WO2011019015A1 - 微細加工処理剤、及びそれを用いた微細加工処理方法 - Google Patents
微細加工処理剤、及びそれを用いた微細加工処理方法 Download PDFInfo
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- WO2011019015A1 WO2011019015A1 PCT/JP2010/063480 JP2010063480W WO2011019015A1 WO 2011019015 A1 WO2011019015 A1 WO 2011019015A1 JP 2010063480 W JP2010063480 W JP 2010063480W WO 2011019015 A1 WO2011019015 A1 WO 2011019015A1
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- Prior art keywords
- component
- oxide film
- film
- silicon oxide
- fine processing
- Prior art date
Links
- 238000000034 method Methods 0.000 title abstract description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 76
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 64
- 229910052581 Si3N4 Inorganic materials 0.000 claims abstract description 50
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims abstract description 50
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 10
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims abstract description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000005368 silicate glass Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 13
- 238000003672 processing method Methods 0.000 claims description 9
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 6
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 239000011737 fluorine Substances 0.000 claims description 3
- 239000010408 film Substances 0.000 description 162
- 238000005530 etching Methods 0.000 description 62
- 239000000243 solution Substances 0.000 description 22
- 239000003990 capacitor Substances 0.000 description 13
- 239000004065 semiconductor Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 239000000758 substrate Substances 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 238000001039 wet etching Methods 0.000 description 6
- 229910021642 ultra pure water Inorganic materials 0.000 description 5
- 239000012498 ultrapure water Substances 0.000 description 5
- 239000005380 borophosphosilicate glass Substances 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 230000010354 integration Effects 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 238000005459 micromachining Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229920001223 polyethylene glycol Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- HSNJERRVXUNQLS-UHFFFAOYSA-N 1-(4-tert-butylphenyl)propan-2-one Chemical compound CC(=O)CC1=CC=C(C(C)(C)C)C=C1 HSNJERRVXUNQLS-UHFFFAOYSA-N 0.000 description 1
- FHCUSSBEGLCCHQ-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;fluoride Chemical compound [F-].C[N+](C)(C)CCO FHCUSSBEGLCCHQ-UHFFFAOYSA-M 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 241000862969 Stella Species 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000005215 alkyl ethers Chemical class 0.000 description 1
- 125000005037 alkyl phenyl group Chemical group 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- BTBJBAZGXNKLQC-UHFFFAOYSA-N ammonium lauryl sulfate Chemical compound [NH4+].CCCCCCCCCCCCOS([O-])(=O)=O BTBJBAZGXNKLQC-UHFFFAOYSA-N 0.000 description 1
- 229940063953 ammonium lauryl sulfate Drugs 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical class OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- -1 fatty acid ester Chemical class 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- MOVBJUGHBJJKOW-UHFFFAOYSA-N methyl 2-amino-5-methoxybenzoate Chemical compound COC(=O)C1=CC(OC)=CC=C1N MOVBJUGHBJJKOW-UHFFFAOYSA-N 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 239000012788 optical film Substances 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 229920005591 polysilicon Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003460 sulfonic acids Chemical class 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 1
- QSUJAUYJBJRLKV-UHFFFAOYSA-M tetraethylazanium;fluoride Chemical compound [F-].CC[N+](CC)(CC)CC QSUJAUYJBJRLKV-UHFFFAOYSA-M 0.000 description 1
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 1
- ASVMCHUOIVTKQQ-UHFFFAOYSA-M triethyl(methyl)azanium;fluoride Chemical compound [F-].CC[N+](C)(CC)CC ASVMCHUOIVTKQQ-UHFFFAOYSA-M 0.000 description 1
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
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31105—Etching inorganic layers
- H01L21/31111—Etching inorganic layers by chemical means
-
- 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
- C09K13/08—Etching, surface-brightening or pickling compositions containing an inorganic acid containing a fluorine compound
Definitions
- the present invention relates to a fine processing agent and a fine processing method used for etching processing, cleaning processing, and the like in the manufacture of semiconductor devices, liquid crystal display devices, micromachine (MEMS) devices, and the like. Relates to a fine processing agent and a fine processing method used for etching processing, cleaning processing, and the like for a structure in which at least a silicon nitride film and a silicon oxide film are stacked.
