TW200849391A - Heat processing method and apparatus for semiconductor, and computer readable medium - Google Patents
Heat processing method and apparatus for semiconductor, and computer readable medium Download PDFInfo
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- TW200849391A TW200849391A TW097105221A TW97105221A TW200849391A TW 200849391 A TW200849391 A TW 200849391A TW 097105221 A TW097105221 A TW 097105221A TW 97105221 A TW97105221 A TW 97105221A TW 200849391 A TW200849391 A TW 200849391A
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- gas
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- oxidizing
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- 239000004065 semiconductor Substances 0.000 title claims abstract description 36
- 238000003672 processing method Methods 0.000 title abstract 2
- 239000007789 gas Substances 0.000 claims abstract description 191
- 238000000034 method Methods 0.000 claims abstract description 95
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 56
- 230000003647 oxidation Effects 0.000 claims abstract description 54
- 238000000137 annealing Methods 0.000 claims abstract description 51
- 230000001590 oxidative effect Effects 0.000 claims abstract description 46
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000010438 heat treatment Methods 0.000 claims abstract description 43
- 239000000758 substrate Substances 0.000 claims abstract description 39
- 239000001301 oxygen Substances 0.000 claims abstract description 27
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 27
- 230000008569 process Effects 0.000 claims abstract description 26
- 238000012545 processing Methods 0.000 claims description 136
- 238000011282 treatment Methods 0.000 claims description 68
- 238000005121 nitriding Methods 0.000 claims description 29
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 239000000839 emulsion Substances 0.000 claims description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims 2
- UFHFLCQGNIYNRP-VVKOMZTBSA-N Dideuterium Chemical compound [2H][2H] UFHFLCQGNIYNRP-VVKOMZTBSA-N 0.000 claims 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 235000012431 wafers Nutrition 0.000 description 48
- 230000000052 comparative effect Effects 0.000 description 17
- 239000001257 hydrogen Substances 0.000 description 16
- 229910052739 hydrogen Inorganic materials 0.000 description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 238000002347 injection Methods 0.000 description 12
- 239000007924 injection Substances 0.000 description 12
- 229910052681 coesite Inorganic materials 0.000 description 9
- 229910052906 cristobalite Inorganic materials 0.000 description 9
- 229910052682 stishovite Inorganic materials 0.000 description 9
- 229910052905 tridymite Inorganic materials 0.000 description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 8
- 229910052814 silicon oxide Inorganic materials 0.000 description 8
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 230000007246 mechanism Effects 0.000 description 7
- 235000012239 silicon dioxide Nutrition 0.000 description 7
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000002485 combustion reaction Methods 0.000 description 6
- 238000005755 formation reaction Methods 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- 238000009279 wet oxidation reaction Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 4
- 239000004020 conductor Substances 0.000 description 4
- 230000005284 excitation Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 229910052707 ruthenium Inorganic materials 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- 239000004575 stone Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 229910000449 hafnium oxide Inorganic materials 0.000 description 3
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- IUVCFHHAEHNCFT-INIZCTEOSA-N 2-[(1s)-1-[4-amino-3-(3-fluoro-4-propan-2-yloxyphenyl)pyrazolo[3,4-d]pyrimidin-1-yl]ethyl]-6-fluoro-3-(3-fluorophenyl)chromen-4-one Chemical compound C1=C(F)C(OC(C)C)=CC=C1C(C1=C(N)N=CN=C11)=NN1[C@@H](C)C1=C(C=2C=C(F)C=CC=2)C(=O)C2=CC(F)=CC=C2O1 IUVCFHHAEHNCFT-INIZCTEOSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 239000011553 magnetic fluid Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 2
- 239000001272 nitrous oxide Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-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
- 241000251468 Actinopterygii Species 0.000 description 1
- 241000239226 Scorpiones Species 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 210000003323 beak Anatomy 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 210000000078 claw Anatomy 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 210000004907 gland Anatomy 0.000 description 1
- 239000003779 heat-resistant material Substances 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
- 150000002431 hydrogen Chemical class 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 238000006213 oxygenation reaction Methods 0.000 description 1
- APTZNLHMIGJTEW-UHFFFAOYSA-N pyraflufen-ethyl Chemical compound C1=C(Cl)C(OCC(=O)OCC)=CC(C=2C(=C(OC(F)F)N(C)N=2)Cl)=C1F APTZNLHMIGJTEW-UHFFFAOYSA-N 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000010405 reoxidation reaction Methods 0.000 description 1
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 1
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 210000003802 sputum Anatomy 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
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- 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
- H01L21/324—Thermal treatment for modifying the properties of semiconductor bodies, e.g. annealing, sintering
-
- 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
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02538—Group 13/15 materials
- H01L21/0254—Nitrides
-
- 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
- H01L21/02104—Forming layers
- H01L21/02365—Forming inorganic semiconducting materials on a substrate
- H01L21/02518—Deposited layers
- H01L21/02521—Materials
- H01L21/02551—Group 12/16 materials
- H01L21/02554—Oxides
-
- 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
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67017—Apparatus for fluid treatment
-
- 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
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/67098—Apparatus for thermal treatment
-
- 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
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67242—Apparatus for monitoring, sorting or marking
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Formation Of Insulating Films (AREA)
Abstract
Description
200849391 九、發明說明： 【發明所屬之技術領域】 本發明係關於一種用於半導體處理之熱處理方法及裝 置，其係用於實行一熱處理以在一目標基板（例如一半導 體晶圓）上形成一氧化物膜或氮氧化物膜。本文中所用術 語"半導體處理"包括用於藉由在—目標基板上以預定圖安7 形成半導體層、絕緣層與導電層從而在該目標基板上製:200849391 IX. INSTRUCTIONS OF THE INVENTION: TECHNICAL FIELD The present invention relates to a heat treatment method and apparatus for semiconductor processing for performing a heat treatment to form a film on a target substrate (for example, a semiconductor wafer) An oxide film or an oxynitride film. The term "semiconductor treatment" as used herein includes a method for forming a semiconductor layer, an insulating layer and a conductive layer on a target substrate by using a predetermined pattern on the target substrate:
