WO2020085469A1 - 硫黄含有フルオロカーボン化合物を含むドライエッチングガス組成物及びそれを用いたドライエッチング方法 - Google Patents
硫黄含有フルオロカーボン化合物を含むドライエッチングガス組成物及びそれを用いたドライエッチング方法 Download PDFInfo
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- WO2020085469A1 WO2020085469A1 PCT/JP2019/041827 JP2019041827W WO2020085469A1 WO 2020085469 A1 WO2020085469 A1 WO 2020085469A1 JP 2019041827 W JP2019041827 W JP 2019041827W WO 2020085469 A1 WO2020085469 A1 WO 2020085469A1
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- film
- dry etching
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- 238000001312 dry etching Methods 0.000 title claims abstract description 49
- 239000000203 mixture Substances 0.000 title claims abstract description 41
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 24
- 239000011593 sulfur Substances 0.000 title claims abstract description 24
- -1 fluorocarbon compound Chemical class 0.000 title claims abstract description 19
- 238000000034 method Methods 0.000 title claims description 21
- 238000005530 etching Methods 0.000 claims abstract description 93
- 150000001875 compounds Chemical class 0.000 claims abstract description 26
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 19
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 125000004122 cyclic group Chemical group 0.000 claims abstract description 4
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 66
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 18
- 229910052710 silicon Inorganic materials 0.000 claims description 18
- 239000010703 silicon Substances 0.000 claims description 18
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 229910021420 polycrystalline silicon Inorganic materials 0.000 claims description 10
- 238000001020 plasma etching Methods 0.000 claims description 8
- 229910003481 amorphous carbon Inorganic materials 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- 239000001301 oxygen Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- 229920002120 photoresistant polymer Polymers 0.000 claims description 6
- 229920005591 polysilicon Polymers 0.000 claims description 6
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 6
- JUTLAXFVSZJSHM-UHFFFAOYSA-N 2,2,3,3,4,4,5,5-octafluorothiolane Chemical compound FC1(F)SC(F)(F)C(F)(F)C1(F)F JUTLAXFVSZJSHM-UHFFFAOYSA-N 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 5
- 229910021417 amorphous silicon Inorganic materials 0.000 claims description 4
- 229910021419 crystalline silicon Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000000463 material Substances 0.000 abstract description 13
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 8
- 239000013077 target material Substances 0.000 description 8
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 5
- 125000004430 oxygen atom Chemical group O* 0.000 description 4
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 3
- 230000007246 mechanism Effects 0.000 description 3
- 239000002210 silicon-based material Substances 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- BCCOBQSFUDVTJQ-UHFFFAOYSA-N octafluorocyclobutane Chemical compound FC1(F)C(F)(F)C(F)(F)C1(F)F BCCOBQSFUDVTJQ-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- KDKGPLZMKATCHY-UHFFFAOYSA-N 1,1,4,4-tetrafluorobuta-1,3-diene Chemical compound FC(F)=CC=C(F)F KDKGPLZMKATCHY-UHFFFAOYSA-N 0.000 description 1
- LAJVPVPQYKBOEF-UHFFFAOYSA-N 2,2,3,3,4,4,5,5,6,6-decafluorothiane Chemical compound FC1(F)SC(F)(F)C(F)(F)C(F)(F)C1(F)F LAJVPVPQYKBOEF-UHFFFAOYSA-N 0.000 description 1
- FKYDOQLHWKVIKP-UHFFFAOYSA-N 2,2,3,3,4,4-hexafluorothietane Chemical compound FC1(F)SC(F)(F)C1(F)F FKYDOQLHWKVIKP-UHFFFAOYSA-N 0.000 description 1
- AHNNUHWQOFRROY-UHFFFAOYSA-N 2,2,3,3-tetrafluorothiirane Chemical compound FC1(F)SC1(F)F AHNNUHWQOFRROY-UHFFFAOYSA-N 0.000 description 1
- UCYHFCTVZCAVRH-UHFFFAOYSA-N 2,2,3-trifluoro-3-(trifluoromethyl)thiirane Chemical compound FC1(SC1(C(F)(F)F)F)F UCYHFCTVZCAVRH-UHFFFAOYSA-N 0.000 description 1
- FITDWPCYNXAJID-UHFFFAOYSA-N 2,2-difluoro-3,3-bis(trifluoromethyl)thiirane Chemical compound FC1(SC1(C(F)(F)F)C(F)(F)F)F FITDWPCYNXAJID-UHFFFAOYSA-N 0.000 description 1
- XLVGYOOLJUHKQA-UHFFFAOYSA-N 2,3-difluoro-2,3-bis(trifluoromethyl)thiirane Chemical compound FC(C1(SC1(F)C(F)(F)F)F)(F)F XLVGYOOLJUHKQA-UHFFFAOYSA-N 0.000 description 1
- BSYNRYMUTXBXSQ-UHFFFAOYSA-N Aspirin Chemical compound CC(=O)OC1=CC=CC=C1C(O)=O BSYNRYMUTXBXSQ-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002149 energy-dispersive X-ray emission spectroscopy Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 235000019407 octafluorocyclobutane Nutrition 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003071 parasitic effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000002230 thermal chemical vapour deposition Methods 0.000 description 1
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- 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
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- C09K13/00—Etching, surface-brightening or pickling compositions
