Classifications

• • 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
  • C09K13/04—Etching, surface-brightening or pickling compositions containing an inorganic acid
  • C09K13/06—Etching, surface-brightening or pickling compositions containing an inorganic acid with organic material
• • 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
• • 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
  • H10P50/69—Etching of wafers, substrates or parts of devices using masks for semiconductor materials
  • H10P50/691—Etching of wafers, substrates or parts of devices using masks for semiconductor materials for Group V materials or Group III-V materials

Definitions

• etching solution composition that combines water, phosphoric acid, and a hydroxyl group-containing solvent, as described in Patent Document 2.
• examples of the hydroxyl group-containing solvent include polyols, glycols, and monohydric alcohols, and it is said that these components function to protect the silicon oxide film, so that the silicon nitride film is preferentially and selectively etched (see paragraph 0025 of the specification of Patent Document 2).
• the etching solution composition of this configuration contains a compound suitable as a first etching inhibitor, so that it is possible to achieve both the etching inhibitor's effect of inhibiting etching of silicon oxide and the precipitation inhibitor's effect of inhibiting the precipitation of silica on the silicon oxide surface, thereby further improving the etching selectivity for silicon nitride.
• the second etching suppressor is preferably a silane compound having at least one functional group selected from the group consisting of an alkyl group, an amino group, and a halogen group.
• siloxane compound represented by the following chemical structural formula (3):
• the etching solution composition of this configuration does not contain silicon nitride-derived Si in the liquid when unused, i.e., by using a brand new etching solution composition, etching selectivity for silicon nitride can be maintained for a long period of time.
• the second etch inhibitor generally has the chemical structure shown in formula (I) below:
• the above compounds and compounds may be used alone or in a mixture of two or more.
• the use of two or more different deposition inhibitors can be very useful not only in terms of performance in the etching process, but also in terms of extending the life of the solution and reducing costs.
• the content of the deposition inhibitor in the etching solution composition is preferably 0.1 to 1% by weight, more preferably 0.3 to 0.4% by weight.
• pyrazoles examples include 3,5-dimethylpyrazole, 3-methyl-5-pyrazole, etc.
• the above pyrazoles may be used alone or in a mixture of two or more kinds.
• Examples of compounds having a purine skeleton include purine, adenine, guanine, uric acid, caffeine, hypoxanthine, xanthine, theophylline, theobromine, isoguanine, and nucleosides, ribonucleotides, and deoxyribonucleotides of the above-mentioned compounds.
• the above-mentioned compounds having a purine skeleton may be used alone or in a mixture of two or more kinds.
• a surfactant When the etching inhibitor and the precipitation inhibitor are dissolved or suspended in a solvent, a surfactant may be used in combination.
• the surfactant any of cationic surfactants, anionic surfactants, amphoteric surfactants, and nonionic surfactants may be used, and these surfactants may be used in combination.
• the etching solution composition according to the present invention has a major feature that it can be used when the concentration of silicon nitride-derived Si in the solution reaches a predetermined concentration range or reaches a predetermined concentration.
• concentration of silicon nitride-derived Si in the solution increases as the time of use or the number of uses increases, and when the concentration of Si reaches a certain level, silica precipitation occurs, making it necessary to either discard the solution as fatigue liquid or to recover and regenerate the fatigue liquid.
• the etching solution composition according to the present invention is capable of suppressing silica precipitation even if the concentration of silicon nitride-derived Si in the solution increases.
• the selectivity [R 1 /R 2 ] of the etching solution composition of the present invention relative to the selectivity of an etching solution consisting of only inorganic acid is preferably 9 times or more, more preferably 18 times or more. If an etching treatment is performed using an etching solution composition having a high selectivity [R 1 /R 2 ] relative to an etching solution consisting of only inorganic acid, it is possible to prevent defects such as short circuits and wiring defects from occurring in semiconductor products, which is very advantageous in industrial production (process) of semiconductor products.
• Example 2 A predetermined amount of silicon nitride was dissolved in advance in the etching solution composition of Example 1, and the concentration of silicon nitride-derived Si in the solution was adjusted to 200 ppm to prepare the etching solution composition of Example 2.
• the concentration of silicon nitride-derived Si in the solution was measured by the "Method for Measuring Concentration of Silicon Nitride-derived Si" described below (the same applies to the following Examples and Comparative Examples).
• Example 3 To 87% phosphoric acid obtained by the same procedure as in Example 1, 3.00 wt % of 3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) as a first etching inhibitor, 0.09 wt % of a siloxane compound having the following chemical structural formula (2) as a second etching inhibitor, and 0.30 wt % of adipic acid dihydrazide (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) as a precipitation inhibitor were added, and dissolved in the liquid to prepare an etching solution composition of Example 3.
• Example 13 To 87% phosphoric acid obtained by the same procedure as in Example 1, 3.00 wt % of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) as a first etching inhibitor, 0.12 wt % of the siloxane compound shown in chemical structural formula (2) as a second etching inhibitor, and 0.30 wt % of adipic acid dihydrazide (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) as a precipitation inhibitor were added, and dissolved in the liquid to prepare the etching solution composition of Example 13.
• N-2-(aminoethyl)-3-aminopropyltrimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.
• 0.12 wt % of the siloxane compound shown in chemical structural formula (2) as a second etching inhibitor
• Example 15 To 87% phosphoric acid obtained by the same procedure as in Example 1, 6.00 wt % of N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd.) as a first etching inhibitor, 0.09 wt % of the siloxane compound shown in chemical structural formula (2) as a second etching inhibitor, and 0.30 wt % of acetohydrazide chloride (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) as a precipitation inhibitor were added, and dissolved in the liquid to prepare the etching solution composition of Example 15.
• N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane manufactured by Shin-Etsu Chemical Co., Ltd.
• 0.09 wt % of the siloxane compound shown in chemical structural formula (2) as a second etching inhibitor
• Example 32 The etching solution composition of Example 32 was prepared by dissolving a predetermined amount of silicon nitride in advance in the etching solution composition of Example 31 and adjusting the concentration of Si derived from silicon nitride in the solution to 3000 ppm.
• Comparative Example 8 To 87% phosphoric acid obtained by the same procedure as in Example 1, 0.15 wt % of the siloxane compound shown in chemical structural formula (2) as a second etching inhibitor and 0.10 wt % of adipic acid dihydrazide (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.) as a precipitation inhibitor were added and dissolved in the liquid, and then a predetermined amount of silicon nitride was dissolved in advance, and the concentration of Si derived from silicon nitride in the liquid was adjusted to 50 ppm, to obtain the etching solution composition of Comparative Example 8.
• adipic acid dihydrazide manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.

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• Chemical & Material Sciences (AREA)
• Inorganic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Weting (AREA)

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• 2023
  • 2023-08-03 JP JP2024562570A patent/JPWO2024122103A1/ja active Pending
  • 2023-08-03 WO PCT/JP2023/028410 patent/WO2024122103A1/ja not_active Ceased
  • 2023-08-03 KR KR1020257007856A patent/KR20250044782A/ko active Pending
  • 2023-08-15 TW TW112130593A patent/TWI881428B/zh active

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