TW492081B - Dopant pastes for the production of p, p+ and n, n+ regions in semiconductors - Google Patents
Dopant pastes for the production of p, p+ and n, n+ regions in semiconductors Download PDFInfo
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- TW492081B TW492081B TW089104087A TW89104087A TW492081B TW 492081 B TW492081 B TW 492081B TW 089104087 A TW089104087 A TW 089104087A TW 89104087 A TW89104087 A TW 89104087A TW 492081 B TW492081 B TW 492081B
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Classifications
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- 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
- H01L21/24—Alloying of impurity materials, e.g. doping materials, electrode materials, with a semiconductor body
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- H—ELECTRICITY
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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
- H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
- H01L21/225—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities using diffusion into or out of a solid from or into a solid phase, e.g. a doped oxide layer
- H01L21/2251—Diffusion into or out of group IV semiconductors
- H01L21/2254—Diffusion into or out of group IV semiconductors from or through or into an applied layer, e.g. photoresist, nitrides
- H01L21/2255—Diffusion into or out of group IV semiconductors from or through or into an applied layer, e.g. photoresist, nitrides the applied layer comprising oxides only, e.g. P2O5, PSG, H3BO3, doped oxides
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D183/00—Coating compositions based on macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon, with or without sulfur, nitrogen, oxygen, or carbon only; Coating compositions based on derivatives of such polymers
- C09D183/02—Polysilicates
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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
- H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
- H01L21/2225—Diffusion sources
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- H—ELECTRICITY
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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
- H01L21/22—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities
- H01L21/228—Diffusion of impurity materials, e.g. doping materials, electrode materials, into or out of a semiconductor body, or between semiconductor regions; Interactions between two or more impurities; Redistribution of impurities using diffusion into or out of a solid from or into a liquid phase, e.g. alloy diffusion processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/028—Inorganic materials including, apart from doping material or other impurities, only elements of Group IV of the Periodic Table
- H01L31/0288—Inorganic materials including, apart from doping material or other impurities, only elements of Group IV of the Periodic Table characterised by the doping material
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/06—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers
- H01L31/068—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices characterised by potential barriers the potential barriers being only of the PN homojunction type, e.g. bulk silicon PN homojunction solar cells or thin film polycrystalline silicon PN homojunction solar cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/546—Polycrystalline silicon PV cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/547—Monocrystalline silicon PV cells
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S252/00—Compositions
- Y10S252/95—Doping agent source material
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S438/00—Semiconductor device manufacturing: process
- Y10S438/914—Doping
- Y10S438/923—Diffusion through a layer
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- Engineering & Computer Science (AREA)
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- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Sustainable Development (AREA)
- Photovoltaic Devices (AREA)
- Die Bonding (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Description
492081 經濟部智慧財產局員工消費合作社印製 Λ7 B7 五、發明說明(1 ) 本發明係關於用以在單晶和多晶s JI晶片中製造P , P 和N,N 1區域用之新穎的硼、磷或硼一鋁摻雜糊料, 及相關糊料作爲半導體製造、電力電子零件或於光電池用 途之遮蔽糊料之使用。 在光電池技術和在電子半導體情況中(如:二極體、 閘流晶體管),於單晶S i晶片摻雜硼或磷係藉由蒸汽相 (P〇C 1 3、磷化氫、BB Γ3)或固體(膜或固體薄片 )或使用液態介質(如:磷酸)和他種有機B或p系統實 施。 使用這些技巧無法直接成型。可以在未使用繁複程序 (如:照相平版印刷程序)來遮蔽不欲摻雜區域的情況下 選擇性地摻雜定義的區域。 在光電池技巧中,因爲在背面上摻雜P 而能得到大 規模或局部背表面電場(B S F )。目前所用的生產線僅 以大規模背表面電場操作,其由A 1金屬層或液態硼來源 得到。局部B S F目前僅侷限於實驗室規模,下文中會詳 述其原因。 大規模背面電場特別有利,在薄S i晶片(^ 2 5〇 微米)的情況中更是如此,在不是這樣的情況下,電池效 能會顯著降低。以厚度> 3 0 0微米的S 1晶片爲例’這 樣的B S F目前藉由以鋁糊料大規模印刷而得〔P.Lolgen; F.J.Bisschop; W.C.Sinke; R.A.Steeman; L.A Verhoef 等人編 輯,第六版 PV Science and Engineering Conference,New
Delhi ,1 9 9 2,p P,2 3 9〕。其優點在於P 1摻雜 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ----* ^---^------衣--------訂---------線 {請先閱讀背面之注意事項再填寫本頁} -4- 492081 經濟部智慧財產局員工消費合作社印製 Λ7 Β7 五、發明說明(2 ) 物(即,B S F )因鋁而累積’另一方面,電池中產生的 電力也會因鋁而散逸。但在薄晶片的例子中,在鋁燒入之 後,晶片會彎曲。因此’因爲將這樣的彎曲電池加至一般 爲便設計的模具中相當困難,所以,這樣的晶片的進一步 操作和加工須要特別的設備。 在 DE 1 9 5 0 8 7 1 2 C2 和 K.A. Muzer,R. R. King, R.E. Schlosser, H.J. Schmidt, J. Schamlzbauer, S.