C Ο -半導體器件或具有欲連接至—半導體器件的佈線層、電 極及類似物之一結構而實杆夕久絲+ 再貝仃之各種處理，該目標基板係 (例如）用於一 FPD(平板顯示哭ν也丨丄 τ 、 、丁衩”貝不)(例如一 LCD(液晶顯示器）） 之一半導體晶圓或一玻璃基板。 【先前技術】 在製造半導體積體電路時，讓一主道触γ 了 表 +導體基板（例如一石夕 晶圓）經受各種處理，一般而+ 力又而。，例如臈形成、蝕刻、氧 化、擴散及重組。例如，氧化包括_單晶石夕膜或一多晶石夕 膜之表面之氧化及一金屬膜之氧化。特定言之’藉由氧化 形成之一氧化矽膜係應用於一 口口件隔離膜、閘極氧化物 膜、電容器絕緣膜或類似物。 對於用於實行一氧化處理之 # ^ 万’去’右就壓力類型來看待 此寺方法，其中有一正規壓 ^ σ 乳化方法，其中將在一處理 谷器内部的氣體環境設定為幾 ,^ L 丁寺於大氣壓力。另外，有 一低壓力氧化方法，其中將在一 叩 严 定A —直介 ^ ^ 里合态内的氣體環境設 疋為 異二。右就用於氣化的备遍 的乳體類型來看待此等方法， 則有一濕式氧化方法，其中 女）在一外部燃燒裝置中燃 127295.doc 200849391 k ι氧以產生水蒸汽’以便藉由使用該水蒸汽來實行氧 化（例如，日本專利申含主 π KOKAI公告案第3-14〇453號（專 文獻D)。另外’有—乾式氧化方法，其中將臭氧或氧單獨 供應到-處理容器内以實行氧化而不使用水蒸汽(例如， 日本專利申請κ〇ΚΑΙ公告㈣57_1232號（專利文獻2))。 如上所述，可以藉由採用氧氣的乾式氧化或採用水蒸汽 之濕式氧化來實行梟务 , 、‘ 、丁虱化一叙地，藉由濕式氧化形成的氧C Ο - a semiconductor device or a structure having a structure of a wiring layer, an electrode, and the like to be connected to a semiconductor device, and a target substrate, for example, for an FPD (for example) The flat panel displays one of a semiconductor wafer or a glass substrate, such as an LCD (Liquid Crystal Display). [Prior Art] When manufacturing a semiconductor integrated circuit, let a master The touch gamma gamma + conductor substrate (such as a stone wafer) is subjected to various treatments, generally + force, such as yttrium formation, etching, oxidation, diffusion, and recombination. For example, oxidation includes _ single crystal or Oxidation of the surface of a polycrystalline stone film and oxidation of a metal film. Specifically, one of the oxide films formed by oxidation is applied to a one-mouth separator, a gate oxide film, a capacitor insulating film or the like. For the method of performing the oxidation treatment, the method of treating the temple is to have a normal pressure σ emulsification method in which the gas environment inside the processing tank is set to , ^ L Ding Temple is at atmospheric pressure. In addition, there is a low-pressure oxidation method in which the gas environment in a closed state of A-straight is set to be a different. The right is used for gasification. Regarding the type of the emulsion type, there is a wet oxidation method in which a female ignites 127295.doc 200849391 k methoxy to produce water vapor in order to perform oxidation by using the water vapor. (For example, the Japanese patent application contains the main π KOKAI announcement No. 3-14〇453 (special document D). In addition, there is a dry-oxidation method in which ozone or oxygen is separately supplied into the treatment vessel to perform oxidation without Water vapor is used (for example, Japanese Patent Application Laid-Open No. Hei 57 No. 57_1232 (Patent Document 2)). As described above, it is possible to carry out the work by dry oxidation using oxygen or wet oxidation using steam. Ding Yuhua, a form of oxygen formed by wet oxidation
C 化物膜之膜品質高於益+ #』^ 、、精由乾式氧化形成的氧化物臈。據 :匕’就膜性f (例如崩潰電、抗腐蝕性及可靠性)來考 量，濕式氧化膜膜優於絕緣膜。另一方面，欲形成的氧化 物膜（絕緣膜）之膜形成速率及在—晶圓上該財的平面均 $度亦為重要因素。在此方面，一般地，在一正規壓力下 藉由濕式氧化形成之一膜顯示一高氧化速率，但顯示膜厚 度之低劣的平面均句庚 勺度相反地，在一真空壓力下藉由渴 式氧化形成之一臈顯示一低氧化速率，但顯示膜厚度之、 好的平面均勻度。 ^ 在半導體器件或半導體積體電路之設計規則並非如此嚴 格之情況下’對（例如）氧化物膜之預期目的、處理條件及 衣置成本加以考！來選擇性地使用如上所述各種氧化方 之該些方法。另一方面，近年來， / *曰 7田砹牛术牛導體态件之線寬度及 膜厚度已減小’而因此該設計規則已變得更加嚴格。由此 趨勢而產生在氧化物膜的品質及厚度方面對更佳的平面均 =度之需求、。但是，就此方面而言傳統的氧化方法現正變 知不足’因為其無法充分滿足需求。 I27295.doc 200849391 一曰本專利申請〖〇尺八1公告案第4-1 8727號（專利文獻3)揭 丁種使用一濕式氧化方法之氧化裝置。依據此裝置，分 別將Η?乳體與A氣體供應到由石英製成之一垂直反應管之 底邛内，並在形成於一石英蓋中之一燃燒區段中將其燃燒 以產生水^气。此水蒸汽沿晶圓陣列向上流動而對該等晶 圓實仃一氧化處理。在此情況下，由於在該燃燒區段中燃 IH2氣體，因此在該區段附近的處理容器之底部富含水蒸 ^另一方面，該處理容器之頂部缺乏水蒸汽，因為該水 蒸/飞在其向上流動時會消耗。因此，形成於該等晶圓上之 氧化物膜之厚度可能依據晶圓舟之晶圓支撐位置而有很 大變化，從而使得該氧化物膜厚度之基板間均勻度劣化。 依據上述日本專利申請K〇KAp:告案第57_1232號（專利 文獻2)中揭示之一裝置，使用批次類型之一水平反應管將 複數個半導體晶圓並排排列。從該反應管之一側單獨供應 〇2氣體或同時供應〇2氣體與私氣體，以在一真空氣體環境 内形成一氧化物膜。此裝置經配置用以藉由使用一氫燃燒 氧化方法在具有一相對較高壓力之一氣體環境内實行膜形 成，因此主要由水蒸汽成分引起反應。在此情況下，該水 瘵汽之濃度可能在該處理容器内的氣體流之上游側與下游 側之間有很大變化，從而使得該氧化物膜厚度之基板間均 勻度劣化，正如上述情況。 1；8 6,037,273(專利文獻4)揭示另一類型之一氧化裝置。 依據此衣置將氧氣體與氫氣體供應到一具有加熱燈之單 基板類型的處理室内。此等氣體互相反應以在放置於該 127295.doc 10 200849391 處理至内之一半導體晶圓之表面附近產生水蒸汽，從而使 侍该晶圓表面上的矽受此水蒸汽之氧化而形成一氧化物 膜。 但疋’依據此裝置，氧氣體與氫氣體係從距該晶圓20至 3 0 mm遠的氣體入口輸送進該處理室，並互相反應以在該 半導體晶圓之表面附近產生水蒸汽。另外，處理壓力係設 Ο ϋ 疋於一相對較高的值。此等條件可使得該氧化物膜厚度之 平面均勻度劣化。 曰本專利申請KOKAI公告案第2002_176052號（專利文獻 5) 揭示另一類型之一氧化方法。依據此方法，一氧化氣體 (例如〇2氣體）及一還原氣體（例如H2氣體）係同時供應進一 處理室並在一真空氣體環境内互相反應。結果，產生氧自 由基與羥基自由基，而該等自由基用作該氣體環境之主要 部分’在該氣體環境内將矽晶圓或類似物氧化。 曰本專利申請KOKAI公告案第200(M83〇55號（專利文獻 6) 揭示用於形成一具有高品質的氮氧化物膜（Si〇N膜）作為 一非氧化物膜的絕緣膜之一方法。依據此方法，藉由使用 氨、一氧化氮（NO)或氧化二氮（N20)來讓藉由該些上述方 法之一方法形成之一 Si〇2膜經受一氮化處理，從而形成一 SiON膜。在該氮化處理後，藉由使用（例如）〇2氣體來實行 一重新氧化處理以移除多餘的N成分。 【發明内容】 本發明之-目的係提供-種用於—半導體處理之熱處理 方法及裝置’其可以形成一具有良好電性質之氧化物膜或 127295.doc 200849391 氮氧化膜。 依據本發明之一第一態樣，提供一種用於在一半導體處 理中形成一氧化物膜之熱處里 且 一 ^ 处埋方去，該方法包含：將以間The film quality of the C film is higher than that of the beneficial oxides formed by dry oxidation. According to 匕', considering the film properties f (such as collapse electricity, corrosion resistance and reliability), the wet oxide film is superior to the insulating film. On the other hand, the film formation rate of the oxide film (insulating film) to be formed and the uniformity of the plane on the wafer are also important factors. In this respect, generally, a film formed by wet oxidation at a normal pressure exhibits a high oxidation rate, but the inferior plane showing the thickness of the film is inversely proportional to a vacuum pressure. One of the formations of thirsty oxidation shows a low oxidation rate, but shows a good planar uniformity of the film thickness. ^ In the case where the design rules for semiconductor devices or semiconductor integrated circuits are not so strict, the expected purpose, processing conditions, and cost of clothing of, for example, oxide films are examined! These methods of various oxidation methods as described above are selectively used. On the other hand, in recent years, the line width and film thickness of the conductors of the / 曰 7 砹 砹 牛 have been reduced' and thus the design rule has become more stringent. From this trend, there is a demand for better planar uniformity in terms of the quality and thickness of the oxide film. However, in this respect, conventional oxidation methods are becoming under-recognized because they are not sufficient to meet demand. I27295.doc 200849391 A patent application 〇 八 8 1 Announcement No. 4-1 8727 (Patent Document 3) discloses an oxidizing device using a wet oxidation method. According to the apparatus, the tantalum emulsion and the A gas are respectively supplied into the bottom crucible of a vertical reaction tube made of quartz, and are burned in a combustion section formed in a quartz cover to generate water. gas. This water vapor flows upward along the wafer array to oxidize the crystals. In this case, since the IH2 gas is burned in the combustion section, the bottom of the treatment vessel near the section is rich in water vapor. On the other hand, the top of the treatment vessel lacks water vapor because the water is steamed/ The fly consumes as it flows upwards. Therefore, the thickness of the oxide film formed on the wafers may vary greatly depending on the wafer support position of the wafer boat, thereby deteriorating the uniformity between the substrates of the oxide film thickness. According to one of the devices disclosed in the above-mentioned Japanese Patent Application K. KAp: No. 57_1232 (Patent Document 2), a plurality of semiconductor wafers are arranged side by side using one of the batch type horizontal reaction tubes. The 〇2 gas or the 〇2 gas and the private gas are supplied separately from one side of the reaction tube to form an oxide film in a vacuum gas atmosphere. The apparatus is configured to effect film formation in a gas environment having a relatively high pressure by using a hydrogen combustion oxidation process, thereby causing a reaction mainly by a water vapor component. In this case, the concentration of the water vapor may vary greatly between the upstream side and the downstream side of the gas flow in the processing vessel, so that the uniformity between the substrates of the oxide film thickness is deteriorated, as in the above case. . 1; 8 6, 037, 273 (Patent Document 4) discloses another type of oxidation device. Oxygen gas and hydrogen gas are supplied to a processing chamber of a single substrate type having a heat lamp in accordance with the coating. The gases react with each other to generate water vapor near the surface of a semiconductor wafer disposed within the 127295.doc 10 200849391 process, thereby causing the ruthenium on the surface of the wafer to be oxidized by the water vapor to form an oxidation Film. However, according to the apparatus, an oxygen gas and hydrogen system are fed into the processing chamber from a gas inlet 20 to 30 mm from the wafer, and react with each other to generate water vapor near the surface of the semiconductor wafer. In addition, the process pressure is set at a relatively high value. These conditions can deteriorate the planar uniformity of the thickness of the oxide film. Another type of oxidation method is disclosed in Japanese Patent Application KOKAI Publication No. 2002_176052 (Patent Document 5). According to this method, an oxidizing gas (e.g., helium 2 gas) and a reducing gas (e.g., H2 gas) are simultaneously supplied into a processing chamber and reacted with each other in a vacuum gas atmosphere. As a result, oxygen radicals and hydroxyl radicals are generated which act as a major part of the gaseous environment in which the tantalum wafer or the like is oxidized. Japanese Patent Application KOKAI Publication No. 200 (M83-55 (Patent Document 6) discloses a method for forming an insulating film having a high-quality oxynitride film (Si〇N film) as a non-oxide film According to this method, one of the Si〇2 films formed by one of the above methods is subjected to a nitriding treatment by using ammonia, nitrogen monoxide (NO) or nitrous oxide (N20) to form a film. SiON film. After the nitriding treatment, a reoxidation treatment is performed by using, for example, ruthenium 2 gas to remove excess N component. SUMMARY OF THE INVENTION The present invention is directed to providing a semiconductor A heat treatment method and apparatus for treating 'which can form an oxide film having good electrical properties or an oxynitride film of 127295.doc 200849391. According to a first aspect of the present invention, there is provided a method for forming an oxidation in a semiconductor process In the heat of the film, and at a place where it is buried, the method includes:
隔堆宜於一垂直方向上的複數個目標基板放置於一處理容 器之-處理場内，該等目標基板之每—基板包括在其表面 上之-處理目標層；在加熱該處理場時向該處理場供應一 氧化氣體與-還原氣體’從而使得該氧化氣體與該還職 體互相反應以產生氧自由基與羥基自由基；以及藉由使用 該等氧自由基及該等經基自由基來對該目標基板之處理目 標層實行氧化；以及在-包含臭氧或氧化自由基之_退火 氣體的氣體環境内加熱經該氧化處理之處理目標層，從而 對該處理目標層實行退火。 依據本發明之-第二態樣’提供—種用於在—半導體處 理中形成一氧化物膜之熱處理方法，該方法包含：將以： 隔堆疊於一垂直方向上的複數個目標基板放置於一處理容 器之-處理場内，該等目標基板之每—基板包括在其表面 上之-處理目標層；在加熱該處理場時向該處理場供應— 氧化氣體與一還原氣體，從而使得該氧化氣體與該還：氣 體互相反應以產生氧自由基與經基自由基；以及藉由使用 該等氧自由基及該等經基自由基來對該目標基板之處理目 標層實行氧化；以及在-氮化氣體之—氣體環境内加熱經 該氧化處理之處理目標層，從而對該處理目標層實行氮 化；以及在包含臭氧或氧化自由基的退火氣體之一氣體埽 境内加熱經該氮化處理之處理目標層，從而對該處理二: 127295.doc -12- 200849391 層實行退火。 依據本發明之一第三態樣，提供一種用於一半導體處理 之熱處理裝置，該裝置包含·· -處理容器，其具有配置成 用以谷納以間隔堆疊於一垂直方向上的複數個目標基板之 處理場’一加熱器，其係佈置於該處理容器周圍並配置 成用以加熱該處理場；一真空排氣系、統，其配置成用以從 》處理场排出氣體；一氧化氣體供應管路，其配置成用以 ΓThe plurality of target substrates, which are preferably arranged in a vertical direction, are placed in a processing field of a processing container, each of the substrate includes a processing target layer on the surface thereof; when the processing field is heated The treatment field supplies an oxidizing gas and a reducing gas to cause the oxidizing gas to react with the working body to generate oxygen radicals and hydroxyl radicals; and by using the oxygen radicals and the radicals The treatment target layer of the target substrate is oxidized; and the treatment target layer subjected to the oxidation treatment is heated in a gas atmosphere containing - an annealing gas containing ozone or oxidized radicals, thereby annealing the treatment target layer. According to the second aspect of the present invention, there is provided a heat treatment method for forming an oxide film in a semiconductor process, the method comprising: placing a plurality of target substrates stacked in a vertical direction by: In the processing field of the processing container, each of the target substrates includes a processing target layer on the surface thereof, and an oxidation gas and a reducing gas are supplied to the processing field when the processing field is heated, thereby causing the oxidation And the gas: reacting with each other to generate oxygen radicals and radical radicals; and oxidizing the target layer of the target substrate by using the oxygen radicals and the radical radicals; Nitrogen gas-heating treatment of the target layer by the oxidation treatment, thereby performing nitridation on the treatment target layer; and heating in the gas enthalpy of one of the annealing gases containing ozone or oxidizing radicals The target layer is treated to anneal the layer 2: 127295.doc -12- 200849391. According to a third aspect of the present invention, there is provided a heat treatment apparatus for a semiconductor process, the apparatus comprising: - a processing vessel having a plurality of targets configured to be stacked in a vertical direction at intervals a processing field of the substrate, a heater disposed around the processing container and configured to heat the processing field; a vacuum exhaust system configured to discharge gas from the processing field; an oxidizing gas Supply line, configured to Γ
向錢理场供應一氧化氣體；一還原氣體供應管路，其配 置f用以向該處理場供應一還原氣體；以及一退火氣體供 應吕路，其配置成用以向該處理場供應包含臭氧或氧化自 由基之一退火氣體。 依據本發明之—第四態樣，提供-種含有用於在-處理 盗上執行的程式指令之電腦可讀取媒體，#中程式指令在 精由該處理器執行時控制一 ^ 用於+導體處理之熱處理裝 置以實施一熱處理方法，哕 σ亥方法包含·將以間隔堆疊於一 垂直方向上的複數個目標 加丞板放置於一處理容器之一處理 場内，該等目標基板之每一 基板匕括在其表面上之一處理 目標層；在加熱該處理場時 卞门β處理％供應一氧化氣體與 一還原氣體，從而使得兮_ a ^ 匕氣體14該還原氣體互相反應 某及兮耸由基’以及稭由使用該等氧自由 基及忒專經基自由基來對 ^ ^ 目私基板之處理目標層實行氧 化，以及在加熱該處理場卑 ,,,.^ 向该處理場供應含有臭氧或氧 化自由基之一退火氣體以在該 火氣體之一魚體ί罗措肉Λ口 熱經該氧化處理之處理目萨 〃且衣兄内力 ”該處理目標層實行 127295.doc -13- 200849391 可=日ΓΓ中將提出本發明額外目的與優勢，而其部分將 之目㈣::解，或可藉由本發明之實作而習得。本發明 現並獲得。 下文令特射曰出之手段及其組合來實 【實施方式】 =發:::發程序中，本發明者結合用於藉由—熱處 =成—魏_錢氧化物膜之—方法來 =處理㈣統技W結果，本發明者_下述發 、例如’依據上述專利文獻1至6所揭示之熱處理方法，可 =^具有相對較佳膜品f a在氧化物膜厚度方面具有相 對較高的平面均勻卢: 1度之1化物膜。但是，近年來，根據 丰導體器件所使用的絕緣膜需要具有更佳性質及/或特性 一事實頃么現，此等傳統技術可造成若干問題。例如， 就诸如-SILC(石夕引起的茂漏電流）特性及—TD〇B(與時間 相關的直接崩潰)特性之類的某些電氣特性而言，此等傳 、、先技術無法充为滿足日趨嚴格的要求。該爪匸特性係關於 在將一氧化石夕膜用作-閑極絕緣膜之情況下該氧化石夕膜之 f貝並颁不"IL經该臈之一洩漏電流。該TDDB特性係 關於在將一氧化秒腺用私 _ 7膜用於一電晶體之情況下該氧化矽膜之 义f生胃ϋ顯不在—值定電流流經該電晶體時直至崩潰之 刖的/主人電何1 ’其呈現為閘極電壓之〆變化。依據實 驗口等.心為此等特性之劣化係因該絕緣膜中的殘餘氣所 127295.doc 200849391 致。 現在將參考附圖來說明依據上述發現而實現 具體實施例。在以下說明中，具有實 ▲ χ之 :=?係由相同的參考數字來表示，並且僅在需要時 才予以重歿說明。 Τ <第一具體實施例> 圖1係依據本發明之一_呈*香 “之#具體實施例的-垂直熱處理 f ί； 衣置之結構之一視圖。如圖i所示，處理裝置2包括具有— 圓柱職（其具有—開放的底部）之_垂直處理容器4，其中 一處理場5係定義用於容納並處理以間隔堆疊於一垂直方 向上的複數個半導體晶圓（目標基板）。該處理容器4係由一 熱阻材料（例如石英）製成。 一排氣埠6係形成於該處理容器4之頂部且係連接至一排 氣線8，該排氣線8係（例如）在一水平方向上彎曲成直角。 該排氣線8係、連接至—真空排氣系統14，該真空排氣系統 14包括一壓力控制閥1〇、一真空幫浦12等，以對該處理容 器4内部的氣體環境進行真空排氣。 該處理谷裔4之底部開口係透過一密封部件2〇(例如一 〇 幵y環）連接至一圓柱形歧管3 8，以便可以使得該處理容器4 之内部保持氣密。該處理容器可完全由一圓柱形石英柱形 成，而無分離形成之一歧管1 6。該歧管1 6係由（例如）不銹 鋼製成，並支撐該處理容器4之底部。將由石英製成之一 晶圓舟18透過該歧管16之底部埠上下移動，以便將該晶圓 舟18載入處理容器4及從該處理容器4將該晶圓舟18卸載。 127295.doc -15- 200849391 若干目標基板或半導體晶圓W係堆疊於一晶圓舟丨8上。例 如，在此具體實施例中，該晶圓舟1 8可以支撐（例如）以本 質上規則的間隔處於該垂直方向上之約5 〇個直徑為3 〇 〇 mm的晶圓。 透過由石英製成之一絕熱圓柱22將晶圓舟is放置於一台 面24上。該台面24受一旋轉軸28支撐，該旋轉軸28穿透用 於開啟/閉合該歧管1 6的底部埠之一蓋子2 6。該旋轉軸2 8 所牙透之a亥盖子2 6的部分具有（例如）一磁性流體密封件 30，從而使得該旋轉軸28在一氣密密封狀態中以可旋轉的 方式受到支撐。一密封部件32(例如〇形環）係***於該蓋 子26的周邊與該歧管16的底部之間，致使處理容器4的内 部可以保持氣密。 旋轉軸28係附接於由一升降機構34(例如舟升降機）支撐 之一臂36的末梢端部。該升降機構34向上及向下整體地移 動晶圓舟18與蓋子26。該台面24可以係固定於蓋子26，以 便處理晶圓W時不必旋轉晶圓舟1 8。 該處理容器4受一碳線路加熱器38包圍，該碳線路加熱 器38係用於加熱該處理容器4内的氣體環境及半導體晶圓 W。該碳線路加㉟器可以實現一清潔處理並在增加與:低 溫度方面具有良好的特性。該加熱器38受_絕熱外殼包 圍，該絕熱外殼40係用於確保熱穩定性。 省歧s 1 6係連接至用於將個別氣體供應到該處理容器4 内，各個氣體供應管路1確言之，該歧管16係連接至： -氧化氣體供應管路42 ’其係用於向該處理場5供應一氧 127295.doc 16 200849391 虱篮，一還原氣體供應管路44，其係用於向該處理場5 供應一還原氣體；以及一臭氧供應管路46，其係用於向該 處理場5供應臭氧。該歧管16係進一步連接至一用於供應 一沖洗氣（例如N2氣體）之沖洗氣供應管路（未顯示）。該兩 =體供應管路42與44分別包括一氧化氣體喷射喷嘴48與 一還原氣體嘴射喷嘴50，該等喷嘴穿透該歧管16之側壁^ 使其末梢端部向該處理容器4之内部開放。Supplying a oxidizing gas to the money field; a reducing gas supply line configured to supply a reducing gas to the processing field; and an annealing gas supply lyo, configured to supply ozone to the processing field Or an annealing gas that oxidizes one of the free radicals. According to a fourth aspect of the present invention, there is provided a computer readable medium containing program instructions for performing on-handling, and a program instruction in # is controlled by the processor to control a ^ The heat treatment device for the conductor treatment is implemented by a heat treatment method, and the method includes: placing a plurality of target twisting plates stacked in a vertical direction at intervals in a processing field of a processing container, each of the target substrates The substrate is disposed on one of the surfaces of the processing target layer; when heating the processing field, the threshold β process % supplies an oxidizing gas and a reducing gas, so that the 兮 a ^ 匕 gas 14 reacts with the reducing gas to each other The base layer and the straw are oxidized by using the oxygen radicals and the ruthenium-based radicals to treat the target layer of the target substrate, and heating the processing field to hue, and, Supplying an annealing gas containing ozone or an oxidizing radical to treat the fish body in the fire gas, which is treated by the oxidation treatment, and the treatment target layer is implemented 127295.doc -13- 200849391 The additional objects and advantages of the present invention may be set forth in the following paragraphs, and some of them may be obtained by (4):: or may be learned by the practice of the present invention. The present invention is now available. The method of extracting and the combination thereof are implemented. [Embodiment] = Hair::: In the program, the inventors combine the method of using the method of heat-heating-forming-wei-money oxide film to process (four) As a result of the technique, the