TW201314746A - Phosphorous-comprising dopants, methods for forming phosphorous-doped regions in semiconductor substrates using such phosphorous-comprising dopants, and methods for forming such phosphorous-comprising dopants - Google Patents
Phosphorous-comprising dopants, methods for forming phosphorous-doped regions in semiconductor substrates using such phosphorous-comprising dopants, and methods for forming such phosphorous-comprising dopants Download PDFInfo
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- H—ELECTRICITY
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
- 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 at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System 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
Abstract
Description
本發明大致係關於摻雜劑、摻雜含半導體之材料之區域之方法及形成摻雜劑之方法，且更特定言之係關於實質上無矽烷之含磷摻雜劑、觸變含磷摻雜劑、使用此等含磷摻雜劑在半導體材料中形成磷摻雜區域之方法，及形成此等含磷摻雜劑之方法。 The present invention relates generally to dopants, methods of doping regions of semiconductor-containing materials, and methods of forming dopants, and more particularly to phosphorus-containing dopants, thixotropic phosphorus-containing dopants substantially free of decane A dopant, a method of forming a phosphorus doped region in a semiconductor material using such a phosphorus-containing dopant, and a method of forming such a phosphorus-containing dopant.
此為2008年8月20日申請之申請案第12/194,688號的部分接續。 This is a partial continuation of application No. 12/194,688 of the application filed on August 20, 2008.
用導電性決定型雜質(諸如n型及p型元素)摻雜半導體材料用於需要半導體材料之電特性之改質之多種應用中。光微影術係用於執行半導體材料之此摻雜之已知方法。為摻雜半導體材料，光微影術需要使用在半導體材料上形成及圖案化之遮罩。執行離子植入以將導電性決定型離子植入半導體材料中。隨後執行高溫退火以導致雜質摻雜劑擴散至半導體材料中。 Doping semiconductor materials with conductivity-determining impurities, such as n-type and p-type elements, is used in a variety of applications requiring modification of the electrical properties of semiconductor materials. Photolithography is a known method for performing this doping of semiconductor materials. To dope semiconductor materials, photolithography requires the use of a mask that is formed and patterned on the semiconductor material. Ion implantation is performed to implant conductivity-determining ions into the semiconductor material. A high temperature anneal is then performed to cause the impurity dopant to diffuse into the semiconductor material.
在一些應用中，舉例而言諸如，太陽能電池，需以具有非常精細之線或特徵之圖案摻雜半導體材料。最常見類型之太陽能電池被組態為由矽製成之大面積p-n接面。在圖1所示之一種類型之此太陽能電池10中，具有光接收前側14及後側16之矽晶圓12具有基本摻雜，其中基本摻雜可為n型或p型。矽晶圓在一側上(圖1中前側14)用與基本摻雜電荷相反之摻雜劑進一步摻雜，因此在矽晶圓內形成p-n接 面18。來自光之光子被矽晶圓之光接收側14吸收至p-n接面，其中電荷載子(即電子及電洞)被分離並傳導至導電接觸件，因此產生電。太陽能電池通常分別在光接收前側以及後側上具有金屬接觸件20、22以帶走太陽能電池所產生之電流。光接收前側上之金屬接觸件在太陽能之效率度方面存在挑戰，因為前側表面之金屬覆蓋導致太陽能電池之有效區域之遮蔽。雖然需儘可能減少金屬接觸件以減小遮蔽，但是大約10%的金屬覆蓋仍不可避免，因為金屬化必須以保持小電損耗之方式發生。此外，鄰近電接觸件之矽內之接觸電阻隨金屬接觸件之大小減小而明顯增大。但是，接觸電阻可藉由在直接鄰近光接收前側14上之金屬接觸件之窄區域24中摻雜矽而減小。 In some applications, such as, for example, solar cells, the semiconductor material needs to be doped in a pattern having very fine lines or features. The most common type of solar cell is configured as a large area p-n junction made of tantalum. In one type of solar cell 10 of the type shown in FIG. 1, the germanium wafer 12 having the light receiving front side 14 and the back side 16 has a substantially doped shape, wherein the basic doping may be n-type or p-type. The germanium wafer is further doped on one side (front side 14 in FIG. 1) with a dopant that is opposite to the substantially doped charge, thus forming a p-n junction in the germanium wafer. Face 18. The photons from the light are absorbed by the light receiving side 14 of the germanium wafer to the p-n junction where the charge carriers (i.e., electrons and holes) are separated and conducted to the conductive contacts, thereby generating electricity. The solar cells typically have metal contacts 20, 22 on the front and rear sides of the light receiving, respectively, to carry away the current generated by the solar cells. Metal contacts on the front side of the light receiving are challenging in terms of solar efficiency because the metal coverage of the front side surface results in shadowing of the active area of the solar cell. While metal contacts are required to be minimized to reduce shadowing, approximately 10% metal coverage is still unavoidable because metallization must occur in a manner that maintains small electrical losses. In addition, the contact resistance in the turns of the adjacent electrical contacts increases significantly as the size of the metal contacts decreases. However, the contact resistance can be reduced by doping the germanium in the narrow region 24 of the metal contact directly adjacent the light receiving front side 14.
圖2圖解說明另一常見類型之太陽能電池30。太陽能電池30亦具有具光接收前側14及後側16之矽晶圓12且具有基本摻雜，其中基本摻雜可為n型或p型。光接收前側14具有充當光阱之粗糙或紋理化表面，防止所吸收的光被反射出太陽能電池。太陽能電池之金屬接觸件32形成在晶圓之後側16上。矽晶圓在相對於金屬接觸件之後側上摻雜，因此在矽晶圓內形成p-n接面18。太陽能電池30相較於太陽能電池10之優點在於電池之金屬接觸件之所有位於後側16上。就此而言，不存在太陽能電池之有效區域之遮蔽。但是，對於待形成在後側16上之所有接觸件，鄰近接觸件之摻雜區域必須非常窄。 FIG. 2 illustrates another common type of solar cell 30. The solar cell 30 also has a germanium wafer 12 having a light receiving front side 14 and a back side 16 and having a basic doping, wherein the basic doping can be either n-type or p-type. The light receiving front side 14 has a rough or textured surface that acts as a light trap to prevent the absorbed light from being reflected out of the solar cell. A metal contact 32 of the solar cell is formed on the wafer back side 16. The germanium wafer is doped on the back side with respect to the metal contacts, thus forming a p-n junction 18 in the germanium wafer. An advantage of solar cell 30 over solar cell 10 is that all of the metal contacts of the cell are located on the back side 16. In this regard, there is no obscuration of the active area of the solar cell. However, for all contacts to be formed on the back side 16, the doped regions of adjacent contacts must be very narrow.
磷常用於在半導體材料中形成n型區域。太陽能電池10 及太陽能電池30兩者得益於使用形成在半導體基板內之非常精細、窄的磷摻雜區域。但是，上述目前的摻雜方法(即光微影術)存在明顯缺陷。舉例而言，雖然可使用光微影術以細線圖案摻雜基板，但是光微影術係昂貴且耗時之製程。 Phosphorus is commonly used to form n-type regions in semiconductor materials. Solar cell 10 Both solar cells 30 benefit from the use of very fine, narrow phosphorous doped regions formed within the semiconductor substrate. However, the above current doping method (ie, photolithography) has significant drawbacks. For example, although photolithography can be used to dope a substrate in a thin line pattern, photolithography is an expensive and time consuming process.
執行半導體材料摻雜之其他已知方法(諸如網版印刷、輥筒印刷、噴塗及旋塗)使用施加至半導體材料之液體摻雜劑。雖然此等方法可克服光微影術之缺點，但是摻雜劑通常藉由在使用矽烷之溶膠-凝膠製程中水解及聚合而形成。在溶膠-凝膠製程中使用矽烷具有許多缺點。舉例而言，所得摻雜劑之分子量趨於繼續隨時間而增大。摻雜劑之分子量增大導致摻雜劑之膠化。因此，摻雜劑不穩定且必須在低溫下運送及儲存。此外，若膠化在使用期間發生，則其可能在網版印刷期間導致網版堵塞。此外，溶膠-凝膠製程通常需要在製造期間可能不安全且不環保之溶劑或溶劑體系。亦難以控制此等摻雜劑之線寬度，當在印刷精細特徵時尤為如此。在摻雜劑擴散或「摻雜劑驅入」期間，通常發生「外擴散」。「外擴散」係重新安定在半導體材料上之摻雜劑之蒸發，導致半導體材料之未印刷區域在擴散期間摻雜。 Other known methods of performing doping of semiconductor materials, such as screen printing, roller printing, spray coating, and spin coating, use liquid dopants applied to the semiconductor material. While these methods overcome the shortcomings of photolithography, dopants are typically formed by hydrolysis and polymerization in a sol-gel process using decane. The use of decane in a sol-gel process has a number of disadvantages. For example, the molecular weight of the resulting dopant tends to continue to increase over time. An increase in the molecular weight of the dopant results in gelation of the dopant. Therefore, the dopant is unstable and must be transported and stored at low temperatures. Furthermore, if gelation occurs during use, it may cause screen clogging during screen printing. In addition, sol-gel processes typically require solvents or solvent systems that may be unsafe and environmentally unfriendly during manufacture. It is also difficult to control the line width of such dopants, especially when printing fine features. "External diffusion" typically occurs during dopant diffusion or "dopant drive-in". "External diffusion" is the evaporation of dopants that are re-stabilized on a semiconductor material, resulting in the unprinted regions of the semiconductor material being doped during diffusion.
因此，需提供可用於導致細微特徵圖案之摻雜製程中之含磷摻雜劑。亦需要提供不含矽烷之含磷摻雜劑。此外，需提供用於形成實質上不包括矽烷且可用於省時且便宜的摻雜製程之含磷摻雜劑之方法。此外，可結合附圖及此先 前技術從後續實施方式及隨附申請專利範圍中瞭解本發明之其他所要特徵及特性。 Therefore, it is desirable to provide a phosphorus-containing dopant that can be used in a doping process that results in a fine feature pattern. It is also desirable to provide a phosphorus-containing dopant that does not contain decane. In addition, there is a need to provide a method for forming a phosphorus-containing dopant that does not substantially include decane and that can be used in a time-consuming and inexpensive doping process. In addition, it can be combined with the drawings and this first The prior art is aware of other desirable features and characteristics of the present invention from the scope of the following embodiments and the accompanying claims.