Sterk, H.L. Mayer,13th European Photovoltaic Solar Energy Conference 5 2 3 — 2 7 1〇·1995,ρ· 1 3 9 8中意欲藉由使用硼的旋塗法解決此問題。此處, Ρ + +摻雜料以硼和鋁爲基礎地製得,其在後續印刷中藉由 鋁糊補充。 此方法的缺點在於 a )旋塗法須大量材料 b )昂貴的設備花費才能使角形的晶片以旋塗法被均勻地 塗覆 c )高遍佈和昂貴的操作成本對於大量生產而言有相當大 的困難 d )如前述者,晶片無法選擇圖案。 本發明的目的是要提出一種用於半導體技術之經改良 、不昂貴的摻雜糊料,其無前述缺點且可以直接使用。本 發明的另一目的是要提出相關網板可印刷的糊料。 以藉網板、滚筒、軋板、模板印刷法或半導體技術中 常用以在S i晶片中製造p、p f-、p 1 h、η、η '、 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ----I---訂------- 丨!線0· (請先閱讀背面之注意事項再填寫本頁) -5- 492081 A7 B7 五、發明說明(3 ) n i 1區域的他種印刷技巧選擇性和大規模地印刷s 1晶片 的摻雜糊料達成本發明,此摻雜糊料中含有: a ) —或多種具有摻雜作用的組份, b ) S 1〇2基質, c )溶劑, d )視情況使用酸和水’及視情況使用的 e )添加物,如:稠化劑或潤濕劑, 總組成物的金屬離子類雜質濃度低於5 0 0 p p b ,以低 於2〇〇ppb爲佳。 經由測試,已經知道前述缺點可以藉此處發現之網板 可印刷的摻雜糊料而消除。 根據本發明之糊料含有摻雜物來源,選自硼鹽、氧化 硼、硼酸、有機硼化合物、硼-鋁化合物和磷鹽、氧化磷 、五氧化磷、磷酸、有機磷化合物、有機鋁化合物和鋁鹽 〇 基本上,嫻於此技藝者已經知道之主要選自週期表第 m和v主族的化合物可適用。 此相關糊狀物另含有s 1〇2、由一或多種s 1〇2先 質構成的基質。 此摻雜糊料可以含有一或多種摻雜來源,選自氧化硼 (B 2 0 3 )、磷酸(Η 3 P〇4 )、五氧化磷(Ρ 2〇5 ) 和鋁鹽,此摻雜來源亦可以不同濃度使用。 本發明亦係關於含有一或多種摻雜來源的摻雜糊料’ 此摻雜來源選自有機硼、磷和鋁化合物’此摻雜來源亦可 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) 訂---------線4 經濟部智慧財產局員工消費合作社印製 ⑽2081 經濟部智慧財產局員工消費合作社印製 Λ7 137 五、發明說明(4 ) 以不同濃度使用。 ’ 本發明之目的另由含有一或多種摻雜來源的摻雜糊料 達成,此摻雜來源選自包括氧化硼(B 2〇3 )、磷酸( Η 3 P〇4 )、五氧化磷(Ρ 2〇5 )和鋁鹽或有機鋁化合物 及視情況使用的一或多種摻雜來源(選自有機硼、有磷和 鋁化合物),此摻雜來源亦可以不同濃度使用。 根據本發明,摻雜糊料所含的S i〇2基質可製自通式 爲R ’ n S i (〇R ) 4 - η的有機矽化合物,其中, R/代表甲基、乙基或苯基, R 代表甲基、乙基、正丙基或異丙基,而 η 代表0、1或2。 本發明另係關於含有製自矽烷之S 1〇2基質的摻雜糊 料,選自單獨使用或倂用的四甲氧基矽烷、四乙氧基矽烷 、四丁氧基矽烷。 