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WO2025225327A1 - Agent de traitement par micro-usinage et procédé de traitement par micro-usinage - Google Patents

Agent de traitement par micro-usinage et procédé de traitement par micro-usinage

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Publication number
WO2025225327A1
WO2025225327A1 PCT/JP2025/013667 JP2025013667W WO2025225327A1 WO 2025225327 A1 WO2025225327 A1 WO 2025225327A1 JP 2025013667 W JP2025013667 W JP 2025013667W WO 2025225327 A1 WO2025225327 A1 WO 2025225327A1
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WO
WIPO (PCT)
Prior art keywords
treatment agent
mass
micro
silicon oxide
etching
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/013667
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English (en)
Japanese (ja)
Inventor
陽介 山崎
豊 小島
啓一 二井
哲郎 西田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Stella Chemifa Corp
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Stella Chemifa Corp
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Filing date
Publication date
Application filed by Stella Chemifa Corp filed Critical Stella Chemifa Corp
Publication of WO2025225327A1 publication Critical patent/WO2025225327A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
    • H01L21/302—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to change their surface-physical characteristics or shape, e.g. etching, polishing, cutting
    • H01L21/306—Chemical or electrical treatment, e.g. electrolytic etching

Definitions

  • the present invention relates to a micro-processing treatment agent and a micro-processing method used in micro-processing, including etching and cleaning processes, in the manufacture of semiconductor devices, liquid crystal display devices, microelectromechanical systems (MEMS) devices, etc., and in particular to a micro-processing treatment agent and a micro-processing method used in the micro-processing of silicon oxide films.
  • a micro-processing treatment agent and a micro-processing method used in micro-processing including etching and cleaning processes, in the manufacture of semiconductor devices, liquid crystal display devices, microelectromechanical systems (MEMS) devices, etc.
  • 3D-NAND nonvolatile memory One example of a semiconductor device manufacturing process that uses wet etching is 3D-NAND nonvolatile memory.
  • Conventional NAND nonvolatile memory is a planar type, and while it has increased in capacity through miniaturization, this has led to a decline in electrical reliability and has reached its limit in miniaturization.
  • 3D-NAND nonvolatile memory has therefore been developed, which uses a trench type in which memory cells are stacked vertically, allowing for increased capacity without reducing the size of the memory cells.
  • the manufacturing process for this 3D-NAND nonvolatile memory includes, for example, a wet etching process in which a silicon oxide film is used as a sacrificial layer to selectively remove a stack of silicon oxide and polysilicon films stacked sequentially on a silicon substrate.
  • This wet etching process takes advantage of the difference in etching speed between silicon oxide and polysilicon films, and the etching solution used can be, for example, an etching solution made from hydrofluoric acid or an etchant containing dilute hydrofluoric acid and a surfactant (Patent Document 1).
  • Non-Patent Document 1 According to Non-Patent Document 1, under certain conditions, the etching rate decreases as the etching area narrows.
  • Patent Document 1 claims that an etchant containing dilute hydrofluoric acid and a surfactant can improve the etching rate of silicon oxide films in recesses in narrow spaces. However, because it contains a surfactant, bubbles are generated during use. As a result, the etchant does not come into uniform contact with the silicon oxide film, resulting in uneven etching of the silicon oxide film and the problem of uneven etching.
  • the present invention was developed in consideration of the above-mentioned problems, and its purpose is to provide a micro-processing treatment agent and a micro-processing method that reduce or inhibit foaming, have excellent defoaming properties, enable selective micro-processing of silicon oxide films to be performed effectively even in narrow spaces, and can improve throughput and yield.
  • the fine-processing treatment agent of the present invention is a fine-processing treatment agent for selectively fine-processing a silicon oxide film on a workpiece having at least the silicon oxide film, the fine-processing treatment agent comprising: (a) hydrogen fluoride in a content of 25 mass% or less relative to the total mass of the fine-processing treatment agent; (b) at least one water-soluble polymer in a content of 1 x 10-4 mass% or more and 1 mass% or less relative to the total mass of the fine-processing treatment agent, the water-soluble polymer having a mass-average molecular weight of 600 or more and 50,000 or less; and (c) water, wherein the water-soluble polymer contains a structural unit having a primary amino group and/or a secondary amino group.
