TW200924052A - Method for ethcing silicon - Google Patents
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- TW200924052A TW200924052A TW97138332A TW97138332A TW200924052A TW 200924052 A TW200924052 A TW 200924052A TW 97138332 A TW97138332 A TW 97138332A TW 97138332 A TW97138332 A TW 97138332A TW 200924052 A TW200924052 A TW 200924052A
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- 238000000034 method Methods 0.000 title claims description 34
- 229910052710 silicon Inorganic materials 0.000 title abstract 3
- 239000010703 silicon Substances 0.000 title abstract 3
- 239000007789 gas Substances 0.000 claims abstract description 153
- 239000011737 fluorine Substances 0.000 claims abstract description 97
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 97
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 95
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 76
- 229910001868 water Inorganic materials 0.000 claims abstract description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 55
- 238000005530 etching Methods 0.000 claims abstract description 53
- 239000012495 reaction gas Substances 0.000 claims abstract description 45
- 239000000463 material Substances 0.000 claims abstract description 32
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 14
- 238000006243 chemical reaction Methods 0.000 claims description 59
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 41
- 239000002994 raw material Substances 0.000 claims description 38
- 229910052707 ruthenium Inorganic materials 0.000 claims description 33
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 30
- 230000001590 oxidative effect Effects 0.000 claims description 27
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 23
- 239000001301 oxygen Substances 0.000 claims description 23
- 229910052760 oxygen Inorganic materials 0.000 claims description 23
- 239000000126 substance Substances 0.000 claims description 18
- 238000007664 blowing Methods 0.000 claims description 17
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 6
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 125000004429 atom Chemical group 0.000 claims description 2
- 239000008267 milk Substances 0.000 claims description 2
- 210000004080 milk Anatomy 0.000 claims description 2
- 235000013336 milk Nutrition 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 230000007774 longterm Effects 0.000 claims 1
- 101100328843 Dictyostelium discoideum cofB gene Proteins 0.000 abstract description 19
- IYRWEQXVUNLMAY-UHFFFAOYSA-N carbonyl fluoride Chemical compound FC(F)=O IYRWEQXVUNLMAY-UHFFFAOYSA-N 0.000 abstract description 16
- 125000001153 fluoro group Chemical group F* 0.000 abstract description 12
- 239000000203 mixture Substances 0.000 abstract description 4
- 239000000376 reactant Substances 0.000 abstract description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 abstract 2
- 239000000758 substrate Substances 0.000 description 62
- TXEYQDLBPFQVAA-UHFFFAOYSA-N tetrafluoromethane Chemical compound FC(F)(F)F TXEYQDLBPFQVAA-UHFFFAOYSA-N 0.000 description 49
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 32
- 239000010408 film Substances 0.000 description 21
- 238000009833 condensation Methods 0.000 description 19
- 230000005494 condensation Effects 0.000 description 19
- 229960002050 hydrofluoric acid Drugs 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 15
- 238000007254 oxidation reaction Methods 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 12
- 230000003647 oxidation Effects 0.000 description 12
- 230000008569 process Effects 0.000 description 12
- 239000003085 diluting agent Substances 0.000 description 10
- 230000007246 mechanism Effects 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 238000012545 processing Methods 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 239000001257 hydrogen Substances 0.000 description 7
- 229910052739 hydrogen Inorganic materials 0.000 description 7
- 238000009792 diffusion process Methods 0.000 description 6
- 238000005755 formation reaction Methods 0.000 description 6
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910004014 SiF4 Inorganic materials 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 229910052732 germanium Inorganic materials 0.000 description 5
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000002002 slurry Substances 0.000 description 5
- 239000004575 stone Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000005192 partition Methods 0.000 description 4
- 150000003254 radicals Chemical class 0.000 description 4
- 230000001105 regulatory effect Effects 0.000 description 4
- -1 ruthenium radicals Chemical class 0.000 description 4
- 230000008859 change Effects 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000010790 dilution Methods 0.000 description 3
- 239000012895 dilution Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000004020 luminiscence type Methods 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- 230000002159 abnormal effect Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 150000002221 fluorine Chemical class 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- IGELFKKMDLGCJO-UHFFFAOYSA-N xenon difluoride Chemical compound F[Xe]F IGELFKKMDLGCJO-UHFFFAOYSA-N 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- 241001123248 Arma Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 229920006926 PFC Polymers 0.000 description 1
- 206010036790 Productive cough Diseases 0.000 description 1
- 229910004016 SiF2 Inorganic materials 0.000 description 1
- 239000004990 Smectic liquid crystal Substances 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021417 amorphous silicon Inorganic materials 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical group [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000003776 cleavage reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- RWRIWBAIICGTTQ-UHFFFAOYSA-N difluoromethane Chemical compound FCF RWRIWBAIICGTTQ-UHFFFAOYSA-N 0.000 description 1
- MGNHOGAVECORPT-UHFFFAOYSA-N difluorosilicon Chemical compound F[Si]F MGNHOGAVECORPT-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000005304 joining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 210000003205 muscle Anatomy 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000002831 nitrogen free-radicals Chemical class 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 238000005268 plasma chemical vapour deposition Methods 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000001226 reprecipitation Methods 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 229910021647 smectite Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 210000003802 sputum Anatomy 0.000 description 1
- 208000024794 sputum Diseases 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 239000010409 thin film Substances 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
- H01L21/3065—Plasma etching; Reactive-ion etching
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- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Plasma & Fusion (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Drying Of Semiconductors (AREA)
Abstract
Description
200924052 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種使用氟系氣體來對基板表面之矽進行 敍刻之方法。 【先前技術】 例如，於專利文獻1、2中記載有：利用臭氧將晶圓表面 之矽加以氧化而製成氧化矽後（式1}，使用氫氟酸（氟化氫200924052 IX. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method of using a fluorine-based gas to smear the surface of a substrate. [Prior Art] For example, Patent Literatures 1 and 2 disclose that after the ruthenium of the surface of the wafer is oxidized by ozone to form yttrium oxide (Formula 1), hydrofluoric acid (hydrogen fluoride) is used.
Μ進行蝕刻。氫氟酸係於氫氟酸蒸氣發生器中蒸發，將 其導至晶圓表面。又，記載有晶圓溫度為5〇〇c以上，較好 的是60°C以上。 於專利文獻3中記载有：藉由在eh等氟系氣體中進行大 氣壓附近之放電而生成HF、c〇F2等，進而使c〇F2與預先 犯。MCF4等中之水進行反應而生成HF(式2)，利用以上述 方式獲得之HF來對氧化矽進行蝕刻（式3)。Μ etch. Hydrofluoric acid is evaporated in a hydrofluoric acid vapor generator and directed to the surface of the wafer. Further, the wafer temperature is described as 5 〇〇 c or more, preferably 60 ° C or more. In Patent Document 3, it is described that HF, c〇F2, and the like are generated by discharge in the vicinity of atmospheric pressure in a fluorine-based gas such as eh, and c〇F2 is further caused in advance. Water in MCF4 or the like is reacted to form HF (Formula 2), and cerium oxide is etched by the HF obtained in the above manner (Formula 3).
Si+2〇3—Si02+202 (式 ^ cof2+h2o->co2+2hf (式 2)Si+2〇3—Si02+202 (Formula ^ cof2+h2o->co2+2hf (Formula 2)
Si02+4HF+H20- SiF4+3H2〇 (式 3) 於專利文獻4中記载有：藉由大氣I電漿放電而自經加 濕之W獲得HF’於其中添加〇3，對氧切進行㈣。〇3 並非反應原料，而是發揮觸媒之作用。藉由大㈣電漿亦 生成c〇F2,但生成有濃度約為該⑶匕之2 7倍的HF。 於專利文獻5中記载有：使CF盥〇 _ 4興〇2進仃大氣壓放電而獲 付自由基’將其自電漿空間導 守I，皿度為20 C或1〇〇。(：之基 板上’對皁晶梦進行敍刻。 I34995.doc 200924052 於專利文獻6中記載有：使加濕cf4或乾燥cf4進行大氣 ^放電’於基板溫度為90。(：之條件下對結晶矽進行蝕刻。 於專利文獻7中記載有：將eh、〇2及h2〇進行混合，使 該混合氣體進行電漿化而對多晶矽進行蝕刻。 [專利文獻1]曰本專利特開2003_264160號公報 [專利文獻2]日本專利特開2〇〇4_55753號公報 [專利文獻3]日本專利特開2〇〇〇 585〇8號公報 [專利文獻4]曰本專利特開2〇〇2 27〇575號公報 [專利文獻5]日本專利特開平〇4_358〇76號公報 [專利文獻6]曰本專利特開2〇〇〇_164559號公報 [專利文獻7]日本專利特開2〇〇4 356557號公報 【發明内容】 [發明所欲解決之問題] ^之夕触刻中無法明顯提高钱刻速度。發明者以下述 方式對其原因進行考察。 例如於以上所揭示之專利文獻丨、2等中，係從一開始就 將作為姓刻劑之氫氣酸以1氟酸之形式供給至包含晶圓之 基板上因此，一般涊為於基板之表面上除了發生上式】 之氧化反應以外’僅發生上式3之㈣反應。於該式3之反 應中’ 1W著氧化⑪成為揮發性之仰4，而新生成水⑻⑺。 «，於基板溫度低之情料，上述新生成之水會凝縮 而心入基板表面上之氫氟酸之凝縮層中。因此，隨著蝕刻 反應之進行，凝縮層會成長，厚度會增加。另一方面，石夕 之乳化所必需之臭氧係溶解於凝縮層中，在凝縮層中擴散 134995.doc 200924052 而到達基板表面之後，可參與矽之4 氧化，但若凝縮層之厚 X杧大，則到達基板表面之比率減 ^ 囚此，產生臭童力 凝縮層中之擴散控制，導致矽氧化速度之降低。、 又二凝縮層之亂化氫濃度減少亦有可能為降低速率之原 因之 。 相反’於基板溫度高之情形時’氫氟酸凝縮層之成長的 問題消失，但另一方面，如圖6所示，臭氧在氣-液間之分 配係數降低。即’溫度越高，則袁、惫 ^ j旲乳越難以溶解於氫氟酸 凝縮層中。㈣’產生臭氧之溶解控制，仍然會導致石夕氧 化速度之降低。 因此’基板溫度存在使矽氧化速度成為峰值之值。先 丽’ 60°C左右被認為係較佳之基板溫度。如^ 6所示的 °C附近之分配係數為()·ι左右，係僅可溶解臭氧整體之^成 左右的水準。然而’自抑制氫氟酸凝縮層之成長的必要性 考慮’ 60°C係最大限度之下限溫度，低於_則會低溫化 而難以提高分配係數。X ’ 一般認為高濃度之氫氟酸水中 氟化氫比水更容易蒸發，因此若為高s，則氫氟酸濃度本 身亦會減少。 自上述情況考慮，習知之矽蝕刻中，矽氧化速度即使於 峰值點亦不會達到充分之值，當然蝕刻速率亦無法達到充 分之大小。 依據專利文獻4之實施例來推測，由於生成濃度約為 COF2之2.7倍的HF ’故蝕刻反應之H2〇生成量大。因此， 一般認為在應用於矽之蝕刻的情形時，凝縮層中之臭氧擴 134995.doc 200924052 政文阻，蝕刻速率不會明顯增大。 又如專利文獻5等所示，使用以電漿所生成之自由基 進仃餘刻的情形時，若電衆空間與基板之間的距離過遠， 貝J自由基會在到達基板之前失去#十生，導致蚀㈣速率之降 低另方面，若電漿空間與基板之間的距離過近，則可 月匕會由於電漿而損傷基板。因此，電毁空間與基板之相隔 距離的設定範圍之自由度小。 述是縮層中之擴散控制在臭氧以外之氧化性氣體（例 如〇自由基等）時亦可同樣地產生。 [解決問題之技術手段] 所式3*之#刻反應中生成新的水係由於H F等氟系反應物 有氫原子。發明者藉由以上考察而獲得如下知識見 解：触刻氣體中存在氫原子，亦會對㈣刻造成負面影 本發明係基於上述知識見解而形成者，Si02+4HF+H20-SiF4+3H2〇 (Formula 3) In Patent Document 4, it is described that HF is obtained from the humidified W by atmospheric I plasma discharge, and 〇3 is added thereto. (4). 〇3 is not a reaction to raw materials, but acts as a catalyst. c〇F2 is also generated by the large (four) plasma, but HF having a concentration of about 27 times that of the (3) 生成 is generated. Patent Document 5 discloses that CF 盥〇 4 〇 〇 仃 仃 仃 仃 仃 仃 仃 仃 仃 仃 仃 仃 仃 仃 仃 仃 仃 ’ ’ ’ ’ ’ ’ ’ ’ ’ 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 〇〇 (: On the substrate, 'Sapphire crystal dreams are described. I34995.doc 200924052 In Patent Document 6, it is described that the humidification cf4 or the dry cf4 is subjected to atmospheric discharge> at a substrate temperature of 90. The crystal enthalpy is etched. In Patent Document 7, it is described that eh, 〇2, and h2 混合 are mixed, and the mixed gas is pulverized to etch the polycrystalline silicon. [Patent Document 1] Japanese Patent Laid-Open No. 2003-264160 [Patent Document 2] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. [Patent Document 5] Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. [Summary of the Invention] [Problems to be Solved by the Invention] ^The moment of engraving cannot significantly increase the speed of money engraving. The inventors examined the cause in the following manner. For example, the patent documents disclosed above, 2, etc. In the beginning, it will be used as a surname Hydrogen acid is supplied to the substrate containing the wafer in the form of 1 fluoric acid. Therefore, generally, only the (4) reaction of the above formula 3 occurs on the surface of the substrate except for the oxidation reaction of the above formula. In the reaction, 1W is oxidized and becomes volatility, and the newly formed water is (8) (7). «In the case of low substrate temperature, the newly formed water will condense and condense into the condensation layer of hydrofluoric acid on the surface of the substrate. Therefore, as the etching reaction proceeds, the condensed layer will grow and the thickness will increase. On the other hand, the ozone necessary for the emulsification of Shi Xi is dissolved in the condensed layer and diffuses in the condensed layer to reach 134995.doc 200924052. After the surface of the substrate, it can participate in the oxidation of ruthenium. However, if the thickness of the condensed layer is large, the ratio of reaching the surface of the substrate is reduced, and diffusion control in the condensed layer of the odor is generated, resulting in a decrease in the oxidation rate of ruthenium. The reduction of the hydrogen concentration of the two condensation layers may also be the reason for reducing the rate. On the contrary, the problem of the growth of the hydrofluoric acid condensation layer disappears when the substrate temperature is high, but on the other hand, As shown in Fig. 6, the partition coefficient of ozone in gas-liquid is reduced. That is, the higher the temperature, the more difficult it is to dissolve in the hydrofluoric acid condensation layer. (4) The ozone dissolution control will still occur. This results in a decrease in the oxidation rate of the shixi. Therefore, the substrate temperature has a value that causes the ruthenium oxidation rate to become a peak. The temperature of the smelting of about 60 °C is considered to be a better substrate temperature. The distribution coefficient near °C as shown in Fig. 6 is () · ι or so, is only soluble in the overall level of ozone. However, 'self-inhibition of the growth of hydrofluoric acid condensation layer needs to consider '60 ° C system maximum limit temperature, below _ It is difficult to increase the partition coefficient by lowering the temperature. X ′ It is generally considered that hydrogen fluoride in a high concentration of hydrofluoric acid water is more likely to evaporate than water, so if it is high s, the hydrofluoric acid concentration itself is also reduced. In view of the above, in the conventional etch, the enthalpy oxidation rate does not reach a sufficient value even at the peak point, and of course, the etch rate cannot reach a sufficient size. According to the embodiment of Patent Document 4, it is presumed that the amount of H2〇 generated by the etching reaction is large because the HF is formed to have a concentration of about 2.7 times that of COF2. Therefore, it is generally considered that in the case of etching applied to ruthenium, the ozone in the condensed layer is etched, and the etching rate is not significantly increased. Further, as shown in Patent Document 5 and the like, when a radical generated by a plasma is used, if the distance between the space and the substrate is too far, the shell J radical will be lost before reaching the substrate. Ten years, causing the eclipse (four) rate reduction. On the other hand, if the distance between the plasma space and the substrate is too close, the moon will damage the substrate due to the plasma. Therefore, the degree of freedom in the setting range of the distance between the electric destruction space and the substrate is small. It is described that the diffusion in the polycondensation layer is controlled in the same manner as in the case of an oxidizing gas other than ozone (e.g., ruthenium radicals). [Technical means for solving the problem] A new water system is formed in the #3 engraving reaction of the formula 3* because the fluorine-based reactant such as H F has a hydrogen atom. The inventors obtained the following knowledge through the above investigations: the presence of a hydrogen atom in the etched gas also causes a negative impact on the (four) engraving. The present invention is formed based on the above knowledge.