本發明提供含磷摻雜劑、在半導體材料中形成磷摻雜區域之方法，及製作含磷摻雜劑之方法。根據例示性實施例，含磷摻雜劑包括：磷源，其包括含磷鹽、含磷酸、含磷陰離子或其等之組合；鹼性材料、來自鹼性材料之陽離子或其等之組合；及液體介質。含磷摻雜劑包括小於0.1重量%之矽烷、衍生自矽烷之低聚物及/或聚合物或其等之組合。 The present invention provides a phosphorus-containing dopant, a method of forming a phosphorus-doped region in a semiconductor material, and a method of making a phosphorus-containing dopant. According to an exemplary embodiment, the phosphorus-containing dopant includes: a phosphorus source including a phosphorus-containing salt, a phosphoric acid-containing, a phosphorus-containing anion, or the like; a basic material, a cation derived from a basic material, or a combination thereof; And liquid medium. The phosphorus-containing dopant includes less than 0.1% by weight of decane, oligomers derived from decane, and/or polymers or combinations thereof.
根據另一例示性實施例，一種在半導體材料中形成磷摻雜區域之方法包括提供含磷摻雜劑，該含磷摻雜劑使用含磷酸、含磷鹽或其等之組合及鹼性材料、來自鹼性材料之陽離子或其等之組合在液體介質中形成。含磷摻雜劑包括小於0.1重量%之矽烷、衍生自矽烷之低聚物及/或聚合物或其等之組合。含磷摻雜劑沈積為覆蓋半導體材料之至少一部分。使含磷摻雜劑之液體介質蒸發且源自含磷摻雜劑之磷元素擴散至半導體材料中。 In accordance with another exemplary embodiment, a method of forming a phosphorus doped region in a semiconductor material includes providing a phosphorus-containing dopant using a combination of phosphoric acid, a phosphorus-containing salt, or the like, and a basic material A cation derived from an alkaline material or a combination thereof is formed in a liquid medium. The phosphorus-containing dopant includes less than 0.1% by weight of decane, oligomers derived from decane, and/or polymers or combinations thereof. The phosphorus-containing dopant is deposited to cover at least a portion of the semiconductor material. The liquid medium containing the phosphorus dopant is evaporated and the phosphorus element derived from the phosphorus-containing dopant is diffused into the semiconductor material.
根據另一例示性實施例，一種形成含磷摻雜劑之方法包括提供包括含磷酸或含磷鹽或其等之組合之磷源及將磷源與鹼性材料及液體介質組合。含磷摻雜劑包括小於0.1重量%之矽烷、衍生自矽烷之低聚物及/或聚合物或其等之組合。 In accordance with another exemplary embodiment, a method of forming a phosphorus-containing dopant includes providing a phosphorus source comprising a phosphoric acid or phosphorus-containing salt or a combination thereof, and combining the phosphorus source with an alkaline material and a liquid medium. The phosphorus-containing dopant includes less than 0.1% by weight of decane, oligomers derived from decane, and/or polymers or combinations thereof.
在又一實施例中，含磷摻雜劑包括：磷源，其包括含磷 鹽、含磷酸、含磷陰離子或其等之組合；鹼性材料、來自鹼性材料之陽離子或其等之組合；液體介質；及經處理之二氧化矽微粒。 In yet another embodiment, the phosphorus-containing dopant comprises: a phosphorus source comprising phosphorus a salt, a phosphoric acid-containing, a phosphorus-containing anion or a combination thereof; an alkaline material, a cation derived from a basic material, or a combination thereof; a liquid medium; and treated cerium oxide particles.
根據又一實施例，含磷摻雜劑包括：磷源，其包括含磷鹽、含磷酸、含磷陰離子或其等之組合物；含烴基之鹼性材料、來自含烴基之鹼性材料之陽離子或其等之組合；及液體介質。 According to still another embodiment, the phosphorus-containing dopant includes: a phosphorus source including a phosphorus-containing salt, a phosphoric acid-containing, a phosphorus-containing anion, or the like; a hydrocarbon-containing basic material, and a hydrocarbon-containing alkaline material. a combination of a cation or the like; and a liquid medium.
下文將結合下列圖式描述本發明，其中相同參考數字表示相同元件。 The invention is described below in conjunction with the following drawings in which like reference numerals refer to the like.
下文實施方式本質上僅為例示性且不旨在限制本發明或本發明之應用及使用。此外，不希望受限於上文先前技術或下文實施方式中提出的任何理論。 The following embodiments are merely illustrative in nature and are not intended to limit the invention or the application and use of the invention. Moreover, it is not intended to be limited to any of the teachings set forth in the prior art or the embodiments below.
本文提供在半導體材料中形成磷摻雜區域之含磷摻雜劑、製作此等含磷摻雜劑之方法及使用此等含磷摻雜劑在半導體材料中形成磷摻雜區域之方法。磷摻雜區域使用「摻雜製程」形成。如本文所使用，術語「摻雜製程」包含沈積及擴散，其中沈積包含「非接觸印刷製程」及接觸印刷製程兩者。 Provided herein are phosphorus-containing dopants for forming phosphorus-doped regions in semiconductor materials, methods of making such phosphorus-containing dopants, and methods of forming phosphorus-doped regions in semiconductor materials using such phosphorus-containing dopants. The phosphorus doped region is formed using a "doping process." As used herein, the term "doping process" includes deposition and diffusion, wherein the deposition includes both "non-contact printing processes" and contact printing processes.
非接觸印刷製程之實例包含但不限於「噴墨印刷」及「噴霧印刷」。通常，術語「噴墨印刷」、「噴墨印刷製程」、「噴霧印刷」及「噴霧印刷製程」指的是非接觸印刷製程，其中流體直接從噴嘴噴射至基板上以形成所要圖案。如圖3所示，在噴墨印刷機之噴墨印刷機構50中，印 刷頭52具有數個微小噴嘴54，亦稱作噴口。當基板58移動經過印刷頭52時，或當印刷頭52移動經過基板時，噴嘴將墨56以微小液滴噴灑或「噴射」至基板上，形成所要圖案之影像。圖4所示之噴霧印刷機構60使用使流體64霧化之生霧器或霧化器62。霧化流體66使用導流沈積頭68氣動聚焦，該導流沈積頭68形成箭頭72所示之夾套氣體之環流以準直霧化流體66。同軸流透過導向基板74之噴嘴70離開導流頭68，該噴嘴70用於將霧化材料流76聚焦為小至噴嘴口之大小之十分之一(通常100 μm)。圖案化係藉由將基板附接至電腦控制壓板或在基板位置保持固定時平移導流頭而完成。 Examples of non-contact printing processes include, but are not limited to, "inkjet printing" and "spray printing." Generally, the terms "inkjet printing", "inkjet printing process", "spray printing" and "spray printing process" refer to a non-contact printing process in which a fluid is sprayed directly from a nozzle onto a substrate to form a desired pattern. As shown in FIG. 3, in the inkjet printing mechanism 50 of the ink jet printer, printing The head 52 has a plurality of tiny nozzles 54, also referred to as spouts. As the substrate 58 moves past the printhead 52, or as the printhead 52 moves past the substrate, the nozzles spray or "spray" the ink 56 onto the substrate with minute droplets to form an image of the desired pattern. The spray printing mechanism 60 shown in FIG. 4 uses a mist or atomizer 62 that atomizes the fluid 64. The atomizing fluid 66 is aerodynamically focused using a flow deposition deposition head 68 that forms a loop of jacket gas as indicated by arrow 72 to collimate the atomizing fluid 66. The coaxial flow exits the flow director 68 through the nozzle 70 of the guide substrate 74, which is used to focus the atomized material stream 76 as small as one tenth (typically 100 μm) the size of the nozzle opening. Patterning is accomplished by attaching the substrate to a computer controlled platen or by translating the flow director while the substrate position remains fixed.
出於多種原因，此等非接觸印刷製程係用於在半導體材料中製作摻雜區域之尤佳製程。首先，僅用於形成摻雜區域之摻雜劑碰觸或接觸上面施加摻雜劑之基板表面。因此，由於與其他已知製程相比半導體基板之破裂可最小化，故非接觸製程適於多種基板，包含剛性及撓性基板。此外，此等非接觸製程係添加製程，意味著摻雜劑以所要圖案施加至基板。因此，免除諸如光微影術所需之在印刷製程後移除材料之步驟。此外，由於此等非接觸製程係添加製程，故其等適於具有光滑、粗糙或紋理化表面之基板。非接觸製程亦允許在半導體材料上形成非常精細之特徵。在一實施例中，可形成具有小於大約200微米(μm)之至少一尺寸之特徵，舉例而言諸如，線、點、矩形、圓或其他幾何形狀。在另一例示性實施例中，可形成具有小於 至少100 μm之至少一尺寸之特徵。在較佳實施例中，可形成具有小於大約20 μm之至少一尺寸之特徵。此外，由於非接觸製程涉及可用所選擇之圖案程式化以形成在基板上或可從主機電腦提供圖案之數位電腦印刷機，故當需要改變圖案時，無需產生新遮罩或網版。所有上述原因使非接觸印刷製程成為用於在半導體材料中製作摻雜區域之便宜製程，其與光微影術相比使生產率提高。 These non-contact printing processes are a particularly preferred process for making doped regions in semiconductor materials for a variety of reasons. First, only the dopant used to form the doped region touches or contacts the surface of the substrate on which the dopant is applied. Therefore, since the cracking of the semiconductor substrate can be minimized compared to other known processes, the non-contact process is suitable for a variety of substrates, including rigid and flexible substrates. Moreover, such non-contact processes add processes, meaning that the dopants are applied to the substrate in the desired pattern. Therefore, the steps required to remove the material after the printing process, such as photolithography, are eliminated. In addition, since such non-contact processes add processes, they are suitable for substrates having smooth, rough or textured surfaces. The non-contact process also allows for very fine features to be formed on the semiconductor material. In an embodiment, features having at least one dimension of less than about 200 micrometers (μm) may be formed, such as, for example, lines, dots, rectangles, circles, or other geometric shapes. In another exemplary embodiment, it may be formed to have less than At least one dimension of at least 100 μm. In a preferred embodiment, features having at least one dimension of less than about 20 μm can be formed. In addition, since the non-contact process involves a digital computer printer that can be programmed with a selected pattern to form on a substrate or that can provide a pattern from a host computer, there is no need to create a new mask or screen when the pattern needs to be changed. All of the above reasons make the non-contact printing process an inexpensive process for making doped regions in semiconductor materials, which increases productivity compared to photolithography.