本發明亦係關於所描述之新穎的摻雜糊料在半導體技 術、光電池技術和電力電子零件方面之使用。 除了摻雜糊料之外,本發明亦提出遮蔽糊料,含有 a) Si〇2基質, b )溶劑, c )視情況使用的酸和水,及視情況使用的 d )添加物’如:稠化劑或潤濕劑, 總添加物的金屬離子類雜質量低於5 〇 〇 p p b ,以低於 2〇〇P p b爲佳。 此遮蔽糊料組成類似於摻雜糊料,但沒有摻雜物的遮 --------訂·-------1 (請先閱讀背面之注意事項再填寫本頁)
Α7 Α7 經濟部智慧財產局員工消費合作社印製 ^_____Β7__ 1、發明說明(5 ) 蔽糊料根據本發明地用於半導體技術、光電池技術和電力 電子零件方面。 類似地,藉由網板可印刷的糊料,可以使大量或選擇 性(選擇性發光)的磷以不昂貴且遍佈的方式摻雜。 形成圖案的階段(目前可以光蝕刻法達成)可以藉由 使用網板可印刷的摻雜糊料而以價格較低廉的方式代替。 以被描述成無摻雜添加物之純s 1 0 2基質糊料的遮蔽 糊料可用以形成故蒽定義的保護層。此處,此糊料可以大 量用於S i晶片或者以圖案施用。此使得定義出的區域受 到保護而不會在擴散法中被摻雜。 藉由用選擇性產製ί爹有磷、硼和硼-銘的砂酸鹽層的 新穎糊料達到此目的。這些糊料適用於電子工業的印刷技 術。迨些特別包括’網版印刷技巧或乳印。 視所欲用途而定地,可以改變糊料中之各個組份的濃 度和黏度。 根據本發明,此摻雜糊料的另一特點在於定義的基質 。其製自在擴散法之加熱期間內會形成S i〇2的組份。與 提供硼或磷的組份述於文獻〔K . Spanowsky,The Diffusion of Boron with the aid of Spin Glasses m MOS T e c h η o 1 o g y (藉由旋轉玻璃之助而使硼擴散進入M〇S的 技巧),siploma dissertation,1996; R · Fischer,
Experiments to Clarify the Diffusion Mechanism of P h o s p h o r u s i n S i 1 i c ο n (磷進入砂中之擴散機構的實驗), d i p 1 〇 m a d e s s e r t a t i ο η ,1 9 9 4〕中,且嫻於此技術者已 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ---^ :-----------------訂---- (請先閱讀背面之注意事項再填寫本頁) -8- 492081 經濟部智慧財產局員工消費合作社印製 Α7 Β7 五、發明說明(6 ) 經知道形成硼——磷石夕酸鹽玻璃(B 2〇3 ) X * ( S 1〇2 ) V或(P 2〇5 ) X * ( S i〇2 ) y。此玻璃形成在摻雜期間 內的摻雜物來源。 摻雜糊料中之形成S 1〇2的組份的量在0 . 1 - 5重 量%範圍內◦與摻雜組份B 2〇3或P 2〇5之間的關係中, 可以限制S 1〇2與B 2〇3或P 2〇5之比例,但S 1〇2 中的摻雜物以1 0 — 8 0 %爲佳。可以藉由此比例良好地 控制在矽中的摻雜物濃度。如文獻〔A. Goetzberger; B.