- One of the most important processes in the manufacturing process of semiconductor devices is to pattern and etch a silicon oxide film, silicon nitride film, polysilicon film, metal film, etc. formed on the wafer surface into a desired shape. It is.
- wet etching which is a kind of etching technique, a fine processing method capable of selectively etching only a film to be etched is required.
- Examples of a method for etching a silicon oxide film in the fine processing include a method using buffered hydrofluoric acid or hydrofluoric acid.
- the buffered hydrofluoric acid or hydrofluoric acid is used as the microfabrication processing agent for the laminated film in which the silicon nitride film and the silicon oxide film are laminated, the silicon nitride film is also etched at the same time. As a result, it becomes difficult to pattern into a desired shape.
- the fine processing agent As a fine processing method that can solve such problems and selectively etch only the silicon oxide film, for example, a hydrofluoric acid added with an anionic surfactant such as ammonium lauryl sulfate The method of using is mentioned (refer the following patent document 1).
- the fine processing agent has a very high foaming property, which makes it unsuitable as a fine processing method used in a semiconductor element manufacturing process.
- a DRAM Dynamic Random Access Memory
- the DRAM cell is composed of one transistor and one capacitor. This DRAM has been highly integrated about four times over the past three years. High integration of DRAM is mainly due to high integration of capacitors. Therefore, in order to secure a capacitance value necessary for stable storage operation while reducing the area occupied by the capacitor, the capacitor area is increased, the capacitor insulating film is thinned, and a high dielectric constant film is introduced.
- the capacitor insulating film As the capacitor insulating film, a silicon oxide film is used, and until now, its thinning has been studied. However, the thinning of the silicon oxide film as the capacitor insulating film has reached the limit with 1Mbit DRAM. Therefore, a silicon nitride film is used as an insulating film in a 4M bit DRAM. Furthermore, application of a tantalum oxide film has been started as higher integration progresses.
- the capacitor structure of a 64 Mbit generation DRAM is a cylinder type.
- the silicon oxide film thus formed is removed by wet etching to form a capacitor after forming the cylinder-type capacitor lower electrode, the following problems occur when a conventional etching solution is used.
- Patent Document 2 discloses a technique for forming a support film made of a silicon nitride film between capacitor lower electrodes.
- Patent Document 3 listed below discloses a technique for forming a silicon nitride film as an insulating film in order to improve the insulation characteristics with respect to the bit line. A technique for forming a film as an etching stop film in an etching process of a silicon oxide film is disclosed.
- the silicon nitride film as the support film in Patent Document 2 the silicon nitride film in Patent Document 3, and the etching stop film in Patent Document 4 are used. There is a problem that the silicon nitride film is etched together with the object to be etched.
- the present invention has been made in view of the above-described problems, and an object of the present invention is to selectively finely process a silicon oxide film when finely processing a laminated film in which at least a silicon oxide film and a silicon nitride film are laminated.
- An object of the present invention is to provide a fine processing agent that can be used, and a fine processing method using the same.
- the inventors of the present application have studied a fine processing agent and a fine processing method using the same in order to solve the conventional problems.
- the microfabrication processing agent is obtained by adding a certain concentration of acid to an aqueous solution containing hydrogen fluoride or at least one of ammonium fluoride or quaternary ammonium fluoride, a silicon oxide film and silicon nitride
- the inventors have found that only a silicon oxide film can be selectively microfabricated with respect to a laminated film in which films are laminated, and have completed the present invention.
- the microfabrication processing agent according to the present invention is a micromachining treatment agent used for microfabrication of an object on which a silicon nitride film and a silicon oxide film are formed in order to solve the above-described problems.
- the total content of the components is 90% by weight or less based on the total amount of the fine processing agent.
- component 0.01 wt% to 20 wt% hydrogen fluoride
- component at least one of 0.1 wt% to 20 wt% ammonium fluoride or quaternary ammonium fluoride
- component C 1% to 80% by weight of at least one acid selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid
- component water
- the selection ratio of the etching of the silicon oxide film with respect to a silicon nitride film by setting it as the composition which combined at least any one of said (A) component or (B) component, and said (C) component (Silicon oxide film / silicon nitride film) can be increased.
- the micro-processing agent of the present invention when the micro-processing agent of the present invention is applied to the micro-processing of an object in which a silicon oxide film and a silicon nitride film are sequentially stacked, the silicon oxide film can be selectively micro-processed with respect to the silicon nitride film. become. Thereby, for example, the yield in the semiconductor element manufacturing process can be improved.