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- 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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02109—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates
- H01L21/02112—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer
- H01L21/02123—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon
- H01L21/02164—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing silicon the material being a silicon oxide, e.g. SiO2
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- 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
- H01L21/3065—Plasma etching; Reactive-ion etching
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- 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
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- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
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- H01L21/311—Etching the insulating layers by chemical or physical means
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- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
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- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
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- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32135—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only
- H01L21/32136—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by vapour etching only using plasmas
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- 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
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
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- 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
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- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
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- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
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- H—ELECTRICITY
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- H01J2237/00—Discharge tubes exposing object to beam, e.g. for analysis treatment, etching, imaging
- H01J2237/32—Processing objects by plasma generation
- H01J2237/33—Processing objects by plasma generation characterised by the type of processing
- H01J2237/334—Etching
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- H01J37/3244—Gas supply means
Definitions
- the present invention relates to a dry etching gas composition containing a sulfur-containing fluorocarbon compound and a dry etching method using the same.
- Patent Document 1 An etching gas composition containing a specific hydrofluorocarbon (1,1,4,4-tetrafluoro-1,3-butadiene) is effective as a means for solving the above problems.
- an object of the present invention is to provide a novel etching gas composition containing a sulfur-containing compound and capable of selectively etching SiO 2 with respect to a low dielectric constant material (Low-k material (SiON, SiCN, SiOCN, SiOC)). Is to provide.
- a dry etching method comprising the step of performing plasma etching using the dry etching gas composition described above, and selectively or separately etching other than (a6) the amorphous carbon film and (a7) the photoresist film.
- etching is performed by converting the etching gas composition according to any one of [1] to [5] into plasma so that ions containing S or active species are generated. Dry etching method to be performed.
- a novel etching gas composition containing a sulfur-containing compound and capable of selectively etching SiO 2 with respect to a low dielectric constant material Liow-k material (SiON, SiCN, SiOCN, SiOC)) is provided. To be done.
- the dry etching gas composition in the present invention includes a mixed gas containing a saturated and cyclic sulfur-containing fluorocarbon compound represented by the following general formula (1), or a gas simple substance.
- General formula (1) CxFySz (In the formula, x, y and z are 2 ⁇ x ⁇ 5, y ⁇ 2x + 2, 1 ⁇ z ⁇ 2)
- Suitable compounds include, for example: Tetrafluorothiirane (C 2 F 4 S), 2,2,3,3,4,4-hexafluorothietane (C 3 F 6 S), 2,2,3-trifluoro-3- (trifluoromethyl) -thiirane (C 3 F 6 S), 2,2,3,3,4,4,5,5-octafluorotetrahydrothiophene (C 4 F 8 S), 2,3-difluoro-2,3-bis (trifluoromethyl) -thiirane (C 4 F 8 S), 2,2-difluoro-3,3-bis (trifluoromethyl) -thiirane (C 4 F 8 S), 2,2,3,3,4,4,5,5,6,6-decafluorotetrahydro-2H-thiopyran (C 5 F 10 S), and the like
- a sulfur-containing fluorocarbon compound represented by the general formula (1) having a purity of 95.0 vol% to 100.0 vol%. It is more preferable to use one having a purity of 99 vol% or more, and further preferable to use one having a purity of 99.9 vol% or more.
- Impurity components contained include N 2 , O 2 , CO 2 , H 2 O, HF, HCl, SO 2 , CH 4 and the like. Among these impurity components, H 2 O, HF, HCl, SO Since 2 and the like have a high possibility of corroding the passage through which gas flows, it is preferable to remove them by refining as much as possible.