Vob; J. Knobloch, Solar Power : Photovoltaic Technology (太陽能:光電池技巧),Teubner Studienbucher Stuttagart 1997,pp.4〇;l〇7〕中已知者, 由擴散時間和擴散溫度參數控制。 此摻雜程序藉由調節在空氣或氧氣中之擴散的方式進 行。磷擴散溫度是如:9 0 0 - 9 5 0 °C,而硼擴散溫度 是約9 5 0 — 1 2 5 0 °C。此擴散溫度視所用的S 1晶片 而定。以單晶晶片爲例,因爲它們的熱安定性優於多晶晶 片,所以擴散溫度可以更高,如:高至約1 2 5 0 °C。 此擴散亦可以快速熱加工(R T P )技巧進行。 擴散時間可以視用途目的而疋’由幾分鐘高至6 0小 時或以上。擴散之後,晶片以H F (濃度約2 — 5 0 % Η F )處理,以溶解形成的磷或硼矽酸(P S G,B S G ) 玻璃。此處理之後’ S 1晶片無S 1表面。 摻雜組份的濃度範圍是以摻雜糊料計之0 - 1 0 %。 組成物未摻雜(〇重量% )時’製得遮蔽糊料。其製法與 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) —►—·--------------訂·-------- (請先閱讀背面之注意事項再填寫本頁) -9- 492081 Λ7 H7 五、發明說明(7 ) 摻雜糊料之製法相同。 溶劑是糊料的主要構份。以總量計,其量在5 〇 一 8 0重量%範圍內。 用以調整黏度範圍和摻雜物之可印刷性(即,形成可 印刷的糊料)的稠化劑比例在以糊料總量計之約1 一 2〇 重量%範圍內。 具有有利於所欲目的的他種添加物有:抗起泡劑、黏 著性調整劑、稠化劑、潤濕劑、均化劑或觸變劑。這些對 於糊料的可印刷性有正面影響。 烷氧基矽烷一般適用以形成矽基質,特別是通式爲 R、S i (〇R ) 4 — η的矽烷,其中, R’代表甲基、乙基或苯基, R 代表甲基、乙基、正丙基或異丙基,而 η 代表〇、1或2 。 適當矽烷的例子有四甲氧基矽烷、四乙氧基矽烷、四 丁氧基矽烷、四丙氧基矽烷及高碳和混合的例子,即,具 長鏈烷基鏈的矽烷或具有多個烷基殘基的矽烷。 亦可有利地使用多種烷基-或烷氧基矽烷之混合物。 可能要預先水解這些化合物。使用不須事先處理的矽 氧烷(如:聚矽氧烷)有利於產製根據本發明之糊料。 基質於擴散爐中加熱時,有機矽化合物形成二氧化矽 ,例如,根據下列式子: C 8 Η 2 〇 〇 i S i > C 〇2 + H2O + S i Ο 2 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) ——>lll·-----% (請先閱讀背面之注意事項再填寫本頁) 訂---------線. 經濟部智慧財產局員工消費合作社印製 -10- 492081 經濟部智慧財產局員工消費合作社印製 A7 B7 五、發明說明(8 ) (TEOS ,四乙基正矽酸鹽) 欲製備摻雜基質’可以使用硼和磷的化合物及鋁化合 物作爲無機組份。例子包括氧化硼B 2 0 3、硼酸 B (〇H) 3、鱗酸H3P〇4、P2〇5和A 1鹽或有機隹呂 化合物。 硼和磷的有機化合物及有機鋁化合物可以作爲有機組 份。 本發明之糊料可以進一步地與添加物混合。這些可以 是有機和無機酸,如:硝酸、氫氯酸、乳酸、草酸、甲酸 之類。特別地,在有機s i化合物必須水解時添加這些酸 。通常,可以使用院基鏈長η = 1 - 1 〇的這樣的有機酸 。可資利用的鹽的烷基殘基可爲直鏈或帶有支鏈者。 有機矽化合物必須事先水解時,須使用根據本發明之 糊料中的相關添加物。但是,在矽氧烷的例子中,可以省 略此添加物。 適當稠化劑包括T h i X 〇 t ο η ® (蓖麻油)、B q r c h 1 g e η TS® (用於矽酸的流變添加物)、具各種量和性質的膨潤土 (一般是用於極性溶劑混合物的無機流變添加物)、硝基 纖維素、乙基纖維素和他種纖維素化合物、品質不童的聚 乙烯基吡咯啉酮、澱粉(+ N Η 4〇Η )、明膠、藻酸、高 度分散非晶狀矽酸(Aerosol®)、聚乙烯基丁醛(
