TWI255256B - Method and apparatus for oxidizing a nitride film - Google Patents
Method and apparatus for oxidizing a nitride film Download PDFInfo
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- TWI255256B TWI255256B TW092136907A TW92136907A TWI255256B TW I255256 B TWI255256 B TW I255256B TW 092136907 A TW092136907 A TW 092136907A TW 92136907 A TW92136907 A TW 92136907A TW I255256 B TWI255256 B TW I255256B
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- conductive
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- nitride layer
- nitride
- conductive substrate
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- 150000004767 nitrides Chemical class 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims abstract description 34
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 13
- 239000000523 sample Substances 0.000 claims abstract description 52
- 239000000758 substrate Substances 0.000 claims abstract description 37
- 229910052751 metal Inorganic materials 0.000 claims description 16
- 239000002184 metal Substances 0.000 claims description 16
- 230000003647 oxidation Effects 0.000 claims description 16
- 238000007254 oxidation reaction Methods 0.000 claims description 16
- 239000004020 conductor Substances 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 10
- 229910001218 Gallium arsenide Inorganic materials 0.000 claims description 9
- 239000013307 optical fiber Substances 0.000 claims description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 7
- 239000004065 semiconductor Substances 0.000 claims description 7
- -1 ITO) Chemical compound 0.000 claims description 6
- 229910000673 Indium arsenide Inorganic materials 0.000 claims description 6
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 6
- 229910052738 indium Inorganic materials 0.000 claims description 6
- RPQDHPTXJYYUPQ-UHFFFAOYSA-N indium arsenide Chemical compound [In]#[As] RPQDHPTXJYYUPQ-UHFFFAOYSA-N 0.000 claims description 6
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 claims description 6
- 239000004575 stone Substances 0.000 claims description 6
- 229910052721 tungsten Inorganic materials 0.000 claims description 6
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 229910052736 halogen Inorganic materials 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- 238000010079 rubber tapping Methods 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910000980 Aluminium gallium arsenide Inorganic materials 0.000 claims description 3
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 claims description 3
- 229910000530 Gallium indium arsenide Inorganic materials 0.000 claims description 3
- 229910005987 Ge3N4 Inorganic materials 0.000 claims description 3
- 229910000577 Silicon-germanium Inorganic materials 0.000 claims description 3
- 229910045601 alloy Inorganic materials 0.000 claims description 3
- 239000000956 alloy Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052805 deuterium Inorganic materials 0.000 claims description 3
- 229910003460 diamond Inorganic materials 0.000 claims description 3
- 239000010432 diamond Substances 0.000 claims description 3
- 229910003437 indium oxide Inorganic materials 0.000 claims description 3
- 229910052741 iridium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052753 mercury Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- SBIBMFFZSBJNJF-UHFFFAOYSA-N selenium;zinc Chemical compound [Se]=[Zn] SBIBMFFZSBJNJF-UHFFFAOYSA-N 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052724 xenon Inorganic materials 0.000 claims description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 230000005284 excitation Effects 0.000 claims 1
- 229910052735 hafnium Inorganic materials 0.000 claims 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 claims 1
- 238000007747 plating Methods 0.000 claims 1
- 230000001678 irradiating effect Effects 0.000 abstract 1
- 239000010408 film Substances 0.000 description 35
- 230000003287 optical effect Effects 0.000 description 14
- 238000005286 illumination Methods 0.000 description 10
- 229910002601 GaN Inorganic materials 0.000 description 6
- 230000005684 electric field Effects 0.000 description 4
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910017083 AlN Inorganic materials 0.000 description 2
- PIGFYZPCRLYGLF-UHFFFAOYSA-N Aluminum nitride Chemical compound [Al]#N PIGFYZPCRLYGLF-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910001195 gallium oxide Inorganic materials 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
- 239000002784 hot electron Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000001443 photoexcitation Effects 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000263 scanning probe lithography Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 238000001039 wet etching 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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
- H01L21/76822—Modification of the material of dielectric layers, e.g. grading, after-treatment to improve the stability of the layers, to increase their density etc.