但是，雖然非接觸印刷製程可用於根據本文預期之方法之特定例示性實施例在半導體材料中形成摻雜區域之非接觸印刷製程，但是本發明不限於此且在其他例示性實施例中，含磷摻雜劑可使用其他施加製程諸如網版印刷、噴塗、旋塗及輥塗沈積。網版印刷涉及沈積在半導體材料上方之圖案化網版或模板之使用。液體摻雜劑放置在網版頂部且被強壓穿過網版以對應於網版之圖案之圖案沈積在半導體材料上。旋塗涉及以高旋轉速度舉例而言諸如高至1200轉/分或甚至更高速度旋轉半導體材料，同時以所要流體壓力將液體摻雜劑噴射至旋轉之半導體材料上。旋轉導致液體摻雜劑實質上均勻地跨半導體材料向外散佈。液體摻雜劑亦可以所要流體壓力在實質上位於半導體材料之中心之位置上噴射至固定之半導體材料。流體壓力導致摻雜劑徑向及實質上均勻地跨晶圓散佈。輥筒印刷涉及其上雕刻圖案之輥筒。液體摻雜劑施加至輥筒之雕刻圖案，該雕刻圖案抵壓半導體材料並滾過半導體材料，藉此根據輥筒上之圖案將液體摻雜劑轉印至半導體材料。 However, while the non-contact printing process can be used in a non-contact printing process for forming doped regions in a semiconductor material in accordance with certain exemplary embodiments of the methods contemplated herein, the invention is not limited thereto and in other exemplary embodiments, The phosphorous dopant can be deposited using other application processes such as screen printing, spray coating, spin coating, and roll coating. Screen printing involves the use of patterned screens or stencils deposited over a semiconductor material. The liquid dopant is placed on top of the screen and is forced through the screen to deposit on the semiconductor material in a pattern corresponding to the pattern of the screen. Spin coating involves rotating the semiconductor material at high rotational speeds, such as, for example, up to 1200 rpm or even higher, while spraying the liquid dopant onto the rotating semiconductor material at the desired fluid pressure. Rotation causes the liquid dopant to spread substantially evenly across the semiconductor material. The liquid dopant can also be ejected to the fixed semiconductor material at a location substantially at the center of the semiconductor material at the desired fluid pressure. Fluid pressure causes the dopant to spread radially and substantially evenly across the wafer. Roller printing involves a roll on which the pattern is engraved. A liquid dopant is applied to the engraved pattern of the roll that resists the semiconductor material and rolls over the semiconductor material, thereby transferring the liquid dopant to the semiconductor material according to the pattern on the roll.
參考圖5，根據例示性實施例，用於在半導體材料中形成磷摻雜區域之方法100包含提供半導體材料之步驟(步驟102)。如本文所使用，術語「半導體材料」可用於涵蓋製造電裝置之半導體行業中習知使用之半導體材料。半導體材料包含單晶矽材料，諸如通常用於半導體行業之相對較純或輕微摻雜雜質之單晶矽材料以及多晶矽材料及與其他元素諸如鍺、碳及類似元素混合之矽。此外，「半導體材料」涵蓋其他材料，諸如相對較純及摻雜雜質之鍺、砷化鎵、氧化鋅、玻璃及類似物。就此而言，該方法100可用於製作多種半導體裝置，包含但不限於微電子裝置、太陽能電池、顯示器、RFID組件、微機電系統(MEMS)裝置、光學裝置諸如微透鏡、醫用裝置及類似裝置。 Referring to FIG. 5, a method 100 for forming a phosphorus doped region in a semiconductor material includes the step of providing a semiconductor material (step 102), in accordance with an illustrative embodiment. As used herein, the term "semiconductor material" can be used to encompass semiconductor materials that are conventionally used in the semiconductor industry for fabricating electrical devices. The semiconductor material comprises a single crystal germanium material such as a single crystal germanium material which is generally used for relatively pure or lightly doped impurities in the semiconductor industry, and a polycrystalline germanium material and a germanium mixed with other elements such as germanium, carbon and the like. In addition, "semiconductor materials" encompass other materials such as relatively pure and doped impurities, gallium arsenide, zinc oxide, glass, and the like. In this regard, the method 100 can be used to fabricate a variety of semiconductor devices including, but not limited to, microelectronic devices, solar cells, displays, RFID components, microelectromechanical systems (MEMS) devices, optical devices such as microlenses, medical devices, and the like. .
在視需要實施例中，半導體材料經歷摻雜前處理(步驟112)。摻雜前處理係促進下文更詳細描述之隨後施加之摻雜劑之形成圖案黏附及執行至半導體材料及促進隨後施加之摻雜劑之磷元素擴散至半導體材料中之任意處理。舉例而言，摻雜前處理包含清潔半導體材料以移除來自半導體材料之微粒、原生氧化物、有機或無機污染物或類似物或處理半導體材料使得其變得更親水或疏水。摻雜前處理之實例包含將酸，諸如氫氟酸(HF)、鹽酸(HCl)、硫酸(H2SO4)及/或硝酸(HNO3)；鹼，諸如氫氧化銨(NH4OH)、氫氧化鈉(NaOH)、氫氧化鉀(KOH)及氫氧化四甲銨(TMAH)；氧化劑，諸如過氧化氫(H2O2)；溶劑，諸如水、丙酮、異丙醇(IPA)、乙醇及/或四氫呋喃(THF)施加至 半導體材料；將半導體材料加熱至不高於800℃之溫度或其等之組合。 In an embodiment as desired, the semiconductor material undergoes a pre-doping process (step 112). The doping pretreatment facilitates patterning adhesion of subsequently applied dopants as described in more detail below and performing any processing to the semiconductor material and diffusion of the phosphorus element of the subsequently applied dopant into the semiconductor material. For example, pre-doping treatment involves cleaning the semiconductor material to remove particulates, native oxides, organic or inorganic contaminants or the like from the semiconductor material or to process the semiconductor material such that it becomes more hydrophilic or hydrophobic. Examples of the pre-doping treatment include an acid such as hydrofluoric acid (HF), hydrochloric acid (HCl), sulfuric acid (H 2 SO 4 ), and/or nitric acid (HNO 3 ); a base such as ammonium hydroxide (NH 4 OH). , sodium hydroxide (NaOH), potassium hydroxide (KOH) and tetramethylammonium hydroxide (TMAH); oxidizing agents such as hydrogen peroxide (H 2 O 2 ); solvents such as water, acetone, isopropanol (IPA) Ethanol and/or tetrahydrofuran (THF) is applied to the semiconductor material; the semiconductor material is heated to a temperature not higher than 800 ° C or a combination thereof.
該方法100進一步包含提供含磷摻雜劑之步驟(步驟104)，該步驟可在提供半導體材料之步驟之前、期間或之後執行。參考圖6更詳細地描述製作此一摻雜劑之方法。在本發明之例示性實施例中，調配摻雜劑使得其可被印刷以形成精細或小特徵，諸如線、點、圓、正方形或其他幾何形狀。在本發明之一例示性實施例中，調配摻雜劑使得可印刷具有小於大約200 μm之至少一尺寸之特徵。在本發明之另一例示性實施例中，調配摻雜劑使得可印刷具有小於大約100 μm之至少一尺寸之特徵。在本發明之較佳實施例中，調配摻雜劑使得可印刷具有小於大約20 μm之尺寸之特徵。在另一例示性實施例中，在印刷製程期間及在印刷製程暫停期間，摻雜劑導致噴墨印刷機噴嘴之最小堵塞(若有)。噴嘴之堵塞導致印刷機停機，因此減小處理量。在又一例示性實施例中，調配墨使得在其沈積在基板上並執行高溫退火(在下文中更詳細討論)後，所得摻雜區域具有不小於大約1歐姆/平方(Ω/sq.)之範圍中之薄層電阻。 The method 100 further includes the step of providing a phosphorus-containing dopant (step 104), which may be performed before, during or after the step of providing the semiconductor material. A method of making such a dopant is described in more detail with reference to FIG. In an exemplary embodiment of the invention, the dopant is formulated such that it can be printed to form fine or small features such as lines, dots, circles, squares or other geometric shapes. In an exemplary embodiment of the invention, the dopant is formulated such that features having at least one dimension of less than about 200 μm can be printed. In another exemplary embodiment of the invention, the dopant is formulated such that features having at least one dimension of less than about 100 μm can be printed. In a preferred embodiment of the invention, the dopant is formulated such that features having a size of less than about 20 μm can be printed. In another exemplary embodiment, the dopant causes minimal clogging (if any) of the ink jet printer nozzle during the printing process and during the printing process pause. The clogging of the nozzle causes the press to shut down, thus reducing the throughput. In yet another exemplary embodiment, the ink is formulated such that after it is deposited on the substrate and high temperature annealing is performed (discussed in more detail below), the resulting doped regions have no less than about 1 ohm/square (Ω/sq.). Sheet resistance in the range.