L 本發明係對包含石夕之被處理物進行钱刻之方法， 广寺徵在於：實行對溫度被設為阶〜㈣之被處理物 〇人附反應氣體之吹附步驟， 上述反應氣體含有： (a)可將矽進行氧化之氧化性氣體、 (b)含有〇.4 ν〇ι%以上（軔 曰 mF、日目士 （奴好的疋2〜2.5 v〇l%)之氟化氫 ()且”有氧化石夕之姓刻能力的氟系反應物質、 ()’、水反應而形成上述氟系反應物質的非自由基之氟 系中間物質，且哕及廡# 土疋氣 應乳體中之氟原子數(F)與氫原子數 I34995.doc 10- 200924052 (H)之比為（F)/(H)>1.8。 作為上述氧化性氣體，可列舉〇2、〇3、 >fer - X A 2 乳’ H2〇2蒸氣等。 作又*，，可藉由將含有氧之氣體導人至大氣壓錢中，而獲 知0等自由基或〇3等氧化性反應成分；亦可將含有該氧 化性反應成分之氣體用作上述氧化性氣體。 自氧化力或氣體之敎性等觀點考慮，較好的是使用03 來作為上述氧化性氣體。 較好的疋上述反應氣體含有i vol%以上之臭氧來作為上 述氧化性氣體。 、、更好的是上述反應氣體含有3〜Π)满之臭氧來作為上 述氧化性氣體。 依據本發明，可利用臭氧等氧化性氣體使石夕氧化，以 ㈣氟系反應物f對該氧切進行㈣卜氟系反應物質中 尤其是HF與氧化矽之敍刻反應中生成水；該水與i系中間 物質反應而生細等氟系反應物質；藉此，可消耗蚀刻反 應中所生成之水。即使被處理物溫度為i〇£>c〜5〇艽之低 溫，亦可抑制凝縮層在被處理物之表面上成長；藉由被處 理物之低溫化’可提高臭氧等氧化性氣體在凝縮層中之溶 解度，且藉由抑制臭氧等氧化性氣體之成長，可確保臭氧 等氧化性氣體在凝縮層中之擴散度，·並且，藉由使反應氣 體之氫原子數（H)與氟原子數（F)之比成為（f)/(h)>i 8，可 使钱刻反應中所生成之水在與氟系中間物f之反應中確實 地消耗，從而可確實地抑制凝縮層之成長；藉此，可充分 I34995.doc 200924052 確保臭氧等氧化性氣體在凝縮層中之擴散。 於使用臭氧來作為氧化性氣體，且將上述反應氣體中之 臭氧濃度設為1 v〇l%以上（較好的是3〜1〇 v〇I%)之情形時， 該臭氧濃度條件和上述反應氣體中之氟原子數（F)與氳原 子數（H)之比的條件相互作用，可使矽氧化速度充分提 高，從而可使蝕刻速率大幅提高。 進而’藉由使反應氣體中含有0.4 v〇1%以上（較好的是 2〜2.5 vol%)2HF，可使蝕刻反應確實地開始，同時可防 止被處理物表面之凝縮層蒸發、消失，可確保穩定的蝕刻 反應。 又，藉由使用非自由基之氟系中間物質，可回避由於反 應氣體之吹出部與被處理物之間的相隔距離而造成的蝕刻 速率降低、或被處理物受損等情況，從而可使距離設定等 設計之自由度提高。 為了將氣系中間物質確實地轉變為氟系反應物質，亦可 僅於反應之最初向反應氣體中添加水蒸氣。於被處理物為 非晶石夕之情形等時’亦可由該被處理物中所含之氫與反應 氣體中之氧而獲得水，藉由與該水之反應而將氟系中間物 質轉變為氟系反應物質。 根據被處理物之溫度等，可能會有水蒸發而造成氫氟酸 凝縮相消失之情況，此時’較好的是藉由在蝕刻反應或供 給氣體中添加水蒸氣來補充所蒸發之部分的水。 更理想的是上述反應氣體中之氟原子數（F)與氫原子數 (H)之比為（F)/(H)>3。藉此，可更確實地消耗水（h2〇)，從 134995.doc 200924052 而可更確實地抑制凝縮層之成長。 再者，上述之比（F)/(H)可以下述方式測定。 (1) 利用傅立葉變換紅外分光器（Fourier Transform Infrared，FTIR)來測定反應氣體中之氟系中間物質的濃 度’求出氟系中間物質中之氫原子數（H)。 (2) 使一定量的反應氣體通過水（驗性水），同時測定pH 值’求出通過前與通過後之氫的濃度變化AH。該濃度變 化係由與上述反應氣體之水的HF生成反應而引起，因此由 該濃度變化來求出上述反應氣體中之氟原子數（F)。 (3) 根據上述（1)與（2)來算出比（F)/(H)。 上述氟系中間物質較好的是不含氫之氟系分子，例如較 好的是COF2。COF2可與HF同樣地利用FTIR來容易地計測 出。因此，可容易進行製程之監視或控制。 反應氣體中之COF2的莫耳濃度較好的是HF的〇 4倍以 上，可為0.4<(COF2/HF)g 1，亦可為 1<(c〇F2/HF)g i 5， 亦可為 1.5<(COF2/HF)各2，且亦可為 2<(c〇F2/HF)。 上述氟系中間物質若為與水反應而生成耶等敦系反應 物質者即可，並不限定於c〇f2，亦可為CF3〇H等含有氫 者’亦可為F2。 上述臭氧等氧化性氣體之生成、及上述氟系反應物質以 及既系中間物質之生成較好的是分料行，其後，加以混 合而生成上述反應氣體；藉此，可確實地增大钮刻速率。 來含有氧之氣體導入臭氧發生器中，生成臭氧 來作為上述乳化性氣體；藉此，可確實地獲得高濃度之臭 I34995.doc 200924052 氧來作為上述氧化性氣體。 臭氧添加量較好的是僅 ΓΟΡ ^ ^ 僅了月b地夕。於氟系令間物質為 COF2之情形時，臭負 ^ 旦她“心之添加流置必須至少為將啊之流 里與HF之流量的2分$丨蛐#工/曰 2倍左右。 總相得之大小以上，較好的是其 較：的是將在不具有與石夕之反應性的氣系原料氣體中、 添加路，達到】代〜贼（水蒸氣分麼為i 2282咖〜7The present invention relates to a method of engraving a material containing the object of Shi Xi, and the method of engraving is to carry out a blowing step of the reaction gas containing the object to be treated with the temperature of the step (4), wherein the reaction gas contains : (a) an oxidizing gas capable of oxidizing hydrazine, (b) hydrogen fluoride containing 〇.4 ν〇% or more (轫曰mF, Nisshin (2~2.5 v〇l%) And "a fluorine-based reaction substance having the ability to etch the name of the oxidized stone, ()', a non-radical fluorine-based intermediate substance which reacts with water to form the fluorine-based reaction substance, and 哕 and 庑# The ratio of the number of fluorine atoms (F) in the body to the number of hydrogen atoms I34995.doc 10-200924052 (H) is (F)/(H)> 1.8. Examples of the oxidizing gas include 〇2, 〇3, >fer - XA 2 milk 'H2〇2 vapor, etc.. Also, by introducing oxygen-containing gas into atmospheric pressure, it is known that 0 or other oxidative components such as ruthenium or ruthenium 3; A gas containing the oxidizing reaction component can be used as the oxidizing gas. From the viewpoints of oxidizing power or gas enthalpy, it is preferred to use 03. Preferably, the reaction gas contains i vol% or more of ozone as the oxidizing gas. More preferably, the reaction gas contains 3 to Π) of ozone as the oxidizing property. According to the present invention, the oxidizing gas such as ozone can be used to oxidize the cerium, and the (iv) fluorine-based reactant f can be used to carry out the oxygen cleavage. (IV) The fluorine-based reaction material, especially the HF and cerium oxide, generates water. The water reacts with the i-based intermediate substance to produce a fine fluorine-based reaction material; thereby, the water generated in the etching reaction can be consumed. Even if the temperature of the object to be treated is low temperature of i〇>c~5〇艽, It is also possible to suppress the growth of the condensed layer on the surface of the object to be treated; and to improve the solubility of the oxidizing gas such as ozone in the condensed layer by lowering the temperature of the object to be treated, and by suppressing the growth of an oxidizing gas such as ozone. The degree of diffusion of the oxidizing gas such as ozone in the condensation layer is ensured, and the ratio of the number of hydrogen atoms (H) of the reaction gas to the number of fluorine atoms (F) is (f) / (h) > i 8 , which can generate money in the reaction It is surely consumed in the reaction with the fluorine-based intermediate f, so that the growth of the condensed layer can be surely suppressed; thereby, it is sufficient to ensure the diffusion of an oxidizing gas such as ozone in the condensed layer by using I34995.doc 200924052. In the case where the concentration of ozone in the reaction gas is 1 v〇l% or more (preferably 3 to 1〇v〇I%) as the oxidizing gas, the ozone concentration condition and the reaction gas are The conditional interaction of the ratio of the number of fluorine atoms (F) to the number of cesium atoms (H) allows the ruthenium oxidation rate to be sufficiently increased, so that the etching rate can be greatly increased. Further, by making the reaction gas contain 0.4 v 〇 1% The above (preferably 2 to 2.5 vol%) 2HF allows the etching reaction to be surely started, and at the same time, the condensation layer on the surface of the object to be treated is prevented from evaporating and disappearing, and a stable etching reaction can be ensured. Further, by using a non-radical fluorine-based intermediate material, it is possible to avoid a decrease in the etching rate due to the distance between the blowing portion of the reaction gas and the workpiece, or damage of the workpiece, and the like. The freedom of design such as setting is increased. In order to reliably convert the gas-based intermediate material into a fluorine-based reaction material, water vapor may be added to the reaction gas only at the beginning of the reaction. When the object to be treated is amorphous or the like, it is also possible to obtain water from the hydrogen contained in the treated object and the oxygen in the reaction gas, and convert the fluorine-based intermediate substance into a reaction with the water. Fluorine-based reaction substance. Depending on the temperature of the object to be treated, etc., there may be a case where water vaporizes and the hydrofluoric acid condensation phase disappears. At this time, it is preferable to supplement the evaporated portion by adding water vapor to the etching reaction or the supply gas. water. More preferably, the ratio of the number of fluorine atoms (F) to the number of hydrogen atoms (H) in the above reaction gas is (F) / (H) > 3. Thereby, water (h2〇) can be consumed more reliably, and the growth of the condensed layer can be more reliably suppressed from 134995.doc 200924052. Further, the above ratio (F) / (H) can be measured in the following manner. (1) The concentration of the fluorine-based intermediate substance in the reaction gas is measured by Fourier Transform Infrared (FTIR). The number of hydrogen atoms (H) in the fluorine-based intermediate material is determined. (2) A certain amount of the reaction gas is passed through water (acceptable water), and the pH value is measured at the same time to determine the concentration change AH of the hydrogen before and after the passage. This change in concentration is caused by the reaction with HF of the water of the above reaction gas. Therefore, the number of fluorine atoms (F) in the above reaction gas is obtained from the change in concentration. (3) Calculate the ratio (F)/(H) based on the above (1) and (2). The fluorine-based intermediate material is preferably a fluorine-based molecule containing no hydrogen, and for example, COF2 is preferred. COF2 can be easily measured by FTIR in the same manner as HF. Therefore, the monitoring or control of the process can be easily performed. The molar concentration of COF2 in the reaction gas is preferably 4 times or more of HF, and may be 0.4 < (COF2/HF)g 1, or 1 < (c〇F2/HF) gi 5 , It is 1.5 < (COF2 / HF) 2 each, and may also be 2 < (c〇F2 / HF). The fluorine-based intermediate material may be formed by reacting with water to form a reaction substance such as yttrium, and is not limited to c〇f2, and may be hydrogen containing CF3〇H or the like. The formation of the oxidizing gas such as ozone and the formation of the fluorine-based reaction material and the intermediate material are preferably a branching line, and then mixing to form the reaction gas; thereby, the button can be surely increased. Engraving rate. The gas containing oxygen is introduced into the ozone generator to generate ozone as the emulsified gas. Thereby, oxygen having a high concentration of odor I34995.doc 200924052 can be surely obtained as the oxidizing gas. The better amount of ozone added is only ΓΟΡ ^ ^ only for the month b. In the case where the fluorine-based intercalation substance is COF2, the odor is negative. She must add at least 2 points of the flow of HF and HF to the flow of HF. More than the size of the phase, it is better to: in the gas source gas that does not have the reactivity with Shi Xi, add road, to reach the generation of thief (water vapor is i 2282 coffee ~ 7