MowUal® )(於,如:丁二醇中溶解度高者)、羧基甲基 纖維素(viV1stai‘)、熱塑性聚醯胺樹脂(Eurelon®)(須 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) I I i ·ϋ n n in HI - ^ I 1_1 1_1 I— n· _1 n I _ -J-U 口 为 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消費合作社印製 492081 A7 B7 五、發明說明(9 ) 於約1 8 0 °C煮沸)、有機蓖麻油衍生物(ThiXin R® )、 二醯胺蠘(T h丨x a t r ο 1 ρ 1 u s ® )、溶脹用聚丙嫌酸酯( Rheolate®)、聚醚脲—聚胺基甲酸乙酯(Rheolate®)、聚 醚一多元醇(Rheolate®)。 聚矽氧烷、矽氧烷和三矽氧烷可以作爲均化劑。 特別適合的添加物是與他種組份結合良好,以能夠於 低於2 0 0 °C的溫度預先乾燥、不發黏且於2 0 0 -5 0 0 °C燃燒之後不會留下渣質者爲佳。 以稠化劑及以使用的溶劑調整高純度摻雜糊料的黏度 〇 對於光電池技巧中之良好的摻雜糊料的基本要求在於 儘可能不會被金屬化合物所污染。特別地,不希望有在文 獻中通常被稱爲載體壽命”殺手’’的金屬鐵、鉻、銅、鎳、金 、鈣.·等的陽離子。它們在糊料中的濃度應儘可能遠低 於5 0 0 p p b。在特別的情況中,濃度應儘可能遠低於 2〇0 P P b。要符合這些條件,在特別的情況中,只能 使用經純化的起始物。 除了前面提到的組份之外,也必須添加溶劑以產製糊 料。 穩定的有機溶劑包括親水性多元醇(如:乙二醇、甲 基溶纖素、甲基溶纖素乙酸酯、乙基溶纖素、二乙基溶纖 素、溶纖素乙酸酯、乙二醇、一 丁醚、乙二醇一苯醚、甲 氧基甲氧基乙醇、乙二醇一乙酸酯、乙二醇二乙酸酯、二 甘醇、二甘醇一甲醚、二甘醇一***乙酸酯、二甘醇一丁 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) -HI m I -1 m —1« HI m ·ϋ ϋ— II β I— n —ϋ a_i_i n I ϋ— 一 口 f I n It m n in m m I (請先閱讀背面之注意事項再填寫本頁) -12- 492081 經濟部智慧財產局員工消費合作社印製 Λ7 B7 五、發明說明(1〇) 醚、二甘醇一丁醚乙酸酯、二甘醇二甲酸、二甘醇甲基乙 基醚、二甘醇二***、二甘醇乙酸酯、二甘醇、二甘醇〜 甲醚、三甘醇一***、四甘醇、液態聚乙二醇、丙二醇、 丙二醇一甲醚、丙二醇一***、丙一醇一丁醚、1 一丁氧 基乙氧基丙醇、二丙二醇、二丙二醇一甲醚、二丙二醇〜 ***、三丙二醇一甲醚、聚丙二醇、伸丙二醇、丁二醛、 1 ,5 -戊二醛、己二醇、丙三醇、乙酸甘油酯、二乙酸 甘油酯、三乙酸甘油酯、三羥甲基丙炔、1 ,2 ,6〜己 三醇)或其親水衍生物及脂族和芳族多價醇(如:1 ’ 2 一丙二醇、1 ,5 —戊二醇、辛二醇)和其醚類或這些溶 劑之混合物。 適當構份可以,如,含有1 ,2 — 丁二醇作爲其主要 構份。已經證實含有3 0 — 9 5重量% 1 ,5 —戊二醇的 這樣的溶劑適用。這樣的混合物可以含有乙二醇一丁醚( EGB) 、二甘醇一丁醚(DGB)、二丙二醇一甲醚( DPM) 、1 ,4 — 丁二醇(1 ,4 — BD)和 1 ,3 — 丁二醇(1 ,3 B D )作爲其他溶劑。 可進一步使用親水醚(如:二噁烷、三噁烷、四氫呋 喃、四氫吡喃)作爲溶劑。甲醛、二乙縮醛、丁酮、甲基 異丁基酮、二乙酮、乙醯丙酮、二丙酮醇或親水酯(如: 甲酸甲酯、甲酸乙酯、甲酸丙酯、乙酸甲酯和乙酸乙酯) 亦適用。 試驗顯示將5 0 - 1 〇 〇毫克糊料施用於慣用的晶片 (如:4英吋晶片)中,足以達到摻雜效果。可藉嫻於此 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) -----.----U------^^衣 (請先閱讀背面之注意事項再填寫本頁}
T . n 11 «ϋ —me tm— i « a n >ϋ n n In ·ϋ —Ml I -13- 492081 Λ7 Β7 五、發明說明(11 ) 技藝者已經知道的方法將根據本發明之糊料施用於欲加以 處理的晶片上。特別地,網板印刷法適用於此處。已知者 中’藉由加熱至2〇〇至6〇〇°C (以約5〇〇°c爲佳) ’可將施用的糊料轉化成所欲摻雜層。所須加熱時間視施 用的糊料層厚度而定。 根據本發明之糊料適用以產製p - η接線,如:特別 是在半導體技術中,但亦可用於產製太陽能技術中所用的 太陽能電池。 例如’已經知道藉由將根據本發明的硼糊料用於產製 經摻雜的玻璃層,太陽能電池產製效率由一般的1 4 %提 商約1 . 5至2 %。 爲能更瞭解及明瞭,下面提出屬本發明之保護作用範 圍內的例子,但不欲因這些實例而限制本發明。 實例1 : Τ Ε 0 S ( 1 · 4 3克)置於燒杯中。之後添加溶劑 Ν-甲基吡咯啉酮ΝΜΡ(83克),藉攪拌器製得基礎 混合物。之後連續添加聚乙烯基吡咯啉酮(1 1克)、三 氧化二硼(4 . 6克)和最後添加的乳酸(3克)。添加 期間內,必須要進一步劇烈攪拌。完全添加之後,混合物 攪拌3 0分鐘以上。短暫的等待時間之後,移至容器中。 此等待時間用以使混合物中形成的氣泡能夠破掉。 