-containing compound having the composition shown in Table 3.
  • Example 26 a treatment liquid was prepared in the same manner as in Example 18 so as to have the composition shown in Table 3 except that tetradecyltrimethylammonium bromide was used as the alkylammonium salt represented by the formula (1). Evaluation was performed using a tungsten film (sample piece) prepared in the same manner as in Example 14.
  • Example 27 a treatment liquid was prepared in the same manner as in Example 18 so as to have the compositions of Tables 3 and 4 except that dodecyltrimethylammonium bromide was used as the alkylammonium salt represented by the formula (1). did. Evaluation was performed using the molybdenum film (sample piece) prepared in the same manner as in Example 15.
  • Example 28 the treatment liquid was prepared in the same manner as in Example 18 so as to have the compositions of Tables 3 and 4 except that decyltrimethylammonium bromide was used as the alkylammonium salt represented by the formula (1). Prepared. Evaluation was performed using a chromium film (sample piece) prepared in the same manner as in Example 16.
  • Comparative Examples 7 to 11 a treatment liquid was prepared in the same manner as in Example 18 except that the alkylammonium salt represented by the formula (1) was not added.
  • Comparative Example 7 was evaluated using a ruthenium film (sample piece) prepared in the same manner as in Example 1.
  • Comparative Example 8 was evaluated using the ruthenium dioxide film (sample piece) prepared in the same manner as in Example 14.
  • Comparative Example 9 was evaluated using the tungsten film (sample piece) prepared in the same manner as in Example 15.
  • Comparative Example 10 was evaluated using the molybdenum film (sample piece) prepared in the same manner as in Example 16.
  • Comparative Example 11 was evaluated using a chromium film (sample piece) prepared in the same manner as in Example 17. As described above, the compositions of the treatment solutions prepared in Examples and Comparative Examples are shown in Tables 3 and 4, and the obtained results are shown in Table 4.
  • Example 29> Preparation of tetramethylammonium chlorate ((CH 3 ) 4 NCO 3 )
  • the saturated solution obtained by adding sodium chlorate manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.
  • the recovered sodium chlorate was diluted with ultrapure water and analyzed using an ion chromatography analyzer.
  • CO 3- , SO 4- , and Cl - in the diluted solution it was confirmed that Na 2 CO 3 , Na 2 SO 4 , and NaCl contained as impurities were reduced.
  • the recovered tetramethylammonium chlorate was analyzed for Na concentration using a high-frequency inductively coupled plasma emission spectroscopy (iCAP6500DuO, manufactured by Thermo SCIENTIFIC), and it was confirmed that ion exchange was sufficiently performed. When it was insufficient, the above operation was repeated to obtain a 10 mass% tetramethylammonium chlorate solution having a Na concentration of 500 ppb or less. The obtained solution was heat-treated to obtain tetramethylammonium chlorate powder. Tetramethylammonium chlorate was added to the treatment liquid prepared by the same method as in Example 4 so as to have the composition shown in Table 5.
  • the obtained treatment liquid was stored in a 30 mL fluororesin container and stored in a dark place at 25 ° C. for 30 days. The presence or absence of precipitation of the alkylammonium salt was visually confirmed. The case with precipitation was designated as C. If there was no precipitation, it was stored in a dark place for another 15 days, and the presence or absence of precipitation was visually confirmed. The case without precipitation was designated as A, and the case with precipitation was designated as B.
  • Example 30 Tetramethylammonium chloride (manufactured by Tokyo Chemical Industry Co., Ltd., purity> 98%) was added to the treatment liquid prepared by the same method as in Example 18 so as to have the composition shown in Table 5. The stability of the treatment liquid obtained by the same method as in Example 29 was evaluated.
  • Tetramethylammonium chloride was added to the treatment liquid prepared by the same method as in Example 18 so as to have the composition shown in Table 5. The stability of the treatment liquid obtained by the same method as in Example 29 was evaluated.
  • Table 5 shows the composition of the treatment liquid prepared in the examples and the obtained results.
  • Example 32 47% hydrobromic acid (ultra-high purity hydrobromic acid, manufactured by Tama Chemical Industry Co., Ltd.) is mixed with SD-25 (ultra-high purity tetramethylammonium hydroxide aqueous solution, manufactured by Tokuyama Corporation) and ultrapure water, and pH 12. A 0, 0.1 mL / L aqueous solution of tetramethylammonium bromide was prepared. 1 g of decyltrimethylammonium bromide was added to 999 g of the obtained tetramethylammonium bromide aqueous solution to obtain a chemical solution having the composition shown in Table 6.
  • the chemical solution was circulated and filtered using a filtration filter (manufactured by Entegris Japan, Polytetrafluoroethylene, pore diameter 20 nm) until the metal impurity concentration of the obtained chemical solution became 1 ppb or less.
  • a filtration filter manufactured by Entegris Japan, Polytetrafluoroethylene, pore diameter 20 nm
  • a volumetric flask was prepared with ultrapure water and diluted 100-fold to prepare a measurement sample. Further, a high-resolution inductively coupled plasma mass spectrometer (Element 2 manufactured by Thermo Fisher Scientific) was used, and metal atoms were quantified by a calibration curve method.
  • the obtained chemical solution was stored in a 30 mL fluororesin container and stored at 80 ° C. for 15 days.
  • the concentration of the alkylammonium salt in the chemical solution after storage for 15 days was measured, and the ratio of the concentration of the alkylammonium salt after storage for 15 days to the concentration of the alkylammonium salt before storage was 0.5 or more as A and less than 0.5. It was designated as B.
  • the concentration of the alkylammonium salt was measured using a liquid chromatograph mass spectrometer (Xevo QT of MS, manufactured by Waters Corp.).
