WO2011040484A1 - シリコンエッチング液およびエッチング方法 - Google Patents
シリコンエッチング液およびエッチング方法 Download PDFInfo
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- WO2011040484A1 WO2011040484A1 PCT/JP2010/066978 JP2010066978W WO2011040484A1 WO 2011040484 A1 WO2011040484 A1 WO 2011040484A1 JP 2010066978 W JP2010066978 W JP 2010066978W WO 2011040484 A1 WO2011040484 A1 WO 2011040484A1
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- Prior art keywords
- etching
- thiourea
- silicon
- thioureas
- solution
- Prior art date
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- 238000005530 etching Methods 0.000 title claims abstract description 168
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 74
- 239000010703 silicon Substances 0.000 title claims abstract description 74
- 238000000034 method Methods 0.000 title claims abstract description 33
- UMGDCJDMYOKAJW-UHFFFAOYSA-N aminothiocarboxamide Natural products NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 32
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims abstract description 25
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910021421 monocrystalline silicon Inorganic materials 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 58
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 50
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 34
- 150000003585 thioureas Chemical class 0.000 claims description 28
- 239000000758 substrate Substances 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 17
- POXAIQSXNOEQGM-UHFFFAOYSA-N propan-2-ylthiourea Chemical compound CC(C)NC(N)=S POXAIQSXNOEQGM-UHFFFAOYSA-N 0.000 claims description 16
- VUVPNTYTOUGMDG-UHFFFAOYSA-N 1-(2-hydroxyethyl)-3-prop-2-enylthiourea Chemical compound OCCNC(=S)NCC=C VUVPNTYTOUGMDG-UHFFFAOYSA-N 0.000 claims description 11
- KQJQICVXLJTWQD-UHFFFAOYSA-N N-Methylthiourea Chemical compound CNC(N)=S KQJQICVXLJTWQD-UHFFFAOYSA-N 0.000 claims description 11
- XGEGHDBEHXKFPX-UHFFFAOYSA-N N-methylthiourea Natural products CNC(N)=O XGEGHDBEHXKFPX-UHFFFAOYSA-N 0.000 claims description 11
- UCGFRIAOVLXVKL-UHFFFAOYSA-N benzylthiourea Chemical compound NC(=S)NCC1=CC=CC=C1 UCGFRIAOVLXVKL-UHFFFAOYSA-N 0.000 claims description 10
- RYYXDZDBXNUPOG-UHFFFAOYSA-N 4,5,6,7-tetrahydro-1,3-benzothiazole-2,6-diamine;dihydrochloride Chemical compound Cl.Cl.C1C(N)CCC2=C1SC(N)=N2 RYYXDZDBXNUPOG-UHFFFAOYSA-N 0.000 claims description 9
- VLCDUOXHFNUCKK-UHFFFAOYSA-N N,N'-Dimethylthiourea Chemical compound CNC(=S)NC VLCDUOXHFNUCKK-UHFFFAOYSA-N 0.000 claims description 8
- FCSHMCFRCYZTRQ-UHFFFAOYSA-N N,N'-diphenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NC1=CC=CC=C1 FCSHMCFRCYZTRQ-UHFFFAOYSA-N 0.000 claims description 8
- FULZLIGZKMKICU-UHFFFAOYSA-N N-phenylthiourea Chemical compound NC(=S)NC1=CC=CC=C1 FULZLIGZKMKICU-UHFFFAOYSA-N 0.000 claims description 8
- FLVIGYVXZHLUHP-UHFFFAOYSA-N N,N'-diethylthiourea Chemical compound CCNC(=S)NCC FLVIGYVXZHLUHP-UHFFFAOYSA-N 0.000 claims description 7
- DQMWMUMCNOJLSI-UHFFFAOYSA-N n-carbamothioylbenzamide Chemical compound NC(=S)NC(=O)C1=CC=CC=C1 DQMWMUMCNOJLSI-UHFFFAOYSA-N 0.000 claims description 6
- OVRQXQSDQWOJIL-UHFFFAOYSA-N 1,1-dibutylthiourea Chemical compound CCCCN(C(N)=S)CCCC OVRQXQSDQWOJIL-UHFFFAOYSA-N 0.000 claims description 5
- 239000000470 constituent Substances 0.000 claims description 5
- KREOCUNMMFZOOS-UHFFFAOYSA-N 1,3-di(propan-2-yl)thiourea Chemical compound CC(C)NC(S)=NC(C)C KREOCUNMMFZOOS-UHFFFAOYSA-N 0.000 claims description 4
- 150000004679 hydroxides Chemical class 0.000 claims description 3
- 229910001854 alkali hydroxide Inorganic materials 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- -1 thiourea compound Chemical class 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000004065 semiconductor Substances 0.000 abstract description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 10
- 238000007654 immersion Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- 239000003513 alkali Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 239000002253 acid Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002443 hydroxylamines Chemical class 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 229910052814 silicon oxide Inorganic materials 0.000 description 3
- 229910021642 ultra pure water Inorganic materials 0.000 description 3