此混合物形成糊料,以彼於晶片上形成硼玻璃,即’ 以經調節的方式得到具所欲硼濃度之摻雜的單晶和多晶 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) (請先閱讀背面之注意事項再填寫本頁) 訂---------. 經濟部智慧財產局員工消費合作社印製 -14- 經濟部智慧財產局員工消費合作社印製 492081 A7 B7 五、發明說明(12) S 1晶片。 此糊料於儲存時穩定’容易處理並可印刷。可以使用 標準溶劑而自網板印刷布上移除。 具溶劑或溶劑混合物的糊料例: ----,2---------- (請先閱讀背面之注意事項再填寫本頁) 丨訂---------線_ I . P 糊料 30克 1.4-丁二醇 5克 Ρ2Ο3 53克 1,2-丙二醇 1.5克 Trasil® (矽來源;具烷氧基的烷基矽酮樹脂) 0.2克 Foamex N® (聚二甲基矽氧烷;除氣泡劑) 0.2克 Aerex® (摻有矽酮的高分子量有機聚合物;抗 起泡劑) 3克 Byk 410® (經修飾的尿素;觸變劑) 0.05 克 TEG〇 Glide 400® (經聚醚修飾的聚矽氧烷;均化劑) 4克 PVP (聚乙烯基吡咯啉酮;稠化劑) Π .硼糊料 83克 1.2-丙二醇 4·6克 B2〇3 1.43 克 TEOS 3克 乳酸 2.5克 Byk 410® 觸變劑 0.05 克 TEG〇 Glide 400® 均化劑 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) -15- 492081 A7 B7 五、發明說明(13 ) 0_2克 Aerex® 抗起泡齊ij 0.2克 Foamex N® 除氣泡齊ij 4克 PVP 稠化劑 Π . Si 糊料 48克 1.2-丙二醇 3克 TEOS 3克 乳酸 35克 乙二醇一丁醚 3克 Trasil® 5克 Byk 41〇® 觸變劑 0.4克 TEGO Glide 400® 均化劑 4克 PVP 稠化劑 -Hi In n ϋ ϋ n HI n 1 0 n ·ϋ n emmmme l II ·ϋ 一 _口1 a «ϋ i a·^ n i (請先閱讀背面之注意事項再填寫本頁) 線 經濟部智慧財產局員工消費合作社印製 本紙張尺度適用中國國家標準(CNS)A4規格(210 X 297公釐) -16-
Claims (1)
- 492081 A8 h月6 3修正/笔1/補錢 D8 六、申請專利範圍 附件一:第89104087號專利申請案 中文申請專利範圍修正本 (請先閲讀背面之注意事項再填寫本頁) 民國91年2月修正 1 · 一種用以藉網板、滾筒、軋板、模板印刷法或半 導體技術中常用以在S i晶片中製造p、p+、p++、n ' η +、η + +區域的他種印刷技巧選擇性和大規模地印刷 S i晶片的摻雜糊料,其特徵在於其中含有: a ) —或多種具有摻雜作用的組份, b ) S i〇2基質, c )溶劑, d )視情況使用酸和水, 及視情況使用的 e )添加物,如:稠化劑或潤濕劑, 總組成物的金屬離子類雜質濃度低於5 0 0 p p b,以低 於200ppb爲佳。 經濟部智慧財產局員工消費合作社印製 2 ·如申請專利範圍第1項之摻雜糊料,其中,含有. 摻雜物來源,選自硼鹽、氧化硼、硼酸、有機硼化合物、 硼-鋁化合物和磷鹽、氧化磷、五氧化磷、磷酸、有機磷 化合物、有機鋁化合物和鋁鹽。 3 ·如申請專利範圍第1項之摻雜糊料,其中,含有 由一或多種S i〇2先質構成的S i〇2基質。 4 ·如申請專利範圍第1至3項中任何一項之摻雜糊 料,其中,含有一或多種摻雜來源,選自包括氧化硼( 本紙張尺度逋用中國國家梂率(CNS ) A4規格(210X297公釐) 492081 A8 B8 C8 D8 六、申請專利範圍 (請先閲讀背面之注意事項再填寫本頁) B 2 0 3 )、硼酸B (〇H)3、磷酸(H3P〇4)、五氧 化磷(P 2〇5 )和鋁鹽及有機A 1化合物,摻雜來源可以 不同濃度使用。 5 .如申請專利範圍第1至3項中任何一項之摻雜糊 料’其中,含有一或多種摻雜來源,包括有機硼、磷和鋁 化合物,摻雜來源可以不同濃度使用。 6 .如申請專利範圍第1至3項中任何一項之摻雜糊 ’料,其中,含有一或多種摻雜來源,包括氧化硼(B 2〇3 )、硼酸B(〇H)3、磷酸(H3P〇4)、五氧化磷(‘ P 2〇5 )和鋁鹽及視情況使用的一或多種摻雜來源,包括 有機硼、磷和鋁化合.物,摻雜來源可以不同濃度使用。 7 .如申請專利範圍第1至3項中任何一項之摻雜糊 料,其中,含有S 1〇2基質,其製自通式爲 R、S i (〇R ) 4 - η的矽烷, 其中, 代表甲基、乙基或苯基, 經濟部智慧財產局員工消費合作社印製 R 代表甲基、乙基、正丙基或異丙基,而 η 代表〇、1或2 。 