- H01L21/76825—Modification of the material of dielectric layers, e.g. grading, after-treatment to improve the stability of the layers, to increase their density etc. by exposing the layer to particle radiation, e.g. ion implantation, irradiation with UV light or electrons etc.
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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
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76801—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing
- H01L21/76829—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the dielectrics, e.g. smoothing characterised by the formation of thin functional dielectric layers, e.g. dielectric etch-stop, barrier, capping or liner layers
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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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/02227—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process
- H01L21/0223—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate
- H01L21/02233—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate of the semiconductor substrate or a semiconductor layer
- H01L21/02241—III-V semiconductor
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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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02225—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer
- H01L21/02227—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process
- H01L21/0223—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate
- H01L21/02244—Forming insulating materials on a substrate characterised by the process for the formation of the insulating layer formation by a process other than a deposition process formation by oxidation, e.g. oxidation of the substrate of a metallic layer
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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
- H01L21/02104—Forming layers
- H01L21/02107—Forming insulating materials on a substrate
- H01L21/02296—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer
- H01L21/02318—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment
- H01L21/02321—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment introduction of substances into an already existing insulating layer
- H01L21/02323—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment introduction of substances into an already existing insulating layer introduction of oxygen
- H01L21/02326—Forming insulating materials on a substrate characterised by the treatment performed before or after the formation of the layer post-treatment introduction of substances into an already existing insulating layer introduction of oxygen into a nitride layer, e.g. changing SiN to SiON
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/314—Inorganic layers
- H01L21/3143—Inorganic layers composed of alternated layers or of mixtures of nitrides and oxides or of oxinitrides, e.g. formation of oxinitride by oxidation of nitride layers
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- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Plasma & Fusion (AREA)
- Chemical Vapour Deposition (AREA)
- Weting (AREA)
- Led Devices (AREA)
Description
1255256 玖、發明說明: 【發明所屬之技術領域】 本發明係關於一種氧化氮化物的方法與裝置,尤指一 種適用於形成奈米圖樣(Pattern)結構之氧化氮化物的方法 5 與裝置。 【先前技術】 、氮化物因具有優良之介電性質,已成為半導體元件中 非系重要之材料。另一方面,氮化物對酸鹼具有抗腐钱特 1〇性,故$被用來作為製作微結構時之遮罩(Mask)材料。此 外、’,氮化物因具有優良之光學性f,近年來亦已成為重要 之光學材料之一。例如,氮化矽(Silicon nitdde,Si3N4)可 作為半導體元件之絕緣層,也是CM〇s製程中常用之遮罩 層(Mask layer),氮化紹(Aluminum nitride,A1N)是半導體 15元件重要之絕緣層,亦被用來作為導熱層,或應用於紫外 光(UV)感測器。一些相關且重要的化合物能隙(B抓d㈢邛 energy,A)如下:InN (19eV),GaN (3 4eV),ain (6 2eV), BN(7.5eV) ’ Si3N4 (5.1eV),InP (l.35eV),GaP (2.26eV), A1P (2.45eV),BP (2eV),InAs (0.36eV),GaAs (1.43eV), 20 AlAs (2.16eV)。 氮化物薄膜有豐富之潛在應用,但由於其具有非常穩 疋之化學性質,因此不易在上面蝕刻出微結構。另外,其 氧化速度極低,當欲對其氧化或轉質以供後續其他應用 日才,往往需要相當繁複的程序,造成加工困難。例如,習 1255256 知需要在1100 °C的高溫下將氮化石夕濕氧化(Wet thermal oxidation) ’才能將其轉化為氧化梦(Silicon oxide,Si〇2) [T. Enomoto, R. Ando, H. Morita, an(i H. Nakayama, Jpn. J. Appl· Phys· Vol· 17, p· 1049 (1978)] ° 另外,氮化鎵與炙熱 5 乾燥空氣反應需達900°C高溢方能緩慢地轉化為氧化鎵 (Gallium oxide,Ga203) [S. D· Wolter,et al,Αρρι· PhyS· Lett. Vol.70, ρ·2156 (1997)]。然而’上述加熱方法又會使 氮化物薄膜中的氮原子分解,因而導致薄膜劣化[C. b