  • the fine-processing treatment agent can penetrate more easily into narrow spaces than conventional fine-processing treatment agents, preventing uneven etching and other fine processing problems caused by the generation of bubbles, enabling good fine processing of a laminate including a silicon oxide film in narrow spaces, and improving yield.
  • the content of the fine processing treatment agent is in the range of 1 ⁇ 10 ⁇ 4 mass % or more and 1 mass % or less, based on the total mass of the fine processing treatment agent , and the fine processing treatment agent further contains a compound having at least one counter ion selected from the group consisting of Cl ⁇ , Br ⁇ , CH 3 COO ⁇ , HSO 4 ⁇ , SO 4 2 ⁇ , NO 3 ⁇ , H 2 PO 4 ⁇ , HPO 4 2 ⁇ , and PO 4 3 ⁇ .
  • the compound having a counter ion in the range of 1 ⁇ 10 ⁇ 4 mass % or more and 1 mass % or less, based on the total mass of the fine processing treatment agent it is possible to maintain a better etching rate for silicon oxide films in narrow areas while suppressing foaming. As a result, it is possible to further improve throughput and yield, even in selective fine processing of silicon oxide films in narrow areas, compared to conventional fine processing treatment agents.
  • the fine processing treatment agent having the above-described configuration is a treatment agent that does not contain a surfactant.
  • a fine processing treatment agent that does not contain a surfactant By using a fine processing treatment agent that does not contain a surfactant, the generation of foaming during use can be further prevented. This reduces uneven contact of the fine processing treatment agent with the silicon oxide film caused by the generation of foam, and further prevents the occurrence of uneven etching.
  • the micro-processing method of the present invention is characterized by using the micro-processing agent having the above-mentioned configuration to selectively micro-process the silicon oxide film on a workpiece having at least the silicon oxide film.
  • the micro-processing agent can effectively perform selective micro-processing on silicon oxide films while reducing or suppressing the generation of bubbles. Therefore, with this configuration, the etching rate for silicon oxide films can be maintained at a good level, even when selectively micro-processing silicon oxide films in narrow spaces, such as in semiconductor manufacturing processes for 3D-NAND non-volatile memories. As a result, increases in the etching time for silicon oxide films can be suppressed, improving throughput. Furthermore, because the agent reduces or suppresses the generation of bubbles and has excellent defoaming properties, it is easier for the agent to penetrate narrow spaces compared to conventional micro-processing agents. Therefore, uneven micro-processing, such as uneven etching caused by the generation of bubbles, can be prevented, allowing for effective micro-processing of silicon oxide films in narrow spaces, and improving yield.
  • the present invention provides the following effects by the means described above. That is, according to the present invention, it is possible to provide a fine processing treatment agent and a fine processing method which reduce or inhibit foaming, have excellent defoaming properties, and can perform selective fine processing on silicon oxide films even in narrow spaces, thereby improving throughput and yield.
  • FIG. 1(a) is a cross-sectional view showing a state in which a silicon oxide film is formed in a blanket state on a substrate
  • FIG. 1(b) is a cross-sectional view showing a state in which the silicon oxide film has been subjected to micro-fabrication using the micro-fabrication treatment agent of the present embodiment
  • FIG. 2(a) is a cross-sectional view showing a state in which a silicon oxide film and a polysilicon film are sequentially stacked on a substrate
  • FIG. 2(b) is a cross-sectional view showing a state in which fine processing has been performed on a narrow area of the silicon oxide film using the fine processing treatment agent of this embodiment.
  • FIG. 1 is a plan view schematically illustrating a state in which bubbles of etching solution adhere to the inner wall of a polystyrene bottle.
  • the fine processing treatment agent according to the present embodiment contains at least (a) hydrogen fluoride, (b) at least one water-soluble polymer, and (c) water.
  • the fine processing treatment agent according to the present embodiment further contains a compound having a counter ion.
  • water-soluble polymers include cationic water-soluble polymers and amphoteric water-soluble polymers.