- the acid content of the component (C) is in the range of 1 to 80% by weight.
- the lower limit By setting the lower limit to 1% by weight, the effect of acid addition can be exhibited, and the silicon oxide film can be selectively etched.
- the upper limit By setting the upper limit to 80% by weight, the reaction product produced by finely processing the silicon oxide film is promoted to dissolve in the fine processing agent, and the silicon oxide film is finely processed. Can be promoted.
- an increase in the viscosity of the fine processing agent can be suppressed, thereby improving the removal performance of the fine processing agent with a rinse agent such as ultrapure water.
- “microfabrication” includes etching of a film to be processed and surface cleaning.
- the silicon oxide film is a natural oxide film, a thermal silicon oxide film, a non-doped silicate glass film, a phosphorus-doped silicate glass film, a boron-doped silicate glass film, a phosphorus-doped silicate glass film, a TEOS film, or a fluorine-containing silicon oxide film. It is preferable that
- microfabrication processing method selectively microfabricates a silicon oxide film using the microprocessing agent described above in order to solve the above-mentioned problems.
- the present invention has the following effects by the means described above. That is, according to the present invention, only the silicon oxide film can be selectively finely processed with respect to the laminated film in which at least the silicon oxide film and the silicon nitride film are laminated.
- a semiconductor device a liquid crystal display device, It enables fine processing suitable for manufacturing micromachine devices and the like.
- the fine processing agent according to the present embodiment includes at least one of the following component (A) or component (B), the following component (C), and the following component (D).
- component 0.01 wt% to 20 wt% hydrogen fluoride
- component at least one of 0.1 wt% to 20 wt% ammonium fluoride or quaternary ammonium fluoride
- Component C 1% to 80% by weight of at least one acid selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid and phosphoric acid
- Component water
- the content of hydrogen fluoride as the component (A) is in the range of 0.01 to 20% by weight and in the range of 0.1 to 10% by weight with respect to the total amount of the fine processing agent. Is preferred.
- the content of hydrogen fluoride is less than 0.01% by weight, it is difficult to control the concentration of hydrogen fluoride, and thus there may be a large variation in the etch rate with respect to the silicon oxide film.
- the content of hydrogen fluoride exceeds 20% by weight, the etching rate for the silicon oxide film becomes too high, and the controllability of etching is lowered. Further, the evaporation of hydrogen fluoride gas becomes remarkable, and it may be difficult to handle the fine processing agent.
- the component (B) may contain at least one of ammonium fluoride and quaternary ammonium fluoride.
- the quaternary ammonium fluoride is not particularly limited, and examples thereof include tetramethylammonium fluoride, tetraethylammonium fluoride, triethylmethylammonium fluoride, and choline fluoride.
- the content of the component (B) is in the range of 0.1 to 20% by weight and preferably in the range of 0.5 to 10% by weight with respect to the total amount of the fine processing agent.
- the content of the component (B) is less than 0.1% by weight, it is difficult to control the concentration of the component (B) in the fine processing agent, and the variation in the etch rate with respect to the silicon oxide film may increase.
- the content of the component (B) exceeds 20% by weight, the saturation solubility of the component (B) is approached, so that crystals may precipitate depending on the liquid temperature of the fine processing agent.
- the component (C) is at least one acid selected from the group consisting of hydrochloric acid, nitric acid, sulfuric acid, and phosphoric acid. Of these acids, sulfuric acid is preferred from the viewpoint of the selectivity of the silicon oxide film relative to the silicon nitride film.
- the content of the component (C) is in the range of 1 to 80% by weight and preferably in the range of 40 to 70% by weight with respect to the total amount of the fine processing agent. If the content of the component (C) is less than 1% by weight, the effect of adding an acid cannot be exhibited, and selective etching of the silicon oxide film may be difficult. On the other hand, when the content of the component (C) exceeds 80% by weight, dissolution of the reaction product generated by etching the silicon oxide film into the fine processing agent is suppressed, and etching of the silicon oxide film is inhibited. There is a case. In addition, the viscosity of the fine processing agent may increase, and the rinse removal performance of the fine processing agent with a rinse agent such as ultrapure water may decrease.