- 239000012498 ultrapure water Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 235000014413 iron hydroxide Nutrition 0.000 description 2
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910052581 Si3N4 Inorganic materials 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 150000005846 sugar alcohols Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 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
- H01L21/302—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
- H01L21/30604—Chemical etching
- H01L21/30608—Anisotropic liquid etching
-
- 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
- C09K13/02—Etching, surface-brightening or pickling compositions containing an alkali metal hydroxide
Definitions
- the present invention relates to a silicon etching process, and more particularly to a silicon etching solution and a silicon etching method used for manufacturing MEMS parts and semiconductor devices.
- TMAH tetramethylammonium
- the silicon surface is oxidized by a component having an oxidizing action such as nitric acid to produce silicon oxide, and this silicon oxide is dissolved as silicon fluoride by hydrofluoric acid or the like, so that etching is performed. proceed.
- a feature of etching with an acid-based etching solution is that etching proceeds isotropically.
- the etching rate of the acidic etching solution varies depending on the mixing ratio of hydrofluoric acid and nitric acid, and is about 1 to 100 ⁇ m / min.
- the acidic etching solution corrodes metal wiring such as Cu and Al, and has a drawback that it is difficult to use in a process in which metal coexists.
- etching when an alkaline etching solution is used, silicon is dissolved as silicate ions by the hydroxy anion in the solution, and at this time, water is reduced to generate hydrogen.
- etching when etching is performed with an alkaline etching solution, unlike an acid etching solution, etching with single crystal silicon proceeds while having anisotropy. This is based on the fact that there is a difference in the dissolution rate of silicon for each crystal plane orientation of silicon, which is also called crystal anisotropic etching. Microscopically, etching proceeds while maintaining anisotropy when viewed microscopically, but since the crystal grain orientation is randomly distributed, macroscopically isotropic etching seems to proceed. Looks like. In amorphous, etching proceeds isotropically both microscopically and macroscopically.
- an aqueous solution of sodium hydroxide (NaOH), ammonia, hydrazine, or the like is used in addition to an aqueous solution of KOH and TMAH.
- NaOH sodium hydroxide
- TMAH TMAH
- a long processing time of several hours to several tens of hours is often required depending on a target processing shape, temperature conditions for processing, and the like.
- Patent Document 1 discloses a technique of using an aqueous solution obtained by adding hydroxylamines to TMAH as an etching solution.
- Patent Document 2 discloses a technique in which an aqueous solution obtained by adding a specific compound such as iron, iron chloride (III), iron hydroxide (II) or the like to TMAH is used as an etching solution, and the effect of increasing the etching rate is disclosed. It is disclosed that a combination of iron and hydroxylamine is particularly suitable at a height of 5 mm.
- Patent Document 3 discloses a technique using an aqueous solution obtained by adding hydroxylamines to KOH as an etching solution.
- Patent Document 4 discloses an etching solution comprising an alkali reducing compound and an anticorrosive agent (such as sugar, sugar alcohol, catechol).
- the alkaline etching solution containing hydroxylamine as disclosed in Patent Document 1 has a feature that the etching rate is greatly improved as compared with an alkaline etching solution not containing hydroxylamine, but the etching solution is heated for a long time. Then, there is a drawback that hydroxylamine is decomposed and the etching rate is lowered.
- Patent Document 5 discloses a technique for suppressing decomposition of hydroxylamine by adding an acid to an alkali and suppressing a decrease in etching rate.
- Patent Document 6 discloses a technique for suppressing decomposition of hydroxylamine by adding an alkali salt to alkali and hydroxylamine, thereby suppressing a decrease in etching rate.