特定言之，本文所預期之摻雜劑實質上不用矽烷調配，即摻雜劑具有小於0.1重量百分比(wt.%)之矽烷、衍生自矽烷之低聚物及/或聚合物或其等之組合。較佳，本文預期之摻雜劑不含矽烷、衍生自矽烷之低聚物及/或聚合物或其等之組合。如上所述，將矽烷(諸如在溶膠-凝膠製程中)用於形成液體摻雜劑展現許多缺陷。舉例而言，在室溫 下，由矽烷形成之摻雜劑之分子量趨於繼續隨時間而增大。摻雜劑之分子量增大導致摻雜劑之膠化。因此，摻雜劑不穩定且必須在低溫下運送及儲存。相比之下，由於本文預期之摻雜劑不使用矽烷形成，故其等具有穩定分子量。因此，其等可在室溫下運送及儲存。此外，由於分子量穩定，故在使用期間不發生膠化且摻雜劑不會在印刷期間導致噴墨印刷機之噴嘴或網版印刷機之網版堵塞。此外，溶膠-凝膠製程通常需要在製造期間可能昂貴、不安全且不環保之溶劑或溶劑體系。相比之下，如下所述，本文預期之摻雜劑可利用含水體系。此外，使用矽烷形成之摻雜劑之線寬度比本文預期之摻雜劑之線寬度更難以控制，尤其在印刷較小特徵大小時。與本文預期之摻雜劑相對，部分歸因於水解及聚合步驟，矽烷形成之摻雜劑製作亦更昂貴且複雜。 In particular, the dopants contemplated herein are substantially free of decane, i.e., the dopant has less than 0.1 weight percent (wt.%) of decane, oligomers derived from decane, and/or polymers, or the like. combination. Preferably, the dopants contemplated herein are free of decane, oligomers derived from decane, and/or polymers or combinations thereof. As noted above, the use of decane, such as in a sol-gel process, to form liquid dopants exhibits a number of drawbacks. For example, at room temperature The molecular weight of the dopant formed from decane tends to continue to increase over time. An increase in the molecular weight of the dopant results in gelation of the dopant. Therefore, the dopant is unstable and must be transported and stored at low temperatures. In contrast, since the dopants contemplated herein are not formed using decane, they have a stable molecular weight. Therefore, they can be transported and stored at room temperature. In addition, since the molecular weight is stable, gelation does not occur during use and the dopant does not cause clogging of the screen of the ink jet printer or the screen of the screen printer during printing. In addition, sol-gel processes typically require solvents or solvent systems that can be expensive, unsafe, and environmentally unfriendly during manufacturing. In contrast, as described below, the dopants contemplated herein can utilize aqueous systems. Furthermore, the line width of the dopant formed using decane is more difficult to control than the line width of the dopants contemplated herein, especially when printing smaller feature sizes. In contrast to the dopants contemplated herein, the dopant formation of decane is also more expensive and complicated, due in part to the hydrolysis and polymerization steps.
馬上參考圖6，根據本發明之例示性實施例，用於製作諸如圖5之方法中所使用之含磷摻雜劑之方法150包含提供磷源之步驟(步驟152)。圖5之方法中所使用之含磷摻雜劑可使用多種含無機或有機非金屬之磷源。在本發明之較佳實施例中，磷源係無機非金屬含磷酸、含磷鹽或其等之組合。無機及有機含磷酸之實例包含但不限於磷酸(H3PO4)、亞磷酸(H3PO3)、次磷酸(H3PO2)、焦磷酸(H4P2O7)及具有化學式HR1R2PO2及H2RPO3之酸，其中R、R1及R2為烷基、芳基或其等之組合。無機及有機含磷鹽之實例包含但不限於磷酸銨((NH4)3PO4)、磷酸二氫銨 (NH4H2PO4)、磷酸氫二銨((NH4)2HPO4)、亞磷酸銨((NH4)3PO3)、亞磷酸氫二銨((NH4)2HPO3)、亞磷酸二氫銨(NH4H2PO3)、次磷酸銨((NH4)3PO2)、次磷酸氫二銨((NH4)2HPO2)、次磷酸二氫銨(NH4H2PO2)、焦磷酸銨((NH4)4P2O4)、焦磷酸氫三銨((NH4)3HP2O4)、焦磷酸二氫二銨((NH4)2H2P2O4)、焦磷酸三氫銨(NH4H3P2O4)及具有化學式(NR3R4R5R6)3PO4、(NR3R4R5H)3PO4、(NR3R4H2)3PO4及(NR3H3)3PO4之磷酸鹽，其中R3、R4、R5及R6各獨立為烷基、芳基或其等之組合。或者，含磷鹽可諸如在下文更詳細描述之液體介質及/或鹼性材料中形成以形成含磷源。半導體材料中之所得摻雜區域之磷濃度至少部分取決於含磷摻雜劑中磷之濃度。但是，雖然可較佳在摻雜劑中具有儘可能高之磷濃度而無不穩定問題，但是在本發明之一實施例中，含磷摻雜劑中存在磷源使得摻雜劑具有在從大約0至大約10之範圍中之pH。就此而言，可控制含磷摻雜劑之pH以使摻雜劑對印刷機之噴嘴及/或任何其他零件的腐蝕效應最小化。在較佳實施例中，含磷摻雜劑具有大約從1至7之pH。在本發明之另一實施例中，磷源之磷重量百分比包括不大於大約60重量%之含磷摻雜劑。 Referring now to Figure 6, a method 150 for fabricating a phosphorus-containing dopant, such as used in the method of Figure 5, includes the step of providing a source of phosphorus (step 152), in accordance with an illustrative embodiment of the present invention. The phosphorus-containing dopant used in the method of Figure 5 can use a variety of inorganic or organic non-metallic phosphorus sources. In a preferred embodiment of the invention, the phosphorus source is an inorganic non-metal containing phosphoric acid, a phosphorus containing salt or combinations thereof. Examples of inorganic and organic phosphoric acid include, but are not limited to, phosphoric acid (H 3 PO 4 ), phosphorous acid (H 3 PO 3 ), hypophosphorous acid (H 3 PO 2 ), pyrophosphoric acid (H 4 P 2 O 7 ), and chemical formulas. An acid of HR 1 R 2 PO 2 and H 2 RPO 3 wherein R, R 1 and R 2 are alkyl, aryl or a combination thereof. Examples of inorganic and organic phosphorus-containing salts include, but are not limited to, ammonium phosphate ((NH 4 ) 3 PO 4 ), ammonium dihydrogen phosphate (NH 4 H 2 PO 4 ), diammonium hydrogen phosphate ((NH 4 ) 2 HPO 4 ) , ammonium phosphite ((NH 4 ) 3 PO 3 ), diammonium hydrogen phosphite ((NH 4 ) 2 HPO 3 ), ammonium dihydrogen phosphate (NH 4 H 2 PO 3 ), ammonium hypophosphite ((NH 4 ) 3 PO 2 ), diammonium hydrogen phosphate ((NH 4 ) 2 HPO 2 ), ammonium dihydrogen phosphate (NH 4 H 2 PO 2 ), ammonium pyrophosphate ((NH 4 ) 4 P 2 O 4 ), Triammonium hydrogen pyrophosphate ((NH 4 ) 3 HP 2 O 4 ), diammonium dihydrogen diphosphate ((NH 4 ) 2 H 2 P 2 O 4 ), ammonium trihydrogen pyrophosphate (NH 4 H 3 P 2 O) 4 ) and having the formula (NR 3 R 4 R 5 R 6 ) 3 PO 4 , (NR 3 R 4 R 5 H) 3 PO 4 , (NR 3 R 4 H 2 ) 3 PO 4 and (NR 3 H 3 ) a phosphate of PO 4 , wherein each of R 3 , R 4 , R 5 and R 6 is independently alkyl, aryl or a combination thereof. Alternatively, the phosphorus containing salt can be formed, for example, in a liquid medium and/or a basic material as described in more detail below to form a phosphorus containing source. The phosphorus concentration of the resulting doped regions in the semiconductor material depends, at least in part, on the concentration of phosphorus in the phosphorus-containing dopant. However, although it is preferred to have as high a phosphorus concentration as possible in the dopant without instability problems, in one embodiment of the invention, the phosphorus source is present in the phosphorus-containing dopant such that the dopant has A pH in the range of from about 0 to about 10. In this regard, the pH of the phosphorus-containing dopant can be controlled to minimize the corrosive effects of the dopant on the nozzles of the printer and/or any other parts. In a preferred embodiment, the phosphorus-containing dopant has a pH of from about 1 to 7. In another embodiment of the invention, the phosphorus source weight percentage of the phosphorus source comprises no more than about 60% by weight phosphorus-containing dopant.
該方法進一步包含將磷源與鹼性材料、液體介質或鹼性材料與液體介質兩者組合(步驟154)。適用於調配含磷摻雜劑之液體介質之實例包含醇溶劑，諸如甲醇、乙醇、丙醇、2-丙醇、異丙醇(IPA)、丁醇、戊醇及乙二醇、1,2,6-己三醇、β-苯乙醇、聚乙二醇；酚溶劑，諸如苯酚及甲 酚；醚及其衍生物，諸如二甘醇一甲醚、三甘醇一甲醚、四氫呋喃(THF)、二惡烷、三惡烷、二甘醇一丁醚醋酸酯、丙二醇甲醚醋酸酯(PGMEA)；酮溶劑及其衍生物，諸如丙酮、甲基丙酮、2-庚酮、環己酮、2,5-己二酮、丙酮基丙酮、雙丙酮醇；酸溶劑及其衍生物，諸如甲酸、乙酸、丙酸、油酸、N-甲基吡咯啶酮(NMP)、二甲基甲醯胺(DMF)、二甘醇醋酸酯、三醋酸甘油酯；水及其混合物。在一例示性實施例中，液體介質包括不大於大約95體積%之含磷摻雜劑。 The method further comprises combining the phosphorus source with an alkaline material, a liquid medium, or both an alkaline material and a liquid medium (step 154). Examples of suitable liquid media for formulating phosphorus-containing dopants include alcohol solvents such as methanol, ethanol, propanol, 2-propanol, isopropanol (IPA), butanol, pentanol, and ethylene glycol, 1,2 ,6-hexanetriol, β-phenylethyl alcohol, polyethylene glycol; phenolic solvents such as phenol and nail Phenol; ethers and derivatives thereof, such as diethylene glycol monomethyl ether, triethylene glycol monomethyl ether, tetrahydrofuran (THF), dioxane, trioxane, diethylene glycol monobutyl ether acetate, propylene glycol methyl ether acetate (PGMEA); ketone solvents and derivatives thereof, such as acetone, methyl acetone, 2-heptanone, cyclohexanone, 2,5-hexanedione, acetonyl acetone, diacetone alcohol; acid solvents and derivatives thereof, Such as formic acid, acetic acid, propionic acid, oleic acid, N-methylpyrrolidone (NMP), dimethylformamide (DMF), diethylene glycol acetate, triacetin; water and mixtures thereof. In an exemplary embodiment, the liquid medium includes no more than about 95% by volume of the phosphorus-containing dopant.