inventors of the present invention, for example, the heat treatment method disclosed in the above Patent Documents 1 to 6, can have a relatively high uniformity in the thickness of the oxide film in the film material fa. Lu: 1 degree compound film. However, in recent years, according to the fact that the insulating film used for the conductor device needs to have better properties and/or characteristics, such conventional techniques may cause several problems. For example, In terms of certain electrical characteristics such as -SILC (leak-current induced by Shi Xi) and certain characteristics of -TD〇B (direct collapse associated with time), such transmission and prior art cannot be filled to meet increasingly stringent requirements. The requirements of the claws are related to In the case where the fossil lithography film is used as the idler insulating film, the oxidized stone is not leaking current. The TDDB characteristic is related to the use of the oxidized second gland. When the membrane is used in the case of a transistor, the sputum sputum membrane is not present. The value of the constant current flows through the transistor until the collapse of the host/host 1', which appears as the gate voltage. The change is based on the experimental port, etc. The deterioration of the characteristics of the core is due to the residual gas in the insulating film. 127295.doc 200849391. A specific embodiment will be described based on the above findings with reference to the accompanying drawings. , with real ▲ :: =? is represented by the same reference number, and will only be repeated when needed. Τ <First Specific Embodiment> Fig. 1 is a view showing a structure of a garment according to a specific embodiment of the present invention - a vertical heat treatment; as shown in Fig. The apparatus 2 includes a vertical processing container 4 having a cylindrical member (which has an open bottom), wherein a processing field 5 defines a plurality of semiconductor wafers for receiving and processing to be stacked in a vertical direction at intervals (target The processing container 4 is made of a heat-resistant material (for example, quartz). An exhaust gas 6 is formed on the top of the processing container 4 and is connected to an exhaust line 8 which is an exhaust line 8 (for example) curved at right angles in a horizontal direction. The exhaust line 8 is connected to a vacuum exhaust system 14 including a pressure control valve 1 , a vacuum pump 12 , etc. The gas atmosphere inside the processing container 4 is evacuated. The bottom opening of the treatment 4 is connected to a cylindrical manifold 3 through a sealing member 2 (for example, a y ring) so that it can be made The inside of the processing container 4 is kept airtight. The vessel may be formed entirely of a cylindrical quartz column without separation forming one of the manifolds 16. The manifold 16 is made of, for example, stainless steel and supports the bottom of the processing vessel 4. It will be made of quartz. A wafer boat 18 is moved up and down through the bottom of the manifold 16 to load the wafer boat 18 into the processing vessel 4 and unload the wafer boat 18 from the processing vessel 4. 127295.doc -15- 200849391 The target substrate or semiconductor wafer W is stacked on a wafer boat 8. For example, in this embodiment, the wafer boat 18 can support, for example, at substantially regular intervals in the vertical direction. About 5 wafers having a diameter of 3 mm. The wafer boat is placed on a surface 24 through an insulating cylinder 22 made of quartz. The table 24 is supported by a rotating shaft 28, which is 28 Passing through a cover 26 for opening/closing the bottom 埠 of the manifold 16. The portion of the rotary shaft 28 that is diametrically permeable has, for example, a magnetic fluid seal 30, thereby The rotating shaft 28 is rotatably supported in a hermetic sealed state A sealing member 32 (e.g., a beak ring) is inserted between the periphery of the cover 26 and the bottom of the manifold 16, such that the interior of the processing container 4 can remain airtight. The rotating shaft 28 is attached to a lifting mechanism 34 (e.g., a boat lift) supports a distal end of one of the arms 36. The lift mechanism 34 integrally moves the wafer boat 18 and the cover 26 up and down. The table 24 can be secured to the cover 26 for processing the wafer W It is not necessary to rotate the wafer boat 18. The processing vessel 4 is surrounded by a carbon line heater 38 for heating the gas atmosphere in the processing vessel 4 and the semiconductor wafer W. The 35 device can achieve a cleaning process and has good characteristics in terms of increase and low temperature. The heater 38 is surrounded by a heat insulating outer casing 40 for ensuring thermal stability. The provincial s 16 6 is connected to supply individual gases into the processing vessel 4, and the respective gas supply lines 1 are connected, the manifold 16 is connected to: - an oxidizing gas supply line 42 ' The treatment field 5 is supplied with an oxygen 127295.doc 16 200849391 basket, a reducing gas supply line 44 for supplying a reducing gas to the processing field 5, and an ozone supply line 46 for Ozone is supplied to the treatment field 5. The manifold 16 is further coupled to a flushing gas supply line (not shown) for supplying a flushing gas (e.g., N2 gas). The two body supply lines 42 and 44 respectively include an oxidizing gas injection nozzle 48 and a reducing gas nozzle nozzle 50, and the nozzles penetrate the side wall of the manifold 16 such that the distal end thereof faces the processing container 4. Open inside.
V 該等噴射噴嘴48及50係分別連接至氣體線52及54，該等 =線分別具有切換閥56及58與流速控制㈣㈣，例如 Df量流量控制器。分別控制該等切換閥56及58與流速控制 益60及62，始得控制個別氣體供應之開始/停止及其 /氣速。在此具體實施例中 八一 广Μ 作馮靶例，該氧化氣體係〇2 氣體而該還原氣體係為氣體，並將其供應至該處理容器4 該臭氧供應管路46包括―臭氧噴射 喷嘴64穿透該歧管16之側 ^贺射 4之内邱門说 使八末梢端部向該處理容器 之内。卩開放。該臭氧噴射啥峨以及、圭 γ _ 赁射嘴鳥64係連接至-氣體線66， ^虱體線具有（按以下說明順 哭7fU仓丨上 „ 斤）切換閥68、一流速控制 口口 70(例如一質量流量控制器）及一* 接兩Iw ^ * 六虱產生器72。據此， 而《 2生臭氧並將其以受控 理容器4之底部。 迷仏應主4處 二二：構Ϊ的處理敦置2之操作係作為-整體受-拴制為74(例如一電腦）之控制。 雷腦铲―在μ 士 用於執仃該裝置2的操作之 迅細転式係儲存於一儲存區 亍 子L蚁76中，該儲存區段％包含一 127295.doc •17- 200849391 體。^文例如軟碟、CD(光碟）、石更碟及/或快閃記憶 ㈣氧?：：控制器74之指令，控制該等個別氣體(包 ㈣）的（、應之開始/停止、其氣體流速、處理溫度及處V The injection nozzles 48 and 50 are connected to gas lines 52 and 54, respectively, which have switching valves 56 and 58 and flow rate control (4) (4), such as a Df flow controller. Controlling the switching valves 56 and 58 and the flow rate control benefits 60 and 62, respectively, controls the start/stop of the individual gas supplies and/or the gas velocity. In this embodiment, in the case of the VIII, the oxidizing gas system 〇2 gas and the reducing gas system is a gas, and supplies it to the processing vessel 4. The ozone supply line 46 includes an "ozone spraying nozzle". 64 penetrates the side of the manifold 16 within the Hee 4, Qiu Men said that the end of the eight ends are directed into the processing container.卩 Open. The ozone injection 啥峨 and the γ γ _ 射 射 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 70 (for example, a mass flow controller) and one *two Iw ^ * six-inch generator 72. According to this, and "2 raw ozone and it is controlled to the bottom of the container 4. The confused should be the main 4 Second: the structure of the processing of the Dunhuang 2 operating system as a whole - controlled by a system of 74 (such as a computer). Thunderbolt - in the use of the device for the operation of the device 2 Stored in a storage area, the scorpion L ant 76, which contains a 127295.doc • 17- 200849391 body. For example, floppy disk, CD (CD), stone disc and/or flash memory (4) Oxygen::: The command of controller 74 controls the individual gases (package (4)) (should start/stop, their gas flow rate, processing temperature, and