- the total content of at least one of the component (A) or the component (B) and the component (C) is 90% by weight or less and 70% by weight or less based on the total amount of the fine processing agent. It is preferable that By making the total content of at least one of the component (A) or the component (B) and the component (C) 90% by weight or less, the reaction product generated when the silicon oxide film is etched is fine. It is possible to promote dissolution in the processing agent and suppress variation in the etching rate with respect to the silicon oxide film. In addition, an increase in the viscosity of the fine processing agent can be suppressed, thereby improving the removal performance of the fine processing agent with a rinse agent such as ultrapure water.
- the third processing component may be contained in the fine processing agent according to the present embodiment.
- the third component include a surfactant.
- the surfactant is not particularly limited.
- nonionic surfactants such as polyethylene glycol alkyl ether, polyethylene glycol alkyl phenyl ether, and polyethylene glycol fatty acid ester are preferable. It is.
- the pH of the fine processing agent is 2 or more
- aliphatic alcohol, aliphatic carboxylic acid, hydrofluoroalkyl alcohol, hydrofluoroalkyl carboxylic acid, hydrofluoroalkyl carboxylate, aliphatic amine salt, and aliphatic At least one selected from the group consisting of sulfonic acids is preferred.
- the fine processing agent may be solid or liquid.
- the addition amount of the surfactant is preferably in the range of 0.001 to 0.1% by weight, and more preferably in the range of 0.003 to 0.05% by weight.
- the surfactant By adding the surfactant, it is possible to suppress the roughness of the surface of the silicon nitride film or semiconductor substrate subjected to the etching process.
- conventional fine processing agents tend to remain locally on the surface of a semiconductor substrate on which a fine pattern has been applied due to ultra-high integration, and uniformly when the resist interval is about 0.5 ⁇ m or less. It is more difficult to etch.
- the fine processing agent of the present invention to which a surfactant is added is used as an etching solution, the wettability to the surface of the semiconductor substrate is improved, and the uniformity of etching in the substrate surface is improved.
- the addition amount is less than 0.001% by weight, the surface tension of the fine processing agent is not sufficiently lowered, and the effect of improving wettability may be insufficient.
- the addition amount exceeds 0.1% by weight, not only the effect corresponding to that can not be obtained, but also the defoaming property deteriorates, the bubbles adhere to the etched surface, the etching unevenness occurs, or the fine gaps are formed. Bubbles may enter and cause etching failure.
- the fine processing agent of the present embodiment can be mixed with additives other than surfactants within a range that does not impede its effect.
- additives other than surfactants include hydrogen peroxide and a chelating agent.
- the fine processing agent according to the present embodiment can be produced by mixing the components (A) to (D) in any order.
- (B) component is obtained by adding a hydrofluoric acid suitably and neutralizing it, when the raw material is a hydroxide, and making it into a fluoride. Further, without neutralizing the raw material which is a hydroxide with hydrofluoric acid, by adding to a solution containing at least hydrogen fluoride which is the component (A), a neutralization reaction with a part of the hydrogen fluoride is performed, As a result, it is good also as an aspect in which (B) component was contained in the solution.
- examples of such a hydroxide include ammonium hydroxide, tetramethylammonium hydroxide, tetraethylammonium hydroxide, triethylmethylammonium hydroxide, or Examples thereof include ammonium hydroxides such as choline.
- micromachining method using the micromachining agent according to the present embodiment will be described by taking wet etching as an example.
- the fine processing agent according to the present embodiment is used for, for example, an object to be processed in which a silicon nitride film and a silicon oxide film are formed on a substrate.
- a stacked film that is sequentially stacked can be given.
- Examples of the silicon oxide film include a natural oxide film, a thermal silicon oxide film, a non-doped silicate glass film, a phosphorus-doped silicate glass film, a boron-doped silicate glass film, a phosphorus-doped silicate glass film, a TEOS film, and a fluorine-containing silicon oxide film. Can be mentioned.
- the fine processing agent according to the present embodiment is employed in various wet etching methods.
- an etching method there are an immersion method, a spray method, and the like, and the microfabrication processing agent of the present invention can be adopted in any method.
- the immersion method is preferable because the composition change of the fine processing agent is small due to evaporation in the etching process.