Pa)之置的水而形成的加濕氟系原料氣體，於大氣麼附近 仃電衆化；藉此’可生成上耗系反應物質以及氣系令 間物貝，《其可獲得高濃度的以CO。為代表之敦系中間物 質；又，可實現操作之容易化。再者，於電聚放電之投入 電力比較大之情形時，較好的是於敗系原料中除了添加水 以外，亦添加氧。 此處，所謂大氣麼附近，係指〇 5 bar〜2 bar之範圍，較 好的是0_9 bar〜1 · 1 bar之範圍。 作為上述氟系原料，可列舉：全氟碳（PFC)、氫氟碳 (HFC)、SF6、NF3、XeF2 等。作為 pFC，可列舉·· Cf4、 c2；f6、c3f6、（:3f8 等。作為 HF(：，可列舉：cHF3、 CH2F2、CH3F 等。 較好的是上述氟系原料氣體不僅含有CF4來作為氟系原 料，並且進而含有Ar。藉由將Ch用作氟系原料，可由電 漿化而獲得COF2、CFjOH、Fa等來作為氟系中間物質，進 而由所添加之水與CF4之電漿反應而獲得HF來作為氟系反 應物質。可藉由使氟系原料氣體中含有Ar而獲得良好之電 134995.doc 14- 200924052 漿。 上述添加水之前的氟系原料氣體中之cf4之濃度較好的 疋4〜90 V〇1% ’更好的是5〜90 vol%，進而好的是10〜90 v〇l%，剩餘部分較好的是Ar。 上述氟系原料氣體可含有01?4與。 上述氟系原料氣體亦可含有CF4、心與乂。 較好的是上述添加水之前的氟系原料氣體含有4〜90 v〇l%之氟系原料（較好的是^^及剩餘部分，且上述剩餘 部分含有Ar與N2中之至少一者。 較好的是上述剩餘部分之氣體成分或混合比依賴於用以 形成電漿空間之電極間電壓；放電之容易度或放電之強度 係根據電極間電壓而變化。因此，較好的是根據電極間電 壓Vpp來調節剩餘部分之斛與乂之混合比。^為稀有氣 體因此即使電極間電壓Vpp比較低亦可進行電漿化。& 進行電漿化時必須有高的電極間電麼Vpp。 較好的是上述剩餘部分中含有Ar。 車乂好的疋上述剩餘部分之5〜100 vol%為Ar，且〇〜45 vol/。為N2 ;藉此，即使於電漿空間之每單位厚度之峰間電 壓vpp(電場強度）為例如小於13 kv/mm的比較低之電壓條 件下，亦可充分提高蝕刻速率（參照實施例3)。藉由將乂 用作上述剩餘部分之一成分，可降低運轉成本。 電漿空間之每單位厚度之峰間電壓Vpp較好的是13 kV/mm以上’更好的是15 kv/mm以上；藉此，心自不待 言，乂亦可經充分地電漿化，可獲得高蝕刻速率。因此， 134995.doc 200924052 可任意地設定上述剩餘部分的心與a之混合比，可將上述 剩餘部分中之N2的比率設定為大於45 ν〇ι%，亦可將上述 剩餘部分設為1 〇〇%之N2 ^當然，亦可將上述剩餘部分設 為 100%之 Ar。 電漿空間之每單位厚度的峰間電壓Vpp之上限較好的是 20 kV/mm左右。藉此，可防止發生異常放電。 上述電聚化後之水的濃度較好的是電漿化前之1/1〇以 下；藉此，可在氟系中間物質之蝕刻氣體化反應中消耗大 部分之水’可確實地抑制被處理物表面之凝縮層之成長， 從而可確實地提高蝕刻速率。 形成上述電漿空間之電極較好的是經40°c以上之調溫介 質來調節溫度；藉此，可防止電漿空間内產生結露。於上 述電漿空間中經電漿化之氣體較好的是在其後與臭氧等氧 化性氣體混合之時刻達到5(TC以下，更好的是與被處理物 之溫度（10〜50。〇大致相等。藉由在與臭氧等氧化性氣體 混合之時刻達到50。(：以下，可防止臭氧等氧化性氣體失去 活性。 上述露點較好的是10。(：〜30t (水蒸氣分壓為丨228 ]^&〜4.2467 1^3)’更好的是10。(：〜2〇。(：（水蒸氣分壓為1228 kPa〜2.3392 kPa)’進而更好的是1(rc〜17t(水蒸氣分壓為 1.2282 kPa〜1.9383 kPa)。 藉此，可確實地提高姓刻速率。 上述被處理物之溫度之上限可低於5〇°c，亦可為以 下。 134995.doc 200924052 更子的是將上述被處理物之溫度設為^。 藉此’可使臭氧等氧化性氣體容易溶解於被處理物表面 之凝縮層中，可提高石夕氧化速度。或者HF等變得易於溶 解，而可提高氫氟酴普由 _ , 、' 门轧贶馱展度。因此，可進一步提高蝕刻速 率〇 將上述被處理物之溫度範圍之下限設為IGt：，係為了防 止被處理物表面之結露（室溫為说時，相對濕度為38%以 内即可）。 亦可將上述被處理物之溫度範圍之下限設為室㈣ 代替10°c。 ” 藉此，可防止室内之水分於被處理物表面上結露，可更 確實地防止被處理物表面之凝縮層之成長。 更好的是將上述被處理物之溫度設為室溫。 藉此，無須對被處理物進行加熱或冷卻，可省略被處理 物之溫度調節步驟。 [發明之效果] 依據本發明，即使蝕刻反應時產生水，亦可將該水用於 HF等氟系反應物質之生成反應中。因此，即使被處理物溫 度為低溫，亦可抑制凝縮層在被處理物之表面上成長。藉 此’可提高矽氧化速度，並且可提高蝕刻速率。 【實施方式】 以下，對本發明之第丨實施形態進行說明。 如圖1所示，於玻璃等基板90之上表面形成有矽臈91(被 處理物）。構成膜91之矽可為非晶矽（a_Si)，亦可為微晶 134995.doc -17- 200924052The humidified fluorine-based source gas formed by the water of Pa) is electrically charged in the vicinity of the atmosphere; thereby, it is possible to generate an upper-emission reaction substance and a gas-phase substance, which can obtain a high concentration. Take CO. It is the intermediate substance represented by the system; in addition, the operation can be facilitated. Further, in the case where the electric power is relatively large in the electric discharge, it is preferable to add oxygen in addition to water in the raw material. Here, the vicinity of the atmosphere means a range of 5 bar to 2 bar, preferably a range of 0_9 bar to 1 · 1 bar. Examples of the fluorine-based raw material include perfluorocarbon (PFC), hydrofluorocarbon (HFC), SF6, NF3, and XeF2. Examples of the pFC include Cf4 and c2; f6, c3f6, (3f8, etc.), and HF (:, cHF3, CH2F2, CH3F, etc.). Preferably, the fluorine-based source gas contains not only CF4 as fluorine. The raw material is further contained in Ar. By using Ch as a fluorine-based raw material, COF2, CFjOH, Fa, or the like can be obtained by plasma formation as a fluorine-based intermediate material, and further, the added water reacts with the plasma of CF4. HF is obtained as a fluorine-based reaction material. A good electric 134995.doc 14-200924052 slurry can be obtained by containing Ar in the fluorine-based raw material gas. The concentration of cf4 in the fluorine-based raw material gas before the above-mentioned water addition is good.疋4~90 V〇1% 'better is 5 to 90 vol%, and further preferably 10 to 90 v〇l%, and the remainder is preferably Ar. The above fluorine-based raw material gas may contain 01?4 and The fluorine-based source gas may further contain CF4, a core, and a ruthenium. Preferably, the fluorine-based source gas before the addition of water contains 4 to 90 v〇% of a fluorine-based raw material (preferably ^^ and the remainder) And the remaining portion contains at least one of Ar and N2. It is preferred that the remaining portion The gas composition or the mixing ratio depends on the voltage between the electrodes for forming the plasma space; the ease of discharge or the intensity of the discharge varies depending on the voltage between the electrodes. Therefore, it is preferable to adjust the remaining portion according to the voltage Vpp between the electrodes.混合 混合 乂 。 ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ ^ It contains Ar. The ruthenium of the ruthenium is 5 to 100 vol% of Ar, and 〇~45 vol/ is N2; thereby, even between the peak-to-peak voltage per unit thickness of the plasma space vpp (electric field) The strength can be sufficiently increased under a relatively low voltage condition of, for example, less than 13 kV/mm (refer to Example 3). By using yttrium as one of the remaining components, the running cost can be reduced. The peak-to-peak voltage Vpp per unit thickness of the space is preferably 13 kV/mm or more, and more preferably 15 kV/mm or more; thereby, it is self-evident that the crucible can also be fully plasmad. High etch rate. Therefore, 134995.doc 2 00924052 arbitrarily setting the mixing ratio of the heart and a of the remaining portion, and setting the ratio of N2 in the remaining portion to be greater than 45 ν〇ι%, or setting the remaining portion to N ^% of 1 〇〇%. Of course, the remaining portion may be set to 100% Ar. The upper limit of the peak-to-peak voltage Vpp per unit thickness of the plasma space is preferably about 20 kV/mm, thereby preventing abnormal discharge from occurring. The concentration of the water after the polymerization is preferably 1/1 〇 or less before the plasma formation; thereby, most of the water can be consumed in the etching gasification reaction of the fluorine-based intermediate material, and the object to be treated can be surely suppressed. The growth of the condensation layer on the surface can surely increase the etching rate. It is preferable that the electrode for forming the plasma space is a temperature adjusting medium of 40 ° C or more to adjust the temperature; thereby preventing condensation from occurring in the plasma space. Preferably, the pulverized gas in the plasma space is 5 (TC or less), and more preferably the temperature of the object to be treated (10 to 50. 〇 at the time of mixing with an oxidizing gas such as ozone. It is approximately equal to 50. When it is mixed with an oxidizing gas such as ozone, it reaches 50. (: The following is effective to prevent the oxidizing gas such as ozone from deactivating. The above dew point is preferably 10. (: ~30t (the partial pressure of water vapor is丨 228 ] ^ & ~ 4.2467 1 ^ 3) 'Better is 10. (: ~ 2 〇. (: (water vapor partial pressure is 1228 kPa ~ 2.3392 kPa) 'and then better is 1 (rc ~ 17t (The partial pressure of water vapor is 1.2282 kPa to 1.9383 kPa.) Thereby, the rate of surname can be surely increased. The upper limit of the temperature of the object to be treated can be less than 5 〇 ° C, or can be as follows. 134995.doc 200924052 By setting the temperature of the object to be treated to ^, the oxidizing gas such as ozone can be easily dissolved in the condensed layer on the surface of the object to be treated, and the oxidation rate of the stagnation can be improved. , and can improve the hydrofluorination of _ , , ' door rolling spread. Therefore, can further mention Etching rate 〇 The lower limit of the temperature range of the object to be treated is IGt: in order to prevent condensation on the surface of the object to be treated (the relative humidity is 38% or less at room temperature). The lower limit of the temperature range of the object is set to the chamber (4) instead of 10 °c. ” By this, it is possible to prevent condensation of moisture in the room on the surface of the object to be treated, and it is possible to more reliably prevent the growth of the condensation layer on the surface of the object to be treated. The temperature of the object to be treated is set to room temperature. Therefore, the temperature adjustment step of the object to be processed can be omitted without heating or cooling the object to be processed. [Effect of the Invention] According to the present invention, even when an etching reaction occurs Water can also be used for the formation reaction of a fluorine-based reaction material such as HF. Therefore, even if the temperature of the material to be treated is low, the condensed layer can be prevented from growing on the surface of the object to be treated. The oxidation rate is increased, and the etching rate can be increased. [Embodiment] Hereinafter, a third embodiment of the present invention will be described. As shown in Fig. 1, a crucible 9 is formed on the upper surface of a substrate 90 such as glass. 1 (object to be treated). The crucible constituting the film 91 may be amorphous germanium (a_Si) or microcrystalline 134995.doc -17- 200924052