  • cationic water-soluble polymers include polyallylamine (chemical formula (5) below), partially carbamoylated polyallylamine (chemical formula (6) below), and allylamine amide sulfate polymer (chemical formula (7) below).
  • amphoteric water-soluble polymers include allylamine-sodium allylsulfonate copolymer (chemical formula (8) below) and allylamine-maleic acid copolymer (chemical formula (9) below).
  • Water-soluble polymers can be obtained, for example, by polymerizing monomer components containing at least one monomer having a primary amino group and/or a secondary amino group.
  • monomers include allylamine, carbamoylated allylamine, carboxymethylated allylamine, and allylamine amide sulfate.
  • the monomer components may also contain other monomers, resulting in a water-soluble polymer as a copolymer of the monomer and the other monomer.
  • examples of such other monomers include sodium allylsulfonate and maleic acid.
  • water-soluble polymers containing structural units having primary amino groups and/or secondary amino groups can be obtained by polymerizing ethyleneamine with the carboxyl groups of water-soluble (meth)acrylic polymers.
  • water-soluble (meth)acrylic polymer encompasses both water-soluble acrylic polymers and water-soluble methacrylic polymers.
  • the mass average molecular weight of the water-soluble polymer is in the range of 600 or more and 50,000 or less, and preferably in the range of 1,500 or more and 50,000 or less.
  • the mass average molecular weight of the water-soluble polymer is 600 or more, it is possible to maintain a good selectivity ratio of the etching rate of a silicon oxide film relative to a polysilicon film, for example, and prevent a decrease in controllability of microfabrication.
  • the mass average molecular weight of the water-soluble polymer is 50,000 or less, it is possible to suppress the microfabrication of films other than silicon oxide films, such as polysilicon films, and prevent a decrease in controllability of microfabrication.
  • the weight average molecular weight of the water-soluble polymer may be, for example, 600, 1,000, 1,500, 2,000, 2,500, 3,000, 3,500, 4,000, 4,500, 5,000, 5,500, 6,000, 6,500, 7,000, 7,500, 8,000, 8,500, 9,000, 9,500, 10,000, 15,000, 20,000, 25,000, 30,000, 35,000, 40,000, or 50,000, or may be within a range between any two of the values listed here.
  • the weight average molecular weight (Mw) of the water-soluble polymer can be measured, for example, by gel permeation chromatography (GPC), osmometry, viscosity analysis, light scattering, or sedimentation velocity analysis.
  • the content of the water-soluble polymer is in the range of 1 ⁇ 10 ⁇ 4 mass % or more and 1 mass % or less, preferably 1 ⁇ 10 ⁇ 3 mass % or more and 1 mass % or less, and more preferably 1 ⁇ 10 ⁇ 3 mass % or more and 1 ⁇ 10 ⁇ 1 mass % or less, based on the total mass of the microprocessing treatment agent.
  • the content of the water-soluble polymer is, for example, 1 ⁇ 10 ⁇ 4 , 1 ⁇ 10 ⁇ 3 , 1 ⁇ 10 ⁇ 2 , 2 ⁇ 10 ⁇ 2 , 3 ⁇ 10 ⁇ 2 , 4 ⁇ 10 ⁇ 2 , 5 ⁇ 10 ⁇ 2 , 6 ⁇ 10 ⁇ 2 , 7 ⁇ 10 ⁇ 2 , 8 ⁇ 10 ⁇ 2 , 9 ⁇ 10 ⁇ 2 , 1 ⁇ 10 ⁇ 1 , 2 ⁇ 10 ⁇ 1 , 3 ⁇ 10 ⁇ 1 , 4 ⁇ 10 ⁇ 1 , 5 ⁇ 10 ⁇ 1 , 6 ⁇ 10 ⁇ 1 , 7 ⁇ 10 ⁇ 1 , 8 ⁇ 10 ⁇ 1 , 9 ⁇ 10 ⁇ 1 , or 1 mass % relative to the total mass of the microprocessing agent, and may
  • Two or more different types of water-soluble polymers can be used in combination.
  • “different types of polymers” here refers to polymers with different molecular structures, as well as polymers with the same molecular structure but different mass average molecular weights.