鹼性材料可用於含磷摻雜劑中以至少部分中和磷源使得所得摻雜劑具有在從大約0至大約10之範圍中之pH。在一例示性實施例中，鹼性材料(或來自其之陽離子)存在於所得摻雜劑中使得摻雜劑具有在從大約1至大約7之範圍中之pH。在另一例示性實施例中，鹼性材料包括不大於大約50重量%之含磷摻雜劑。適用於形成含磷摻雜劑之鹼性材料包含可溶於液體介質(若存在)之任意非金屬鹼性材料。適用於含磷摻雜劑之鹼性材料之實例包含但不限於銨鹼性材料，諸如氫氧化銨(NH4)OH及含烴基之鹼性材料舉例而言諸如，(NR7R8R9R10)OH、(NR7R8R9H)OH、(NR7R8H2)OH、(NR7H3)OH，其中R7、R8、R9及R10各獨立為烷基、芳基或類似物，或其等之任意組合。 An alkaline material can be used in the phosphorus-containing dopant to at least partially neutralize the phosphorus source such that the resulting dopant has a pH in the range of from about 0 to about 10. In an exemplary embodiment, the alkaline material (or cations therefrom) is present in the resulting dopant such that the dopant has a pH in the range of from about 1 to about 7. In another exemplary embodiment, the alkaline material includes no more than about 50% by weight of the phosphorus-containing dopant. Suitable alkaline materials for forming phosphorus-containing dopants include any non-metallic alkaline material that is soluble in a liquid medium, if any. Examples of alkaline materials suitable for use in phosphorus-containing dopants include, but are not limited to, ammonium basic materials such as ammonium hydroxide (NH 4 ) OH and basic materials containing hydrocarbon groups such as, for example, (NR 7 R 8 R 9 R 10 )OH, (NR 7 R 8 R 9 H)OH, (NR 7 R 8 H 2 )OH, (NR 7 H 3 )OH, wherein R 7 , R 8 , R 9 and R 10 are each independently an alkane Any combination of aryl, aryl or the like, or the like.
磷源及液體介質及/或鹼性材料使用形成混合物之任意適當混合或攪拌製程混合。舉例而言，迴流冷凝器、低速超音波器粉碎機或高剪切混合裝置，諸如均質器、微射流 均質機、整流葉片高剪切混合機、自動化介質研磨機或球磨機可使用數秒至一小時或更長時間以形成含磷摻雜劑。應瞭解雖然磷源、液體介質及鹼性材料可為添加在一起之單獨組份之形式，但是應瞭解兩種或更多種組份可先組合在一起，隨後添加第三組份。舉例而言，鹼性材料可提供為含水鹼性材料組合物之形式，其中組合物之水部分包括所得摻雜劑之液體介質之至少一部分。或者，磷源可提供為含水磷源組合物之形式，其中組合物之水部分包括所得摻雜劑之液體介質之至少一部分。 The phosphorus source and the liquid medium and/or the alkaline material are mixed using any suitable mixing or agitation process to form a mixture. For example, a reflux condenser, a low speed ultrasonic pulverizer or a high shear mixing device such as a homogenizer, a microjet A homogenizer, a rectifying blade high shear mixer, an automated media mill or a ball mill can be used for a few seconds to an hour or more to form a phosphorus-containing dopant. It should be understood that while the phosphorus source, liquid medium, and alkaline material can be in the form of separate components that are added together, it should be understood that two or more components can be combined first, followed by the addition of a third component. For example, the alkaline material can be provided in the form of an aqueous alkaline material composition wherein the water portion of the composition includes at least a portion of the liquid medium of the resulting dopant. Alternatively, the phosphorus source can be provided in the form of an aqueous phosphorus source composition wherein the water portion of the composition comprises at least a portion of the liquid medium of the resulting dopant.
在本發明之視需要例示性實施例中，在與液體介質及/或鹼性材料組合之前、期間及/或之後將功能添加劑添加至磷源(步驟156)。舉例而言，可能需要使在達到退火製程之預定退火溫度之前散佈超出限定區域(即摻雜劑所沈積之區域)進入半導體材料之未限定區域之所得含磷摻雜劑之數量最小化。磷及/或含磷摻雜劑在退火之前散佈超出限定區域進入非限定區域可明顯影響利用隨後形成之摻雜區域之所得半導體裝置之電特性。因此，在另一例示性實施例中，添加黏度調節劑。此等黏度調節劑之實例包含纖維素、丙三醇、聚乙二醇、聚丙二醇、乙二醇/丙二醇共聚物、有機改性矽氧烷、乙二醇/矽氧烷共聚物、聚電解質、油酸及類似物及其等之組合物。可用於形成含磷摻雜劑之其他適當添加劑之實例包含分散劑、表面活性劑、聚合抑製劑、濕潤劑、消泡劑、清潔劑及其他表面張力調節劑、阻燃劑、色素、塑化劑、增稠劑、流變改質劑及其等 之混合物。 In an exemplary embodiment of the invention, the functional additive is added to the phosphorus source before, during, and/or after combination with the liquid medium and/or the alkaline material (step 156). For example, it may be desirable to minimize the amount of resulting phosphorus-containing dopant that is dispersed beyond the defined region (ie, the region where the dopant is deposited) into the undefined region of the semiconductor material prior to reaching the predetermined annealing temperature of the annealing process. The diffusion of the phosphorus and/or phosphorus-containing dopants beyond the defined regions into the undefined regions prior to annealing can significantly affect the electrical characteristics of the resulting semiconductor device utilizing the subsequently formed doped regions. Thus, in another exemplary embodiment, a viscosity modifier is added. Examples of such viscosity modifiers include cellulose, glycerol, polyethylene glycol, polypropylene glycol, ethylene glycol/propylene glycol copolymers, organically modified alkane, ethylene glycol/nonane copolymer, polyelectrolyte , oleic acid and the like and combinations thereof and the like. Examples of other suitable additives that can be used to form phosphorus-containing dopants include dispersants, surfactants, polymerization inhibitors, wetting agents, defoamers, detergents, and other surface tension modifiers, flame retardants, pigments, plasticization. Agent, thickener, rheology modifier and etc. a mixture.
在本發明之另一例示性實施例中，二氧化矽微粒可添加至含磷摻雜劑中以調節摻雜劑之黏度、表面張力及/或可濕性並藉此允許摻雜劑沈積在半導體材料上使得可達成具有非常精細之尺寸之特徵。圖7圖解說明根據本發明之另一例示性實施例之製作諸如用於圖5之方法之含磷摻雜劑之方法200。如同圖6之方法150，方法200包含提供磷源之步驟(步驟202)。可使用上文參考方法150之步驟152所述之任意磷源。磷源與鹼性材料組合(步驟204)。可使用上文參考方法150之步驟154所述之任意鹼性材料並可使用用於組合組份之任意上述方法。液體介質，諸如任意上述液體介質亦可添加至磷源。 In another exemplary embodiment of the invention, cerium oxide particles may be added to the phosphorus-containing dopant to adjust the viscosity, surface tension and/or wettability of the dopant and thereby allow dopant deposition The semiconductor material makes it possible to achieve features with very fine dimensions. FIG. 7 illustrates a method 200 of fabricating a phosphorus-containing dopant, such as that used in the method of FIG. 5, in accordance with another exemplary embodiment of the present invention. As with method 150 of Figure 6, method 200 includes the step of providing a source of phosphorus (step 202). Any of the phosphorus sources described above with reference to step 152 of method 150 can be used. The phosphorus source is combined with an alkaline material (step 204). Any of the basic materials described above with reference to step 154 of method 150 can be used and any of the above methods for combining the components can be used. A liquid medium, such as any of the above liquid medium, may also be added to the phosphorus source.
方法200進一步包含將二氧化矽微粒與液體介質組合(步驟206)。二氧化矽微粒可包含具有不大於100 μm，較佳不大於1 μm之平均粒度且調節摻雜劑之黏度、表面張力及/或可濕性之任意二氧化矽微粒。術語「粒度」包含用於特徵化如使用透射電子顯微術(TEM)量測之非聚合形式之二氧化矽微粒之大小之直徑、長度、寬度或任意其他適當尺寸。適用之二氧化矽微粒之實例包含溶膠-凝膠微粒，諸如可購自日本FOSO CHEMICAL之溶膠-凝膠微粒及較佳發烟二氧化矽微粒，諸如可購自德國法蘭克福Evonik Degussa Gmbh之Aerosil®系列、可購自馬薩諸賽州Billerica之Cabot Corporation之CAB-O-SIL®系列；及可購自德國Wacker Chemie AG之HDK®系列；及其他氧化物微 粒。液體介質可包括上文針對方法150之步驟154所述之任意液體介質並可使用用於上述組合之任意方法與二氧化矽微粒組合。 The method 200 further includes combining the ceria particles with a liquid medium (step 206). The cerium oxide microparticles may comprise any cerium oxide microparticles having an average particle size of not more than 100 μm, preferably not more than 1 μm, and adjusting the viscosity, surface tension and/or wettability of the dopant. The term "particle size" encompasses the diameter, length, width or any other suitable size used to characterize the size of the non-polymerized form of cerium oxide particles as measured by transmission electron microscopy (TEM). Examples of suitable cerium oxide microparticles include sol-gel microparticles such as sol-gel microparticles and preferably fumed cerium oxide microparticles available from Japan's FOSO CHEMICAL, such as Aerosil® available from Evonik Degussa Gmbh, Frankfurt, Germany. Series, CAB-O-SIL ® series available from Cabot Corporation of Billerica, Mass.; and HDK ® series available from Wacker Chemie AG, Germany; and other oxide particles. The liquid medium can include any of the liquid media described above for step 154 of method 150 and can be combined with the ceria particles using any of the methods described above.