Si、多晶Si等結晶性矽。亦可為以矽作為主成分且含有 0〜20%左右之氫的膜。基板9〇係由晶圓等的矽所構成該 矽基板90本身亦可作為被處理物而成為蝕刻對象。亦可為 摻雜有P或B等之n型或p型矽。列舉一例，液晶用之 TFT(Thin Film Transistor ’薄膜電晶體）中所使用之基板， 係將SiN成膜力玻璃，其冑，成為本實施形態之被處理 物的非晶 si 以電漿 CVD(Chemical Vap〇r Dep〇shi〇n，化學 氣相沈積）而成膜。 圖中，基板90以及矽臈91之厚度係放大表示。 蝕刻裝置1具備基板支持部2、基板溫度調節機構3、反 應氣體供給系統4。 於基板支持部2上設置有基板9〇。基板支持部2以及基板 90係利用未圖示之移動機構，相對於反應氣體供給系統4 而於例如圖1之左右方向a上進行相對移動。亦可為反應氣 體供給系統4之氣體吹出部相對於基板9〇而移動。 基板溫度調節機構3包含加熱器或冷卻器（省略圖示）， 將需處理之基板90的溫度調節為特定溫度。基板9〇之溫度 較好的是nrc〜5〇°c，更好的*1(rc〜3(rc ’進而更好的是 «又為至溫。溫度範圍之下限亦可設為室内露點來代替iοι。 於將基板溫度設為室溫之情形時，基板溫度調節機構3可 省略。 反應氣體供給系統4具備臭氧供給系統1〇、氟系氣體供 給糸統2 0。 臭氧供給系統1 〇包含氧（〇2)之供給部i丨、氮（N2)之供給 134995.doc -18· 200924052 量流量控 部12、臭氧發生器13。臭氧發生器13具有2個質 制器14A、14B以及放電部1 6。 於氧供給部11上連接有質量流量控制HMA，於氮供給 部！2上連接有質量流量控制器MB。於來自氧用之質量 量控制器i4A的導出管路15上合流有來自氮用之質量流量 控制器⑽的導出管路15b。合流後之導出管路⑽接於放 電部16上。雖省略了詳細之圖示，但於放電部16上設置有 複數個電極，以使藉由該等電極間之放電來使氧進行臭氧 化。臭氧供給管路1 7自放電部16延伸。 齓系氣體供給系統20具備CF4(不具有與矽之反應性的氟 系原料）之供給部21、氬（Ar)之供給部22、加濕、器23、大氣 壓電漿放電部24。於CF4供給部上連接有質量流量控制器 25A，於Ar供給部22上連接有質量流量控制器25b。來自 該等質量流量控帝J||25A、25B之導出管路26&、抓相互 合流’。合流後之導出管路26連接於加濕器23上。於加濕器 23中蓄積有加濕用之水（H2〇)。 於力口屬器23上連接有大氣壓電黎放電部24。於大氣壓電 浆放電部24上設置有一對電極27、27。該等電極27、27係 、在中門挾持有1 mm左右之間隙27a而相對向的方式來配 置，於相互的對向面上設置有固體介電質層（省略圖示）。 藉由來自電源（省略圖示）之電壓供給而於電極27、27之間 形成大氣壓輝光放電，間隙27a内成為電漿空間。從而使 導入至该電浆空間27a中之氣體經電漿化。電壓波形可為 脈衝等間歇波，亦可為正.弦波等連續波。 134995.doc -19· 200924052 於電極27上設置有調溫管路28。於調溫管路28中流通有 溫度經調整為40°C以上之水來作為調溫介質。 吹出管路29自電黎空間27a向基板90延伸。於該吹出管 路29上合流有來自臭氧發生器13之臭氧供給管路17。 S 自吹出管路29之前端開口（吹出口）離開上述移動方向&而 配置有吸引官路41之端部開口（吸引口）。吸引管路41與真 泵等排氣機構42相連接。 、 利用上述蝕刻裝置1，來說明對基板9〇之矽膜91進行蝕 刻之方法。 1. 基板溫度調節步称 利用基板溫度調節機構3，將需處理之基板9〇調節為W =〜5〇°C、較好的是抓〜3〇t之特定溫度。於基板9〇之特 定溫度為室溫之情形時，無須特別進行溫度調節。 2. 臭氧生成步驟 > :用質量流量控制器14A對來自供給部n之氧進行流量 周即且向導出官路! 5導出。於該氧中微量添加經質量流 量控制器_調節流量之氮。氮之添加量較好的是 Ν2/(〇:+Ν2)=小於3 VGl%。藉此，生成以氧為主的氧與氮之 混合氣體（含有氧之氣體）。 一將°亥3有氧之氣體導入至臭氧發生器13之放電部16中。 藉：，含有氧之氣體中的氧經臭氧化，生成含有臭氧(〇3) ^體曰放電部16之出口處的含臭氧之氣體之臭氧濃度較 的疋8 1〇 v〇m。將該含臭氧之氣體向供給管路η導 I34995.doc •20- 200924052 3.氣系處理氣想生成步琢 又’利用質量流量控制器25 Α對來自供給部21之CF4進行 流量調節，同時利用質量流量控制器25B對來自供給部22 之Ar進行流量調節。將流量調節後之CF4與Ar在導出管路 26中加以混合’生成CF4與Ar之混合氣體（經Ar稀釋之氟系 原料氣體）。該混合氣體中之CF*之濃度較好的是 CF4/(CF4+Ar)=4~90 vol%，更好的是 CF4/(CF4+Ar)=5〜90 vol%，進而好的是 CF4/(CF4+Ar)=5〜20 v〇l〇/0。 將在導出管路26中;^合之氣體（CF4+Ar)通入至加濕器23 中’使加濕器23内之水（H2〇)氣化而添加於混合氣體中。 水添加量較好的是露點達到l〇〇c 〜4〇χ：之量，更好的是達 到l〇°C〜30°C之量，進而好的是達到1〇〇c 〜2〇<t之量。藉 此，獲得露點比先前低之加濕氟系原料氣體（CF4+Ar+H2〇)。 將上述加濕氟系原料氣體（CF4+Ar+H2〇)導入至電漿放電 部24之大氣壓電漿空間27a中，進行電漿化。可利用氣體 中之Ar來獲得良好之電漿。藉此，生 cf3〇h、f2等謝間物質，或氧系反應物質即hf等的2氟 系處理氣體。該氟系處理氣體經導出至吹出管路29中。 電聚化後之水分量較好的是達到電聚化前之⑽以下。 由於電極27經贼以上之調溫介質進行溫度調節，故可防 止在電漿空間27a内產生結露。 丹者，於電漿放電之投 Η π八心W形吋，較好的 疋：中除了添加水以外，亦添加例如相對於CF4而為 vo 帅2)°藉此’可更確實地生成咖2來作為氟 I34995.doc •21 - 200924052 系中間物質。 4.混合步驟 使來自電漿放電部24的包含COF2、HF等之氟系處理氣 體以及來自臭氧發生器16的含臭氧之氣體於吹出口 27中合 流，並加以混合。藉此，生成包含臭氧、COF2等氟系中間 物質、HF等氟系反應物質的反應氣體。 來自電漿放電部24之氟系處理氣體、與來自臭氧發生器 16的含臭氧之氣體的體積流量比，較好的是（氟系處理氣 體）/(含臭氧之氣體）=0.2-5 ’更好的是1〜3。該等氣體混人 後之反應氣體中的臭氧濃度為1 vol%以上，較好的是3〜ι〇 vol%。又，反應氣體中之HF濃度為〇4 v〇1%以上，較好的 是 2〜2.5 vol%。 吹附步驟 將該反應氣體自吹出管路29中吹出，吹附至基板9〇之矽 膜91之表面。藉此，於矽膜91之表面上發生反應，來進行 矽膜91之蝕刻。與反應相關之c〇F2、HF、ο;等係非自= 基，因此可回避由於大氣壓電漿放電部24與基板9〇之間的 工作距離所引起的蝕刻速率降低或者基板9〇受損等情^ 可使喷頭高度之設定等變得容易，可提高設計之自^度。’ 處理完畢之氣體由吸引管路4卜及人，且由排氣機構42排 出。進而，使基板90沿著移動方向a進行相對移動 基板90整體進行敍刻處理。 該矽蝕刻之詳細機制並不明確，一般認為係 ^ ^ , 卜所 134995.doc •22- 200924052 [案例1] (氧化過程） (式 11) (式 12)Crystalline germanium such as Si or polycrystalline Si. It may be a film containing ruthenium as a main component and containing about 0 to 20% of hydrogen. The substrate 9 is made of a crucible such as a wafer, and the substrate 90 itself can be an object to be processed as a workpiece. It may also be an n-type or p-type ruthenium doped with P or B or the like. For example, a substrate used in a TFT for a liquid crystal (Thin Film Transistor) is a SiN film forming force glass, and the amorphous Si of the object to be processed in the present embodiment is plasma CVD ( Chemical Vap〇r Dep〇shi〇n, chemical vapor deposition). In the figure, the thicknesses of the substrate 90 and the crucible 91 are shown enlarged. The etching apparatus 1 includes a substrate supporting unit 2, a substrate temperature adjusting mechanism 3, and a reaction gas supply system 4. A substrate 9A is provided on the substrate supporting portion 2. The substrate supporting portion 2 and the substrate 90 are relatively moved in the horizontal direction a of Fig. 1 with respect to the reaction gas supply system 4 by a moving mechanism (not shown). The gas blowing portion of the reaction gas supply system 4 may be moved relative to the substrate 9A. The substrate temperature adjustment mechanism 3 includes a heater or a cooler (not shown), and adjusts the temperature of the substrate 90 to be processed to a specific temperature. The temperature of the substrate 9 is preferably nrc~5〇°c, and more preferably *1 (rc~3 (rc 'and thus better « is also to the temperature. The lower limit of the temperature range can also be set as the indoor dew point. In the case where the substrate temperature is set to room temperature, the substrate temperature adjustment mechanism 3 can be omitted. The reaction gas supply system 4 includes the ozone supply system 1 and the fluorine-based gas supply system 20. The ozone supply system 1 includes Supply of oxygen (〇2) i丨, supply of nitrogen (N2) 134995.doc -18· 200924052 Quantity flow control unit 12, ozone generator 13. Ozone generator 13 has two mass units 14A, 14B and discharge The mass flow control HMA is connected to the oxygen supply unit 11, and the mass flow controller MB is connected to the nitrogen supply unit !2. The flow is connected to the outlet line 15 of the mass controller i4A for oxygen. The outlet line 15b of the mass flow controller (10) for nitrogen is connected to the discharge unit 16 after the joining. Although the detailed illustration is omitted, a plurality of electrodes are provided on the discharge unit 16 to Oxygen is ozoned by discharge between the electrodes. Ozone The supply line 17 extends from the discharge unit 16. The 齓-based gas supply system 20 includes a supply unit 21 of CF4 (a fluorine-based raw material having no reactivity with ruthenium), a supply unit 22 of argon (Ar), and a humidifier. 23. The atmospheric piezoelectric discharge unit 24. The mass flow controller 25A is connected to the CF4 supply unit, and the mass flow controller 25b is connected to the Ar supply unit 22. The mass flow control unit J||25A, 25B The outlet line 26 & and the catching flow merges. The merged outlet line 26 is connected to the humidifier 23. The humidifier 23 accumulates water for humidification (H2〇). The atmospheric piezoelectric discharge portion 24 is connected to the atmosphere. The atmospheric piezoelectric discharge portion 24 is provided with a pair of electrodes 27 and 27. The electrodes 27 and 27 are opposed to each other with a gap 27a of about 1 mm in the middle gate. The solid dielectric layer (not shown) is disposed on the opposite surface of each other. An atmospheric pressure glow discharge is formed between the electrodes 27 and 27 by voltage supply from a power source (not shown), and the gap 27a is formed. The inside becomes a plasma space, thereby introducing the gas introduced into the plasma space 27a. The voltage waveform may be an intermittent wave such as a pulse, or a continuous wave such as a positive sine wave. 134995.doc -19· 200924052 A temperature regulating pipe 28 is disposed on the electrode 27. In the temperature regulating pipe 28 The water having a temperature adjusted to 40 ° C or higher is used as the temperature control medium. The blowing line 29 extends from the electric space 27a toward the substrate 90. The ozone supply from the ozone generator 13 is merged on the blowing line 29. The pipe 17 is opened from the front end opening (blowing port) of the pipe 29 away from the moving direction & the end opening (suction port) of the suction main road 41 is disposed. The suction line 41 is connected to an exhaust mechanism 42 such as a genuine pump. A method of etching the ruthenium film 91 of the substrate 9 is described by the etching apparatus 1. 1. Substrate temperature adjustment step The substrate temperature adjustment mechanism 3 is used to adjust the substrate 9 to be processed to W = ~ 5 〇 ° C, preferably to a specific temperature of ~ 3 〇 t. When the specific temperature of the substrate 9 is room temperature, no special temperature adjustment is required. 