- the etching temperature (the liquid temperature of the fine processing agent) is preferably within a range of 5 to 50 ° C., and within a range of 15 to 35 ° C. Is more preferable, and is more preferably within a range of 20 to 30 ° C. Within the above range, evaporation of the fine processing agent can be suppressed, and a change in composition can be prevented. In addition, it becomes difficult to control the etching rate due to evaporation of the fine processing agent at a high temperature, and components in the fine processing agent are likely to crystallize at a low temperature, resulting in a decrease in the etching rate and an increase in particles in the liquid.
- the etching temperature is within the above range, the disadvantage can be avoided. Since the etch rate varies from film to film depending on the etching temperature, the difference between the etch rate for the silicon oxide film and the etch rate for the silicon nitride film may be affected.
- the etch rate for the silicon oxide film at 25 ° C. is preferably in the range of 1 to 10,000 nm / min, and 15 to 3000 nm / min. More preferably within the range. If the etch rate is less than 1 nm / min, it takes time for fine processing such as etching, which may lead to a decrease in production efficiency. Further, if it exceeds 10,000 nm / min, the controllability of the film thickness after etching and the roughness of the substrate surface (surface opposite to the surface on which the silicon oxide film etc. are formed) become prominent and the yield may decrease. is there.
- Etch rate for silicon oxide film and silicon nitride film The film thickness of the silicon oxide film and the silicon nitride film before and after etching was measured using an optical film thickness measuring device (Nanospec 6100, manufactured by Nanometrics Japan Co., Ltd.), and the change in film thickness due to etching was measured. The above measurement was repeated at three different etching times to calculate the etch rate. As the object to be processed, a silicon nitride film or a silicon oxide film formed on the substrate was used.
- Example 1 In a solution obtained by mixing 10 parts by weight of hydrogen fluoride (manufactured by Stella Chemifa Co., Ltd., high purity grade for semiconductor, concentration 50% by weight) and 7 parts by weight of ultrapure water, sulfuric acid (Mitsubishi Chemical) After 83 parts by weight were added and stirred and mixed, the mixture was adjusted to 25 ° C. and allowed to stand for 3 hours. Thus, an etching solution (fine processing agent) of 5 wt% hydrogen fluoride and 80 wt% sulfuric acid was prepared.
- hydrogen fluoride manufactured by Stella Chemifa Co., Ltd., high purity grade for semiconductor, concentration 50% by weight
- sulfuric acid Mitsubishi Chemical
- the respective substrates on which the silicon nitride film or the silicon oxide film was formed were immersed, and the etch rates for the BPSG film as the silicon oxide film and the silicon nitride film were measured. Furthermore, the etch rate selectivity (silicon oxide film / silicon nitride film) was evaluated. In addition, the liquid temperature of the etching liquid at this time was 25 degreeC. The results are shown in Table 1 below.
- Example 2 to 9 In Examples 2 to 9, as shown in Table 1, the content of component (A) (hydrogen fluoride), the content and type of component (B), the content of component (C) and An etching solution was prepared in the same manner as in Example 1 except that the type was changed. Furthermore, using the etching solution obtained in each example, the etching rate with respect to the BPSG film and the silicon nitride film and the selectivity of the etching rate (silicon oxide film / silicon nitride film) were evaluated. The results are shown in Table 1 below.
- Comparative Examples 1 and 2 In Comparative Example 1, an etching solution was prepared in the same manner as in Example 1 except that the acid of component (C) was not added as shown in Table 1. In Comparative Example 2, an etching solution was prepared in the same manner as in Example 7 except that the acid of component (C) was not added as shown in Table 1. Further, using the etching solutions obtained in the comparative examples, the etching rate with respect to the BPSG film and the silicon nitride film and the selectivity of the etching rate (silicon oxide film / silicon nitride film) were evaluated in the same manner as in Example 1. . The results are shown in Table 1 below.
- the composition includes at least one of the component (A) or the component (B) and the component (C) as in the etching solutions according to Examples 1 to 9, the etch rate for the silicon oxide film is increased. It was confirmed that the selective ratio of the silicon oxide film to the silicon nitride film can be increased selectively (silicon oxide film / silicon nitride film).
- Example 10 to 14 In Examples 10 to 14, as shown in Table 2, the content of component (A) (hydrogen fluoride), the content and type of component (B), the content of component (C) and An etching solution was prepared in the same manner as in Example 1 except that the type was changed. Further, using the etching solution obtained in each example, in the same manner as in Example 1, the etch rate with respect to the non-doped silicate glass film and the silicon nitride film as the silicon oxide film, and the selectivity of the etch rate (silicon oxide film / (Silicon nitride film) was evaluated. The results are shown in Table 2 below.