在一預期之實施例中，含磷摻雜劑可由未處理之二氧化矽微粒、處理之二氧化矽微粒或其等之組合形成。就此而言，所得含磷摻雜劑展現觸變性質，其使摻雜劑之「外擴散」最小化。如本文所使用，術語「未處理之二氧化矽微粒」指的是具有未經改質具有有機及/或無機官能基之表面之二氧化矽微粒。「處理之二氧化矽微粒」係具有已至少部分藉由有機及/或無機官能基改質之表面之二氧化矽微粒。未處理之二氧化矽微粒之實例包含但不限於可購自Evonik Degussa Gmbh之Aerosil® 380、Aerosil® 200及Aerosil® 150、可購自Cabot Corporation之CAB-O-SIL® M-5/M-5P、HP 60及EH-5；可購自Wacker Chemie AG之WACKER HDK-N20及HDK® V15/V15P；及可購自FOSO CHEMICAL之Quartron PL-06L。處理之微粒之實例包含但不限於可購自Evonik Degussa GHbh之Aerosil® R816、Aerosil® R812、Aerosil® R972及Aerosil® R974、可購自Cabot Corporation之CAB-O-SIL® TS 610及CAB-O-SIL® H-300、及可購自Wacker CheHie AG之HDK-H15及HDK-H20及可購自FUSO CHEMICAL之Quartron PL-2L-PGME。摻雜劑之觸變性質可透過藉由溶劑體系與二氧化矽微粒選擇之極性匹配而形成二氧化矽微粒而實現。此組合可涉及具有類似及/或不同極性之一種類型或多種類型之二氧化 矽微粒。當施加剪力時，此二氧化矽微粒網格破裂成較小塊，導致黏度降低。當剪力移除時，二氧化矽微粒網格再建且黏度增大。 In a contemplated embodiment, the phosphorus-containing dopant can be formed from untreated cerium oxide particles, treated cerium oxide particles, or combinations thereof. In this regard, the resulting phosphorus-containing dopant exhibits thixotropic properties that minimize the "out-diffusion" of the dopant. As used herein, the term "untreated cerium oxide microparticles" refers to cerium oxide microparticles having a surface that has not been modified with organic and/or inorganic functional groups. The "treated cerium oxide microparticles" are cerium oxide microparticles having a surface which has been modified at least in part by organic and/or inorganic functional groups. Examples of silicon dioxide particles of the untreated but not limited to commercially available from Evonik Degussa Gmbh of Aerosil® 380, Aerosil® 200 and Aerosil® 150, commercially available from Cabot Corporation of CAB-O-SIL ® M- 5 / M- 5P, HP 60 and EH-5; WACKER HDK-N20 and HDK ® V15/V15P available from Wacker Chemie AG; and Quartron PL-06L available from FOSO CHEMICAL. Examples of treated particulates include, but are not limited to, Aerosil® R816, Aerosil® R812, Aerosil® R972, and Aerosil® R974, available from Evonik Degussa GHbh, CAB-O-SIL® TS 610 and CAB-O, available from Cabot Corporation. -SIL® H-300, and HDK-H15 and HDK-H20 available from Wacker CheHie AG and Quartron PL-2L-PGME available from FUSO CHEMICAL. The thixotropic properties of the dopant can be achieved by forming a cerium oxide particle by matching the polarity of the solvent system with the cerium oxide particle selection. This combination may involve one or more types of cerium oxide microparticles having similar and/or different polarities. When a shear force is applied, the grid of cerium oxide particles breaks into smaller pieces, resulting in a decrease in viscosity. When the shear force is removed, the ceria particle mesh is rebuilt and the viscosity is increased.
在二氧化矽微粒與液體介質組合後，磷源/鹼性材料組合及微粒/液體介質組合可使用任意上述方法混合以形成含磷摻雜劑(步驟208)。在本發明之一實施例中，含磷摻雜劑具有在從大約0至大約10之範圍中之pH。在較佳實施例中，含磷摻雜劑具有從大約1至7之pH。在本發明之另一實施例中，來自磷源之磷重量百分比包括不大於大約60重量%之含磷摻雜劑；鹼性材料包括大於零且不大於大約50重量%之含磷摻雜劑；液體介質包括大約大於零且不大於大約60體積%之含磷摻雜劑；且二氧化矽微粒包括不大於大約0.1至大約40重量%之含磷摻雜劑。雖然方法200闡釋磷源與鹼性材料組合以形成第一組合且二氧化矽微粒與液體介質組合以形成第二組合，第一組合及第二組合隨後混合以形成摻雜劑，但是應瞭解磷源、鹼性材料、二氧化矽微粒及液體介質可以滿意地形成含磷摻雜劑之任意適當順序組合。在本發明之視需要例示性實施例中，在與鹼性材料、二氧化矽微粒及/或液體介質組合之前、期間及/或之後將功能添加劑添加至磷源(步驟210)。 After the ceria particles are combined with the liquid medium, the phosphorus source/alkaline material combination and the particulate/liquid medium combination can be mixed using any of the above methods to form a phosphorus-containing dopant (step 208). In one embodiment of the invention, the phosphorus-containing dopant has a pH in the range of from about 0 to about 10. In a preferred embodiment, the phosphorus-containing dopant has a pH of from about 1 to 7. In another embodiment of the invention, the weight percentage of phosphorus from the phosphorus source comprises no more than about 60% by weight of the phosphorus-containing dopant; the alkaline material comprises more than zero and no more than about 50% by weight of the phosphorus-containing dopant. The liquid medium includes a phosphorus-containing dopant that is greater than zero and no greater than about 60% by volume; and the cerium oxide particles includes no more than about 0.1 to about 40% by weight of the phosphorus-containing dopant. While method 200 illustrates that a phosphorus source is combined with an alkaline material to form a first combination and the cerium oxide particles are combined with a liquid medium to form a second combination, the first combination and the second combination are subsequently mixed to form a dopant, but phosphorus should be understood The source, alkaline material, cerium oxide microparticles, and liquid medium can satisfactorily form any suitable sequential combination of phosphorus-containing dopants. In an exemplary embodiment of the invention, a functional additive is added to the phosphorus source before, during, and/or after combination with the alkaline material, the cerium oxide particulate, and/or the liquid medium (step 210).
取決於摻雜劑中所使用之液體介質及/或鹼性材料，磷源可以或可以不解離以形成無機、非金屬含磷陰離子，舉例而言諸如，H2PO4 -、HPO4 2-、PO4 3-、H2PO3 -、HPO3 2-、PO3 3-、H2PO2 -、HPO2 2-、PO2 3-、H3P2O4 -、H2P2O4 2-、 HP2O4 3-、P2O4 4-、R11R12PO2 -、HRPO3 -及R11PO3 2-，其中R11及R12係烷基、芳基或其等之組合。此外，所使用之液體介質及/或鹼性材料之數量可至少部分決定磷源之解離度。此外，液體介質及鹼性材料之相互作用可至少部分決定鹼性材料解離以形成陽離子及氫氧化物陰離子之程度。因此，在形成時，含磷摻雜劑可包括含磷鹽、含磷酸、含磷陰離子或其等之組合；鹼性材料及/或來自鹼性材料之陽離子；及/或液體介質及視需要之功能添加劑。 Depending on the liquid medium and/or alkaline material used in the dopant, the phosphorus source may or may not dissociate to form inorganic, non-metallic phosphorus-containing anions such as, for example, H 2 PO 4 - , HPO 4 2- , PO 4 3- , H 2 PO 3 - , HPO 3 2- , PO 3 3 -, H 2 PO 2 - , HPO 2 2- , PO 2 3 -, H 3 P 2 O 4 - , H 2 P 2 O 4 2- , HP 2 O 4 3- , P 2 O 4 4- , R 11 R 12 PO 2 - , HRPO 3 - and R 11 PO 3 2- , wherein R 11 and R 12 are alkyl, aryl Or a combination thereof. Furthermore, the amount of liquid medium and/or alkaline material used can at least partially determine the degree of dissociation of the phosphorus source. In addition, the interaction of the liquid medium and the alkaline material can at least partially determine the extent to which the basic material dissociates to form cations and hydroxide anions. Thus, at the time of formation, the phosphorus-containing dopant may include a phosphorus-containing salt, a phosphoric acid-containing, a phosphorus-containing anion, or the like; a basic material and/or a cation derived from an alkaline material; and/or a liquid medium and, if desired, Functional additive.
重新參考圖5，方法100繼續施加含磷摻雜劑覆蓋半導體材料(步驟106)。如本文所使用，術語「覆蓋」涵蓋術語「上」及「上方」。因此，摻雜劑可直接施加至半導體材料上或可沈積在半導體材料上方使得一或多種其他材料插置在摻雜劑與半導體材料之間。可插置在摻雜劑與半導體材料之間之材料之實例係不阻礙含磷摻雜劑之磷元素在退火期間擴散至半導體材料中之該等材料。此等材料包含形成在矽材料上之磷矽酸鹽玻璃、硼矽酸鹽玻璃、氮化矽或二氧化矽。通常此等材料在摻雜劑沈積在矽材料上之前移除；但是在各種實施例中，較佳省略移除製程，藉此允許材料保留在半導體材料上。 Referring back to Figure 5, method 100 continues with applying a phosphorus-containing dopant to cover the semiconductor material (step 106). As used herein, the term "overlay" encompasses the terms "upper" and "over". Thus, the dopant can be applied directly to the semiconductor material or can be deposited over the semiconductor material such that one or more other materials are interposed between the dopant and the semiconductor material. Examples of materials that can be interposed between the dopant and the semiconductor material are those materials that do not hinder the diffusion of the phosphorus element of the phosphorus-containing dopant into the semiconductor material during annealing. These materials include phosphonite glass, borosilicate glass, tantalum nitride or hafnium oxide formed on the tantalum material. Typically such materials are removed before the dopant is deposited on the tantalum material; however, in various embodiments, the removal process is preferably omitted, thereby allowing the material to remain on the semiconductor material.
在例示性實施例中，使用非接觸製程印刷機施加含磷摻雜劑為覆蓋半導體材料之至少一部分。就此而言，以儲存在印刷機或另外供應給印刷機之圖案將含磷摻雜劑施加為覆蓋半導體材料。適用之噴墨印刷機之實例包含但不限於可購自加利福尼亞州Santa Clara之Fujifilm Dimatix,Inc.之 Dimatix噴墨印刷機型號DMP 2831。適用之氣霧印刷機之實例包含但不限於可購自新墨西哥州Albuquerque之Optomec,Inc.之M3D氣霧沈積系統。在另一例示性實施例中，如上所述藉由網版印刷、噴塗、旋塗或輥塗摻雜劑而將含磷摻雜劑施加為覆蓋半導體材料之至少一部分。較佳，在大約15℃至大約350℃之範圍中之溫度下、在大約20%至大約80%之濕度下將摻雜劑施加至基板。 In an exemplary embodiment, the phosphorus-containing dopant is applied to cover at least a portion of the semiconductor material using a non-contact process printer. In this regard, the phosphorus-containing dopant is applied to cover the semiconductor material in a pattern stored on the printer or otherwise supplied to the printer. Examples of suitable ink jet printers include, but are not limited to, Fujifilm Dimatix, Inc., available from Santa Clara, California. Dimatix inkjet printer model DMP 2831. Examples of suitable aerosol printers include, but are not limited to, the M3D aerosol deposition system available from Optomec, Inc. of Albuquerque, New Mexico. In another exemplary embodiment, the phosphorus-containing dopant is applied to cover at least a portion of the semiconductor material by screen printing, spray coating, spin coating, or roll coating of dopants as described above. Preferably, the dopant is applied to the substrate at a temperature in the range of from about 15 ° C to about 350 ° C at a humidity of from about 20% to about 80%.