在此具體實施例中，該處理容器4具有一單_管鈐構， =可具有一由内部與外部管形成之雙管結構二；個別 =括臭氧)的喷嘴之配置不限於圖消示配置。例如， :嘴可由沿該晶圓舟i 8的高度延伸並具有形成於其上面 的若干噴射孔（以便橫跨該晶圓舟18之高度均句地喷射對 應氣體）之一導管形成。 接:來，還參考圖2,將對在具有上述結構的處理裝置2 中實行之依據5亥第一具體實施例的熱處理方法進行說 明。圖2係|貝示用於藉由依據該第一具體實施例之—熱處 理方法來形成―叫膜之—處理之—範例之—流程圖^ 2係例示為藉由氧化在半導體晶圓表面上將—s丨〇 2臈形成 一絶緣膜之一情況。 /月確言《，依據此處理方法，首先，令一氧化氣體與一 還原氣體在該處理場5内互相反應以形成一包含氧自由基 與經基自由基之氣體環境，以便在半導體晶圓％之表面上 實行氧化以形成一氧化物膜（氧化步驟S1)。接著，藉由在 包含臭氧或氧化氣體自由基之一氣體環境内進行加^，從 而對該氧化物膜實行退火（退火步驟S2)。在同—處理場5 内依序實行此等步驟，從而形成其中僅含有少量氫之一 Si〇2 膜0 127295.doc -18- 200849391 明確言之’當該處理裝置2係設定為備用而其中未載有 任何半導體晶(例如^曙’該處理場5係保持於低 於》亥處理度之—溫度。當開始該處理時，首先，將若干 ⑽曰如50個)半導體晶圓w在該垂直方向上以預定間隔*** <曰曰圓舟1 8内。接著’ II由該舟升降機34將該晶圓舟1 8向 上移動並將其從下方載入處於-熱壁狀態之處理容器4， 以便將该晶圓舟18放置於該處理場5内。另外，該歧管ΜIn this embodiment, the processing container 4 has a single tube structure, = can have a double tube structure formed by internal and external tubes; the configuration of the nozzles of the individual = including ozone is not limited to the map elimination configuration. . For example, the mouth may be formed by a conduit extending along the height of the wafer boat i 8 and having a plurality of injection holes formed thereon (to uniformly eject the corresponding gas across the height of the wafer boat 18). Next, referring to Fig. 2, a heat treatment method according to the first embodiment of the present invention, which is carried out in the processing apparatus 2 having the above structure, will be described. 2 is a method for forming a film by the heat treatment method according to the first embodiment - an example of a flow chart is exemplified by oxidation on a surface of a semiconductor wafer. A case where -s丨〇2臈 is formed as an insulating film. According to this treatment method, first, an oxidation gas and a reducing gas are mutually reacted in the treatment field 5 to form a gas atmosphere containing oxygen radicals and radical radicals, so as to be in the semiconductor wafer % Oxidation is performed on the surface to form an oxide film (oxidation step S1). Next, the oxide film is annealed by adding in a gas atmosphere containing one of ozone or oxidizing gas radicals (annealing step S2). These steps are sequentially performed in the same-processing field 5 to form a film containing only a small amount of hydrogen, Si 〇 2 film 0 127295.doc -18- 200849391 clearly stated that when the processing device 2 is set to standby, The semiconductor wafer is not loaded with any semiconductor crystals (for example, the processing field 5 is maintained at a temperature lower than the processing level. When the processing is started, first, a plurality of (10), for example, 50 semiconductor wafers w are Insert into the round boat 1 8 at a predetermined interval in the vertical direction. Next, the boat lifter 34 is moved upward by the boat lifter 34 and loaded into the processing vessel 4 in the hot-wall state from below to place the wafer boat 18 in the processing field 5. In addition, the manifoldΜ
t/ 之底部埠係藉由該蓋子26而閉合以氣密密封該處理容器 4 〇 接著藉由该真空排氣系統14對該處理容器4之内部進 行真=排氣，以將該處理場5設定於一預定處理壓力。另 增加向該加熱器38施加之功率以將該等晶圓W及處理 % 5加熱至用於該氧化處理之處理溫度。在該處理場$之溫 度又％疋後，卩受控制㈤流速分別從言亥#氣體供應管路U 的氧化氣體噴射喷嘴48及還原氣體噴射喷嘴5〇向該處 理場5供應氧化步驟所需要的預定處理氣體（即鳴氣體及 Hz氣體）。此時，尚未供應臭氧。 四2等兩氣體在其透過該處理場5向上流動時在真空氣體 %扰内互相反應並產生羥基自由基與氧自由基。該等羥基 自由基及氧自由基接觸到在旋轉中的晶圓舟18上受到支撐 之晶圓w，而將一氧化處理引到晶圓表面上（步驟si)。= 匕處於4處理容器4的頂部之排氣琿6從該處理容器4排出 以此使用的處理氣體及/或藉由該反應產生的氣體。 此時，將&氣體之流速設定為2〇〇至5,〇⑽sccm，例如 127295.doc -19- 200849391 600 seem。將02氣體之流速設定為200至l〇,〇〇〇 seem，例 如1，200 sccm。將該處理溫度設定為5〇〇至i，2〇〇°c，例如 900°C。將該處理壓力設定為〇〇2托（2.7 Pa)至3.0托（400 Pa) ’例如〇·35托（46 Pa)。將處理時間設定為（例如）1()分 鐘。 因此分別供應到該處理容器4内的02氣體及出氣體透過 處於一熱壁狀態的處理容器4内之處理場5向上流動。此等 氣體在晶圓W附近引起一氫燃燒反應，以形成一主要由氫 自由基（Ο*)與羥基自由基（OH*)形成之氣體環境。藉由此 等自由基將該等晶圓W之表面氧化並由此形成一 Si〇2膜。 此時，如下所述繼續進行自由基之產生。明確言之，當分 別將氫與氧供應到處於一熱壁狀態的處理容器4内部之一 真空氣體環境内時，在該等晶圓w之附近引起一氫燃燒反 應，可能係如下所述。在以下分子式中，具有一符號，,*，， 之一化學元素表示其係一自由基。 H2+〇2->H*+H02 o2+h*->oh*+o* h2+o*-^h*+oh* h2+oh*->h*+h2o 如上所述，在分別將H2及〇2供應至該處理場5之情況 下，在一氫燃燒反應之處理中產生〇*(氧自由基）、〇h*(羥 基自由基）及H2〇(水蒸汽），而在該晶圓表面上引起氧化以 形成一 Si〇2膜。此時，上述自由基〇*及〇H*可能主要用於 該氧化。 127295.doc -20- 200849391 由於用作一還原氣體之氫’因此以此形成的Si〇2膜中含 有氫成分，而使得膜之某些電性質劣化。鑑於此問題，接 著在-臭氧氣體環境内實行-丨火步，驟以從該膜移除氨成 分（步驟S2)。 明確言之，停止如上所述之〇2氣體及％氣體之供應，而 操作該臭氧供應管路4 6以藉由該臭氧產生器7 2產生臭氧 (〇3)。受㈣流速將以此產μ臭、氧供應到該處理容 器4内以設定該處理容器4内之一臭氧氣體環境。另外，在 該臭氧氣體環境内加熱該等晶圓w以實行一退火處理。 此時，將該處理壓力設定為〇.丨托〇33 ρ&)至冗托 (10,130 Pa)，而較佳的係〇1托〇33 pa)至⑺托⑴〕川 Pa) ’例如0.3S托⑷Pa)。若該處理壓力低於〇丨托⑴」 Pa) ’則退火效果變得不足。若該處理壓力高於^托 (10，130 Pa)’則臭氧的活性去掉極多。將該處理溫度設定 為500M，200°C ’而較佳的係3〇m，〇〇〇t。若該處理溫 度低於500。。’則退火效果變得不足。若該處理溫度高於 _ u在其熱阻方面受到不利影響。為改良 通量，較佳的係將該退火步驟夕、、w ¢: ^ ^ 1 、人V騍之/皿度设定為與該氧化步驟 之處理溫度相同，4足而排除晶圓溫度增加/減小所需要之 時間。在此具體實施财’例如’該退火步驟之處理溫度 係設定於900。。’此與該氧化步驟之處理溫度相同。 在該退火步驟中，在該處理場5内將臭氧濃度 (〇3/(〇3 +⑽設定為5至20 νο1% (體積百分比)，此係根： 當前臭氧產生器之功能及盥银*拄沾如„ 一退火特性相關的臭氧濃度之成 127295.doc 21 200849391 本效益來決定。但是，一更高的臭氧濃度可進一步改良退 火特性，因此可以使用一（例如約100 v〇1%)之更高濃度。 在此具體實施例中，臭氧流速係設定為0.1至10 slm，而臭 氧濃度（〇3/(〇3 + 〇2))係設定為1〇 vol%。 在该臭氧氣體環境内實行該退火處理之情況下，從該 Si〇2膜移除氫成分，此可能係採取以下方式。明確言之， 氧自由基係藉由分解臭氧而產生並與該Si〇2膜中的氫成分 反應。因此，使得該等氫成分變成〇11及/或出〇，接著從 該膜釋放出OH及/或h20。 <檢查結果> 藉由依據上述第一具體實施例之一膜形成方法形成一 si〇2膜，並對其電性質加以測量及檢查。圖3係顯示一氧 化矽膜之SILC特性與退火的相關性之一曲線圖。如先前所 述而疋義该SILC特性。圖3所示SILC特性表示電荷密度為 5 [C/cm2]之一洩漏電流。 圖3進一步顯示與藉由依據各項比較範例八丨至A4的其他 膜形成方法而形成的Si〇2膜有關之結果。在一比較範例幻 中，藉由乾式氧化形成一 si〇2膜。在一比較範例A2中，藉 由濕式氧化形成一 Si〇2膜。在一比較範例A3中，僅藉由一 氧化處理在圖1所示裝置中（不作臭氧退火）形成一 Si02膜。 在一比較範例A4中，在圖1所示裝置中於_n2氣體環境内 (在1000 c )形成一 si〇2膜並對其進行退火。在一本範例B1 中，藉由依據該第一具體實施例之一方法於一臭氧氣體環 境内（在50(TC)形成一 Si〇2膜並對其進行退火。 127295.doc -22- 200849391 如圖3所示，藉由依據該比較範例A1之乾式氧化形成之 Si02膜呈現約0.3xl(T7(A/cm2)之最大洩漏電流，而因此具 有最差的膜品質。該等比較範例A2至A4呈現約1 x丨0_8 (A/cm2)之洩漏電流，此略小於該比較範例A1之洩漏電流 但其減小得尚不足。特定言之，如該比較範例A4所示，即 使在1000°C實行該退火之情況下，N2氣體環境亦僅呈現一 不足的效果。 另一方面，藉由依據該第一具體實施例之一方法形成的 本範例B 1之Si02膜呈現約0·5χ l(T8(A/cm2)之一更小线漏電 流，因為即便使用一 500°C的較低溫度亦在一臭氧氣體環 境内實行該退火。此洩漏電流遠低於該等比較範例A丨至 A4之該些洩漏電流，因此該膜具有較佳的膜品質。 圖4係顯示一氧化矽膜之TDDB特性與退火的相關性之一 曲線圖。如先前所述而定義該TDDB特性。在此實驗中， CCS(恒定電流應力）係設定為_〇· 1 A/cm2。圖4僅顯示該等 比較範例A3及A4及代表依據該第一具體實施例之一方法 的本範例B 1之結果。 如圖4所示，該等比較範例A3與A4之每一範例呈現一隨 時間明顯減小的閘極電壓Vg(此並非較佳）。另一方面，代 表依據該第一具體實施例之一方法的本範例B丨呈現一隨時 間減小的不太多之閘極電壓Vg，此指示保持良好的膜品 質。換言之，已確認該第一具體實施例可以抑制該閘極電 壓Vg之波動，而因此大大減小電洞截獲量及電子截獲量。 應注意，在本情形下，沒有用於直接測量一膜中的氫成分 127295.doc -23- 200849391 里之方法，但可以藉由該SILC特性或TDDB特性來間接確 認該量，如上所述。 <第二具體實施例> 圖5係顯示依據本發明之第二具體實施例之一垂直熱處 理裝置之結構之一視圖。圖6係顯示藉由依據該第二具體 實施例之一熱處理方法來形成一 Si〇N膜之一處理之一範例 之一流程圖。 圖5所不熱處理裝置具有與圖丨所示熱處理裝置之結構類 似之一結構，但其不同之處在於進一步佈置一氮化氣體供 應官路80以將一氮化氣體供應至該處理容器内。藉由此配 置，此熱處理裝置可用於藉由氮化一 Si〇2膜來形成一 Si〇N 膜，如下所述。 明確言之，該氮化氣體供應管路8〇包括一氮化氣體噴射 喷嘴82，該氮化氣體喷射噴嘴82穿透該歧管16之側壁以使 其末梢端部向該處理容器4之内部開放。 該氮化氣體喷射噴嘴82係連接至一氣體線84，該氣體線 具有一切換閥86與一流速控制器88(例如質量流量控制 器）。據此，按需要，以受控制的流速將該氮化氣體供應 到該處理容器4之底部。 在此具體實施例中，NH3係用作該氮化氣體。但是，該 氮化氣體可以係從*N〇、N20&NH3組成的群組中選擇之 一或多種氣體。 在依據該第二具體實施例之熱處理裝置中，如圖6之流 程圖所示，在該氧化步驟31與退火步驟32之間實行一氮化 127295.doc -24· 200849391 步驟S1-1。明確言之，在步驟81中形成_si〇2膜後，停止 H2氣體及〇2氣體之供應，而以一受控制的流速將該氮化氣 體從該氮化氣體供應管路8 〇供應至該處理場5。結果，藉 由該氮化氣體將形成於該等晶圓W的表面上之一氧化物膜 或Si〇2膜氮化，並由此形成一氮氧化物膜或Si〇N膜。 此時，將該處理壓力設定為1〇〇至760托，例如650托。 將該處理溫度設定為5〇〇至l，2〇(TC。將該氮化氣體之流速 设定為0.1至10 slm。 在藉由上述處理形成該SiON膜後，採取與圖2所示步驟 S2相同之方式實行圖6所示之退火步驟S2以從該SiON膜移 除氮成分。 可以將圖6中步驟S 2中所使用的處理條件（例如處理壓 力、處理溫度及臭氧流速）設定為與參考圖2中步驟S2所述 之該些處理條件相同。但是，圖6中步驟S2中所使用的處 理條件可能不同於圖2中步驟S2之該些處理條件。 而且，在該第二具體實施例中，為改良通量，較佳的係 將該氧化步驟S1、氮化步驟S 1 -1及退火步驟S2之溫度設定 為相同。在此具體實施例中，例如，該氮化步驟及退火步 驟之處理溫度係設定於900°C，此與該氧化步驟之處理溫 度相同。 在該臭氧氣體環境内實行該退火處理之情況下，採取上 面參考一 Si〇2膜所述之方式從該SiON膜移除氫成分。 <檢查結果> 藉由依據上述第二具體實施例之一膜形成方法形成一 127295.doc -25- 200849391The bottom t of the t/ is closed by the cover 26 to hermetically seal the processing container 4, and then the inside of the processing container 4 is subjected to true = exhaust by the vacuum exhaust system 14 to treat the processing field 5 Set at a predetermined processing pressure. The power applied to the heater 38 is additionally increased to heat the wafer W and process % 5 to the processing temperature for the oxidation process. After the temperature of the treatment field $ is again 卩, the 卩 controlled (5) flow rate is required to supply the oxidation step from the oxidizing gas injection nozzle 48 and the reducing gas injection nozzle 5 of the gas supply line U to the treatment field 5, respectively. The predetermined processing gas (ie, the gas and the Hz gas). At this time, ozone has not been supplied. The two gases, such as four and two, react with each other in the vacuum gas % disturbance as they flow upward through the treatment field 5 to generate hydroxyl radicals and oxygen radicals. The hydroxyl radicals and oxygen radicals are brought into contact with the wafer w supported on the rotating wafer boat 18, and the oxidation treatment is directed onto the wafer surface (step si). = 珲 The exhaust gas 匕 6 at the top of the 4 processing vessel 4 is discharged from the processing vessel 4 with the processing gas used thereby and/or the gas produced by the reaction. At this time, the flow rate of the & gas is set to 2 〇〇 to 5, 〇 (10) sccm, for example, 127295.doc -19-200849391 600 seem. The flow rate of the 02 gas is set to 200 to 1 Torr, for example 1,200 sccm. The treatment temperature is set to 5 Torr to i, 2 〇〇 ° C, for example, 900 ° C. The treatment pressure was set to 〇〇2 Torr (2.7 Pa) to 3.0 Torr (400 Pa), for example, 〇35 Torr (46 Pa). Set the processing time to (for example) 1 () minutes. Therefore, the 02 gas and the exhaust gas respectively supplied into the processing container 4 flow upward through the processing field 5 in the processing container 4 in a hot wall state. These gases cause a hydrogen combustion reaction near the wafer W to form a gaseous environment mainly formed by hydrogen radicals (Ο*) and hydroxyl radicals (OH*). The surface of the wafer W is oxidized by the radicals thereby and a Si 2 film is formed thereby. At this time, the generation of radicals was continued as described below. Specifically, when hydrogen and oxygen are supplied to a vacuum gas atmosphere inside the processing vessel 4 in a hot wall state, a hydrogen combustion reaction is caused in the vicinity of the wafers w, which may be as follows. In the following formula, there is a symbol, *,, and one of the chemical elements indicates that it is a radical. H2+〇2->H*+H02 o2+h*->oh*+o* h2+o*-^h*+oh* h2+oh*->h*+h2o as described above, in separate When H2 and 〇2 are supplied to the treatment field 5, 〇* (oxygen radical), 〇h* (hydroxyl radical), and H2 〇 (water vapor) are generated in the treatment of a hydrogen combustion reaction, and Oxidation is induced on the surface of the wafer to form a Si 2 film. At this time, the above radicals 〇* and 〇H* may be mainly used for the oxidation. 