- Patent Document 7 as a patent including KOH, hydroxylamine, and urea, but it is a patent related to development of a photoresist, and there is no description about a silicon etching solution and an etching method. In addition, it is known that in the etching of Si ⁇ 110 ⁇ , if Cu is present, the etching rate is greatly reduced (Non-patent Document 3).
- Cu may be used as a material used for various members including wiring.
- An alkaline etching solution containing hydroxylamine has a feature that the etching rate of silicon is high, but if Cu is present on a substrate immersed in the etching solution, there is a disadvantage that the etching rate of silicon is remarkably reduced. Even when Cu is present on the same substrate as silicon or on another substrate that is immersed at the same time, it causes a decrease in the etching rate.
- an object of the present invention is to provide an etching agent composition that maintains a high etching rate even when Cu is present on a substrate in silicon etching. Furthermore, it is providing the electronic device which has a silicon substrate processed by this etching method.
- an alkaline etchant composition having a composition obtained by adding thioureas to an alkaline etchant containing hydroxylamine contains Cu.
- the etching rate of silicon does not decrease, and have completed the present invention. That is, the present invention relates to a silicon etching solution and an etching method, and is as follows. 1.
- a silicon etching solution for anisotropically dissolving single crystal silicon wherein (1) one or more alkaline hydroxides selected from potassium hydroxide, sodium hydroxide and tetramethylammonium hydroxide, (2) hydroxylamine And (3) a silicon etching solution, which is an alkaline aqueous solution containing thioureas. 2.
- Thioureas are thiourea, N-methylthiourea, 1-allyl-3- (2-hydroxyethyl) -2-thiourea, thiourea dioxide, 1,3-dimethylthiourea, 1-benzoyl- 2-thiourea, isopropylthiourea, 1-phenyl-2-thiourea, 1,3-diethylthiourea, diphenylthiourea, benzylthiourea, Nt-butyl-N′-isopropylthiourea, N, N′-diisopropyl 2.
- the silicon etching solution according to 1 above which is one or more selected from thiourea and di-n-butylthiourea.
- Thioureas are thiourea, N-methylthiourea, 1-allyl-3- (2-hydroxyethyl) -2-thiourea, thiourea dioxide, 1,3-dimethylthiourea, 1-benzoyl- 2.
- the silicon etching solution according to 1 above which is at least one selected from 2-thiourea, isopropylthiourea, 1-phenyl-2-thiourea, 1,3-diethylthiourea, and diphenylthiourea. 4).
- the alkaline hydroxide is at least one selected from potassium hydroxide, sodium hydroxide and tetramethylammonium hydroxide;
- the thioureas are thiourea, N-methylthiourea, 1-allyl -3- (2-hydroxyethyl) -2-thiourea, thiourea dioxide, 1,3-dimethylthiourea, 1-benzoyl-2-thiourea, isopropylthiourea, 1-phenyl 2-thiourea, 1,3
- the above 6 which is at least one selected from diethylthiourea, diphenylthiourea, benzylthiourea, Nt-butyl-N′-isopropylthiourea, N, N′-diisopropylthiourea, and di-n-butylthiourea
- the silicon etching method as described. 8).
- the alkaline hydroxide used in the present invention is preferably potassium hydroxide (KOH), sodium hydroxide (NaOH) or tetramethylammonium hydroxide (TMAH), and particularly preferably potassium hydroxide or tetramethylammonium hydroxide.
- KOH potassium hydroxide
- NaOH sodium hydroxide
- TMAH tetramethylammonium hydroxide
- alkaline hydroxides may be used alone or in combination.
- the concentration of the alkali compound used in the present invention may be a conventional alkali compound concentration capable of obtaining desired etching characteristics, but the solubility of the alkali compound in water and the concentration of hydroxylamines and thioureas in the etching agent composition.
- the concentration is 0.1% by mass or more, the silicon etching rate is not very slow or is not etched. If the concentration is 65% by mass or less, crystal precipitation or solidification occurs in the etching agent composition. It is preferable because there is nothing.
- the concentration of thioureas used in the present invention is preferably 1 to 10000 ppm, more preferably 1 to 5000 ppm, further preferably 1 to 1500 ppm, and particularly preferably 5 to 1200 ppm.