  • Example 33 To obtain the composition shown in Table 6, 47% hydrobromic acid (ultra-high purity hydrobromic acid, manufactured by Tama Chemical Industries, Ltd.) and SD-25 (ultra-high purity tetramethylammonium hydroxide aqueous solution, manufactured by Tokuyama Co., Ltd.), Ultrapure water was mixed with sodium nitrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 99.9%), potassium nitrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 99.9%). The stability of the treatment liquid obtained by the same method as in Example 32 was evaluated.
  • Example 34 To obtain the composition shown in Table 6, 47% hydrobromic acid (ultra-high purity hydrobromic acid, manufactured by Tama Chemical Industry Co., Ltd.) and SD-25 (ultra-high purity tetramethylammonium hydroxide aqueous solution, manufactured by Tokuyama Co., Ltd.), Magnesium nitrate hexahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 99.999%), calcium nitrate tetrahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 99.98%) and ultrapure water. Mixed. The stability of the treatment liquid obtained by the same method as in Example 32 was evaluated.
  • Example 35 To obtain the composition shown in Table 6, 47% hydrobromic acid (ultra-high purity hydrobromic acid, manufactured by Tama Chemical Industry Co., Ltd.) and SD-25 (ultra-high purity tetramethylammonium hydroxide aqueous solution, manufactured by Tokuyama Co., Ltd.), Aluminum nitrate nine hydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 99.999%) and ultrapure water were mixed. The stability of the treatment liquid obtained by the same method as in Example 32 was evaluated.
  • Example 36 To obtain the composition shown in Table 6, 47% hydrobromic acid (ultra-high purity hydrobromic acid, manufactured by Tama Chemical Industry Co., Ltd.) and SD-25 (ultra-high purity tetramethylammonium hydroxide aqueous solution, manufactured by Tokuyama Co., Ltd.), Iron nitrate nine hydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 99.999%) and ultrapure water were mixed. The stability of the treatment liquid obtained by the same method as in Example 32 was evaluated.
  • Example 37 To obtain the composition shown in Table 6, 47% hydrobromic acid (ultra-high purity hydrobromic acid, manufactured by Tama Chemical Industry Co., Ltd.) and SD-25 (ultra-high purity tetramethylammonium hydroxide aqueous solution, manufactured by Tokuyama Co., Ltd.), Nickel nitrate hexahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 99.99985%), cobalt nitrate hexahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 99.999%) and ultrapure water. Mixed. The stability of the treatment liquid obtained by the same method as in Example 32 was evaluated.
  • Example 38 To obtain the composition shown in Table 6, 47% hydrobromic acid (ultra-high purity hydrobromic acid, manufactured by Tama Chemical Industry Co., Ltd.) and SD-25 (ultra-high purity tetramethylammonium hydroxide aqueous solution, manufactured by Tokuyama Co., Ltd.), Copper (II) nitrate trihydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 99.999%) and ultrapure water were mixed. The stability of the treatment liquid obtained by the same method as in Example 32 was evaluated.
  • Example 39 To obtain the composition shown in Table 6, 47% hydrobromic acid (ultra-high purity hydrobromic acid, manufactured by Tama Chemical Industry Co., Ltd.) and SD-25 (ultra-high purity tetramethylammonium hydroxide aqueous solution, manufactured by Tokuyama Corporation), Silver nitrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 99.9995%) and ultrapure water were mixed. The stability of the treatment liquid obtained by the same method as in Example 32 was evaluated.
  • Example 40 To obtain the composition shown in Table 6, 47% hydrobromic acid (ultra-high purity hydrobromic acid, manufactured by Tama Chemical Industry Co., Ltd.) and SD-25 (ultra-high purity tetramethylammonium hydroxide aqueous solution, manufactured by Tokuyama Co., Ltd.), Hydrobromic acid tetrahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 99.9%) and ultrapure water were mixed. The stability of the treatment liquid obtained by the same method as in Example 32 was evaluated.
  • Example 41 To obtain the composition shown in Table 6, 47% hydrobromic acid (ultra-high purity hydrobromic acid, manufactured by Tama Chemical Industry Co., Ltd.) and SD-25 (ultra-high purity tetramethylammonium hydroxide aqueous solution, manufactured by Tokuyama Corporation), Barium nitrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 99.999%) and ultrapure water were mixed. The stability of the treatment liquid obtained by the same method as in Example 32 was evaluated.
  • Example 42 To obtain the composition shown in Table 6, 47% hydrobromic acid (ultra-high purity hydrobromic acid, manufactured by Tama Chemical Industry Co., Ltd.) and SD-25 (ultra-high purity tetramethylammonium hydroxide aqueous solution, manufactured by Tokuyama Corporation), Lead nitrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., purity 99.999%) and ultrapure water were mixed. The stability of the treatment liquid obtained by the same method as in Example 32 was evaluated.
  • the flatness of the transition metal surface after the etching treatment was maintained. Further, as is clear from Examples 1 to 28, it was shown that the etching rate of the transition metal can be controlled to a desired value by adjusting the oxidant concentration, pH, type and / or concentration of the alkylammonium salt. .. As described above, the treatment liquid of the present invention can be suitably used as a treatment liquid for semiconductor manufacturing.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • ing And Chemical Polishing (AREA)
  • Weting (AREA)
  • Internal Circuitry In Semiconductor Integrated Circuit Devices (AREA)
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US17/636,539 US12195658B2 (en) 2020-08-07 2021-08-06 Treatment liquid for semiconductor wafers
CN202180058168.6A CN116057208A (zh) 2020-08-07 2021-08-06 半导体晶片用处理液
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CN116606002A (zh) * 2023-04-24 2023-08-18 西安热工研究院有限公司 一种抑制直接空冷机组空冷岛运行腐蚀的方法

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