127295.doc -20- 200849391 Since hydrogen is used as a reducing gas, the Si 2 film thus formed contains a hydrogen component, which deteriorates certain electrical properties of the film. In view of this problem, a simmering step is then carried out in an ozone gas atmosphere to remove the ammonia component from the membrane (step S2). Specifically, the supply of 〇2 gas and % gas as described above is stopped, and the ozone supply line 46 is operated to generate ozone (〇3) by the ozone generator 7. The (iv) flow rate will supply the odor and oxygen into the processing container 4 to set an ozone gas environment in the processing container 4. Additionally, the wafers w are heated in the ozone gas environment to effect an annealing process. At this time, the treatment pressure is set to 〇.丨 〇 33 ρ &) to redundant (10,130 Pa), and the preferred system 〇1 〇 33 pa) to (7) 托 (1) 〕 川 Pa) 'such as 0.3S (4)Pa). If the treatment pressure is lower than the chin rest (1)" Pa) ', the annealing effect becomes insufficient. If the treatment pressure is higher than ^10 (10,130 Pa)', the activity of ozone is removed much. The treatment temperature is set to 500 M, 200 ° C ' and preferably 3 〇 m, 〇〇〇 t. If the treatment temperature is lower than 500. . 'The annealing effect becomes insufficient. If the treatment temperature is higher than _ u, it is adversely affected in terms of its thermal resistance. In order to improve the flux, it is preferred to set the annealing step, w ¢: ^ ^ 1 , and the V 骒 / dish degree to be the same as the processing temperature of the oxidation step, and eliminate the wafer temperature increase by 4 feet. / Reduce the time required. Here, the processing temperature of the annealing step is set to 900. . This is the same as the processing temperature of the oxidation step. In the annealing step, the ozone concentration (〇3/(〇3 +(10) is set to 5 to 20 νο1% (volume percentage) in the treatment field 5, the radix: the function of the current ozone generator and the silver ** The effect of the ozone concentration associated with an annealing characteristic is 127295.doc 21 200849391. However, a higher ozone concentration can further improve the annealing characteristics, so one can be used (for example, about 100 v〇1%). The higher concentration. In this embodiment, the ozone flow rate is set to 0.1 to 10 slm, and the ozone concentration (〇3/(〇3 + 〇2)) is set to 1 〇 vol%. In the case where the annealing treatment is carried out, the hydrogen component is removed from the Si〇2 film, which may take the following manner. Specifically, the oxygen radical is generated by decomposing ozone and is in the Si〇2 film. The hydrogen component is reacted. Therefore, the hydrogen components are changed to 〇11 and/or yttrium, and then OH and/or h20 are released from the film. <Inspection Result> By a film according to the first specific embodiment described above Forming method to form a si〇2 film, and measuring and checking its electrical properties Fig. 3 is a graph showing the correlation between the SILC characteristics of the hafnium oxide film and the annealing. The SILC characteristics are as described above. The SILC characteristics shown in Fig. 3 indicate a charge density of 5 [C/cm2]. A leakage current. Figure 3 further shows the results associated with the Si〇2 film formed by other film formation methods according to the comparative examples of gossip to A4. In a comparative example, a Si is formed by dry oxidation. 〇2 film. In a comparative example A2, a Si〇2 film was formed by wet oxidation. In a comparative example A3, only one oxidation treatment was performed in the apparatus shown in Fig. 1 (no ozone annealing). Si02 film. In a comparative example A4, a si〇2 film was formed and annealed in a _n2 gas atmosphere (at 1000 c) in the apparatus shown in Fig. 1. In an example B1, by way of One method of the first embodiment is to form a Si〇2 film at 50 (TC) and anneal it in an ozone gas environment. 127295.doc -22- 200849391, as shown in FIG. The SiO 2 film formed by the dry oxidation of Comparative Example A1 exhibited a maximum vent of about 0.3 x 1 (T7 (A/cm 2 )). Leakage current, and thus the worst film quality. These comparative examples A2 to A4 exhibit a leakage current of about 1 x 丨0_8 (A/cm2), which is slightly smaller than the leakage current of the comparative example A1 but which is still reduced. Insufficiently, as shown in the comparative example A4, even in the case where the annealing is performed at 1000 ° C, the N 2 gas environment exhibits only an insufficient effect. On the other hand, according to the first specific embodiment The SiO2 film of this example B1 formed by one method exhibits a smaller line leakage current of about 0. 5 χ l (T8 (A/cm2) because even a lower temperature of 500 ° C is used in an ozone gas environment. This annealing is carried out internally. This leakage current is much lower than the leakage currents of the comparative examples A to A4, so that the film has a better film quality. Fig. 4 is a graph showing the correlation between the TDDB characteristics of the hafnium oxide film and annealing. This TDDB feature is defined as previously described. In this experiment, CCS (constant current stress) was set to _〇·1 A/cm2. Figure 4 shows only the comparison examples A3 and A4 and the results of the present example B 1 representing a method according to one of the first embodiments. As shown in Figure 4, each of these comparative examples A3 and A4 exhibits a gate voltage Vg that is significantly reduced over time (which is not preferred). On the other hand, the present example B, which represents a method according to one of the first embodiment, exhibits a gate voltage Vg which is not reduced too much, which indicates a good film quality. In other words, it has been confirmed that the first embodiment can suppress the fluctuation of the gate voltage Vg, and thus the hole intercept amount and the electron intercept amount are greatly reduced. It should be noted that in this case, there is no method for directly measuring the hydrogen component in a film 127295.doc -23- 200849391, but the amount can be indirectly confirmed by the SILC property or the TDDB property, as described above. <Second Embodiment> Fig. 5 is a view showing a structure of a vertical heat treatment apparatus according to a second embodiment of the present invention. Fig. 6 is a flow chart showing an example of a process of forming a Si〇N film by a heat treatment method according to the second embodiment. The non-heat treatment apparatus of Fig. 5 has a structure similar to that of the heat treatment apparatus shown in Fig. 1, but differs in that a nitriding gas supply path 80 is further disposed to supply a nitriding gas into the processing container. By this configuration, the heat treatment apparatus can be used to form a Si〇N film by nitriding a Si〇2 film as described below. Specifically, the nitriding gas supply line 8A includes a nitriding gas injection nozzle 82 that penetrates the side wall of the manifold 16 to have its distal end toward the inside of the processing container 4. open. The nitriding gas injection nozzle 82 is coupled to a gas line 84 having