- the sulfur-containing fluorocarbon compound represented by the general formula (1) is mixed with other fluorocarbon (FC) gas or hydrofluorocarbon (HFC) gas to be used in the general formula (1). It is possible to further increase the selection ratio of the etching target material with respect to the non-etching target material as compared with the case where the compound shown in (4) is not mixed. Further, in the case of etching the structure patterned by the non-etching target material, the vertical processing accuracy is also improved.
- FC fluorocarbon
- HFC hydrofluorocarbon
- the etching target material is a Si-based material containing oxygen such as SiO 2
- the compound represented by the general formula (1) is added to CF 4 , CHF 3 , C
- an etching gas such as 2 F 6 , C 3 F 8 , C 4 F 8 , C 4 F 6 , C 5 F 8 for selective etching and etching with high vertical processing accuracy.
- the etching target material is a Si-based material containing nitrogen such as SiN
- the gas compound represented by the general formula (1) is changed to CHF 3 , CH 2 F 2 , CH 3 F. It is preferable to mix with HFC gas such as the above and use for plasma etching for selective etching and etching with high vertical processing accuracy. In particular, when high selectivity is required, it is also effective to use HFC gas having 2 or more C atoms.
- the composition containing the compound represented by the general formula (1) is selected from O 2 , O 3 , CO, CO 2 , NO, NO 2 , SO 2 and SO 3.
- at least one oxygen-containing compound selected from the group consisting of: suppressing excessive deposition (deposit), improving the etching rate of the etching target, and selecting the etching target relative to the non-etching target material The effect of improving the property can be obtained.
- At least one inert gas selected from the group consisting of N 2 , He, Ar, Ne and Xe is added to the composition containing the compound represented by the general formula (1). Gas can be added. Of these, He, Ar, and Xe are preferably used.
- Examples of the etching gas used in the method of the present invention include the following.
- the compound represented by the general formula (1) can be carried out with a purity of 90 vol% or more, preferably with a purity of 99 vol% or more, and particularly preferably with a purity of 99.999 vol% or more.
- the compound represented by the general formula (1) is preferably 1 to 100 vol%.
- an oxygen atom consisting of O 2 , O 3 , CO, CO 2 , NO, NO 2 , SO 2 and SO 3.
- the proportion of the compound containing an oxygen atom is preferably 5 to 50%, and particularly preferably 10 to 35%, based on the total amount of the compound represented by the general formula (1) and the compound containing an oxygen atom. .
- the proportion of the inert gas contained in the etching gas composition is preferably 1 to 80% by volume, and particularly preferably 50 to 75% by volume.
- dry etching apparatus used for dry etching in the present invention
- those used in the relevant technical field can be used without particular limitation.
- devices such as a helicon wave system, a high frequency induction system, a parallel plate type system, a magnetron system, and a microwave system can be used.
- the etching apparatus is an apparatus equipped with a vacuum container suitable for ion-assisted etching and capable of reproducing a low gas pressure condition.
- a vacuum container suitable for ion-assisted etching and capable of reproducing a low gas pressure condition.
- the particles in the plasma increase in straightness, and the ions irradiated to the substrate reach the substrate without being blocked by other particles, increasing the number of ions that are vertically incident on the substrate. It is advantageous for vertical machining.
- the pressure in the vacuum container during etching is preferably adjusted to 100 Torr to 0.1 mTorr, more preferably 100 mTorr to 0.1 mTorr.
- the etching apparatus used in the dry etching method according to the present invention is provided with a mechanism for introducing the compound represented by the general formula (1) as a gas and further adjusting the amount of introduction.
- the plasma etching method according to the present invention uses a plurality of other gas compounds such as O 2 and Ar described above in addition to the gas compound represented by the general formula (1) depending on the purpose. Is effective, it is preferable to provide four or more mechanisms for introducing gas and adjusting the amount of gas introduced.
- a parallel plate type capacitively coupled plasma etching apparatus manufactured by SAMCO was used as a plasma etching apparatus.
- the composition of the deposition film was determined by SEM-EDX (scanning electron microscope / energy dispersive X-ray spectroscopy).
- SiOm silicon oxide film
- SiN silicon nitride film
- SiN silicon nitride film
- amorphous carbon film As the amorphous carbon film (ACL), a silicon wafer having 400 nm of ACL deposited by plasma CVD was used.