- concentration of 1 ppm or more the effect of suppressing Cu dissolution by adding thioureas can be clearly obtained, and the decrease in the etching rate of silicon when Cu coexists by adding thioureas can be suppressed.
- the concentration is 10,000 ppm or less, the saturation concentration of thioureas is not approached, so that precipitation of thioureas does not occur due to water evaporation or the like.
- thiourea N-methylthiourea, 1-allyl-3- (2-hydroxyethyl) -2-thiourea dioxide thiourea, 1,3-dimethylthiourea, 1-benzoyl-2-thiourea, Isopropylthiourea, 1-phenyl-2-thiourea, 1,3-diethylthiourea, diphenylthiourea, benzylthiourea, Nt-butyl-N′-isopropylthiourea, diisopropylthiourea, di-n-butylthiourea
- the concentration of hydroxylamine used in the present invention can be appropriately determined according to a desired silicon etching rate, and is preferably in the range of 3 to 15% by mass. The range is more preferably 5 to 15% by mass, still more preferably 7 to 13% by mass, and particularly preferably 9 to 11% by mass.
- the hydroxylamine concentration is 5% by mass or more, the rate of decrease in the etching rate of silicon when coexisting with Cu does not become low, so that the effect of suppressing the decrease in the etching rate of silicon in this etching solution can be clearly obtained.
- the hydroxylamine concentration is increased, the etching rate tends to increase monotonously with this.
- the concentration is 11% by mass or less, the effect of improving the etching rate by the concentration of hydroxylamine can be obtained efficiently.
- the hydroxylamine concentration may be appropriately determined in consideration of a desired etching rate.
- the object is usually immersed in a heated etching solution, taken out after a lapse of a predetermined time, and the etching solution adhering to the object is washed away with water or the like and then attached.
- the etching temperature is preferably 40 ° C. or higher and lower than the boiling point, more preferably 50 ° C. to 90 ° C., particularly preferably 70 ° C. to 90 ° C.
- the etching temperature is 40 ° C. or higher, the etching rate does not decrease, so that the production efficiency can be improved.
- the temperature is 90 ° C.
- the liquid composition hardly changes, and it is easy to keep the etching conditions constant.
- an optimum processing temperature may be appropriately determined in consideration of suppressing a change in the composition of the etching solution.
- Etching time can be appropriately selected depending on etching conditions and etching target.
- the object of the etching treatment in the present invention is a substrate containing single crystal silicon, and single crystal silicon is present in the entire region or a partial region of the substrate.
- the Cu etching rate of the substrate, such as wiring is exposed from the beginning of the substrate surface, or the Cu inside the substrate is exposed to the surface by etching of silicon. Can be suppressed.
- Single crystal silicon may be in a single layer or in a state of being laminated in multiple layers. Those which are ion-doped in the whole region or a partial region of these substrates are also objects of etching treatment.
- the present invention also applies to a case where a material such as a silicon oxide film, a silicon nitride film, a silicon organic film, or a metal film such as an aluminum film, a chromium film, or a gold film is present on the surface of the etching object or inside the object. It is included in the object of the etching process.
- a material such as a silicon oxide film, a silicon nitride film, a silicon organic film, or a metal film such as an aluminum film, a chromium film, or a gold film is present on the surface of the etching object or inside the object. It is included in the object of the etching process.
- the silicon etching solution of the present invention has a high silicon etching rate, which is a feature of an alkaline aqueous solution containing hydroxylamine, even when Cu is present in the solution as in the case where Cu is not present. It can be expressed. Therefore, the silicon etching solution of the present invention is suitably used for etching an object in which a silicon substrate is used and Cu is used as a constituent member thereof.
- the etching object used for the evaluation is a single crystal silicon (100) (sometimes simply referred to as silicon (100)) wafer.
- One side of the silicon (100) wafer is covered with a protective film made of a silicon thermal oxide film, and a part of the silicon thermal oxide film is removed by dry etching on the other side.
- the silicon surface (0.25 cm ⁇ 0.25 cm) has a pattern shape that is regularly exposed.
- This silicon (100) wafer was immersed in a 1% hydrofluoric acid aqueous solution at 23 ° C. for 15 minutes immediately before etching, and then rinsed with ultrapure water and dried. By this hydrofluoric acid aqueous solution treatment, the silicon natural oxide film formed on the surface of the exposed portion of the patterned silicon surface was removed, and then the next etching treatment was performed.