a switching valve 86 and a flow rate controller 88 (e.g., a mass flow controller). Accordingly, the nitriding gas is supplied to the bottom of the processing vessel 4 at a controlled flow rate as needed. In this embodiment, NH3 is used as the nitriding gas. However, the nitriding gas may be one or more selected from the group consisting of *N〇, N20&NH3. In the heat treatment apparatus according to the second embodiment, as shown in the flow chart of Fig. 6, a nitridation 127295.doc - 24 · 200849391 step S1-1 is carried out between the oxidation step 31 and the annealing step 32. Specifically, after the _si〇2 film is formed in step 81, the supply of the H2 gas and the 〇2 gas is stopped, and the nitriding gas is supplied from the nitriding gas supply line 8 to the controlled flow rate to This processing field is 5. As a result, an oxide film or a Si 2 film formed on the surface of the wafer W is nitrided by the nitriding gas, and thereby an oxynitride film or a Si 〇 N film is formed. At this time, the treatment pressure is set to 1 Torr to 760 Torr, for example, 650 Torr. The treatment temperature is set to 5 Torr to 1,2 Torr (TC. The flow rate of the nitriding gas is set to 0.1 to 10 slm. After the SiON film is formed by the above treatment, the steps shown in FIG. 2 are taken. The annealing step S2 shown in Fig. 6 is carried out in the same manner as in S2 to remove the nitrogen component from the SiON film. The processing conditions (e.g., processing pressure, processing temperature, and ozone flow rate) used in step S2 of Fig. 6 can be set to The processing conditions are the same as those described with reference to step S2 in Fig. 2. However, the processing conditions used in step S2 in Fig. 6 may be different from the processing conditions in step S2 in Fig. 2. Moreover, in the second specific In the embodiment, in order to improve the flux, it is preferred to set the temperature of the oxidation step S1, the nitridation step S 1 -1 and the annealing step S2 to be the same. In this embodiment, for example, the nitridation step and The processing temperature of the annealing step is set at 900 ° C, which is the same as the processing temperature of the oxidation step. In the case where the annealing treatment is carried out in the ozone gas environment, the method described above with reference to a Si 2 film is taken from the The SiON film removes hydrogen components. < Search result > a 127295.doc -25- 200849391 formed by film forming method according to one of the above-described second embodiment
SiON膜，並對其電性質加以測量及檢查。圖7係顯示一氧 化矽膜之TDDB特性與退火的相關性之一曲線圖。在此實 驗中，CCS係設定於A/cm2。 圖7進一步顯示與藉由依據各個比較範例A5至A7的其他 膜形成方法而形成的SiON膜有關之結果。在一比較範例 • A5中’形成一 Si〇N膜並接著讓其在900°C於一 〇2氣體環境 内經叉一重新氧化處理。在一比較範例A6中，在形成一 & Si〇N膜後不實行退火處理。在一比較範例A7中，形成一SiON film and its electrical properties were measured and inspected. Fig. 7 is a graph showing the correlation between the TDDB characteristics of a ruthenium oxide film and annealing. In this experiment, the CCS system was set at A/cm2. Fig. 7 further shows the results relating to the SiON film formed by the other film forming methods according to the respective comparative examples A5 to A7. In a comparative example • A5, a Si〇N film was formed and then subjected to a re-oxidation treatment at 900 ° C in a gas atmosphere of one 〇 2 . In a comparative example A6, no annealing treatment was performed after forming a & Si〇N film. In a comparative example A7, a
Si ON膜而接著於一 &氣體環境内（在9〇〇。〇)對其進行退 火。在一本範例B2中，藉由依據該第二具體實施例之一方 法形成一 SiON膜並接著於一臭氧氣體環境内（在6〇0。〇)對 其進行退火。在一本範例B3中，藉由依據該第二具體實施 例之一方法形成一以〇>^膜並接著於一臭氧氣體環境内（在 900°C )對其進行退火。 如圖7所示，該等比較範例A5至A7之每一範例呈現一隨 時間明顯減小的閘極電壓Vg(此並非較佳）。在此順序中， 該比較範例A5至A7之減小程度更加明顯。另一方面，代 表依據該第二具體實施例之一方法的本範例…及B3之每 * 一範例皆呈現一隨時間減小得不太多之閘極電壓Vg，此指 示保持良好的膜品質。換言之，已確認該第二具體實施例 可以抑制該閘極電壓Vg之波動，而因此大大減小電洞戴獲 置及電子截獲量。與具有一 60(TC退火溫度之本範例62相 比’具有一 900°c退火溫度之本範例B3呈現該閘極電壓Vg 之較小的減小。因此，已確認一較高的退火溫度可以保 127295.doc -26- 200849391 持較佳的膜品質。 <第一與第二具體實施例之共同問題> 在上述具體實施例中，在一臭氧氣體環境内實行該退火 步驟。或者，可以在包含氧化氣體自由基而不包含氫成分 之一氣體環境内實行該退火步驟。此氧化氣體可以係〇2、 NO或Ν〇2氣體。例如，在此情況下，可以藉由us 7,300,885 B2所揭示之一電漿激發機構來產生氧化氣體自The Si ON film is then annealed in a & gas environment (at 9 Torr). In an example B2, a SiON film is formed by one of the methods of the second embodiment and then annealed in an ozone gas atmosphere (at 6 Torr). In a sample B3, a ruthenium film was formed by one of the methods of the second embodiment and then annealed in an ozone gas atmosphere (at 900 ° C). As shown in Fig. 7, each of the comparative examples A5 to A7 exhibits a gate voltage Vg which is significantly reduced over time (this is not preferable). In this order, the degree of reduction of the comparative examples A5 to A7 is more pronounced. On the other hand, each of the examples representing the method according to one of the second embodiments, and each of the examples of B3, exhibits a gate voltage Vg that does not decrease too much over time, indicating good film quality. . In other words, it has been confirmed that the second embodiment can suppress the fluctuation of the gate voltage Vg, thereby greatly reducing the hole wearing and the amount of electron interception. This example B3 having an annealing temperature of 900 °c compared to the present example 62 having a 60 (TC annealing temperature) exhibits a small decrease in the gate voltage Vg. Therefore, it has been confirmed that a higher annealing temperature can be confirmed. 127295.doc -26- 200849391 Holding a better film quality. <Common Problems of First and Second Embodiments> In the above specific embodiment, the annealing step is carried out in an ozone gas atmosphere. The annealing step can be carried out in a gas atmosphere containing one of the oxidizing gas radicals and not containing the hydrogen component. The oxidizing gas can be a gas of 〇2, NO or Ν〇2. For example, in this case, it can be by us 7,300,885 B2 One of the plasma excitation mechanisms disclosed to generate an oxidizing gas from
υ 由基，該案之教導内容係以引用的方式併入於此。此電漿 激發機構包括沿一垂直處理容器之側延伸並配置成成獲得 一射頻電壓供應的一對電極。藉由此電漿激發機構，將該 氧化氣體變成電漿而因此產生氧化自由基。或者，可以使 用所謂的遠端電漿類型之一激發機構，以便藉由使用在該 處理谷外邛而供應到該處理容器内之電漿來產生氧化自 由基。 ’該氧域體係〇2氣體。就此方面 而言’該氧化氣體可以係從由〇2、N2〇、N〇、N〇2及〇3组 成的群組中選擇之—或多種氣體。 在上述具體實施你丨φ # 、也例中该選原氣體係H2氣體。就此方面 而言’該還原氣體可以係從由〜、顧3、叫、犯及重氣 組成的群組中選擇之-❹種氣體。 在該氧化氣體係〇 (參惫 3(六虱）之情況下，該氧化氣體供應管 路42亦可用作_真、氧 乳七、應㊂路，而因此可以從圖1所示埶 處理裝置2中省略嗲*今# & …、 ^严 口"六虱夂應管路46。在該氧化氣體與該 氮化氣體係相同新，“丨 、 丨』札體（例如NO或N〇2)之情況下，該氧化氣 127295.doc •27- 200849391 體供應管路42亦可用作一氮化氣體供應管路，而因此可以 從圖5所示熱處理裝置中省略該氮化氣體供應管路8〇。 在上述具體實施例中，在同一處理容器内實行從該氧化 步驟至該退火步驟之步驟。或者，可以在個別的處理容哭 (處理裝置）中實行此等步驟。氧化目標材料不限於矽，= 其可以係另一半導體材料、氧化物膜或氮氧化物臈。至於The teachings of this case are hereby incorporated by reference. The plasma excitation mechanism includes a pair of electrodes extending along a side of a vertical processing vessel and configured to obtain a supply of radio frequency voltage. By this plasma excitation mechanism, the oxidizing gas is turned into a plasma to thereby generate oxidative radicals. Alternatively, one of the so-called far-end plasma type excitation mechanisms can be used to generate an oxidizing radical by using the plasma supplied to the processing vessel in the processing chamber. 'The oxygen domain system 〇 2 gas. In this regard, the oxidizing gas may be selected from the group consisting of 〇2, N2〇, N〇, N〇2, and 〇3—or a plurality of gases. In the above specific implementation, you 丨φ # , also in the case of the original gas system H2 gas. In this respect, the reducing gas may be selected from the group consisting of ~, Gu 3, calling, guilty and heavy gas. In the case of the oxidizing gas system 惫 (惫 惫 3 (six 虱), the oxidizing gas supply line 42 can also be used as _ true, oxidized milk seven, should be three ways, and thus can be treated from the 埶 shown in FIG. In the device 2, 嗲*今# & ..., 严口" 六虱夂应线46 is omitted. The oxidizing gas is the same as the nitriding gas system, and the 丨, 丨 札 ( (such as NO or N In the case of 〇2), the oxidizing gas 127295.doc • 27- 200849391 body supply line 42 can also be used as a nitriding gas supply line, and thus the nitriding gas can be omitted from the heat treatment apparatus shown in FIG. The supply line 8 is. In the above specific embodiment, the steps from the oxidation step to the annealing step are carried out in the same processing vessel. Alternatively, the steps may be carried out in an individual treatment chamber (processing device). Oxidation The target material is not limited to 矽, = it can be another semiconductor material, oxide film or NOx.