  • the compound having a counter ion, which is component (d), is a compound having at least one ion selected from the group consisting of Cl ⁇ , Br ⁇ , CH 3 COO ⁇ , HSO 4 ⁇ , SO 4 2 ⁇ , NO 3 ⁇ , H 2 PO 4 ⁇ , HPO 4 2 ⁇ , and PO 4 3 ⁇ .
  • Preferred compounds having a counter ion are ammonium salts, potassium salts, or carboxylic acids.
  • ammonium salts include at least one selected from the group consisting of ammonium chloride, ammonium bromide, ammonium acetate, ammonium sulfate, ammonium nitrate, diammonium hydrogen phosphate, and triammonium phosphate.
  • Potassium salts include, for example, potassium acetate.
  • carboxylic acids include acetic acid. Of the exemplified compounds, ammonium acetate is preferred from the perspective of a chemical solution for semiconductor manufacturing, as it contains little or no metal impurities or anionic impurities.
  • the content of the compound having a counter ion is in the range of 1 ⁇ 10 ⁇ 4 mass % or more and 1 mass % or less, and preferably in the range of 1 ⁇ 10 ⁇ 3 mass % or more and 5 ⁇ 10 ⁇ 1 mass % or less, relative to the total mass of the microprocessing treatment agent.
  • the selectivity of the etching rate for silicon oxide films relative to polysilicon films and the like can be maintained at a good level, and a decrease in controllability of microprocessing can be prevented.
  • the content of the compound having a counter ion is, for example, 1 ⁇ 10 ⁇ 4 , 1 ⁇ 10 ⁇ 3 , 1 ⁇ 10 ⁇ 2 , 2 ⁇ 10 ⁇ 2 , 3 ⁇ 10 ⁇ 2 , 4 ⁇ 10 ⁇ 2 , 5 ⁇ 10 ⁇ 2 , 6 ⁇ 10 ⁇ 2 , 7 ⁇ 10 ⁇ 2 , 8 ⁇ 10 ⁇ 2 , 9 ⁇ 10 ⁇ 2 , 1 ⁇ 10 ⁇ 1 , 2 ⁇ 10 ⁇ 1 , 3 ⁇ 10 ⁇ 1 , 4 ⁇ 10 ⁇ 1 , 5 ⁇ 10 ⁇ 1 , 6 ⁇ 10 ⁇ 1 , 7 ⁇ 10 ⁇ 1 , 8 ⁇ 10 ⁇ 1 , 9 ⁇ 10 ⁇ 1 , 1 mass %, and may be within a range between any two of the numerical values exemplified here.
  • the water component (c) contained in the microprocessing treatment agent of this embodiment is not particularly limited, but pure water, ultrapure water, etc. are preferred.
  • the water content is preferably 73% by mass or more, more preferably 83% by mass or more, and particularly preferably 93% by mass or more, based on the total mass of the micro-processing agent.
  • the fine processing treatment agent of this embodiment is preferably a surfactant-free treatment agent.
  • a surfactant in the fine processing treatment agent, the generation of foaming during use can be further prevented. This reduces uneven contact of the fine processing treatment agent with the silicon oxide film caused by the generation of foam, and further prevents the occurrence of uneven etching.
  • surfactants that are not preferably contained in the fine processing treatment agent of this embodiment include monoalkyl sulfates.
  • the micro-processing treatment agent of this embodiment may consist only of hydrogen fluoride, a water-soluble polymer, and water, or may consist only of these components to which a compound having a counter ion has been added.
  • the micro-processing treatment agent of this embodiment may also contain other additives as long as the effects of the present invention are not impaired. Examples of other additives include hydrogen peroxide and chelating agents. The content of other additives can be set appropriately as needed.
  • the defoaming time of the micro-processing treatment agent of this embodiment is preferably less than 300 seconds, and more preferably less than 60 seconds. As a result, even if foaming occurs when the micro-processing treatment agent is supplied to the workpiece for micro-processing, the foam quickly disappears, allowing the micro-processing treatment agent to efficiently penetrate into narrow areas. In addition, this prevents the micro-processing treatment agent from coming into uneven contact with the silicon oxide film due to foaming, resulting in uneven micro-processing such as etching.