一旦將摻雜劑施加為覆蓋半導體材料，即使摻雜劑中之液體介質及從氫陽離子(來自含磷酸)與氫氧化物陰離子(來自鹼性材料)之反應形成之任何水蒸發(步驟108)。就此而言，液體介質及/或水可允許在室溫(大約16℃至大約28℃)下蒸發或可加熱至液體介質之沸點達足夠時間以允許液體介質蒸發。較佳，液體介質及/或水在不高於800℃之溫度下蒸發。 Once the dopant is applied to cover the semiconductor material, even the liquid medium in the dopant and any water formed from the reaction of the hydrogen cation (from the phosphoric acid containing) and the hydroxide anion (from the alkaline material) evaporate (step 108) . In this regard, the liquid medium and/or water may allow evaporation at room temperature (about 16 ° C to about 28 ° C) or may be heated to the boiling point of the liquid medium for a time sufficient to allow evaporation of the liquid medium. Preferably, the liquid medium and/or water evaporates at a temperature not higher than 800 °C.
在含磷摻雜劑之圖案形成在半導體材料上後，使摻雜劑之磷元素(處於離子狀態、作為化合物之部分或作為兩者之組合)擴散至半導體材料中(步驟110)。在例示性實施例中，半導體材料經歷高溫熱處理或「退火」以使含磷摻雜劑之磷元素擴散至半導體材料中，因此在材料內形成磷摻雜區域(步驟110)。退火可使用任意適當熱產生方法執行，舉例而言諸如，電加熱、紅外線加熱、雷射加熱、微波加熱或類似加熱。退火的持續時間及溫度由諸如含磷摻雜劑之初始磷濃度、摻雜劑沈積之厚度、所得磷摻雜區域之所要濃度及磷擴散之深度之因素決定。在一例示性實施例 中，基板放置在爐內，其中溫度陡增至在大約800℃與大約1200℃之範圍中之溫度且半導體材料在此溫度下烘烤達大約2分鐘至大約180分鐘。亦可在聯機爐中執行退火以增大處理量。退火氛圍可含有氧氣/氮氣或氧氣/氬氣混合物中之0至100%氧氣。在較佳實施例中，半導體材料在氧氣環境中經歷大約1050℃之退火溫度達大約從5分鐘至大約10分鐘。在另一實施例中，半導體材料在氧氣環境中經歷大約950℃之退火溫度達大約10分鐘至大約180分鐘。在另一實施例中，半導體材料在氧氣環境中經歷大約850℃之退火溫度達大約10分鐘至大約300分鐘。 After the pattern of the phosphorus-containing dopant is formed on the semiconductor material, the phosphorus element of the dopant (in the ionic state, as part of the compound, or a combination of both) is diffused into the semiconductor material (step 110). In an exemplary embodiment, the semiconductor material is subjected to a high temperature heat treatment or "annealing" to diffuse the phosphorus element of the phosphorus containing dopant into the semiconductor material, thereby forming a phosphorus doped region within the material (step 110). Annealing can be performed using any suitable heat generation method, such as, for example, electric heating, infrared heating, laser heating, microwave heating, or the like. The duration and temperature of the anneal are determined by factors such as the initial phosphorus concentration of the phosphorus-containing dopant, the thickness of the dopant deposition, the desired concentration of the resulting phosphorus-doped region, and the depth of the phosphorus diffusion. In an exemplary embodiment The substrate is placed in a furnace wherein the temperature is ramped up to a temperature in the range of about 800 ° C and about 1200 ° C and the semiconductor material is baked at this temperature for about 2 minutes to about 180 minutes. Annealing can also be performed in an in-line furnace to increase throughput. The annealing atmosphere may contain from 0 to 100% oxygen in an oxygen/nitrogen or oxygen/argon mixture. In a preferred embodiment, the semiconductor material is subjected to an annealing temperature of about 1050 ° C in an oxygen environment for from about 5 minutes to about 10 minutes. In another embodiment, the semiconductor material is subjected to an annealing temperature of about 950 ° C in an oxygen environment for from about 10 minutes to about 180 minutes. In another embodiment, the semiconductor material is subjected to an annealing temperature of about 850 ° C in an oxygen environment for from about 10 minutes to about 300 minutes.
在視需要例示性實施例中，半導體材料隨後經歷擴散後處理(步驟114)。擴散後處理移除在半導體材料退火期間形成之任意殘餘物，舉例而言諸如，磷矽酸鹽玻璃、氧化磷、二氧化矽或污染物。若此殘餘物未在退火後移除，其可能對隨後形成之裝置之效能具有不利影響。舉例而言，此殘餘物可極大地增大摻雜半導體材料與其上所形成之金屬接觸件之間之接觸電阻。擴散後處理之實例包含使半導體材料經歷酸，諸如氫氟酸(HF)、鹽酸(HCl)、硫酸(H2SO4)及/或硝酸(HNO3)；鹽，諸如氫氧化銨(NH4OH)、氫氧化鈉(NaOH)、氫氧化鉀(KOH)、氫氧化四甲銨(TMAH)；氧化劑，諸如過氧化氫(H2O2)；溶劑，諸如水、丙酮、異丙醇(IPA)、乙醇及/或四氫呋喃(THF)；將半導體材料加熱至不高於800℃之溫度或其等之組合。 In an exemplary embodiment as desired, the semiconductor material is then subjected to a post-diffusion process (step 114). The post-diffusion process removes any residue formed during annealing of the semiconductor material, such as, for example, phosphonium phosphate, phosphorus oxide, cerium oxide, or contaminants. If the residue is not removed after annealing, it may have an adverse effect on the performance of the subsequently formed device. For example, this residue can greatly increase the contact resistance between the doped semiconductor material and the metal contacts formed thereon. Examples of post-diffusion processing include subjecting a semiconductor material to an acid such as hydrofluoric acid (HF), hydrochloric acid (HCl), sulfuric acid (H 2 SO 4 ), and/or nitric acid (HNO 3 ); a salt such as ammonium hydroxide (NH 4 ) OH), sodium hydroxide (NaOH), potassium hydroxide (KOH), tetramethylammonium hydroxide (TMAH); oxidizing agents such as hydrogen peroxide (H 2 O 2 ); solvents such as water, acetone, isopropanol ( IPA), ethanol and/or tetrahydrofuran (THF); heating the semiconductor material to a temperature not higher than 800 ° C or a combination thereof.
下文係用於製作半導體材料之摻雜區域之含磷摻雜劑之 實例。實例僅為闡釋之目的提供且不意在以任何方式限制本發明之各種實施例。 The following is used to prepare a phosphorus-containing dopant for a doped region of a semiconductor material. Example. The examples are provided for illustrative purposes only and are not intended to limit the various embodiments of the invention in any way.
在1升(L)玻璃容器中，將8.3體積份之85%磷酸與33.3體積份乙二醇及58.3體積份25% TMAH水溶液組合。使用電磁攪拌器在室溫下攪拌溶液達三十分鐘。隨後使用0.45 μm聚偏氟乙烯(PVDF)過濾器過濾溶液以獲得含磷摻雜劑。摻雜劑之pH為7。使用Dimatix噴墨印刷機型號DMP 2831之1皮升(pL)噴嘴以15 μm之液滴間距將含磷摻雜劑沈積在裸P型矽晶圓上。在200℃下將矽晶圓烘烤達大約10分鐘。在矽晶圓上達成薄如20 μm之摻雜劑線寬度。 In a 1 liter (L) glass vessel, 8.3 parts by volume of 85% phosphoric acid was combined with 33.3 parts by volume of ethylene glycol and 58.3 parts by volume of 25% TMAH aqueous solution. The solution was stirred at room temperature for 30 minutes using a magnetic stirrer. The solution was then filtered using a 0.45 μm polyvinylidene fluoride (PVDF) filter to obtain a phosphorus-containing dopant. The pH of the dopant is 7. Phosphorous dopants were deposited on bare P-type germanium wafers using a Dimatix inkjet printer model DMP 2831 1 picoliter (pL) nozzle at a 15 μm drop pitch. The tantalum wafer was baked at 200 ° C for approximately 10 minutes. A dopant line width as thin as 20 μm is achieved on the germanium wafer.
將大約100毫升(mL)乙二醇添加至250 mL玻璃容器。將大約1克(g)之Aerosil® 380發煙二氧化矽添加至乙二醇且混合液係使用Heat Systems-Ultrasonics Inc.超音波處理器型號W-375混合達大約15分鐘以形成均勻分散。將大約100 mL去離子水添加至500 mL玻璃容器。將大約150 g 50% TMAH水溶液及70 mL 85%磷酸水溶液添加至水中並使用電磁攪拌器將所得溶液攪拌達三十分鐘。將大約100 mL二氧化矽/乙二醇分散液與100 mL水/TMAH/磷酸溶液組合並使用電磁攪拌器將混合液連續攪拌達大約三十分鐘以獲得含磷摻雜劑。摻雜劑之pH為7。使用Dimatix噴墨印刷機型號DMP 2831之1 pL噴嘴以12 μm之液滴間距將含磷摻雜劑沈積在裸P型矽晶圓上。在200℃下烘烤矽晶圓達大約10分 鐘。在矽晶圓上達成薄如20 μm之摻雜劑線寬度。 Approximately 100 milliliters (mL) of ethylene glycol was added to the 250 mL glass vessel. Approximately 1 gram (g) of Aerosil® 380 fumed cerium oxide was added to ethylene glycol and the mixture was mixed using a Heat Systems-Ultrasonics Inc. ultrasonic processor model W-375 for approximately 15 minutes to form a uniform dispersion. Add approximately 100 mL of deionized water to the 500 mL glass container. Approximately 150 g of 50% TMAH in water and 70 mL of 85% aqueous phosphoric acid were added to water and the resulting solution was stirred using a magnetic stirrer for thirty minutes. Approximately 100 mL of the ceria/ethylene glycol dispersion was combined with 100 mL of water/TMAH/phosphoric acid solution and the mixture was continuously stirred using a magnetic stirrer for approximately thirty minutes to obtain a phosphorus-containing dopant. The pH of the dopant is 7. Phosphorous dopants were deposited on bare P-type germanium wafers using a Dimatix inkjet printer model DMP 2831 1 pL nozzle at a 12 μm drop pitch. Baking wafers at 200 ° C for approximately 10 minutes bell. A dopant line width as thin as 20 μm is achieved on the germanium wafer.