Vartuli et al.,J. Vac· Sci· Technol· B 14, ρ· 3523 (1996)]。 10另外’習知以電解極氧化方法將氧化之速度又過 於緩慢[Τ· B· Tripp, J· Electrochem· s〇c· v〇1117, p 157 (1970)]。 美國專利US 6,190,508揭露以光昭強 —aN之氧化,但其薄膜氧化範圍= 15合光學微影#刻’否則無法被用來製作微米與奈米尺寸精 細之結構。另有研究揭露以掃描探針微影(Scanning pr〇be Hthography)方法在室溫下僅以5V電壓即可將導電基材上 之氮化矽薄膜氧化成為氧化矽[F. S.-S. Chien,etaL,Appl Phys· Lett·,ν〇1·76, Νο·3, ρ·360 (2000)]。該氧化線寬度可 20以小方;1 〇〇奈米’吾人可以再運用氣化石夕與氧化石夕對酸 驗截然不同之钱刻選擇比,在基材(Substrate)上形成小於 100奈米之南深寬比結構。換言之,可以直接寫出(Direct writing)所欲之結構圖樣(Pattern),而不需要使用光罩 (Photomask),可大幅降低製作奈米結構之費用。不過,雖 25 然此方法可以在室溫下將氣化物薄膜氧化,但因為隨著气^ 1255256 9加電场逐漸被阻隔,電子 應停止,佶搵气儿此h r 电卞机動文阻,化學反 不利於大部分之實際應用。 们示水以内,因此 5 10 15 【發明内容】 法,^發明之主要目的係在提供—種氧化氮化物的方 / ㈣速地局部氧化氮化物,增 亚降低製作奈米圖樣結構之成本。 之减厂子度’ 置,俾本^Λ之主要目的係在提供—種氧化氮化物的裝 納::,广地局部氧化氮化物,增加氮化物之氧化厚度, 亚卩牛低衣作奈米圖樣結構之成本。 • f達成上述目的,本發明氧化氮化物的方法,其包 提供—形成於—導電基板上之氮化物層;以—光源= ^亥^化物層,同時以—導電探針接近該氮化物層;以及' 於該導電基板與該導電探針間施加一偏壓。 為達成上述目的,本發明氧化氮化物的方法,其包 括、·提供—形成於一導電基板上之氮化物層;將一表面二 有笔材料之光纖接近該氮化物層,而以該光纖之導光提 供’放發該氮化物層之能量’·以及於該導電基板與該導電材 料間施加一偏壓,以控制該氮化物層之氧化範圍。 為達成上述目的’本發明氧化氮化物的裝置,其包 括 形成於一導電基板上之氮化物層;一光源,位於爷 導電基板之一側,用以提供激發氮化物之能量;一導電探 針’接近於該氮化物層之表面,用以控制該氮化物層之氧 20 1255256 化範圍;以及一偏壓,施加於該導電基板與該導電探針之 間。 為達成上述目的,本發明氧化氮化物的裝置,其包 括:一形成於一導電基板上之氮化物層;一表面鍍有導電 5 材料之光纖,其接近於該氮化物層之表面,用其導光提供 激發氮化物之能量;以及一偏壓,施加於該導電基板與該 導電材料之間,以控制該氮化物層之氧化範圍。 【實施方式】 10 本發明氧化氮化物的方法與裝置中,該氮化物層之材 質可為任何習用之氮化物,較佳為Si3N4、氮氧化矽、 Ge3N4、TiN、BN、AIN、GaN、InN、InGaN、InAIN、或 AlInGaN。本發明氧化氮化物的方法與裝置中,該導電基 板之材質可為任何習用於製作基板之導電材質,較佳為p 15 型或 η型石夕晶圓、Ge、SiGe、InN、GaN、GaAs、InP、GaP、 A1P、InAs、AlAs、AlGaAs、InGaAs、ZnSe、In2〇3:Sn (Tin-doped Indium oxide,ITO)、Zn〇:F、Zn〇:B、Sn02:F、 ZnSn〇3、Zn2Sn〇4、TiN、Cd2Sn04、Zn〇:Al、Zn〇:Ga、 Zn〇:In 、Ti、V、Cr、Mn、Fe、Co、Ni、Cu、Au、Zr、 20 Nb、Mo、Rh、Ag、In、Se、Hf、Ta、W、Ir、Pt、Au、或 上述金屬之合金。本發明氧化氮化物的方法與裝置中,該 光源之種類無限制,較佳為_素燈(Halogen lamp,254 nm)、Nd-YAG(1064nm,1320nm,532nm,354nm,66nm)、 XeCl (308 nm)、XeF (351 nm)、KrCl (222nm)、KrF (248 1255256 nm)、ArF (193 nm)、F2 (157 nm)、HeCd (325-441nm)、 (337nm,428nm)、Ar (514.5nm)、H2(110-162nm)、Dye laser (400-800nm)、GaAs/GaAlAs (708-905nm)、HeNe (632nm)、 高壓水 I艮燈(High-pressure mercury lamp)、Deuterium 燈、 5 或Xenon燈。