  • the defoaming time can be measured using the method described in the examples.
  • the method for producing the micro-processing treatment agent according to this embodiment is not particularly limited, and various methods can be used.
  • the micro-processing treatment agent according to this embodiment can be produced by adding a water-soluble polymer, an optional compound having a counter ion, and other additives to hydrofluoric acid in any order or simultaneously.
  • the micro-processing agent of this embodiment is suitable for selectively micro-processing a silicon oxide film on a processing object having at least the silicon oxide film with a thickness of, for example, 5 nm or 10 nm.
  • the micro-processing method of this embodiment is suitable for selectively performing micro-processing on a silicon oxide film 2 formed in a blanket shape on a substrate 1, as shown in Figures 1(a) and 1(b).
  • Figure 1(a) is a schematic cross-sectional view showing the silicon oxide film 2 formed in a blanket shape on the substrate 1
  • Figure 1(b) is a schematic cross-sectional view showing the silicon oxide film 2 after micro-processing has been performed using the micro-processing treatment agent of this embodiment.
  • the micro-processing agent of this embodiment is also suitable for selectively micro-processing a silicon oxide film in a stacked structure such as that shown in FIG. 2(a).
  • the stacked structure shown in FIG. 2(a) has a structure in which a silicon oxide film 2 and a polysilicon film 3, which function as sacrificial layers, are sequentially stacked on a substrate 1. Furthermore, this stacked structure has multiple trenches 4 formed parallel to one another, and the surface of the substrate 1 is exposed where the trenches 4 are formed.
  • the micro-processing agent When the micro-processing agent is supplied onto the substrate 1, the agent penetrates the stacked structure from the trenches 4 while reducing or minimizing the generation of bubbles, and contacts and removes the exposed areas of the silicon oxide film 2.
  • FIG. 2(b) is a cross-sectional view showing a silicon oxide film 2 and a polysilicon film 3 sequentially stacked on a substrate 1
  • Figure 2(b) is a cross-sectional view showing a state in which fine processing has been performed on a narrow area of the silicon oxide film 2 using the fine processing agent of this embodiment.
  • the micro-processing treatment agent of this embodiment is employed in various wet etching methods.
  • Wet etching methods include batch and single-wafer methods, and the micro-processing treatment agent of the present invention can be employed in either method.
  • Batch wet etching methods are superior in terms of throughput, as they can wet-etch a large number of wafers at once.
  • Single-wafer wet etching methods are less susceptible to cross-contamination than batch wet etching methods, but are inferior to batch wet etching methods in terms of throughput.
  • methods for contacting the fine processing treatment agent with the workpiece include immersion and spraying.
  • the immersion method is preferred because it reduces or prevents changes in composition due to evaporation of the fine processing treatment agent during the process.
  • the etching temperature (i.e., the liquid temperature of the fine-processing treatment agent) is preferably in the range of 50°C or less, more preferably in the range of 5°C to 50°C, even more preferably in the range of 15°C to 35°C, and particularly preferably in the range of 20°C to 30°C.
  • the etching temperature may be, for example, 5, 10, 15, 20, 25, 30, 35, or 50°C, or may be within a range between any two of the values exemplified here.
  • the etching rate within the aforementioned etching temperature range is preferably 1 nm/min or more, more preferably 4 nm/min or more, and even more preferably 25 nm/min or more.
  • the etching rate within the aforementioned etching temperature range is preferably 1 nm/min or more, more preferably 4 nm/min or more, even more preferably 20 nm/min or more, and even more preferably 25 nm/min or more.
  • the time required for fine processing such as wet etching of the silicon oxide film 2 can be shortened, and a decrease in processing efficiency can be suppressed. Furthermore, by setting the etching rate to 270 nm/min or less, a decrease in controllability of the etching amount of the silicon oxide film 2 can be prevented, and practicality as an etching solution in semiconductor manufacturing processes can be maintained.
  • the etching rate for the silicon oxide film 2 in the narrow area may be, for example, 1, 4, 20, 25, 30, 50, 90, 150, 220, or 270 nm/min, or may be within a range between any two of the values exemplified here.