- the single crystal silicon (100) wafer that has been subjected to the etching process has a pattern portion that is recessed from the surroundings as the single crystal silicon is etched, and the height difference between the etched portion and the unetched portion is measured.
- the etching depth of the single crystal silicon (100) plane in 30 minutes was obtained.
- a value obtained by dividing the etching depth by 30 was calculated as an etching rate (unit: ⁇ m / min) of the single crystal silicon (100) plane.
- the thickness of the Cu flakes was measured again with a fluorescent X-ray analyzer, and the etching depth of the Cu flakes in 60 minutes was determined by determining the difference in film thickness before and after the treatment. A value obtained by dividing the etching depth by 60 was calculated as a Cu etching rate (unit: ⁇ / min).
- the etching rate of Cu is less than 1 ⁇ / min.
- the etching rate of Cu is 10 ⁇ / min or more. From this, it has been found that thioureas have not only the effect of not decreasing the etching rate of Si when Cu coexists, but also the ability to prevent dissolution of Cu.
- Comparative Example 14-33 The results are summarized in Table 4 except that the etching solution shown in Table 4 contains 0.5 ppm of Cu (excluding Cu flakes) and is the same as Example 27. Since the silicon etching solution of the present invention can exhibit a high silicon etching rate, which is a feature of an alkaline aqueous solution containing hydroxylamine, even when Cu is present in the solution, as in the case where Cu is not present.
- One component (3) thioureas is considered to exhibit the ability to form a chelate with Cu.
- the chelating agent used in Comparative Examples 14-33 having the ability to form a chelate with Cu it is shown that the silicon etching performance is significantly inferior to the silicon etching solution of the present invention. It was. That is, according to the present invention, it has been shown that (3) thioureas can provide an excellent effect due to a synergistic effect with other components (1) alkaline hydroxide and (2) hydroxylamine.
- an etching solution that does not reduce the etching rate of silicon and that does not etch Cu can be provided, which is industrially useful.