本發明氧化氮化物的方法與裝置中,該導電 探針可為任何習用之導電探針,較佳為高摻雜 (Heavily-doped)石夕探針、類鑽石探針、鎢探針、或錄有導 電金屬之探針。本發明氧化氮化物的方法中,該導電探針 接近該氣化物層之模式較佳為接觸模式(Contact mode)、半 10 接觸模式(Intermittent contact mode)或敲擊模式(Tapping mode)。本發明氧化氮化物的方法與裝置中,該導電探針 接近該氮化物層之方法無限制,較佳為使用一微致動器使 該導電探針接近該氮化物層。本發明氧化氮化物的方法與 裝置尚可應用於鱗化物、石申化物、金屬或半導體之氧化, 15 較佳地本發明氧化氮化物的方法可應用於氧化Inp、GaP、 A1P、和BP等石粦化物;InAs、GaAs、和AlAs等石申化物;以 及A卜Ti、和Zr等金屬;以及Si等半導體。本發明氧化氮 化物的方法與裝置中,鍍於該光纖表面之該導電材料,其 材質可為任何習用之導電材料,較佳為導電金屬、摻雜鑽 20 石(doped diamond)、WC2、或摻雜之氮化物(doped nitrides)。 為能讓貴番查委貝能更瞭解本發明之技術内容,特 舉氧化氮化物的方法與裝置較佳具體實施例說明如下。 實施例1 1255256 如圖1所示,於p型矽晶圓10上以化學氣象沉積(CVD) 成長厚度約3-1 5奈米之氮化物薄膜20。接著,將具有氮化 物薄膜20之p型矽晶圓10水平安置於樣本台,樣本台與p型 矽晶圓10間為互為導電。另外,使光源30,如鹵素燈 5 (Halogen lamp)發出之254nm UV光投射至氮化物薄膜20上 方。若光線波長能滿足下式 hv > Eg 其中/z為Plank constant,i/為光線頻率,為氮化鎵能 隙(Energy gap),則氮化鎵中電子被激發,使得電子由價帶 10 遷移至傳導帶(Conductive band)之機率增加,意即熱電子/ 電洞(Hot electrons/holes)之形成機率增力口。即使若光照波 長未即刻充分滿足上式’熱電子/電洞未即刻產生’但若有 其他注入能量,或能隙因外加強電場而降低,電子遷移之 機率亦大於未照射光線之狀況。可視需要裝設光學裝置 15 40,以調整光線照射在氮化物薄膜20之面積,以遂行調整 光照度。一般使照度在10mW/cm2或以上。之後,以導電探 針50接近氮化物薄膜20,導電探針50可為原子力顯微鏡 (Atomic force microscope, AFM)所用之高摻雜 (Heavily-doped)石夕探針、類鑽石探針或鍍有導電金屬之探 20 針、或掃描穿隧電流顯微鏡 (Scanning tunneling microscope,STM)所用之鶴探針。使導電探針50接近氮化 物薄膜20之裝置為AFM、或其他微致動器。較佳方式為使 用原子力顯微鏡將原子力顯微鏡探針以接觸模式(Contact mode)、半接觸模式(Intermittent contact mode)或敲擊模 10 Ϊ255256 式(Tapping m〇de)與氮化物薄膜2〇相鄰近。導電探針5〇 與氮化物薄膜20接觸位置位於照射光之光照範圍6〇内。在 大氣環i兄下,氮化物溥膜20上方吸附有水膜,導電探針5 〇 針接近氮化物薄膜20後,兩者間自然形成水橋。施加不同 5偏壓V於導電探針50與p型矽晶圓1〇之間,p型矽晶圓1〇為 回包位$包探針5 0為低電位,較佳為使偏壓與光線波長 滿足# + 。於是,氧化物21產生於氮化物薄膜2〇與 導電楝針50之間。不同電壓可獲致不同高度之氧化物。另 方式,對特定電壓,改變不同之偏壓施加時間,可獲致 10 不同高度之氧化物。 實施例2 本實施例大致上與實施例1相同,惟不同之處在於當 基板100為可透光基板時,可將光源15〇置於基板1〇〇下方, 光源150發出之光同樣經由具有快門或遮光板(shutte〇的 15光學裝置11〇控制光線是否投射至氮化物薄膜120,或控制 光線投射至氮化物薄膜12〇之時間長度;或光學鏡片組,可 控制光照能量。使偏壓與光線波長滿足# + 則可 於氮化物薄膜120與探針130之間產生氧化物14〇,且不同的 光波長、光照時間、照度可獲致不同高度之氧化物。 20 貫施例3 將光纖製成探針(例如近場光學顯微鏡_Scanning fidd optical rmcm)SC()pe,SN〇M_所用之探針),並在針間末端鍍 上電材料’例如導電金屬、doped diani〇nd、WC2、doped mtndes),如圖3所示,光纖2〇〇上面鍍有導電材料2i〇。 