  • Non-doped silicate glass films, phosphorus-doped silicate glass films, boron-doped silicate glass films, boron-phosphorus-doped silicate glass films, TEOS films, fluorine-containing silicon oxide films, carbon-containing silicon oxide films, and nitrogen-containing silicon oxide films can be formed by supplying source gases such as silane and depositing the silicon oxide film using the CVD (chemical vapor deposition) method.
  • SOG films and SOD films can be formed using a coating method such as a spin coater.
  • the micro-processing treatment agent and micro-processing method using the same according to this embodiment can effectively perform selective micro-processing of silicon oxide films in narrow areas in a laminate in which a silicon oxide film and other films are sequentially stacked on a substrate. Furthermore, the micro-processing treatment agent and micro-processing method using the same according to this embodiment can suppress the generation of bubbles when micro-processing silicon oxide films in narrow areas, or can quickly eliminate bubbles if they do occur. This prevents uneven micro-processing of silicon oxide films due to the generation of bubbles.
  • the micro-processing treatment agent and micro-processing method using the same according to this embodiment are suitable for selective micro-processing of silicon oxide films in manufacturing processes for semiconductor devices and the like, which are becoming increasingly highly integrated and miniaturized, particularly in manufacturing processes for 3D-NAND non-volatile memories and the like.
  • Examples 5 to 7 In Examples 5 to 7, the content of hydrogen fluoride was changed to the value shown in Table 1. Furthermore, PAA (registered trademark)-01 (manufactured by Nittobo Medical Co., Ltd., polyallylamine concentration 15% by mass, polyallylamine mass average molecular weight 1,600) was used as the aqueous polyallylamine solution. Furthermore, the contents of the aqueous polyallylamine solution and water were changed to the values shown in Table 1. Except for these, the etching solutions (micro-processing treatment agents) of Examples 5 to 7 were prepared in the same manner as in Example 1.
  • Examples 12 to 14 In Examples 12 to 14, PAA (registered trademark)-15C (manufactured by Nittobo Medical Co., Ltd., polyallylamine concentration 15% by mass, polyallylamine mass average molecular weight 15,000) was used as the aqueous polyallylamine solution. The content of the aqueous polyallylamine solution was changed to the value shown in Table 1. Except for this, the etching solutions (micro-processing treatment agents) of Examples 12 to 14 were prepared in the same manner as in Example 1.
  • Example 15 In Example 15, the contents of hydrogen fluoride and water were changed to the values shown in Table 1. Except for these, an etching solution (fine-processing treatment agent) according to Example 15 was prepared in the same manner as in Example 12.
  • Example 19 to 21 an allylamine-sodium allylsulfonate copolymer (PAA (registered trademark)-1152, manufactured by Nittobo Medical Co., Ltd., concentration of allylamine-sodium allylsulfonate copolymer: 20% by mass, mass average molecular weight of allylamine-sodium allylsulfonate copolymer: 1,500) was used as the water-soluble polymer of component (b). The content of the allylamine-sodium allylsulfonate copolymer was changed to the value shown in Table 2. Except for these, the etching solutions (micro-processing treatment agents) of Examples 19 to 21 were each prepared in the same manner as in Example 1.
  • PAA allylamine-sodium allylsulfonate copolymer
  • Example 22 to 24 In Examples 22 to 24, partially carbamoylated polyallylamine (PAA (registered trademark)-N5050CL, manufactured by Nittobo Medical Co., Ltd., concentration of partially carbamoylated polyallylamine: 15% by mass, mass average molecular weight of partially carbamoylated polyallylamine: 15,000) was used as the water-soluble polymer of component (b). The content of partially carbamoylated polyallylamine was changed to the value shown in Table 2. Except for this, the etching solutions (micro-processing treatment agents) of Examples 22 to 24 were each prepared in the same manner as in Example 1.