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Weting (AREA)
- ing And Chemical Polishing (AREA)
Abstract
Description
また、Si{110}のエッチングにおいて、Cuが存在するとエッチング速度が大きく低下することが知られている(非特許文献3)。
1.単結晶シリコンを異方性に溶解するシリコンエッチング液であって、(1)水酸化カリウム、水酸化ナトリウムおよび水酸化テトラメチルアンモニウムから選ばれる1種以上のアルカリ性水酸化物、(2)ヒドロキシルアミンおよび(3)チオ尿素類を含有したアルカリ性水溶液であることを特徴とするシリコンエッチング液。
2.(3)チオ尿素類がチオ尿素、N-メチルチオ尿素、1-アリル-3-(2-ヒドロキシエチル)-2-チオ尿素、二酸化チオ尿素、1,3-ジメチルチオ尿素、1-ベンゾイル-2-チオ尿素、イソプロピルチオ尿素、1-フェニル2-チオ尿素、1,3-ジエチルチオ尿素、ジフェニルチオ尿素、ベンジルチオ尿素、N-t-ブチル-N’-イソプロピルチオ尿素、N,N’-ジイソプロピルチオ尿素、およびジ-n-ブチルチオ尿素から選ばれる1種以上である上記1記載のシリコンエッチング液。
3.(3)チオ尿素類がチオ尿素、N-メチルチオ尿素、1-アリル-3-(2―ヒドロキシエチル)-2-チオ尿素、二酸化チオ尿素、1,3-ジメチルチオ尿素、1-ベンゾイル-2-チオ尿素、イソプロピルチオ尿素、1-フェニル2-チオ尿素、1,3-ジエチルチオ尿素、ジフェニルチオ尿素から選ばれる1種以上である上記1記載のシリコンエッチング液。
4.(3)チオ尿素類がチオ尿素、N-メチルチオ尿素、1-アリル-3-(2-ヒドロキシエチル)-2-チオ尿素、および二酸化チオ尿素から選ばれる1種以上である上記1記載のシリコンエッチング液。
5.シリコン基板が用いられ、その構成部材にCuが使用される対象物のエッチングに用いられる上記1~4のいずれかに記載のシリコンエッチング液。
6.単結晶シリコンを異方性に溶解するシリコンエッチング方法であって、(1)アルカリ水酸化物と、(2)ヒドロキシルアミンおよび(3)チオ尿素類を含有するアルカリ性水溶液を用いてエッチング対象物をエッチングすることを特徴とするシリコンエッチング方法。
7.(1)アルカリ性水酸化物が水酸化カリウム、水酸化ナトリウムおよび水酸化テトラメチルアンモニウムから選ばれる1種以上であり、(3)チオ尿素類がチオ尿素、N-メチルチオ尿素、1-アリル-3-(2-ヒドロキシエチル)-2-チオ尿素、二酸化チオ尿素、1,3-ジメチルチオ尿素、1-ベンゾイル-2-チオ尿素、イソプロピルチオ尿素、1-フェニル2-チオ尿素、1,3-ジエチルチオ尿素、ジフェニルチオ尿素、ベンジルチオ尿素、N-t-ブチル-N’-イソプロピルチオ尿素、N,N’-ジイソプロピルチオ尿素、およびジ-n-ブチルチオ尿素から選ばれる1種以上である上記6記載のシリコンエッチング方法。
8.エッチング対象物が、シリコン基板が用いられ、その構成部材にCuが使用されるものである上記6又は7に記載のシリコンエッチング方法。
本発明に用いるアルカリ化合物の濃度は、所望のエッチング特性を得られる従来のアルカリ化合物濃度でよいが、アルカリ化合物の水への溶解度並びにエッチング剤組成物中のヒドロキシルアミン類濃度およびチオ尿素類の濃度によって適宜決定することも可能であり、好ましくは0.1~65質量%の範囲、より好ましくは、1~45質量%、さらに好ましくは5~40質量%、特に好ましくは5~30質量%の範囲で使用される。0.1質量%以上の濃度では、シリコンエッチング速度が非常に遅い、あるいはエッチングがなされないということがなく、65質量%以下の濃度ではエッチング剤組成物中での結晶の析出や固化などが生じることがないため好ましい。
エッチング液40gをPTFE(ポリテトラフルオロエチレン)製の容器に入れ、この容器を湯浴中に浸してエッチング液の温度を80℃に加温した。エッチング液の温度が80℃に達した後、単結晶シリコン(100)ウェハ(1cm×1cm)と0.5cm×0.5cmのCu薄片(Cuの厚みは6000Å)をエッチング液の中に同時に浸し、30分間浸漬処理を行い、その後、単結晶シリコン(100)ウェハを取り出して超純水によるリンスおよび乾燥を行った。エッチング処理を行った単結晶シリコン(100)ウェハは、単結晶シリコンのエッチングに伴いパターン部分が周囲よりも窪んだ状態になり、エッチングされた部分とエッチングされていない部分との高低差を測定することによって、30分間での単結晶シリコン(100)面のエッチング深さを求めた。このエッチング深さを30で割った値を単結晶シリコン(100)面のエッチング速度(単位はμm/min)として算出した。
表1記載のエッチング液を用いてエッチング処理を行い、結果を表1に記した。チオ尿素類を含まない比較例1~5、7、8は、対応する実施例1~5、25、26より明らかにエッチング速度が小さかった。