2. Ozone generation step >: The flow rate of the oxygen from the supply unit n is performed by the mass flow controller 14A, and is derived from the export route! The mass flow controller _ adjusts the flow of nitrogen in the oxygen. The amount of nitrogen added is preferably Ν2/(〇:+Ν2)= less than 3 VGl%. Thereby, a mixed gas of oxygen and nitrogen (oxygen-containing gas) mainly composed of oxygen is generated. The gas of the oxygen gas is introduced into the discharge portion 16 of the ozone generator 13. Borrowing: Oxygen in the oxygen-containing gas is ozonated to form an ozone concentration of 含8 1〇 v〇m of the ozone-containing gas at the outlet of the ozone-containing discharge unit 16 . The ozone-containing gas is directed to the supply line η I34995.doc • 20- 200924052 3. The gas-based processing gas is generated and the flow rate is adjusted by the mass flow controller 25 Α to the CF4 from the supply unit 21 The flow rate adjustment is performed on the Ar from the supply unit 22 by the mass flow controller 25B. The flow-adjusted CF4 and Ar are mixed in the outlet line 26 to produce a mixed gas of CF4 and Ar (fluorine-based raw material gas diluted with Ar). The concentration of CF* in the mixed gas is preferably CF4/(CF4+Ar)=4 to 90 vol%, more preferably CF4/(CF4+Ar)=5 to 90 vol%, and further preferably CF4. /(CF4+Ar)=5~20 v〇l〇/0. In the derivation line 26, the gas (CF4+Ar) is introduced into the humidifier 23, and the water (H2〇) in the humidifier 23 is vaporized and added to the mixed gas. The amount of water added is preferably that the dew point reaches l〇〇c 〜4〇χ: the amount is better, and it is better to reach l〇°C~30°C, and then it is better to reach 1〇〇c~2〇<;t the amount. As a result, a humidified fluorine-based material gas (CF4+Ar+H2〇) having a lower dew point than before was obtained. The humidified fluorine-based source gas (CF4+Ar+H2〇) is introduced into the atmospheric piezoelectric space 27a of the plasma discharge unit 24 to be plasma-formed. Ar in the gas can be used to obtain a good plasma. Thereby, a material such as cf3〇h or f2 or a 2 fluorine-based processing gas such as hf which is an oxygen-based reaction material is produced. This fluorine-based processing gas is led to the blowing line 29. The amount of water after electropolymerization is preferably less than (10) before electropolymerization. Since the electrode 27 is temperature-regulated by the temperature-regulating medium above the thief, condensation can be prevented from occurring in the plasma space 27a. Dan, in the discharge of plasma discharge π eight heart W-shaped 吋, better 疋: in addition to adding water, also added, for example, relative to CF4 vo handsome 2) ° by this 'can more certainly generate coffee 2 as a fluorine I34995.doc •21 - 200924052 is an intermediate substance. 4. Mixing step The fluorine-based processing gas containing COF2, HF or the like from the plasma discharge unit 24 and the ozone-containing gas from the ozone generator 16 are combined and mixed in the air outlet 27. Thereby, a reaction gas containing a fluorine-based intermediate material such as ozone or COF2 or a fluorine-based reaction material such as HF is produced. The volume flow ratio of the fluorine-based processing gas from the plasma discharge unit 24 to the ozone-containing gas from the ozone generator 16 is preferably (fluorine-based processing gas) / (ozone-containing gas) = 0.2-5 ' Better is 1~3. The concentration of ozone in the reaction gas after the gas is mixed is 1 vol% or more, preferably 3 to 〇 vol%. Further, the HF concentration in the reaction gas is 〇4 v 〇 1% or more, preferably 2 to 2.5 vol%. The blowing step is performed by blowing the reaction gas from the blowing pipe 29 and blowing it to the surface of the film 91 of the substrate 9. Thereby, a reaction occurs on the surface of the ruthenium film 91 to etch the ruthenium film 91. The reaction is related to c〇F2, HF, ο; etc., which is non-self-base, so that the etching rate due to the working distance between the atmospheric piezoelectric discharge portion 24 and the substrate 9〇 can be avoided or the substrate 9〇 can be damaged. Equivalent ^ It is easy to set the height of the nozzle, etc., and the design can be improved. The treated gas is discharged from the suction line 4 and is discharged by the exhaust mechanism 42. Further, the substrate 90 is relatively moved in the moving direction a to perform the etching process on the entire substrate 90. The detailed mechanism of the ruthenium etching is not clear, and is generally considered to be ^ ^ , 卜 134995.doc • 22- 200924052 [Case 1] (oxidation process) (Equation 11) (Equation 12)
Si + 203-> Si〇2+202 (HF生成過程） C0F2+H20—C〇2+2HF (氫氟酸溶解過程） (式 13) 2HF + 4HF+2HF+4H20-^ 4HF2.+4H3〇 (餘刻過程） (式 14) 之表面上Si + 203-> Si〇2+202 (HF generation process) C0F2+H20-C〇2+2HF (hydrofluoric acid dissolution process) (Formula 13) 2HF + 4HF+2HF+4H20-^ 4HF2.+4H3〇 (remaining process) on the surface of (Equation 14)
Si02+4HF2+4H30+-SiF4+H20+4H20+H20+4HF 如式13所示，於反應之穩定狀態下，在矽膜μ ”一 形成有氫氟酸之凝縮層。上述反應氣體中之各成= (COF2、ο;、HF等）與該凝縮層之表面接觸。 反應氣體中之臭氧若與凝縮層表面接觸，則以根據與基 板溫度相對之分配係數（圖6)的比率溶解至凝縮層中。由於 基板溫度經設定為听〜听等之低^故分配係數大， I充分增大臭氧在凝縮層中之溶解度。又，由於係在低溫 給爲故可防止臭氧分解’可充分延長臭氧壽命。溶解於凝 縮層中之臭氧在凝縮層中擴散而到達石夕膜91之表面。藉由 違臭氧’構切膜91之#氧化㈣ 於臭氧溶解度大，故可充分提高㈣㈣度。 石夕出^ Μ ^層之氣氣酸與如此而形成之氧化石夕接觸，氧化 ^揮發性之他，經吸引管路Μ吸引而除去（式⑷。 刻速率進订石夕#刻。由於石夕氧化速度大’故可充分提高敍 J34995.doc -23- 200924052 由上述蝕刻反應而生成水（蒸氣）（式14)。該水之一部分 (式14之右邊第2項之Η”）與反應氣體中之c〇F2反應，生成 HF(式12)。因此，在式12及式14此2個反應中，水發揮觸 媒之作用。再者，由上述蝕刻反應（式14)而生成之水的剩 餘一部分（式14之右邊第3項之4H2〇)用於形成氫氟酸凝縮 層（式13之左邊第4項），進而於氧化石夕之敍刻反應中被消耗 (式 14)。 式13之左邊第1項的2HF係與反應氣體中之對應。 該反應氣體中之HF自㈣91表面之氫氟酸凝縮層與空氣層 之界面而溶解於氫氟酸凝縮層中。再者，該式13之左邊第 2項的4HF係與敍刻反應中所生成者（式以之右邊第$項）相 對應，式13之左邊第3項的2HF係與c〇F22Hf化反應中所 生成者（式12之右邊第2項）相對應。 式11〜14之反應係以仏〇為媒介之正的反饋發揮作用之連 鎖反應。該連鎖反應可藉由在5(rc以下之範圍内調節基板 溫度，使矽膜表面之HA的存在量增減來加以控制。由於 加濕器23之水添加量少’故矽膜表面之h2〇量亦少，矽膜 表面纽常表現出乾燥之傾向。因此，可藉由5〇t；c以下之溫 度調節來將矽膜表面之化0量控制為充分，並且可確實地 抑制凝縮層之成長。 以上述方式’可防止產生凝縮層中之臭氧的擴散控制， 使臭氧確實地擴散至石夕膜91之表面。因此，可與上述由溫 度條件所引起的臭氧在凝縮層中之溶解度提高相互作用孤 從而進一步提高矽膜91之氧化速度。 134995.doc •24· 200924052 又，對氫氟酸亦可防止產生擴散控制，從而可確實地進 行蝕刻反應。 進而’藉由抑制凝縮層之成長，可使蝕刻反應中所生成 之SiF2自基板90之表面快速地釋放出，可防止si〇2之再析 出。結果’可進一步提高蝕刻速率。 反應氣體中之HF以及在式12中由COF2形成之HF溶解於 氫氟酸凝縮層中（式13) ’可參與氧化矽之蝕刻（式丨4)。由 敍刻反應所生成之HF(式14之右邊第5項）亦同樣地溶解於 虱既酸凝細層中（式13之左邊第2項），可參與氧化石夕之钱刻 (式 14) 〇 石夕膜表面之H2〇量少而容易蒸發’可由反應氣體中之hf 來生成多餘之H2〇(式14之右邊第4項），藉此可確保石夕膜表 面之H20量，來維持反應。 又，藉由反應氣體.中存在HF，可確保在處理開始時用 以將COF2進行HF化之H20。 對式11〜14進行總結，則成為下式：Si02+4HF2+4H30+-SiF4+H20+4H20+H20+4HF As shown in Formula 13, in the steady state of the reaction, a condensation layer of hydrofluoric acid is formed in the ruthenium film "". = (COF2, ο;, HF, etc.) is in contact with the surface of the condensed layer. If the ozone in the reaction gas comes into contact with the surface of the condensed layer, it is dissolved to the condensed layer at a ratio according to the partition coefficient (Fig. 6) relative to the substrate temperature. Since the substrate temperature is set to be low, such as listening, listening, etc., the distribution coefficient is large, I sufficiently increases the solubility of ozone in the condensation layer. Moreover, because it is at a low temperature, ozone can be prevented from decomposing. The ozone dissolved in the condensed layer diffuses in the condensed layer and reaches the surface of the smectic film 91. By oxidizing the ozone of the membrane 91 (4), the solubility of the ozone is large, so that the (four) (four) degree can be sufficiently improved. The gas of the ^ Μ ^ layer is in contact with the oxidized stone formed in this way, and the oxidized ^ volatility is removed by the suction line ( (Formula (4). The engraving rate is entered into the stone eve #刻. Because of Shi Xi The oxidation rate is large, so it can be fully improved. J34995.doc -23- 200924052 Water (vapor) is generated by the above etching reaction (Formula 14). One part of the water (the second item on the right side of Formula 14) reacts with c〇F2 in the reaction gas to form HF (Formula 12). In the two reactions of Formula 12 and Formula 14, water acts as a catalyst. Further, the remaining part of the water produced by the etching reaction (Formula 14) (4H2〇 of the third item on the right side of Formula 14) It is used to form a hydrofluoric acid condensed layer (the fourth term on the left side of Formula 13), and is further consumed in the osmosis reaction of the oxidized stone (Formula 14). The 2HF system of the first item on the left side of Formula 13 and the reaction gas Correspondingly, the HF in the reaction gas is dissolved in the hydrofluoric acid condensation layer from the interface between the hydrofluoric acid condensation layer on the surface of the (F) 91 and the air layer. Further, the 4HF system of the second item on the left side of the formula 13 and the characterization reaction The generator (the formula is the right item on the right) corresponds to the second item of the left side of the formula 13 and the 2HF system corresponding to the c〇F22Hf reaction (the second item on the right side of the formula 12). The reaction of ~14 is a chain reaction in which positive feedback is used as a medium. The chain reaction can be achieved by 5 (rc or less). The temperature of the substrate is adjusted to increase or decrease the amount of HA on the surface of the enamel film. Since the amount of water added to the humidifier 23 is small, the amount of h2 on the surface of the ruthenium film is also small, and the surface of the ruthenium film often exhibits Therefore, it is possible to control the amount of the ruthenium film surface to be sufficient by temperature adjustment of 5 〇t; c or less, and to reliably suppress the growth of the condensed layer. In the above manner, the condensed layer can be prevented from being produced. The diffusion control of the ozone in the ozone allows the ozone to be surely diffused to the surface of the smectite film 91. Therefore, the solubility of the ozone in the condensed layer caused by the above temperature conditions can be increased and the interaction is increased to further increase the oxidation of the ruthenium film 91. speed. 134995.doc •24· 200924052 In addition, the hydrofluoric acid can also prevent diffusion control, so that the etching reaction can be surely performed. Further, by suppressing the growth of the condensed layer, SiF2 generated in the etching reaction can be quickly released from the surface of the substrate 90, and re-precipitation of si 〇 2 can be prevented. As a result, the etching rate can be further increased. The HF in the reaction gas and the HF formed of COF2 in Formula 12 are dissolved in the hydrofluoric acid condensation layer (Formula 13)' to participate in the etching of cerium oxide (Formula 4). The HF (the fifth term on the right side of the formula 14) generated by the characterization reaction is also dissolved in the bismuth acid condensate layer (the second item on the left side of the formula 13), and can participate in the oxidized stone eve of the money (Equation 14) The surface of the ruthenium film is less H2, and it is easy to evaporate. 'The excess H2 可由 can be generated from the hf in the reaction gas (the fourth item on the right side of the formula 14), thereby ensuring the amount of H20 on the surface of the celestial membrane. Maintain the reaction. Further, by the presence of HF in the reaction gas, it is possible to secure H20 for HF-forming COF2 at the start of the treatment. To summarize the formulas 11 to 14, the following formula is obtained:
Si+203+C0F2+2HF-SiF4+202+C02+H20 (式 15) 於式15中，參與反應之氫原子數（H)係左邊第4項之2hf 中的2個，氟原子數（F)係左邊第3項之c〇F2中的2個與左邊 第4項之2HF中的2個，總計為4個。因此，此時參與反應之 氫原子數（H)與氟原子數（F)之比（F)/(H)成為（F)/(H)=2。 比（F)/(H)較好的是至少設為8。 更好的是進一步減少反應氣體中之HF4，成為（f)/(h)>3。 其次’對在電漿放電部24中生成ChOH來作為氟系中間 134995.doc •25· 200924052 物質的情形進行說明。此時，發生如下反應。 [案例2] (氧化過程）Si+203+C0F2+2HF-SiF4+202+C02+H20 (Formula 15) In Formula 15, the number of hydrogen atoms participating in the reaction (H) is two of the 2hf of the fourth term on the left side, and the number of fluorine atoms (F) There are two of the two HF of the third item on the left side and two of the HF of the fourth item on the left side, for a total of four. Therefore, the ratio (F) / (H) of the number of hydrogen atoms (H) participating in the reaction to the number of fluorine atoms (F) at this time becomes (F) / (H) = 2. Preferably, the ratio (F) / (H) is at least 8. More preferably, HF4 in the reaction gas is further reduced to become (f) / (h) > 3. Next, a case where ChOH is generated in the plasma discharge portion 24 as a fluorine-based intermediate 134995.doc • 25· 200924052 will be described. At this time, the following reaction occurs. [Case 2] (oxidation process)
Si+203-Si〇2+2〇2 (式 ilb) (cof2生成過程） cf3oh+h2o-^ cof2+hf+h2o (式 12-lb) (HF生成過程） C0F2+H20— C〇2+2HF (式 l2-2b) (氫氟酸溶解過程） HF+HF + 4HF + 2HF + 4H2〇-> 4HF2-+4H30+ (式 l3b) (蚀刻過程） Si02+4HF2-+4H30+—SiF4+2H20+4H20+4HF (式 l4b) (整體之反應） Si+203+CF30H+HF—SiF4+202+C02+H20 (式 I5b) 如式12-lb所示，CF3OH並不穩定，會分解而形成(：〇]?2 與HF。因此’該分解後，會發生與上述案例1相同之反應 (式 lib、12-2b、13b、14b)。 於式15b中’參與反應之氫原子數（H)係左邊第3項之 CF3OH中的1個與左邊第4項之HF中的1個，總計為2個；氟 原子數（F)係左邊第3項之CF3OH中的3個與左邊第4項之HF 中的1個，總計為4個。因此，參與反應之氫原子數（H)與 氟原子數（F)之比（F)/(H)成為（F)/(H)=2。 於案例2中，亦可藉由操作基板溫度，調節矽臈表面之 H20量’來控制反應。 134995.doc -26· 200924052 繼而對本發明之其他實施形態進行說明。在以下的實 施形態中，對與已述之形態重複之構成，在圖式中附上相 同符號，且省略說明。 圖2係表示本發明之第2實施形態者。於第2實施形態 中，除了使用氬（Ar)以外，進一步使用氮⑽來作為i系 原料（CF4)之稀釋氣體。於氟系氣體供給系統2〇中，除了 氟系原料（CF4)供給部2 1以及氬供給部22以外，進一步設 置有氮供給部22C。於氮供給部22C上連接有質量流量控 制# 25C。來自質量流量控制器25(：之氮導出管路26c與氬 V出官路26b合流，進而與€1?4導出管路26a合流。 利用質量流量控制器25B、25C，將來自供給部22之^ 與來自供給部氮供給部22C之沁調節為任意之混合比。 電極27、27間之每單位厚度之峰間電壓Vpp為小於13 kV/mm時，較好的疋在Aj^55〜1〇〇 v〇i%、a為〇〜ν〇ι% 之範圍内没疋上述混合比。藉此，可將蝕刻速率維持為充 分高（參照實施例3)。電極27、27間之每單位厚度之峰間電 壓VPP為VPP=13 kV/mm以上時，較好的是Vpp=15 kv/mm 以上時，可在N2/(Ar+N2)>45 v〇l%之範圍内設定心與仏之 混合比，可將蝕刻速率維持為充分高（參照實施例3)。電極 27、27間之每單位厚度之峰間電壓Vpp的上限較好的是設 為Vpp=20 kV/mm左右。藉此，可防止在電極27、27之間 發生異常放電。 包含Ar及％之混合氣體的稀釋氣體與CF4混合。藉此， 生成氟系原料氣體（CF4+Ar+N2)。氟系原料氣體 134995.doc -27- 200924052 (CF4+Ar+N2)中的CF4之比率較好的是4〜90 vol%。該氟原 料氣體經由加濕器23而導入至電漿空間27a中，被電衆 化。以後之運作係與第1實施形態相同。 依據第2實施形態’由於不僅使用Ar，並且亦使用N2來 作為稀釋氣體，故可降低運轉成本。藉由將cf4用作氟原 料’且稀釋氣體含有N2，可利用電漿空間27a中經激發之 氮自由基來促進CF4之激發、分解（參照實施例4(圖8))。 本發明並不限定於上述實施形態，可加以各種改變。 例如，可將來自大氣壓電漿放電部24之氟系處理氣體與 來自臭氧發生器13的含臭乳之氣體並不於吹出管路29中混 合，而相互自不同之吹出口中供給至矽膜表面上。亦可在 吹附含臭氧之氣體後，進行氟系處理氣體之吹附。 作為氟系原料，可使用c#6、c#6、c3f8等其他PFC， 亦可使用CHF3、CHA、，或者亦可使用 SF6 NF3、XeF2等除FC(氟碳）以外之含氟化合物，來代替 CF4。 作為稀釋氣體’可使仏、N2、He等其他的稀有氣體或 惰性氣體。 :為氧化性氣體’亦可使用含有〇自由基等氧系活性種 之軋體’來代替臭氧。〇自由基等氧系活性種可 有氧（〇2)之氣體導入至大氣壓電漿中而生成。 、 本發明之㈣方法除了可應用於經光阻劑等進行圖案化 1被處理物之圖㈣_以外，亦可應祕被處理物之表 面所附著的含㈣之污染物質的除去、石夕晶圓或玻璃之粗 134995.doc -28- 200924052 糙化部分的平坦化、矽晶圓或玻璃之表面或背面的粗糙化 等。 [實施例1 ] 對實施例進行說明。 使用圖1中所示之蝕刻裝置1。大氣壓電漿放電部24之電 極27係介電質阻擋放電電極，係使用將相互之對向面以厚 度為1 mm之包含氧化鋁之介電質層加以包覆而成者。電極 27之對向面的面積為140 cm2，電極間之間隙27a之厚度為 1 mm。通過電極調溫管路28中之冷卻水之溫度為65艺。 氟系原料氣體係使用0.2 slm之CF4與1.8 slm之Ar的混合 氣體2.0 slm。利用加濕器23向該混合氣體中添加露點達到 1VC之量的H2〇，生成加濕氟系原料氣體，將該加濕氟系 原料氣體導入至電極間空間27a中，於大氣壓下進行電漿 化。供給電壓係Vpp=0.94 kv、且頻率為3〇 kHz之脈衝電 壓，於100〜4〇〇 w之範圍内調節供給電力。 利用傅立葉變換紅外分光器（FTIR)對電漿化後之氣體成 刀進行刀析，結果如圖3所示，確認生成HF與c〇F2。再 者，於圖3之圖表中，左側之縱軸係表示來自電漿生成部 Μ之導出氣體中的HF與c〇F2之體積濃度，右側之縱軸係 表示氫原子數（H)與氟原子數（F)之比（F)/(H)。COF2之生成 量以體積流量比計，係册之。4倍以上。比（F)《H)達到U 以^ °隨著增大供給電力’册與c〇F2之生成量增加，同 時氫原子數（H)與氟原子數（F)之比（F)/(H)亦變大。 此外，依據專利文獻4(日本專利特開2〇〇2_27〇575號公 134995.doc -29- 200924052 報）之實施例，HF濃度為4.3%，COF2濃度為1.6%，氫原子 數（H)與氟原子數（F)之比（F)/(H)為1.74左右，與該文獻中 者相比，雖然HF濃度以及COF2濃度較低，但比（F)/(H)獲 得較大值。 又’電漿化後之Ηβ幾乎未觀測到，確認達到電衆化前 之1 /10以下。 另外，將添加有微量N2的1.2 slm之〇2供給至臭氧發生器 16中’獲得8 vol〇/〇即0.096 slm之〇3。該臭氧之生成量係來 自電漿生成部24之氟系氣體的4.8%，達到將c〇F2之流量 與HF之流量的2分之1總計而得之值（供給電力為4〇〇 w時， 2.2%)的約2倍左右，可以說是大致適當之大小。 將該含臭氧之氣體與來自電漿放電部24之氟系氣體加以 此合而生成反應氣體，將該反應氣體吹附至玻璃基板表面 之非晶矽上，測定蝕刻量。玻璃基板之溫度經設為3(rc。 將钮刻量之測定結果示於圖4中。在該圖中，钱刻量係 換算為經每單位體積（1 L)之反應氣體進行㈣之非晶石夕的 原子數此外，依據專利文獻4(日本專利特開2繼謂仍 號公報）之實施例，钮刻量經算出為38㈣舰。因此，依 本發月與上述專利文獻4中者相比，雖然HF濃度以及 C〇F2濃度較低，但可獲得其聰以上之#刻速率。 [實施例2 ] ,八肌/又軋乐原科氣體中之水添加量 /、敍刻速率之關係進行調查。對〇5如之CF4調節H2〇之 添加量，進行電漿化化之條件如下所述。 134995.doc •30- 200924052 供給電力：0.165 kW 供給電麼：Vpp= 13 kV 電極面積：35 cm2 又，使狀5 _之〇2且利用臭氧發生器來製作8 ν〇ι%(對 〇2比)之03，將其與上述電渡化後之氣體進行混合而供給 至玻璃基板，進行表面之非晶矽膜之蝕刻。 基板溫度設為2Gt、4〇。(：、贼此三種，敎各溫度條 件下之勉刻速率。（再者，6〇t為先前一般的基板溫度， 係比較例。） 將結果示於圖5中。 由該圖可知，於基板溫度為與先前相同之㈣的情形 時，即使增加氟系原料氣體中之水添加量，敍刻速率亦幾 乎無變化。 對此判明，基板溫度為20。〇日寺，自冑點達到听之水添 加量附近開始，蝕刻速率大幅上升；於露點達到2〇t之水 添加量附近，蝕刻速率達到峰值；並且至露點達到扣力之 水添加量附近為止，獲得充分大於先前（基板溫度為贼 時）的蝕刻速率。 並且判明，基板溫度為4〇時，亦於露點為1 〜 之水添加範圍内獲得充分大於先前（基板溫度為6(rc時）的 I虫刻速率。 [實施例3] 使用圖2之蝕刻裝置，對非晶矽進行蝕刻。將以4用作氟 系原料，且將該I系原料（CF4)以包含氮與氣之混合氣體 134995.doc 200924052 的稀釋氣體加以稀釋’獲得氟系原料氣體。I系原料氣體 (CF4+Ar+N2)中之CF4的比率設為丨〇 v〇l%。利用加濕器η 向氟系原料氣體（CFdAr+N2)中添加露點達到丨8艺之量的 AO。將添加後之氟系原料氣體（CF4+Ar+N2+H2〇)導入至 電極間空間27a中，於大氣壓下進行電漿化。放電條件如 下所述。 電極間空間27a之厚度：1 mm 電極間電壓：Vpp=12、13 ' Mkv 頻率：40 kHz :電漿化後之氟系處理氣體、與來自臭氧發生器η的含 臭氧之氣體（〇3約為8%)進行混合，吹附至試樣非晶石夕膜 上:氟系處理氣體與含臭氧之氣體的流量比經設為款系處 理氣體：含臭氧之氣體=2 : 1。 使構成稀釋氣體（Ar+N2)之射與％的流量比變化，且使 電極間電壓VPP變化’來調查與稀釋氣體中之氮之含旦 (N2/(Ar瑪)）相對的非晶⑪之#刻速率。將結果示於圖里7 中:該圖。之縱轴係表示使被處理物9〇相對於吹出喷切而 進行1次單程移動（掃描）時的蝕刻速率。 由該圖所明示’判明：於電極間電塵VPP為比較低的電 麼(vpp=12kv)時，若稀釋氣體中…含量約為45%以 下’則可將姑刻速率維持為較高。於稀釋氣體中之N2之含 量超過45%之區域，N2含量越大，_速率越降低。 隨著使電極間„vpp高於12kv，在 ㈣速率降低幅度變緩（該圖之Vpp=13kv〜 ㈣ 134995.doc -32- 200924052 於電極㈤電麼Vpp為比較高之電麼（Vpp=i5…時，即使 在乂含量約為45%〜100%區域，钮刻速率亦幾乎未降低， 可獲得不受N2含量限制的良好之钮刻速率。因此，判明可 將Ar與N2以任意混合比進行混合。 [實施例4] 於圖2之蝕刻裝置的電漿空間27a中導入cF4以及K ,加 以電漿化’進行發光分析。I光分析裝置係使用 Hamamatsu Photonics公司製造的ρΜΑ·η。放電條件如下 所述。 電極間空間27a之厚度：！ mm 電極間電塵：Vpp=l 5 kV 頻率：40 kHz 將結果示於圖8中。確認藉由CF4之分解而獲得CF2+(峰 值波長：250〜400 nm)。又，n2被激發，確認到乂第二正 帶（second positive system)的發光峰值（3〇〇 〜4〇〇 nm)。根據 CF2之峰值波長與第二正帶之峰值波長重疊的情況，確 邊可藉由使稀釋氣體中含有n2來促進cf4之激發以及分 解。 [實施例5] 使用圖2之钮刻裝置’進行非晶矽之蝕刻。將cF4用作氟 系原料。使用氬氣作為稀釋氣體，將氟系原料以氬 氣進行稀釋’獲得氟系原料氣體（CF4+Ar)。於1〜100 vol〇/〇 之範圍内調節氟系原料氣體（CF4+Ar)中之CF4之比率。利 用加濕器23向氟系原料氣體（CF4+Ar)中添加露點達到18°c 134995.doc -33· 200924052 之量的H2〇。將添加後之氟系原料氣體（Cf4+Ar+H2〇)導入 至電極間空間27a中，於大氣壓下進行電漿化。放電條件 如下所述。 電極間空間2 7a之厚度：1 mm 電極間電壓：Vpp=12 kV 頻率：40 kHzSi+203-Si〇2+2〇2 (formula ilb) (cof2 generation process) cf3oh+h2o-^ cof2+hf+h2o (formula 12-lb) (HF generation process) C0F2+H20—C〇2+2HF (Formula l2-2b) (Hydrogen fluoride dissolution process) HF+HF + 4HF + 2HF + 4H2〇-> 4HF2-+4H30+ (Formula l3b) (etching process) Si02+4HF2-+4H30+—SiF4+2H20+4H20 +4HF (formula l4b) (integral reaction) Si+203+CF30H+HF-SiF4+202+C02+H20 (formula I5b) As shown in formula 12-lb, CF3OH is unstable and decomposes to form (:〇 ]?2 and HF. Therefore, after the decomposition, the same reaction as in the above case 1 (formula lib, 12-2b, 13b, 14b) occurs. In the formula 15b, the number of hydrogen atoms participating in the reaction (H) is left. One of the CF3OH of the third item and one of the HF of the fourth item of the left side are two in total; the number of fluorine atoms (F) is three of the CF3OH of the third item on the left side and the HF of the fourth item of the left side. One of them has a total of 4. Therefore, the ratio (F)/(H) of the number of hydrogen atoms (H) participating in the reaction to the number of fluorine atoms (F) is (F)/(H)=2. In 2, the reaction can also be controlled by adjusting the substrate temperature and adjusting the amount of H20 on the surface of the crucible. 