- Comparative Examples 3 and 4 In Comparative Example 3, an etching solution was prepared in the same manner as in Example 10 except that the component (C) was not added as shown in Table 2. In Comparative Example 4, an etching solution was prepared in the same manner as in Example 11 except that the component (B) was not added as shown in Table 2. Further, using the etching solution obtained in each comparative example, the etching rate for the non-doped silicate glass film and the silicon nitride film and the selectivity of the etching rate (silicon oxide film / silicon nitride film) were set in the same manner as in Example 1. evaluated. The results are shown in Table 2 below.
- the composition includes at least one of the component (A) or the component (B) and the component (C) as in the etching solutions according to Examples 10 to 14, the etching rate for the silicon oxide film is increased. It was confirmed that the selective ratio of the silicon oxide film to the silicon nitride film can be increased selectively (silicon oxide film / silicon nitride film).
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Abstract
Description
(A)成分:0.01重量%~20重量%のフッ化水素
(B)成分:0.1重量%~20重量%のフッ化アンモニウム、又は第四級アンモニウムフロライドの少なくとも何れか一方
(C)成分:1重量%~80重量%の塩酸、硝酸、硫酸及びリン酸からなる群より選択される少なくとも何れか1種の酸
(D)成分:水
即ち、本発明によれば、シリコン酸化膜とシリコン窒化膜が少なくとも積層された積層膜に対し、シリコン酸化膜のみを選択的に微細加工処理することができるので、例えば半導体装置、液晶表示装置、マイクロマシンデバイス等の製造に於いて好適な微細加工を可能にする。
本実施の形態に係る微細加工処理剤は、下記(A)成分又は(B)成分の少なくとも何れか一方と、下記(C)成分と、下記(D)成分とを含む。
(A)成分:0.01重量%~20重量%のフッ化水素
(B)成分:0.1重量%~20重量%のフッ化アンモニウム、又は第四級アンモニウムフロライドの少なくとも何れか一方
(C)成分:1重量%~80重量%の塩酸、硝酸、硫酸及びリン酸からなる群より選択される少なくとも何れか1種の酸
(D)成分:水
光学式膜厚測定装置(ナノメトリクスジャパン(株)社製、Nanospec6100)を用いてエッチング前後のシリコン酸化膜、及びシリコン窒化膜の膜厚を測定し、エッチングによる膜厚の変化を測定した。3つの異なるエッチング時間に於いて前記測定を繰り返し実施し、エッチレートを算出した。尚、被処理物としては、シリコン窒化膜、又はシリコン酸化膜がそれぞれ基板上に形成されたものを用いた。
フッ化水素(ステラケミファ(株)製、半導体用高純度グレード、濃度50重量%)10重量部と、超純水7重量部とを混合した溶液に、(C)成分としての硫酸(三菱化学(株)製、濃度96重量%)83重量部を添加し、攪拌混合した後、混合液を25℃に調温し3時間静置した。これにより、フッ化水素5重量%、硫酸80重量%のエッチング液(微細加工処理剤)を調製した。
実施例2~9に於いては、表1に示す通りに、(A)成分(フッ化水素)の含有量と、(B)成分の含有量及び種類と、(C)成分の含有量及び種類とを変更したこと以外は、前記実施例1と同様にしてエッチング液を調製した。更に、各実施例で得られたエッチング液を用いて、BPSG膜及びシリコン窒化膜に対するエッチレート、エッチレートの選択比(シリコン酸化膜/シリコン窒化膜)を評価した。結果を下記表1に示す。