- SiOC carbon-containing silicon film
- BD-3 Black Diamond-3
- SiON film a SiON film having a thickness of 500 nm deposited on a silicon wafer by plasma CVD was used.
- SiCN film a SiCN film having a thickness of 500 nm deposited on a silicon wafer by plasma CVD was used.
- SiOCN film a 500 nm SiOCN deposited on a silicon wafer by plasma CVD was used.
- the sample film thickness during etching was measured with an optical interference type film thickness measuring device.
- the etching conditions are shown in Tables 1 and 3 below.
- the gas etching rate was calculated by the following formula.
- a / B selection ratio A film etching rate (nm / min) / B film etching rate (nm / min)
- BD-3 means black diamond 3.
- Ar was always flown in an amount of 50 sccm
- etching gas was always flown in an amount of 20 sccm
- the amount (sccm) of oxygen (O 2 ) was changed.
- the ACL etching started when the amount of oxygen exceeded 20% with respect to the total (x + y) of the etching gas (x) and oxygen (y).
- Etching gas of Example (C 4 F 8 S) maximum is the etching rate of SiO 2 in the vicinity of SiO 2 etching rate rapidly increased O 2 ratio of 25% with the increase of O 2 ratio (approximately 80 nm / min)
- the comparative example (C 4 F 8 ) also showed similar behavior with respect to the etching rate of SiO 2 .
- the etching rate ratios of SiO 2 / BD-3, SiO 2 / SiON, SiO 2 / SiCN, and SiO 2 / SiOCN were obtained and summarized in FIG. As can be seen from FIG. 2, in both the example and the comparative example, a behavior was confirmed that the etching rate ratio was large when the O 2 ratio was 20%, but the etching rate ratio was small when the O 2 ratio was 33%. .
- ACL / SiO 2 , ACL / SiN, ACL / polysilicon (Poly-Si), ACL / BD-3, ACL / SiON, and ACL at 33% of O 2 ratio were obtained.
- the ratios of the etching rates of / SiCN and ACL / SiOCN were determined and summarized in FIG. As can be seen from FIG. 3, it was found that the etching gas of the example has a larger etching rate ratio with ACL for all materials than the etching gas of the comparative example.
- the novel etching gas of the present invention has a high selectivity between SiO 2 and the Low-k material (SiON, SiCN, SiOCN, SiOC) as well as the conventional etching gas.
- the etching rate of the ACL is not increased even if the O 2 ratio is increased by adopting the novel compound containing sulfur, the etching selectivity between the ACL and the Low-k material is different from that of the conventional etching gas. Big compared to.