1255256 10 15 20 =者’將光纖2GG接近氮化物薄膜22Q,並以接觸模式、 +接觸模式或敲擊模式相鄰近。施加偏壓v於導電材料 10與基板230之間,基板23〇為高電位,導電材料21〇 =低電位’偏壓V值小於能使薄膜發生氧化之最小臨界電 全V〇。光源240發出之光經過光學裝置25〇後,進入光纖 2 1 〇。光學裝置250具有快門或遮光板(Shimer),可控制光 $是否投射至氮化物薄膜22G,或控制投射至氮化物薄膜 0之時間長度;或光學元件,可控制光照能量。光學裝 置250可调整光線照射在氮化物薄膜之照度。較佳實 施方式為使偏壓與光線波長滿足eF + Av>~,於是可二^ 化物薄膜220與光纖㈣之間產生氧化物。不同光波 長、光照時間、照度可獲致不同高度之氧化物。 在上述實施例中,於基板上方之氮化物製成氧化物後, 可近一步以選擇性姓刻方式製成精細結構。例如,以HF 將氧化物濕银刻去除’後續以氮化物作為遮罩,或以带將 將氧化物薄膜乾刻去除,㈣以氧化物作為遮罩。= 方面,可用h3p〇4將氮化物薄膜濕钱刻去除,後續以氧化 物作為遮罩,或以電漿將氮化物薄膜乾姓刻去除,後續以 氧化物作為遮罩。最後,以上述結構做遮罩,對基材進 运擇性钱刻,加大深寬比。蝕刻劑可為k〇h、或EDp (Ethylene Diamine Pyrocatechol) . TMah (Tetra.methyl
Amm刪mHydroxlde)等,或以電裝將基材乾钮刻钱入。 本發明運用光照射激發氮化物薄膜電子,並使+ 探針在氮化物薄膜上方產生集中電場。吸收光子能量之車 : 12 1255256 高動能電子於是由價帶(Valence band)遷移至傳導帶 (Conductive band),電子在探針上與氫離子反應,電場與 電洞則協助探針附近之氮化物與氫氧離子化學反應,故受 光激發產生之電子與電洞可加快局部氧化之進行,並增加 5 氧化物厚度。 上述實施例僅係為了方便說明而舉例而已,本發明所 主張之權利範圍自應以申請專利範圍所述為準,而非僅限 於上述貫施例。 10【圖式簡單說明】 圖1係本發明一較佳實施例之氧化氮化物的裝置示意圖。 圖2係本發明—較佳實施例之氧化氮化物的裝置示意圖。 圖3係本發明-較佳實施例之氧化氮化物的裝置示意圖。 20 氮化物薄膜 21 40 光學裝置 50 110 光學裝置 120 140 氣化物 150 210 導電材料 220 240 光源 250 15【圖號說明】 10 P型矽晶圓 3〇 光源 60 光照範圍 10 0基板 130探針 2 〇 〇光纖 230基板 260氧化物 氧化物 導電探針 泰 氮化物薄膜 光源 氮化物薄膜 光學裝置 13
Claims (1)
1255256 拾、申請專利範圍: 1. 一種氧化氮化物的方法,其包括: 提供一形成於一導電基板上之氮化物層; 以一光源照射該氮化物層,同時以一導電探針接近該 5 氮化物層;以及 於該導電基板與該導電探針間施加一偏壓。
2 ·如申請專利範圍第1項所述之氧化氮化物的方法, 其中該氮化物層之材質為Si3N4、氮氧化矽、Ge3N4、TiN、 BN、AIN、GaN、InN、InGaN、InAIN、或 AlInGaN。 10 3 ·如申請專利範圍第1項所述之氧化氮化物的方法,
其中該導電基板之材質為p型或η型石夕晶圓、Ge、SiGe、 InN、GaN、GaAs、InP、GaP、A1P、InAs、AlAs、AlGaAs、 InGaAs、ZnSe、In2〇3:Sn (Tin-doped Indium oxide,ITO)、 ZnO:F、ZnO:B、Sn02:F、ZnSn03、Zn2Sn〇4、TiN、Cd2Sn04、 15 ZnO:Al、ZnO:Ga、ZnO:In 、Ti、V、Cr、Mn、Fe、Co、 Ni、Cu、Au、Zr、Nb、Mo、Rh、Ag、In、Se、Hf、Ta、 W、Ir、Pt、Au、或上述金屬之合金。 4.如申請專利範圍第1項所述之氧化氮化物的方法, 其中該光源為il素燈(Halogen lamp,254 nm)、 20 Nd-YAG(1064nm,1320nm,532nm,354nm,66nm)、XeCl (308 nm)、XeF (351 nm)、KrCl (222nm)、KrF (248 nm)、ArF (193 nm)、F2 (157 nm)、HeCd (325-441nm)、N2 (337nm,428nm)、 Ar (514.5nm)、H2(110-162nm)、Dye laser (400-800nm)、 14 1255256 GaAs/GaAlAs (708-905nm)、HeNe (632nm)、高壓水銀燈 (High-pressure mercury lamp)、Deuterium 燈、或 Xenon燈。 