比較例1に於いては、表1に示す通りに(C)成分の酸を添加しなかったこと以外は、前記実施例1と同様にしてエッチング液を調製した。また、比較例2に於いては、表1に示す通りに(C)成分の酸を添加しなかったこと以外は、前記実施例7と同様にしてエッチング液を調製した。更に、各比較例で得られたエッチング液を用いて、実施例1と同様にして、BPSG膜及びシリコン窒化膜に対するエッチレート、エッチレートの選択比(シリコン酸化膜/シリコン窒化膜)を評価した。結果を下記表1に示す。
下記表1からも明らかな通り、(C)成分である酸が添加されていない比較例1及び2に係るエッチング液では、BPSG膜の選択的なエッチングが抑制されており、シリコン窒化膜に対するシリコン酸化膜のエッチレートの選択比(シリコン酸化膜/シリコン窒化膜)を大きくすることはできなかった。
実施例10~14に於いては、表2に示す通りに、(A)成分(フッ化水素)の含有量と、(B)成分の含有量及び種類と、(C)成分の含有量及び種類とを変更したこと以外は、前記実施例1と同様にしてエッチング液を調製した。更に、各実施例で得られたエッチング液を用いて、実施例1と同様にして、シリコン酸化膜としてのノンドープシリケートガラス膜及びシリコン窒化膜に対するエッチレート、エッチレートの選択比(シリコン酸化膜/シリコン窒化膜)を評価した。結果を下記表2に示す。
比較例3に於いては、表2に示す通りに(C)成分を添加しなかったこと以外は、前記実施例10と同様にしてエッチング液を調製した。また、比較例4に於いては、表2に示す通りに(B)成分を添加しなかったこと以外は、前記実施例11と同様にしてエッチング液を調製した。更に、各比較例で得られたエッチング液を用いて、実施例1と同様にして、ノンドープシリケートガラス膜及びシリコン窒化膜に対するエッチレート、エッチレートの選択比(シリコン酸化膜/シリコン窒化膜)を評価した。結果を下記表2に示す。
下記表2からも明らかな通り、(C)成分である酸が添加されていない比較例3及び4に係るエッチング液では、ノンドープシリケートガラス膜の選択的なエッチングが抑制されており、シリコン窒化膜に対するシリコン酸化膜のエッチレートの選択比(シリコン酸化膜/シリコン窒化膜)を大きくすることはできなかった。
Claims (3)
- シリコン窒化膜及びシリコン酸化膜が形成された被処理物の微細加工に用いる微細加工処理剤であって、
下記(A)成分又は(B)成分の少なくとも何れか一方と、下記(C)成分と、下記(D)成分とを含み、
下記(A)成分又は(B)成分の少なくとも何れか一方と、(C)成分との含有量の合計が、微細加工処理剤の全体量に対し90重量%以下である微細加工処理剤。
(A)成分:0.01重量%~20重量%のフッ化水素
(B)成分:0.1重量%~20重量%のフッ化アンモニウム、又は第四級アンモニウムフロライドの少なくとも何れか一方
(C)成分:1重量%~80重量%の塩酸、硝酸、硫酸及びリン酸からなる群より選択される少なくとも何れか1種の酸
(D)成分:水 - 前記シリコン酸化膜は、自然酸化膜、熱シリコン酸化膜、ノンドープシリケートガラス膜、リンドープシリケートガラス膜、ボロンドープシリケートガラス膜、リンボロンドープシリケートガラス膜、TEOS膜又はフッ素含有シリコン酸化膜の何れかである請求項1に記載の微細加工処理剤。
- 請求項1又は2に記載の微細加工処理剤を用いて、シリコン酸化膜を選択的に微細加工する微細加工処理方法。
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2002246378A (ja) * | 2000-12-15 | 2002-08-30 | Toshiba Corp | 半導体装置の製造方法 |
JP2005167181A (ja) * | 2003-11-10 | 2005-06-23 | Daikin Ind Ltd | Low−k膜用エッチング液及びエッチング方法 |
JP2006179513A (ja) * | 2004-12-20 | 2006-07-06 | Stella Chemifa Corp | 微細加工処理剤、及びそれを用いた微細加工処理方法 |
JP2008053723A (ja) * | 2006-08-21 | 2008-03-06 | Cheil Industries Inc | シリコン酸化膜選択性湿式エッチング溶液 |
JP2010109064A (ja) * | 2008-10-29 | 2010-05-13 | Tosoh Corp | エッチング方法 |
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---|---|---|---|---|
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JP2006179513A (ja) * | 2004-12-20 | 2006-07-06 | Stella Chemifa Corp | 微細加工処理剤、及びそれを用いた微細加工処理方法 |
JP2008053723A (ja) * | 2006-08-21 | 2008-03-06 | Cheil Industries Inc | シリコン酸化膜選択性湿式エッチング溶液 |
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