該目標基板，本發明可應用於—玻璃基板、咖基板或陶 甍基板（替代一半導體晶圓）。 熟習此項技術者輕易便可發現額外優點及修改。因此， 本發明在其更廣義態樣並不限於本文所顯示及說明之特定 細=及代表性具體實施例。據此，只要不㈣隨附申請^ 利犯圍及其等效範圍所定義之—般發明概念的精神 疇’即可進行各種修改。 一 【圖式簡單說明】 併入並建構㈣書之—部分的關解說 施例，並且i查π μ、+、 A ^ ^ ^ 細說明= 說明與上文給定具體實施例的詳 '、用來說明本發明之原理。 依據本發明之—第—具时 處理裝置之結構之—視圖； 丈直'，、、 圖2係顯^於藉由依據該第—具 方法來形成_ Sin _ 貝他1夕J之熱處理 圖3係站之一處理之一範例之-流程圖； “不—氧化矽臈之SILC特性與退火的相 曲線圖1係藉由W相關性之一 獲得； /、q弟一八體汽轭例相關聯之一實驗而 127295.doc -28- 200849391 圖4係顯示一氧化矽膜之TDDB特性與退火的相關性之一 曲線圖’其係藉由與該第一具體實施例相關聯之一實驗而 獲得； 圖5係顯示依據本發明之一第二具體實施例的一垂直熱 處理裝置之結構之一視圖； 圖6係顯示用於藉由依據該第二具體實施例之一熱處理 方法來形成一 SiON膜之一處理之一範例之〆流程圖，以及 .Lg關性之 圖7係顯示一氮氧化石夕膜之TDDB特性與退火、 『 幺 實^ 一曲線圖，其係藉由與該第二具體實施例相關恥之 而獲得。 【主要元件符號說明】 2 處理裝置 4 垂直處理容器 5 處理場 6 排氣埠 8 排氣線 10 壓力控制閥 12 真空幫浦 14 真空排氣系統 16 歧管 18 晶圓舟 20 密封部件 22 絕熱圓柱 24 台面 127295.doc 200849391 Γ: 26 蓋子 28 旋轉軸 30 磁性流體密封件 32 密封部件 34 升降機構 36 臂 38 圓柱形歧管/碳線路加熱器 40 絕熱外殼 42 氧化氣體供應管路 44 還原氣體供應管路 46 臭氧供應管路 48 氧化氣體喷射喷嘴 50 還原氣體喷射喷嘴 52 氣體線 54 氣體線 56 切換閥 58 切換閥 60 流速控制器 62 流速控制器 64 臭氧喷射喷嘴 66 氣體線 68 切換閥 70 流速控制器 72 臭氧產生器 127295.doc -30- 200849391 74 控制器 76 儲存區段 80 氮化氣體供應管路 82 氮化氣體喷射喷嘴 84 氣體線 86 切換閥 88 流速控制器 W 半導體晶圓 127295.doc -31 -The target substrate can be applied to a glass substrate, a coffee substrate or a ceramic substrate (instead of a semiconductor wafer). Those skilled in the art will readily discover additional advantages and modifications. Therefore, the invention in its broader aspects is not limited to the specific details Accordingly, various modifications may be made without the application of the invention and the spirit of the invention. [Simplified description of the schema] Incorporate and construct (4) the part of the book to explain the example, and i check π μ, +, A ^ ^ ^ Detailed description = Description and detailed description of the specific embodiment given above, Used to illustrate the principles of the invention. According to the present invention, the structure of the first-time processing device is viewed as a view; the straightening ',, and FIG. 2 are formed by heat treatment according to the first method to form a heat treatment pattern of _Sin_beta One of the system stations handles one of the examples - the flow chart; "The phase curve of the SILC characteristics of the non-cerium oxide and the annealing phase 1 is obtained by one of the W correlations; /, the q brothers are related to the gas yoke case One experiment and 127295.doc -28- 200849391 Figure 4 is a graph showing the correlation between the TDDB characteristics of the hafnium oxide film and annealing, which is performed by an experiment associated with the first embodiment. Figure 5 is a view showing the structure of a vertical heat treatment apparatus according to a second embodiment of the present invention; Figure 6 is a view showing the formation of a SiON by a heat treatment method according to the second embodiment. One example of the treatment of one of the membranes, and the diagram of the .Lg diagram, shows that the TDDB characteristics of the nitrous oxide film and the annealing, 幺 ^ ^ ^ a graph, by the second The specific embodiment is obtained with shame. [Main component symbol description 】 2 treatment unit 4 vertical processing container 5 treatment field 6 exhaust 埠 8 exhaust line 10 pressure control valve 12 vacuum pump 14 vacuum exhaust system 16 manifold 18 wafer boat 20 sealing parts 22 insulated cylinder 24 table 127295.doc 200849391 Γ: 26 Cover 28 Rotary shaft 30 Magnetic fluid seal 32 Sealing member 34 Lifting mechanism 36 Arm 38 Cylindrical manifold/carbon line heater 40 Insulating housing 42 Oxidizing gas supply line 44 Reduction gas supply line 46 Ozone supply tube Road 48 Oxidizing gas injection nozzle 50 Reduction gas injection nozzle 52 Gas line 54 Gas line 56 Switching valve 58 Switching valve 60 Flow rate controller 62 Flow rate controller 64 Ozone injection nozzle 66 Gas line 68 Switching valve 70 Flow rate controller 72 Ozone generator 127295 .doc -30- 200849391 74 Controller 76 Storage Section 80 Nitriding Gas Supply Line 82 Nitriding Gas Injection Nozzle 84 Gas Line 86 Switching Valve 88 Flow Rate Controller W Semiconductor Wafer 127295.doc -31 -
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|---|---|---|---|---|
| JP2000211998A (en) * | 1999-01-25 | 2000-08-02 | Angstrom Technology Partnership | Oxidation of silicon and production of single crystal silicon oxide film using the same |
| CN100372076C (en) * | 2000-12-05 | 2008-02-27 | 东京毅力科创株式会社 | Treatment method and apparatus of substrate |
| JP4030858B2 (en) * | 2002-10-30 | 2008-01-09 | 東京エレクトロン株式会社 | Heat treatment apparatus and heat treatment method |
| JP4609098B2 (en) * | 2004-03-24 | 2011-01-12 | 東京エレクトロン株式会社 | Process for oxidizing object, oxidation apparatus and storage medium |
| US8119210B2 (en) * | 2004-05-21 | 2012-02-21 | Applied Materials, Inc. | Formation of a silicon oxynitride layer on a high-k dielectric material |
-
2007
- 2007-12-05 JP JP2007315255A patent/JP4386132B2/en not_active Expired - Fee Related
-
2008
- 2008-02-13 KR KR1020080012970A patent/KR101201652B1/en not_active IP Right Cessation
- 2008-02-14 CN CN2008100951139A patent/CN101256957B/en not_active Expired - Fee Related
- 2008-02-14 TW TW097105221A patent/TWI423332B/en not_active IP Right Cessation
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2012
- 2012-03-12 KR KR1020120024990A patent/KR101232970B1/en not_active IP Right Cessation
Also Published As
| Publication number | Publication date |
|---|---|
| TWI423332B (en) | 2014-01-11 |
| JP4386132B2 (en) | 2009-12-16 |
| JP2008227454A (en) | 2008-09-25 |
| CN101256957B (en) | 2011-09-07 |
| KR20080076766A (en) | 2008-08-20 |
| CN101256957A (en) | 2008-09-03 |
| KR20120031290A (en) | 2012-04-02 |
| KR101232970B1 (en) | 2013-02-13 |
| KR101201652B1 (en) | 2012-11-14 |
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