- the difference in the etching rate between the ACL and the Low-k material can be changed, and more precise etching can be performed.
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Abstract
Description
[1]
一般式(1):CxFySz(式中、x、y及びzは、2≦x≦5、y≦2x、1≦z≦2)で表され、飽和かつ環状の硫黄含有フルオロカーボン化合物を含むドライエッチングガス組成物。
[2]
前記硫黄含有フルオロカーボン化合物が2,2,3,3,4,4,5,5-オクタフルオロテトラヒドロチオフェン(C4F8S)である[1]に記載のドライエッチングガス組成物。
[3]
硫黄含有フルオロカーボン化合物を1~100vol%の量で含む、[1]又は[2]に記載のドライエッチングガス組成物。
[4]
前記硫黄含有フルオロカーボン化合物に加えて、O2、O3、CO、CO2、NO、NO2、SO2及びSO3からなる群から選ばれる少なくとも1種の酸素含有化合物を含む、[1]~[3]の何れか1項に記載のドライエッチングガス組成物。
[5]
前記硫黄含有フルオロカーボン化合物に加えて、N2、He、Ar、Ne及びXeからなる群から選ばれる少なくとも1種の不活性ガスを含む、[1]~[4]の何れか1項に記載のドライエッチングガス組成物。
[6]
(a1)炭素を含むシリコン系膜、(a2)結晶シリコン膜、(a3)アモルファスシリコン膜、(a4)多結晶シリコン膜(ポリシリコン膜)、(a5)シリコン酸窒化膜、(a6)アモルファスカーボン膜、(a7)フォトレジスト膜、(a8)シリコン酸化膜及び(a9)シリコン窒化膜からなる群から選ばれる少なくとも2種以上を含む積層構造体を、[1]~[5]のいずれかに記載のドライエッチングガス組成物を用いてプラズマエッチングを行い、(a6)アモルファスカーボン膜及び(a7)フォトレジスト膜以外を個別又は同時に選択的にエッチングする工程を含むドライエッチング方法。
[7]
(a1)炭素を含むシリコン系膜、(a2)結晶シリコン膜、(a3)アモルファスシリコン膜、(a4)多結晶シリコン膜(ポリシリコン膜)、(a5)シリコン酸窒化膜、(a6)アモルファスカーボン膜、(a7)フォトレジスト膜及び(a8)シリコン酸化膜からなる群から選ばれる少なくとも2種以上を含む積層構造体を、[1]~[5]のいずれかに記載のドライエッチングガス組成物を用いてプラズマエッチングを行い、(a8)シリコン酸化膜のみを選択的にエッチングする工程を含むドライエッチング方法。
[8]
[6]又は[7]に記載のドライエッチング方法において、Sを含むイオン又は活性種が生成するように[1]~[5]のいずれかに記載のエッチングガス組成物をプラズマ化してエッチングを行うドライエッチング方法。
[9]
[6]~[8]のいずれかに記載のドライエッチング方法において、(b1)シリコン酸化膜及び(b2)シリコン窒化膜を同時にエッチング可能なプラズマ条件下で[1]~[5]のいずれかに記載のドライエッチングガス組成物によるエッチングを行うドライエッチング方法。
一般式(1):CxFySz
(式中、x、y及びzは、2≦x≦5、y≦2x+2、1≦z≦2)
(a)一般式(1)に示される化合物は、純度90vol%以上で実施することが出来、純度99vol%以上で実施することが好ましく、純度99.999vol%以上で実施することが特に好ましい。
(b)エッチングに用いられるドライエッチング組成物において、一般式(1)に示される化合物は、1~100vol%であることが好ましい。
(c)エッチングに用いられるドライエッチング組成物において、一般式(1)に示される化合物以外に、O2、O3、CO、CO2、NO、NO2、SO2及びSO3からなる酸素原子を含む化合物群から選択される少なくとも一つが含まれることが好ましく、特にO2を用いることが好ましい。酸素原子を含む化合物の割合は、一般式(1)に示される化合物と酸素原子を含む化合物の総量に対して、5~50%であることが好ましく、10~35%であることが特に好ましい。
(d)エッチングに用いられるドライエッチング組成物において、一般式(1)に示される化合物と、上記酸素原子を含む化合物群に加えて/又はそれに代えて希ガスまたはN2からなる不活性ガス群から選択される少なくとも一つが含まれることが好ましく、特にArを用いることが好ましい。エッチングガス組成物に含まれる不活性ガスの割合は、1~80vol%であることが好ましく、50~75vol%であることが特に好ましい。
シリコン酸化膜(SiOm)(mは自然数を表す。)としては、プラズマCVDによってシリコンウエハ上にSiO2膜を1000nm堆積したものを使用した。シリコン窒化膜(SiN)としては、熱CVDによってシリコンウエハ上にSiN膜を300nm堆積したものを使用した。アモルファスカーボン膜(ACL)としては、プラズマCVDによってシリコンウエハ上にACLを400nm堆積したものを使用した。炭素含有シリコン膜(SiOC)としてはシリコンウエハ上にApplied Materials社の登録商標であるBlack Diamond-3(以下BD-3)を500nm堆積したものを使用した。SiON膜としては、プラズマCVDによってシリコンウエハ上にSiONを500nm堆積したものを使用した。SiCN膜としては、プラズマCVDによってシリコンウエハ上にSiCNを500nm堆積したものを使用した。SiOCN膜としては、プラズマCVDによってシリコンウエハ上にSiOCNを500nm堆積したものを使用した。
A/B選択比 = A膜のエッチングレート(nm/min) ÷ B膜のエッチングレート(nm/min)
シリコンウエハ上にそれぞれSiO2、SiN、ACLなどを堆積した異なるサンプルを用いて表1に示す条件でエッチング試験を行った。エッチングガスには、比較例として硫黄を含まないパーフルオロシクロブタン(1,1,2,2,3,3,4,4-オクタフルオロシクロブタン(C4F8))と、本発明の実施例として硫黄を含む式:
Claims (9)
- 一般式(1):CxFySz(式中、x、y及びzは、2≦x≦5、y≦2x、1≦z≦2)で表され、飽和かつ環状の硫黄含有フルオロカーボン化合物を含むドライエッチングガス組成物。
- 前記硫黄含有フルオロカーボン化合物が2,2,3,3,4,4,5,5-オクタフルオロテトラヒドロチオフェン(C4F8S)である請求項1に記載のドライエッチングガス組成物。
- 硫黄含有フルオロカーボン化合物を1~100vol%の量で含む、請求項1又は2に記載のドライエッチングガス組成物。
- 前記硫黄含有フルオロカーボン化合物に加えて、O2、O3、CO、CO2、NO、NO2、SO2及びSO3からなる群から選ばれる少なくとも1種の酸素含有化合物を含む、請求項1~3の何れか1項に記載のドライエッチングガス組成物。
- 前記硫黄含有フルオロカーボン化合物に加えて、N2、He、Ar、Ne及びXeからなる群から選ばれる少なくとも1種の不活性ガスを含む、請求項1~4の何れか1項に記載のドライエッチングガス組成物。
- (a1)炭素を含むシリコン系膜、(a2)結晶シリコン膜、(a3)アモルファスシリコン膜、(a4)多結晶シリコン膜(ポリシリコン膜)、(a5)シリコン酸窒化膜、(a6)アモルファスカーボン膜、(a7)フォトレジスト膜、(a8)シリコン酸化膜及び(a9)シリコン窒化膜からなる群から選ばれる少なくとも2種以上を含む積層構造体を、請求項1~5のいずれかに記載のドライエッチングガス組成物を用いてプラズマエッチングを行い、(a6)アモルファスカーボン膜及び(a7)フォトレジスト膜以外を個別又は同時に選択的にエッチングする工程を含むドライエッチング方法。
- (a1)炭素を含むシリコン系膜、(a2)結晶シリコン膜、(a3)アモルファスシリコン膜、(a4)多結晶シリコン膜(ポリシリコン膜)、(a5)シリコン酸窒化膜、(a6)アモルファスカーボン膜、(a7)フォトレジスト膜及び(a8)シリコン酸化膜からなる群から選ばれる少なくとも2種以上を含む積層構造体を、請求項1~5のいずれかに記載のドライエッチングガス組成物を用いてプラズマエッチングを行い、(a8)シリコン酸化膜のみを選択的にエッチングする工程を含むドライエッチング方法。
- 請求項6又は7に記載のドライエッチング方法において、Sを含むイオン又は活性種が生成するように請求項1~5のいずれかに記載のエッチングガス組成物をプラズマ化してエッチングを行うドライエッチング方法。
- 請求項6~8のいずれかに記載のドライエッチング方法において、(b1)シリコン酸化膜及び(b2)シリコン窒化膜を同時にエッチング可能なプラズマ条件下で請求項1~5のいずれかに記載のドライエッチングガス組成物によるエッチングを行うドライエッチング方法。
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EP19875912.8A EP3872842A4 (en) | 2018-10-26 | 2019-10-25 | DRY ETCHING GAS COMPOSITION CONTAINING A SULFUR-CONTAINING FLUOROCARBON COMPOUND, AND DRY ETCHING METHOD USING SUCH DRY ETCHING GAS COMPOSITION |
US17/288,274 US20210388264A1 (en) | 2018-10-26 | 2019-10-25 | Dry etching gas composition comprising sulfur-containing fluorocarbon compound and dry etching method using the same |
CN201980070063.5A CN112912994A (zh) | 2018-10-26 | 2019-10-25 | 包含含硫碳氟化合物的干蚀刻气体组合物和使用其的干蚀刻方法 |
KR1020217015497A KR20210083291A (ko) | 2018-10-26 | 2019-10-25 | 황 함유 플루오로카본 화합물을 포함하는 드라이 에칭 가스 조성물 및 그것을 사용한 드라이 에칭 방법 |
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US17/577,554 US11795397B2 (en) | 2018-10-26 | 2022-01-18 | Dry etching gas composition comprising sulfur-containing fluorocarbon compound and dry etching method using the same |
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JPH0613351A (ja) * | 1992-06-29 | 1994-01-21 | Sony Corp | ドライエッチング方法 |
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US8133819B2 (en) * | 2008-02-21 | 2012-03-13 | Applied Materials, Inc. | Plasma etching carbonaceous layers with sulfur-based etchants |
CN103633014B (zh) * | 2012-08-21 | 2018-03-30 | 中国科学院微电子研究所 | 半导体器件制造方法 |
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