8 .如申請專利範圍第1至3項中任何一項之摻雜糊 料,其中,含有S i 〇2基質,其製自單獨使用或以混合物 形式使用的四甲氧基矽烷、四乙氧基矽烷、四丁氧基砂院 、四丙氧基矽烷。 9 ·如申請專利範圍第1至3項中任何一項之摻雜糊 料/其中,含有一或多種溶劑,選自親水性多元醇、它們 本紙張尺度逋用中國國家梂準(CNS ) A4規格(210X297公釐) "" -2 - 492081 A8 B8 C8 D8 六、申請專利範圍 的醚類或酯類、親水性醚類、醛類、酮類或酯類或混合物 Ο 1 0 ·如申請專利範圍第9項中之摻雜糊料,其中, 含有30 - 95重量,2 -丙二醇,其爲一或多種選 自乙二醇一丁醚(EGB)、二甘醇一丁醚(DGB)、 二丙二醇一甲醚(DPM) 、1 ,4 — 丁二醇(1 ,4 一 BD)和1 ,3 — 丁二醇(1 ,3BD)之溶劑和/或一 或多種選自二噁烷、三噁烷、四氫呋喃、四氫吡喃 '甲醛 、二乙縮醛、丁酮、甲基異丁基酮、二乙酮、乙醯丙酮、 二丙酮醇、甲酸甲酯、甲酸乙酯、甲酸丙酯、乙酸甲酯和 乙酸乙酯之溶劑之混合物。 1 1 .如申請專利範圍第1至3項中任何一項之摻雜 糊料,其中,含有四乙基正矽酸鹽作爲Si〇2基質,1 , 2 —丙二醇、N —甲基吡咯啉酮、乙二醇一丁醚、1 ,4 -丁二醇或它們的混合物作爲溶劑,乳酸作爲酸,P 2〇5 或B 2〇3作爲摻雜劑及含有添加物、均化劑、觸變劑、稠 化劑和視情況使用的抗起泡劑和除氣劑,形成S i〇2之組 份在摻雜糊料中的量在0 . 1 - 5重量%範圍內,且摻雜 組份P2〇5或B2〇3在s i〇2中的摻雜量在1 〇 — 8 0 %範圍內。 . 1 2 ·如申請專利範圍第1至3項中任何一項之摻雜 糊料,其中,用於半導體技術、光電池技術或電力電子零 件。 . 13·—種遮蔽糊料,其特徵在於其中含有 本紙張尺度適用中國國家梂準(CNS ) A4規格(210X297公釐) : ~ -3 _ · 裝 訂 (請先閲讀背面之注意事項再填寫本頁) 492081 A8 B8 C8 D8 六、申請專利範圍 a ) S i〇2基質, b )溶劑, c )視情況使用的酸和水, 及視情況使用的 d )添加物,如:稠化劑或潤濕劑, 總添加物的金屬離子類雜質量低於5 0 0 p P b,以低於 200ppb 爲佳。 1 4 .如申請專利範圍第1 3項之摻雜糊料,其係用 於半導體技術、光電池技術或電力電子零件。 (請先閱讀背面之注意事項再填寫本頁) 經濟部智慧財產局員工消费合作社印製 本紙張尺度適用中國國家梂準(CNS〉A4規格(210X297公釐) -4-
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- 2000-02-29 JP JP2000604469A patent/JP2002539615A/ja active Pending
- 2000-02-29 PL PL00350966A patent/PL350966A1/xx unknown
- 2000-02-29 EP EP00918752A patent/EP1166366B1/de not_active Expired - Lifetime
- 2000-03-07 TW TW089104087A patent/TW492081B/zh not_active IP Right Cessation
-
2001
- 2001-09-09 IL IL145333A patent/IL145333A/en not_active IP Right Cessation
- 2001-09-10 NO NO20014384A patent/NO20014384D0/no not_active Application Discontinuation
- 2001-09-10 MX MXPA01009113 patent/MXPA01009113A/es unknown
- 2001-10-08 IN IN1049KO2001 patent/IN2001KO01049A/en unknown
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
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TWI480930B (zh) * | 2010-01-25 | 2015-04-11 | Hitachi Chemical Co Ltd | 光伏電池的製造方法 |
TWI482207B (zh) * | 2010-02-03 | 2015-04-21 | Hitachi Chemical Co Ltd | 形成p型擴散層的組合物和p型擴散層的製造方法,及製備光伏電池的方法 |