5. 如申請專利範圍第1項所述之氧化氮化物的方法, 其中該導電探針為高摻雜(Heavily-doped)石夕探針、類鑽 5 石探針、鎢探針、或鍍有導電金屬之探針。 6. 如申請專利範圍第1項所述之氧化氮化物的方法, 其中該導電探針接近該氮化物層之模式為接觸模式 (Contact mode)、半接觸模式(Intermittent contact mode)或 敲擊模式(Tapping mode)。 10 7.如申請專利範圍第1項所述之氧化氮化物的方法, 其係使用一微致動器使該導電探針接近該氮化物層。 8. 如申請專利範圍第1項所述之氧化氮化物的方法, 其尚可應用於磷化物、砷化物、金屬或半導體之氧化。 9. 如申請專利範圍第8項所述之氧化氮化物的方法, 15 其中該磷化物包含InP、GaP、A1P、和BP ;該砷化物包含 InAs、GaAs、和 AlAs ;該金屬包含 Al、Ti、和 Zr。 10. —種氧化氮化物的方法,其包括: 提供一形成於一導電基板上之氮化物層; 將一表面鍍有導電材料之光纖接近該氮化物層,而以 20 該光纖之導光提供激發該氮化物層之能量;以及 於該導電基板與該導電材料間施加' ^以控制該 氮化物層之氧化範圍。 1255256 11. 如申請專利範圍第10項所述之氧化氮化物的方 法,其中該導電材料為導電金屬、摻雜鑽石(doped diamond)、WC2、或摻雜之氮化物(doped nitrides) 〇 12. —種氧化氮化物的裝置,其包括: 5 一形成於一導電基板上之氮化物層; 一光源,位於該導電基板之一側,用以提供激發氮化 物之能量; 一導電探針,接近於該氮化物層之表面,用以控制該 氮化物層之氧化範圍;以及 10 一偏壓,施加於該導電基板與該導電探針之間。 13. 如申請專利範圍第12項所述之氧化氮化物的裝 置,其中該導電基板之材質為p型或η型矽晶圓、Ge、SiGe、 InN、GaN、GaAs、InP、GaP、A1P、InAs、AlAs、AlGaAs、 InGaAs、ZnSe、In2〇3:Sn (Tin-doped Indium oxide,IT〇)、 15 Zn〇:F、Zn〇:B、Sn〇2:F、ZnSn03、Zn2Sn〇4、TiN、Cd2Sn〇4、 Zn〇:Al、Zn〇:Ga、ZnO:In 、Ti、V、Cr、Mn、Fe、Co、 Ni、Cu、Au、Zr、Nb、Mo、Rh、Ag、In、Se、Hf、Ta、 W、Ir、Pt、An、或上述金屬之合金。 14. 如申請專利範圍第12項所述之氧化氮化物的裝 20 置,其中該氮化物層之材質為Si3N4、氮氧化矽、Ge3N4、 TiN、BN、AIN、GaN、InN、InGaN、InAIN、或 AlInGaN。 15. 如申請專利範圍第12項所述之氧化氮化物的裝 置,其中該光源為鹵素燈(Halogen lamp,254 nm)、 Nd-YAG( 1064nm,1 320nm,532nm,354nm,66nm)、XeCl (308 16 1255256 nm)、XeF (351 nm)、KrCl (222nm)、KrF (248 nm)、ArF (193 nm)、F2 (157 nm)、HeCd (325-441nm)、N2 (337nm,428nm)、 Ar (5 14.5nm)、H2(l l〇-162nm)、Dye laser (400-800nm)、 GaAs/GaAlAs (708-905nm)、HeNe. (632nm)、高壓水銀燈 5 (High-pressure mercury lamp)、Deuterium 燈、或 Xenon燈。 16. 如申請專利範圍第12項所述之氧化氮化物的裝 置,其中該導電探針為高摻雜(Heavily-doped)碎探針、類 鑽石探針、鎢探針、或鍍有導電金屬之探針。 17. 如申請專利範圍第12項所述之氧化氮化物的裝 10 置,其中該導電探針亦可提供激發氮化物之能量。 18. 如申請專利範圍第12項所述之氧化氮化物的裝 置,其尚可應用於磷化物、砷化物、金屬或半導體之氧化。 19. 一種氧化氮化物的裝置,其包括: 一形成於一導電基板上之氮化物層; 15 一表面鍍有導電材料之光纖,其接近於該氮化物層之 表面,用其導光提供激發氮化物之能量;以及 一偏壓,施加於該導電基板與該導電材料之間,以控 制該氮化物層之氧化範圍。 20. 如申請專利範圍第19項所述之氧化氮化物的裝 20 置,其中該導電材料為導電金屬、摻雜鑽石(doped diamond)、WC2、或摻雜之氮化物(doped nitrides)。
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