表2記載のエッチング液にCuを0.5ppm含有させた(Cu薄片は含まず)以外は、実施例1~26と同様に行い、結果を表2にまとめた。
Cu薄片のエッチング処理方法およびエッチング速度の算出方法
表3記載のエッチング液40gをPTFE単結晶シリコン(ポリテトラフルオロエチレン)製の容器に入れ、この容器を湯浴中に浸してエッチング液の温度を80℃に加温した。エッチング液の温度が80℃に達した後、あらかじめ膜厚を蛍光X線分析装置で測定済みの2cm×2cmのCuベタ膜(Cuの厚みは6000Å)をエッチング液の中に同時に浸し、60分間浸漬処理を行い、その後、Cu薄片を取り出して超純水によるリンスおよび乾燥を行った。Cu薄片の膜厚を再度蛍光X線分析装置で測定し、処理前後の膜厚の差を求めることによって、60分間でのCu薄片のエッチング深さを求めた。このエッチング深さを60で割った値をCuのエッチング速度(単位はÅ/min)として算出した。エッチング液にチオ尿素類を含む場合は、Cuのエッチング速度は1Å/min未満であるが、チオ尿素を含まない場合はCuのエッチング速度は10Å/min以上になっている。このことから、チオ尿素類は、Cuが共存している場合にSiのエッチング速度を低下させない効果だけでなく、Cuの溶解を防ぐという性能もあることがわかった。
表4記載のエッチング液にCuを0.5ppm含有させた(Cu薄片は含まず)以外は、実施例27と同様に行い、結果を表4にまとめた。本発明のシリコンエッチング液は、該液中にCuが存在する場合においてもCuが存在しない場合と同様にヒドロキシルアミンを含んだアルカリ性水溶液の特長である高いシリコンエッチング速度を発現しうることから、その一成分である(3)チオ尿素類は、Cuとキレートを形成する性能を奏するものと考えられる。しかし、Cuとキレートを形成する性能を有する比較例14-33に使用されるキレート剤を用いた場合、本発明のシリコンエッチング液と比較して、シリコンエッチング性能は著しく劣っていることが示された。すなわち、本発明によって、(3)チオ尿素類が、他の成分である(1)アルカリ性水酸化物及び(2)ヒドロキシルアミンとの相乗効果により、優れた効果が得られることが示された。
Claims (8)
- 単結晶シリコンを異方性に溶解するシリコンエッチング液であって、(1)水酸化カリウム、水酸化ナトリウムおよび水酸化テトラメチルアンモニウムから選ばれる1種以上のアルカリ性水酸化物、(2)ヒドロキシルアミンおよび(3)チオ尿素類を含有したアルカリ性水溶液であることを特徴とするシリコンエッチング液。
- (3)チオ尿素類がチオ尿素、N-メチルチオ尿素、1-アリル-3-(2―ヒドロキシエチル)-2-チオ尿素、二酸化チオ尿素、1,3-ジメチルチオ尿素、1-ベンゾイル-2-チオ尿素、イソプロピルチオ尿素、1-フェニル2-チオ尿素、1,3-ジエチルチオ尿素、ジフェニルチオ尿素、ベンジルチオ尿素、N-t-ブチル-N’-イソプロピルチオ尿素、N,N’-ジイソプロピルチオ尿素、およびジ-n-ブチルチオ尿素から選ばれる1種以上である請求項1記載のシリコンエッチング液。
- (3)チオ尿素類がチオ尿素、N-メチルチオ尿素、1-アリル-3-(2―ヒドロキシエチル)-2-チオ尿素、二酸化チオ尿素、1,3-ジメチルチオ尿素、1-ベンゾイル-2-チオ尿素、イソプロピルチオ尿素、1-フェニル2-チオ尿素、1,3-ジエチルチオ尿素、ジフェニルチオ尿素から選ばれる1種以上である請求項1記載のシリコンエッチング液。
- (3)チオ尿素類がチオ尿素、N-メチルチオ尿素、1-アリル-3-(2-ヒドロキシエチル)-2-チオ尿素、および二酸化チオ尿素から選ばれる1種以上である請求項1記載のシリコンエッチング液。
- シリコン基板が用いられ、その構成部材にCuが使用される対象物のエッチングに用いられる請求項1~4のいずれかに記載のシリコンエッチング液。
- 単結晶シリコンを異方性に溶解するシリコンエッチング方法であって、(1)アルカリ水酸化物と、(2)ヒドロキシルアミンおよび(3)チオ尿素類を含有するアルカリ性水溶液を用いてエッチング対象物をエッチングすることを特徴とするシリコンエッチング方法。
- (1)アルカリ性水酸化物が水酸化カリウム、水酸化ナトリウムおよび水酸化テトラメチルアンモニウムから選ばれる1種以上であり、(3)チオ尿素類がチオ尿素、N-メチルチオ尿素、1-アリル-3-(2-ヒドロキシエチル)-2-チオ尿素、二酸化チオ尿素、1,3-ジメチルチオ尿素、1-ベンゾイル-2-チオ尿素、イソプロピルチオ尿素、1-フェニル2-チオ尿素、1,3-ジエチルチオ尿素、ジフェニルチオ尿素、ベンジルチオ尿素、N-t-ブチル-N’-イソプロピルチオ尿素、N,N’-ジイソプロピルチオ尿素、およびジ-n-ブチルチオ尿素から選ばれる1種以上である請求項6記載のシリコンエッチング方法。
- エッチング対象物が、シリコン基板が用いられ、その構成部材にCuが使用されるものである請求項6又は7に記載のシリコンエッチング方法。
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