  • PAA registered trademark
  • concentration of partially carbamoylated polyallylamine 15% by mass, mass average molecular weight of partially carbamoylated polyallylamine: 15,000
  • the content of partially carbamoylated polyallylamine was changed to the value shown in Table 2. Except for this, the etching solutions (micro-processing treatment agents) of Examples 22 to 24 were each
  • Examples 25 to 27 In Examples 25 to 27, an allylamine amide sulfate polymer (PAA (registered trademark)-SA, manufactured by Nittobo Medical Co., Ltd., allylamine amide sulfate polymer concentration 20 mass%, mass average molecular weight of allylamine amide sulfate polymer 12,000) was used as the water-soluble polymer of component (b). The content of the allylamine amide sulfate polymer was changed to the value shown in Table 2. Except for this, the etching solutions (micro-processing treatment agents) of Examples 25 to 27 were each prepared in the same manner as in Example 1.
  • PAA registered trademark
  • Comparative Examples 8 to 10 Comparative Examples 8 to 10
  • PAA registered trademark
  • -10L-10C manufactured by Nittobo Medical Co., Ltd., polyallylamine concentration 10% by mass, polyallylamine mass average molecular weight 100,000
  • etching solutions micro-processing treatment agents
  • the workpiece was a silicon wafer (manufactured by Global Net Co., Ltd., diameter: 8 inches, see Figure 2(a)) having a laminate on its surface in which a silicon thermal oxide film (film thickness: 10 nm) and a polysilicon film (film thickness: 90 nm) were sequentially stacked, and in which multiple trenches (length: 6 mm, width: 250 nm, depth: 100 nm) were provided in the laminate so as to be parallel to each other at 250 nm intervals.
  • a silicon thermal oxide film film thickness: 10 nm
  • a polysilicon film film thickness: 90 nm
  • This silicon wafer was cut into square test piece sizes (length: 2 cm, width: 2 cm) and then subjected to a batch-type wet etching process using the etching solutions of the above-mentioned Examples and Comparative Examples.
  • the wet etching process was performed by immersing the silicon wafer in etching tanks filled with the respective etching solutions to etch the silicon thermal oxide film, and then exposing the silicon wafer surface to the etching solutions.
  • the etching time was 3 minutes in Examples 1 to 4, 8 to 10, 12 to 14, and 16 to 50, and Comparative Examples 2 and 20, 30 seconds in Examples 5 to 7 and 11, and Comparative Examples 3 to 7, and 10 minutes in Example 15, and Comparative Examples 1, 11 to 15, and 18 to 19.
  • the liquid temperature of the etching solution was 25°C.
  • the silicon wafer was then removed from the etching tank and immersed in a rinse tank overflowing with ultrapure water, where it was washed for 5 minutes. The silicon wafer was then removed from the rinse tank and dried.
  • a silicon wafer manufactured by Global Net Co., Ltd., diameter: 8 inches, see Figure 1(a)
  • a blanket-like silicon thermal oxide film film thickness: 10 nm
  • This silicon wafer was subjected to a batch-type wet etching process using the etching solutions of the above-mentioned Examples and Comparative Examples.
  • the wet etching process involved immersing the silicon wafer in an etching bath filled with each etching solution, and adjusting the etching time appropriately so that a predetermined amount of silicon thermal oxide film remained.
  • the temperature of the etching solution was set to 25°C.
  • the silicon wafer was then removed from the etching bath and immersed in a rinse bath overflowing with ultrapure water, where it was rinsed for 5 minutes.
  • the silicon wafer was then removed from the rinse bath and dried.
  • an optical film thickness measuring device (Nanospec II, manufactured by Onto Innovation Inc.) was used to measure the thickness of the silicon thermal oxide film before and after the wet etching process, and the change in film thickness due to etching was measured.
  • the etching rate V2 (nm/min) at an etching temperature (etchant temperature) of 25°C was calculated for each of the etching solutions in Examples 1 to 50 and Comparative Examples 1 to 7, 11 to 15, and 18 to 20 mentioned above. The results are shown in Tables 6 to 10.
  • Improvement rate (%) ⁇ (V1/V2)/(V10/V20)-1 ⁇ 100
  • V10 (nm/min) represents the etching rate when wet etching process 1 is performed using an etching solution consisting only of HF, the concentration of which is the same as that of the etching solution of the corresponding Example or Comparative Example.