134995.doc -26· 200924052 In the following embodiments, the same reference numerals are given to the same components as those in the above-described embodiments, and the description thereof will be omitted. Fig. 2 shows the second embodiment of the present invention. In the second embodiment, in addition to argon (Ar), nitrogen (10) is further used as the diluent gas of the i-type raw material (CF4). In the fluorine-based gas supply system 2, the fluorine-based raw material (CF4) is supplied. In addition to the unit 21 and the argon supply unit 22, a nitrogen supply unit 22C is further provided. The mass supply control unit 25C is connected to the nitrogen supply unit 22C. The mass flow controller 25 (the nitrogen outlet line 26c and the argon V output) The official road 26b merges and merges with the €1 to 4 outlet line 26a. The mass flow controllers 25B and 25C adjust the ratio from the supply unit 22 to the supply unit nitrogen supply unit 22C to an arbitrary mixing ratio. When the peak-to-peak voltage Vpp per unit thickness between the electrodes 27 and 27 is less than 13 kV/mm, the preferred enthalpy is in the range of Aj^55~1〇〇v〇i% and a is 〇~ν〇ι%. There is no such mixing ratio. Thereby, the etching rate can be maintained as a charge. The height is divided (see Example 3). When the peak-to-peak voltage VPP per unit thickness between the electrodes 27 and 27 is VPP = 13 kV/mm or more, preferably Vpp = 15 kv/mm or more, it is possible to be in N2/. The mixing ratio of the core to the enthalpy is set in the range of (Ar + N2) > 45 v 〇 1%, and the etching rate can be maintained sufficiently high (refer to Example 3). The upper limit of the peak-to-peak voltage Vpp per unit thickness between the electrodes 27 and 27 is preferably set to be about Vpp = 20 kV/mm. Thereby, abnormal discharge between the electrodes 27 and 27 can be prevented. A diluent gas containing a mixed gas of Ar and % is mixed with CF4. Thereby, a fluorine-based source gas (CF4+Ar+N2) is produced. The ratio of CF4 in the fluorine-based raw material gas 134995.doc -27- 200924052 (CF4+Ar+N2) is preferably 4 to 90 vol%. This fluorine raw material gas is introduced into the plasma space 27a via the humidifier 23, and is electrified. The operation in the future is the same as in the first embodiment. According to the second embodiment, since not only Ar but also N2 is used as the diluent gas, the running cost can be reduced. By using cf4 as the fluorine raw material' and the diluent gas containing N2, the excited nitrogen radicals in the plasma space 27a can be used to promote the excitation and decomposition of CF4 (see Example 4 (Fig. 8)). The present invention is not limited to the above embodiment, and various modifications can be made. For example, the fluorine-based processing gas from the atmospheric piezoelectric discharge portion 24 and the odor-containing gas from the ozone generator 13 are not mixed in the blowing line 29, but are supplied to the ruthenium film from different blowing ports. On the surface. It is also possible to perform the blowing of the fluorine-based treatment gas after blowing the ozone-containing gas. As the fluorine-based raw material, other PFCs such as c#6, c#6, and c3f8 may be used, and CHF3, CHA, or a fluorine-containing compound other than FC (fluorocarbon) such as SF6 NF3 or XeF2 may be used. Instead of CF4. As the diluent gas, other rare gases or inert gases such as helium, N2, and He may be used. The oxidizing gas 'may also use a rolled body' containing an oxygen-based active species such as a ruthenium radical instead of ozone. An oxygen-based active species such as a ruthenium radical can be produced by introducing a gas having oxygen (〇2) into the atmospheric piezoelectric slurry. The method of (4) of the present invention can be applied to the removal of the contaminant containing (4) attached to the surface of the object to be treated, in addition to the pattern (1) of the patterned object to be treated by a photoresist or the like. Wafer or glass coarse 134995.doc -28- 200924052 Flattening of the roughened portion, roughening of the surface or back of the wafer or glass. [Example 1] An example will be described. The etching apparatus 1 shown in Fig. 1 is used. The electrode 27 of the atmospheric piezoelectric slurry discharge portion 24 is a dielectric barrier discharge electrode, and is formed by coating a dielectric layer containing alumina having a thickness of 1 mm on the opposing surface. The area of the opposing surface of the electrode 27 is 140 cm2, and the thickness of the gap 27a between the electrodes is 1 mm. The temperature of the cooling water passing through the electrode temperature regulating line 28 is 65 art. The fluorine-based raw material gas system used a mixed gas of 0.2 slm of CF4 and 1.8 slm of Ar, 2.0 slm. H2〇 having a dew point of 1 VC is added to the mixed gas by the humidifier 23 to generate a humidified fluorine-based source gas, and the humidified fluorine-based source gas is introduced into the interelectrode space 27a, and plasma is performed under atmospheric pressure. Chemical. The supply voltage is Vpp = 0.94 kV and the pulse voltage is 3 〇 kHz, and the supply power is adjusted within the range of 100 to 4 〇〇 w. The plasma forming of the plasma was analyzed by a Fourier transform infrared spectroscope (FTIR). As a result, as shown in Fig. 3, it was confirmed that HF and c〇F2 were generated. Further, in the graph of Fig. 3, the vertical axis on the left side indicates the volume concentration of HF and c〇F2 in the derived gas from the plasma generating portion, and the vertical axis on the right side indicates the number of hydrogen atoms (H) and fluorine. The ratio of the number of atoms (F) (F) / (H). The amount of COF2 produced is based on the volumetric flow ratio and is published. 4 times or more. Ratio (F) "H" reaches U with ^ ° with increasing supply power 'the volume of c册F2 increases, and the ratio of the number of hydrogen atoms (H) to the number of fluorine atoms (F) (F) / ( H) has also grown. Further, according to an example of Patent Document 4 (Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. The ratio (F)/(H) to the number of fluorine atoms (F) is about 1.74. Compared with the literature, although the HF concentration and the COF2 concentration are lower, the ratio (F)/(H) is larger. . Further, Ηβ after the plasma formation was hardly observed, and it was confirmed that it was less than 1/10 of that before the electrification. Further, a 1.2 slm of ruthenium 2 to which a trace amount of N2 was added was supplied to the ozone generator 16 to obtain 8 vol / 〇, i.e., 0.096 slm. The amount of ozone generated is 4.8% of the fluorine-based gas from the plasma generating unit 24, and is obtained by summing the flow rate of c〇F2 and one-half of the flow rate of HF (when the supplied electric power is 4 〇〇w). About 2.2 times, about 2.2 times, it can be said that it is roughly appropriate size. The ozone-containing gas and the fluorine-based gas from the plasma discharge unit 24 are combined to form a reaction gas, and the reaction gas is blown onto an amorphous crucible on the surface of the glass substrate, and the amount of etching is measured. The temperature of the glass substrate is set to 3 (rc. The measurement result of the button amount is shown in Fig. 4. In the figure, the amount of money is converted into a reaction gas per unit volume (1 L) (4). In addition, according to the embodiment of the patent document 4 (Japanese Patent Laid-Open No. 2), the button amount is calculated to be 38 (four) ship. Therefore, according to the present disclosure and the above Patent Document 4 In contrast, although the HF concentration and the C〇F2 concentration are lower, it is possible to obtain the above-mentioned rate of Cong. [Example 2], the amount of water added in the gas of the eight muscles The relationship is investigated. The conditions for the addition of H2 CF to CF4, such as CF4, are as follows. 134995.doc • 30- 200924052 Power supply: 0.165 kW Power supply: Vpp = 13 kV electrode Area: 35 cm2 Further, make a shape of 5 _ 〇 2 and use an ozone generator to make a 03 ν 〇 % (% 比 2 ratio) 03, and mix it with the above-mentioned electric gas to supply the glass. The substrate is etched on the surface of the amorphous ruthenium film. The substrate temperature is set to 2 Gt, 4 〇. (:, thief, three kinds, 敎The engraving rate under each temperature condition. (Further, 6 〇t is the previous general substrate temperature, which is a comparative example.) The results are shown in Fig. 5. It can be seen from the figure that the substrate temperature is the same as before (4) In the case of the addition of the amount of water added to the fluorine-based raw material gas, the smear rate is almost unchanged. It is found that the substrate temperature is 20. The 〇日寺 starts from the vicinity of the sputum water addition amount and is etched. The rate is greatly increased; the etching rate reaches a peak near the water addition amount of the dew point of 2 〇t; and until the dew point reaches the vicinity of the water addition amount of the fastening force, an etch rate sufficiently larger than that of the previous (the substrate temperature is a thief) is obtained. It was found that when the substrate temperature was 4 Torr, the I insect etch rate which was sufficiently larger than the previous (the substrate temperature was 6 (rc)) was also obtained in the water addition range of the dew point of 1 〜. [Example 3] The etching apparatus of Fig. 2 was used. The amorphous germanium is etched, and the fluorine-based raw material gas is obtained by using 4 as a fluorine-based raw material, and diluting the I-based raw material (CF4) with a diluent gas containing a mixed gas of nitrogen and gas 134995.doc 200924052. The ratio of CF4 in the I-based raw material gas (CF4+Ar+N2) is 丨〇v〇l%. The dew point is added to the fluorine-based raw material gas (CFdAr+N2) by the humidifier η. The amount of AO is introduced, and the fluorine-based source gas (CF4+Ar+N2+H2〇) is introduced into the interelectrode space 27a, and is plasma-formed under atmospheric pressure. The discharge conditions are as follows. The thickness of the interelectrode space 27a : 1 mm Voltage between electrodes: Vpp = 12, 13 ' Mkv Frequency: 40 kHz : Fluorine-treated gas after plasma treatment, mixed with ozone-containing gas from ozone generator η (〇3 is about 8%) The sample is blown onto the amorphous film of the sample: the flow ratio of the