US10312402B2 (en) | 2010-02-05 | 2019-06-04 | Hitachi Chemical Company, Ltd. | P-type diffusion layer forming composition |
TWI483294B (zh) * | 2010-04-23 | 2015-05-01 | Hitachi Chemical Co Ltd | 形成n型擴散層的組成物、n型擴散層的製造方法及太陽電池元件的製造方法 |
TWI495118B (zh) * | 2010-04-23 | 2015-08-01 | Hitachi Chemical Co Ltd | 形成p型擴散層的組成物、p型擴散層的製造方法及太陽電池元件的製造方法 |
TWI499070B (zh) * | 2010-04-23 | 2015-09-01 | Hitachi Chemical Co Ltd | 形成n型擴散層的組成物、n型擴散層的製造方法及太陽電池元件的製造方法 |
TWI498945B (zh) * | 2010-04-23 | 2015-09-01 | Hitachi Chemical Co Ltd | p型擴散層形成組成物、p型擴散層的製造方法及太陽電池元件的製造方法 |
TWI556289B (zh) * | 2010-04-23 | 2016-11-01 | 日立化成股份有限公司 | 形成p型擴散層的組成物、p型擴散層的製造方法及太陽電池元件的製造方法 |
US9520529B2 (en) | 2010-04-23 | 2016-12-13 | Hitachi Chemical Co., Ltd. | Composition for forming P-type diffusion layer, method of forming P-type diffusion layer, and method of producing photovoltaic cell |
US9608143B2 (en) | 2010-04-23 | 2017-03-28 | Hitachi Chemical Co., Ltd. | Composition for forming N-type diffusion layer, method of forming N-type diffusion layer, and method of producing photovoltaic cell |
TWI485875B (zh) * | 2010-06-24 | 2015-05-21 | Hitachi Chemical Co Ltd | 形成不純物擴散層的組成物、形成n型擴散層的組成物、n型擴散層的製造方法、形成p型擴散層的組成物、p型擴散層的製造方法及太陽能電池的製造方法 |
Also Published As
Publication number | Publication date |
---|---|
EP1166366A1 (de) | 2002-01-02 |
MXPA01009113A (es) | 2002-02-28 |
IN2001KO01049A (zh) | 2006-03-17 |
EP1166366B1 (de) | 2011-11-30 |
ATE535943T1 (de) | 2011-12-15 |
AU3960100A (en) | 2000-09-28 |
US6695903B1 (en) | 2004-02-24 |
KR100697439B1 (ko) | 2007-03-20 |
KR20010112313A (ko) | 2001-12-20 |
CA2367137A1 (en) | 2000-09-14 |
NO20014384L (no) | 2001-09-10 |
PL350966A1 (en) | 2003-02-24 |
EP2276058A1 (de) | 2011-01-19 |
JP2002539615A (ja) | 2002-11-19 |
IL145333A (en) | 2009-06-15 |
AU766807B2 (en) | 2003-10-23 |
NO20014384D0 (no) | 2001-09-10 |
DE19910816A1 (de) | 2000-10-05 |
CN1343376A (zh) | 2002-04-03 |
WO2000054341A1 (de) | 2000-09-14 |
IL145333A0 (en) | 2002-06-30 |
EP2276058B1 (de) | 2016-02-17 |
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