  • V20 (nm/min) represents the etching rate when wet etching process 2 is performed using an etching solution consisting only of HF, the concentration of which is the same as that of the etching solution of the corresponding Example or Comparative Example.
  • the etching solutions of Comparative Examples 8-10, 16, and 17 etched the polysilicon film along with the silicon thermal oxide film, and these etching solutions were unable to selectively etch the silicon thermal oxide film. Furthermore, the etching rate ratios (V1/V2(-)) of the etching solutions of Comparative Examples 11-15 and 18-20 were in the range of 0.67 to 0.72, which was smaller than that of the etching solutions of Examples 1-50 and also resulted in poor improvement rates. This confirms that the etching solutions of Comparative Examples 11-15 and 18-20 did not provide good selective etching of the silicon thermal oxide film in narrow areas.
  • each etching solution was poured into a styrene bottle (internal volume 40 ml).
  • the liquid level of each etching solution immediately after pouring was 25 mm.
  • each styrene bottle was shaken for 10 seconds to generate bubbles, and then allowed to stand.
  • the bubble height (the height from the liquid surface of the etching solution to the peak of the highest bubble) was measured visually after leaving it to stand for 10 seconds and again after leaving it to stand for 60 seconds.
  • the etching solutions of Examples 1 to 50 were all able to effectively suppress the generation of foam, and any foam that did occur was able to disappear within 10 seconds after being left to stand.
  • the space inside the polystyrene bottle was filled with foam, and a larger volume of foam was generated compared to the etching solutions of Examples 1 to 50. Furthermore, the foam could not be eliminated even after 300 seconds had passed since the polystyrene bottle was left to stand.

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Abstract

L'invention concerne un agent de traitement par micro-usinage et un procédé de traitement par micro-usinage qui réduisent ou suppriment le moussage, confèrent d'excellentes propriétés de démoussage et permettent d'effectuer de manière satisfaisante un micro-usinage sélectif sur un film d'oxyde de silicium même dans une zone étroite, ainsi que d'améliorer le débit et le rendement. Cet agent de traitement par micro-usinage est destiné au micro-usinage d'une pièce comportant au moins un film d'oxyde de silicium 2, l'agent comprenant : (a) du fluorure d'hydrogène présentant une teneur se situant dans la plage de 25 % en masse ou moins par rapport à la masse totale de l'agent de traitement par micro-usinage ; (b) au moins un ou plusieurs polymères solubles dans l'eau présentant une teneur se situant dans la plage de 1 × 10-4 à 1 % en masse par rapport à la masse totale de l'agent de traitement par micro-usinage et présentant un poids moléculaire moyen en masse se situant dans la plage de 600 à 50 000 ; et (c) de l'eau. Les polymères solubles dans l'eau comprennent un motif structural comportant un groupe amine primaire et/ou un groupe amine secondaire.
PCT/JP2025/013667 2024-04-23 2025-04-03 Agent de traitement par micro-usinage et procédé de traitement par micro-usinage Pending WO2025225327A1 (fr)

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JP2024069499 2024-04-23
JP2024-069499 2024-04-23

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WO2025225327A1 true WO2025225327A1 (fr) 2025-10-30

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013197213A (ja) * 2012-03-16 2013-09-30 Fujifilm Corp 半導体基板製品の製造方法及びエッチング液
JP2016127065A (ja) * 2014-12-26 2016-07-11 富士フイルム株式会社 エッチング液、これを用いたエッチング方法および半導体基板製品の製造方法
WO2018061582A1 (fr) * 2016-09-29 2018-04-05 富士フイルム株式会社 Fluide de traitement et procédé de traitement de stratifié

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2013197213A (ja) * 2012-03-16 2013-09-30 Fujifilm Corp 半導体基板製品の製造方法及びエッチング液
JP2016127065A (ja) * 2014-12-26 2016-07-11 富士フイルム株式会社 エッチング液、これを用いたエッチング方法および半導体基板製品の製造方法
WO2018061582A1 (fr) * 2016-09-29 2018-04-05 富士フイルム株式会社 Fluide de traitement et procédé de traitement de stratifié

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