fluorine-based treatment gas to the ozone-containing gas is set as the process gas: ozone-containing gas = 2:1. The ratio of the flow rate of the composition of the dilution gas (Ar+N2) to the flow rate of % is changed, and the voltage VPP between the electrodes is changed to investigate the amorphous 11 which is opposite to the nitrogen content (N2/(Arma)) of the nitrogen in the dilution gas. #刻刻率. The results are shown in Figure 7: This figure. The vertical axis indicates the etching rate when the workpiece 9 is subjected to one-pass movement (scanning) once with respect to the blow-out. As is apparent from the figure, when the electrode-to-electrode dust VPP is a relatively low voltage (vpp = 12 kV), if the content of the diluent gas is about 45% or less, the rate can be maintained high. In the region where the content of N2 in the diluent gas exceeds 45%, the larger the N2 content, the lower the _ rate. As the electrode „vpp is higher than 12kv, the rate of decrease in (4) is slower (Vpp=13kv~(4) 134995.doc -32- 200924052 in the figure. Is the Vpp a higher voltage (Vpp=i5)? In the case where the niobium content is in the range of about 45% to 100%, the button engraving rate is hardly lowered, and a good buttoning rate which is not limited by the N2 content can be obtained. Therefore, it is found that Ar and N2 can be arbitrarily mixed. [Example 4] cF4 and K were introduced into the plasma space 27a of the etching apparatus of Fig. 2, and plasma analysis was performed to perform luminescence analysis. The I optical analysis apparatus used ρΜΑ·η manufactured by Hamamatsu Photonics Co., Ltd. The conditions are as follows: Thickness of interelectrode space 27a: ! mm Electrode between electrodes: Vpp = l 5 kV Frequency: 40 kHz The results are shown in Fig. 8. It is confirmed that CF2+ is obtained by decomposition of CF4 (peak wavelength: 250) ~400 nm). Further, n2 is excited to confirm the luminescence peak of the second positive system (3〇〇~4〇〇nm). According to the peak wavelength of CF2 and the peak wavelength of the second positive band In the case of overlap, the edge can be made by including n in the dilution gas. 2 to promote the excitation and decomposition of cf4. [Example 5] The etching of amorphous germanium was performed using the button engraving device of Fig. 2. cF4 was used as a fluorine-based raw material. Argon gas was used as a diluent gas, and fluorine-based raw material was used as an argon gas. The gas is diluted to obtain a fluorine-based raw material gas (CF4+Ar). The ratio of CF4 in the fluorine-based raw material gas (CF4+Ar) is adjusted within a range of 1 to 100 vol〇/〇. In the raw material gas (CF4+Ar), H2〇 having a dew point of 18°c. 134995.doc -33·200924052 is added. The added fluorine-based source gas (Cf4+Ar+H2〇) is introduced into the interelectrode space 27a. The plasma is subjected to plasma pressure at atmospheric pressure. The discharge conditions are as follows. The thickness of the space between the electrodes 2 7a: 1 mm The voltage between the electrodes: Vpp = 12 kV Frequency: 40 kHz
將電漿化後之氟系處理氣體、與來自臭氧發生器13的含 臭氧之氣體（〇3約為8%)進行混合，吹附至試樣非晶矽膜 上。氟系處理氣體與含臭氧之氣體的流量比經設為_處 理氣體：含臭氧之氣體=2: 1。The plasma-treated fluorine-based processing gas was mixed with an ozone-containing gas (about 3 Å from the ozone generator 13) and attached to the sample amorphous ruthenium film. The flow ratio of the fluorine-based treatment gas to the ozone-containing gas is set to _ treatment gas: ozone-containing gas = 2:1.
使構成上述氟系原料氣體（CF4+Ar)2 CP#與心之流量比 在CF4/(CF4+Ar)= 1〜100 vol%之範圍内變化，來調查盘原料 氣體中之CF4之含量（CF4/(CF4+Ar))相對的非晶石夕之敍刻速 率。將結果示於圖9中。該圖之縱轴係表示使被處理物 相對於吹出喷嘴29而進行i次單程移動（掃描）時的触刻速 率。由該圖所明示，確認在原料氣體令含有4,⑽之 CF4時，可穩定地維持高蝕刻速率。 [產業上之可利用性] 本發明可在例如半導體晶圓或液晶等平板玻璃等的製造 中，應用於對表面之矽膜進行蝕刻。 【圖式簡單說明】 圖1係本發明之第1實施形態之触刻裝置的概略構成圖。 :=發明之第2實施形態之敍刻裝置的概略構成圖。 實施例1中的電衆放電部出口之氣體成分濃度 134995.doc -34- 200924052 以及比（F)/(H)之測定結果的圖表。 圖4係表示實施例1中的蝕刻量之測定結果的圖表。 圖5係表示在實施例2中，改變基板溫度來測定與氟系原 料CF4中之水添加量（露點表示）相對之蝕刻速率的結果之 圖表。 圖6係表示與溫度相對的臭氧之氣_液分配係數的圖表。 圖7係表不實施例3之結果，且表示與稀釋氣體中之氮之 含有率相對的非晶矽之蝕刻速率的測定結果的圖表。 圖8係表示在實施例4中冑c F 4與N 2進行電衆化時之發光 分析結果的光譜圖。 圖9係表*實施例9中&與原料中之CF4之含冑率相對的 姓刻速率之測定結果的圖表。 【主要元件符號說明】 1 姓刻裝置 3 基板溫度調節機構 4 反應氣體供給系統 10 臭氧供給系統 11 氧供給部 13 臭氧發生器 17 臭氧供給管路 20 氟系氣體供給系統 21 CF*(氟系原料）供給部 22 Ar供給部 22C 氮供給部 134995.doc •35· 200924052 23 24 27 27a 28 29 90 91 加濕器 大氣壓電漿放電部 電極 大氣壓電漿空間 調溫介質管路 吹出管路 基板 矽膜（被處理物） 134995.doc -36-The flow rate ratio of the fluorine-based source gas (CF4+Ar) 2 CP# to the core was changed within the range of CF4 / (CF4 + Ar) = 1 to 100 vol%, and the content of CF4 in the disk material gas was investigated ( The relative crystallization rate of CF4/(CF4+Ar)). The results are shown in Fig. 9. The vertical axis of the figure indicates the tempo rate when the object to be processed is subjected to i-time single-pass movement (scanning) with respect to the blowing nozzle 29. As is clear from the figure, it was confirmed that the high etching rate can be stably maintained when the material gas contains 4, (10) CF4. [Industrial Applicability] The present invention can be applied to etching a tantalum film on a surface, for example, in the production of a flat glass such as a semiconductor wafer or a liquid crystal. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic configuration diagram of a sizing apparatus according to a first embodiment of the present invention. : = Schematic diagram of the sculpt device of the second embodiment of the invention. The gas component concentration of the outlet of the electric discharge section in the first embodiment is 134995.doc -34 - 200924052 and a graph showing the measurement results of (F)/(H). Fig. 4 is a graph showing the measurement results of the etching amount in the first embodiment. Fig. 5 is a graph showing the results of measuring the etching rate with respect to the water addition amount (indicated by the dew point) in the fluorine-based raw material CF4 in the second embodiment. Fig. 6 is a graph showing the gas-liquid partition coefficient of ozone as opposed to temperature. Fig. 7 is a graph showing the results of measurement of the etching rate of amorphous germanium as compared with the result of Example 3 and showing the ratio of nitrogen in the diluent gas. Fig. 8 is a chart showing the results of luminescence analysis when 胄c F 4 and N 2 were subjected to electrification in Example 4. Fig. 9 is a graph showing the results of measurement of the surname rate in comparison with the content of CF4 in the raw material in Example 9 and Example 9. [Description of main component symbols] 1 Name engraving device 3 Substrate temperature adjustment mechanism 4 Reactive gas supply system 10 Ozone supply system 11 Oxygen supply unit 13 Ozone generator 17 Ozone supply line 20 Fluorine-based gas supply system 21 CF* (Fluorine-based raw material Supply unit 22 Ar supply unit 22C Nitrogen supply unit 134995.doc •35· 200924052 23 24 27 27a 28 29 90 91 Humidifier atmospheric piezoelectric slurry discharge electrode atmospheric piezoelectric slurry space temperature medium pipe blown pipe substrate diaphragm (treated material) 134995.doc -36-
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| TWI415185B (en) * | 2010-02-25 | 2013-11-11 | Sekisui Chemical Co Ltd | Etching method and device |
| TWI822631B (en) * | 2019-02-01 | 2023-11-11 | 法商液態空氣喬治斯克勞帝方法研究開發股份有限公司 | Method to improve profile control during selectively etching of silicon nitride spacers |
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| TWI543948B (en) * | 2009-05-07 | 2016-08-01 | 日本電氣硝子股份有限公司 | Glass substrate and fabricating method thereof |
| KR102030797B1 (en) * | 2012-03-30 | 2019-11-11 | 삼성디스플레이 주식회사 | Manufacturing method for thin film transistor array panel |
| CN107154366B (en) * | 2016-03-03 | 2020-01-21 | 中国科学院微电子研究所 | Silicon wafer polishing device |
| CN107154351B (en) * | 2016-03-03 | 2020-07-21 | 中国科学院微电子研究所 | Silicon wafer polishing method and device |
| JP6956288B2 (en) * | 2020-04-30 | 2021-11-02 | 東京エレクトロン株式会社 | Substrate processing method, plasma processing equipment, and etching gas composition |
| JP7312160B2 (en) * | 2020-12-28 | 2023-07-20 | 株式会社アルバック | Etching apparatus and etching method |
| KR102416875B1 (en) * | 2021-02-19 | 2022-07-05 | 김은도 | Slot die coating device equipped with fine adjustment module |
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| JP2000164559A (en) * | 1998-09-22 | 2000-06-16 | Seiko Epson Corp | Selective etching method and device for silicon substance |
| JP4167542B2 (en) * | 2002-07-17 | 2008-10-15 | 積水化学工業株式会社 | Gas supply apparatus for plasma etching and plasma etching system and method |
| JP4167544B2 (en) * | 2003-05-30 | 2008-10-15 | 積水化学工業株式会社 | Plasma etching method and apparatus |
| DE102004062355A1 (en) * | 2004-12-23 | 2006-07-06 | Siltronic Ag | Process for treating a semiconductor wafer with a gaseous medium and semiconductor wafer treated therewith |
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| TWI415185B (en) * | 2010-02-25 | 2013-11-11 | Sekisui Chemical Co Ltd | Etching method and device |
| TWI822631B (en) * | 2019-02-01 | 2023-11-11 | 法商液態空氣喬治斯克勞帝方法研究開發股份有限公司 | Method to improve profile control during selectively etching of silicon nitride spacers |
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| KR20100072340A (en) | 2010-06-30 |
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| JP5416590B2 (en) | 2014-02-12 |
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