在1 L玻璃容器中，將16.6體積份之85%磷酸與25.0體積份乙二醇及58.3份25% TMAH水溶液組合。使用電磁攪拌器在室溫下攪拌溶液達三十分鐘。隨後使用0.45 μm PVDF過濾器將溶液過濾以獲得含磷摻雜劑。摻雜劑之pH為2.5。使用Dimatix噴墨印刷機型號DMP 2831之1 pL噴嘴以15 μm之液滴間距將含磷摻雜劑沈積在裸P型矽晶圓上。矽晶圓在200℃下烘烤達大約10分鐘且隨後在980℃下經歷爐達大約3小時。在用經稀釋氫氟酸(DHF)去垢後，在摻雜矽晶圓上達成低如3.5歐姆/平方之薄層電阻。 In a 1 L glass vessel, 16.6 parts by volume of 85% phosphoric acid was combined with 25.0 parts by volume of ethylene glycol and 58.3 parts of 25% TMAH aqueous solution. The solution was stirred at room temperature for 30 minutes using a magnetic stirrer. The solution was then filtered using a 0.45 μm PVDF filter to obtain a phosphorus-containing dopant. The pH of the dopant is 2.5. Phosphorous dopants were deposited on bare P-type germanium wafers using a Dimatix inkjet printer model DMP 2831 1 pL nozzle at a 15 μm drop pitch. The tantalum wafer was baked at 200 ° C for approximately 10 minutes and then subjected to furnace at 980 ° C for approximately 3 hours. After descaling with diluted hydrofluoric acid (DHF), a sheet resistance as low as 3.5 ohms/square is achieved on the doped germanium wafer.
在1 L玻璃容器中，40體積份85%磷酸用60體積份25% TMAH水溶液中和。使用電磁攪拌器在室溫下攪拌溶液達三十分鐘。隨後使用0.45 μm PVDF過濾器過濾溶液以獲得含磷摻雜劑。在200℃下烘烤紋理化P型矽晶圓達大約20分鐘且隨後使其冷卻。使用Dimatix噴墨印刷機型號DMP 2831之10 pL噴嘴以20 μm之液滴間距將含磷摻雜劑沈積在紋理化矽晶圓上。矽晶圓在200℃下烘烤達大約10分鐘且隨後在350℃下烘烤達10分鐘。在矽晶圓上達成280 μm摻雜劑線寬度。 In a 1 L glass vessel, 40 parts by volume of 85% phosphoric acid was neutralized with 60 parts by volume of a 25% TMAH aqueous solution. The solution was stirred at room temperature for 30 minutes using a magnetic stirrer. The solution was then filtered using a 0.45 μm PVDF filter to obtain a phosphorus-containing dopant. The textured P-type wafer was baked at 200 ° C for approximately 20 minutes and then allowed to cool. Phosphorous dopants were deposited on the textured tantalum wafer using a 10 pL nozzle of Dimatix inkjet printer model DMP 2831 at a 20 μm drop pitch. The tantalum wafer was baked at 200 ° C for approximately 10 minutes and then baked at 350 ° C for 10 minutes. A 280 μm dopant line width was achieved on the germanium wafer.
在2 L管型反應器中，藉由198份25% TMAH水溶液中和136份85%磷酸水溶液。溶液進一步用190份去離子水稀釋 並添加398份丙三醇。以300 rpm機械攪拌所得溶液達15分鐘。逐漸地，將39份Aerosil 380發煙二氧化矽及39份Aerosil R816添加至溶液中並將轉速調整為500 rpm。將懸浮液攪拌達3小時。使用網版印刷將所得含磷摻雜劑沈積在裸P型矽晶圓上。在300℃下烘烤晶圓達大約1分鐘。在矽晶圓上達成薄如50 μm之摻雜劑線寬度。 In a 2 L tubular reactor, 136 parts of an 85% aqueous phosphoric acid solution was neutralized by 198 parts of a 25% TMAH aqueous solution. The solution was further diluted with 190 parts of deionized water And added 398 parts of glycerol. The resulting solution was mechanically stirred at 300 rpm for 15 minutes. Gradually, 39 parts of Aerosil 380 fuming cerium oxide and 39 parts of Aerosil R816 were added to the solution and the rotation speed was adjusted to 500 rpm. The suspension was stirred for 3 hours. The resulting phosphorus-containing dopant was deposited on a bare P-type germanium wafer using screen printing. The wafer was baked at 300 ° C for approximately 1 minute. A dopant line width as thin as 50 μm is achieved on the germanium wafer.
在2 L玻璃容器中，藉由825份25% TMAH水溶液中和425份85%磷酸水溶液並以200 rpm機械攪拌混合液達15分鐘。將容器附接至旋轉蒸發器且內部的水被蒸發直至溶液為其原始重量的46.5%。添加2470份丙三醇以冷凝並以300 rpm機械攪拌混合液達一小時。將74.8 g Aerosil 380發煙二氧化矽及74.8 g CAB-O-SIL TS-610發煙二氧化矽緩慢添加至溶液中使得兩份發煙二氧化矽完全分散在溶液中。以800 rpm機械攪拌混合液達8小時。使用網版印刷將含磷摻雜劑沈積在裸P型矽晶圓上。在300℃下將晶圓烘烤達大約1分鐘。在矽晶圓上達成薄如50 μm之摻雜劑線寬度。 In a 2 L glass vessel, 425 parts of an 85% aqueous phosphoric acid solution was neutralized by 825 parts of a 25% TMAH aqueous solution and the mixture was mechanically stirred at 200 rpm for 15 minutes. The vessel was attached to a rotary evaporator and the water inside was evaporated until the solution was 46.5% of its original weight. 2470 parts of glycerol were added to condense and the mixture was mechanically stirred at 300 rpm for one hour. 74.8 g of Aerosil 380 fumed cerium oxide and 74.8 g of CAB-O-SIL TS-610 fumed cerium oxide were slowly added to the solution so that the two fuming cerium oxides were completely dispersed in the solution. The mixture was mechanically stirred at 800 rpm for 8 hours. The phosphorous-containing dopant is deposited on the bare P-type germanium wafer using screen printing. The wafer was baked at 300 ° C for approximately 1 minute. A dopant line width as thin as 50 μm is achieved on the germanium wafer.
使用機械攪拌將39份CAB-O-SIL TS-380緩慢添加至1 L燒瓶中的136份85%磷酸水溶液中。以500 rpm攪拌懸浮液達20分鐘且隨後將容器加熱至100℃達五小時。懸浮液用198份25% TMAH水溶液中和且隨後與190份去離子水及398份丙三醇組合。將39份Aerosil 200添加至懸浮液中以調整其最終黏度。以1200 rpm攪拌懸浮液達5小時。使用 網版印刷將含磷摻雜劑沈積在裸P型矽晶圓上。在300℃下將晶圓烘烤達大約1分鐘。在矽晶圓上達成薄如50 μm之摻雜劑線寬度。 39 parts of CAB-O-SIL TS-380 was slowly added to 136 parts of an 85% aqueous phosphoric acid solution in a 1 L flask using mechanical stirring. The suspension was stirred at 500 rpm for 20 minutes and then the vessel was heated to 100 °C for five hours. The suspension was neutralized with 198 parts of a 25% TMAH aqueous solution and then combined with 190 parts of deionized water and 398 parts of glycerol. 39 parts of Aerosil 200 were added to the suspension to adjust its final viscosity. The suspension was stirred at 1200 rpm for 5 hours. use Screen printing deposits phosphorus-containing dopants on bare P-type germanium wafers. The wafer was baked at 300 ° C for approximately 1 minute. A dopant line width as thin as 50 μm is achieved on the germanium wafer.
在2 L管型反應器中，用198份25% TMAH水溶液中和136份85%磷酸水溶液。將溶液與190份去離子水及398份丙三醇組合並以300 rpm將其機械攪拌達15分鐘。逐漸地，將39份Aerosil 380發煙二氧化矽、10份2-羥乙基纖維素及29份Aerosil R816添加至溶液中。以500 rpm攪拌懸浮液達3小時直至其變為半透明。使用網版印刷將含磷摻雜劑沈積在裸P型矽晶圓上。在300℃下烘烤晶圓達大約1分鐘。在矽晶圓上達成薄如50 μm之摻雜劑線寬度。 In a 2 L tubular reactor, 136 parts of an 85% aqueous phosphoric acid solution was neutralized with 198 parts of a 25% TMAH aqueous solution. The solution was combined with 190 parts of deionized water and 398 parts of glycerol and mechanically stirred at 300 rpm for 15 minutes. Gradually, 39 parts of Aerosil 380 fuming cerium oxide, 10 parts of 2-hydroxyethyl cellulose, and 29 parts of Aerosil R816 were added to the solution. The suspension was stirred at 500 rpm for 3 hours until it became translucent. The phosphorous-containing dopant is deposited on the bare P-type germanium wafer using screen printing. The wafer was baked at 300 ° C for approximately 1 minute. A dopant line width as thin as 50 μm is achieved on the germanium wafer.
在2 L燒杯中，使用機械攪拌組合10份羥乙基纖維素、2份可從中國Anhui TaiChang Chemical購得之鈦酸酯偶聯劑TC-WT、39份Aerosil R812、136份85%磷酸水溶液及398份丙三醇。懸浮液以500 rpm攪拌達20分鐘並加熱至100℃達1小時。懸浮液變黏並添加130份去離子水及60份氨水以減小黏度。接下來，添加39份Aerosil 150以調整最終黏度。將轉速調整為1500 rpm並攪拌懸浮液達3小時。使用網版印刷將含磷摻雜劑沈積在裸P型矽晶圓上。在300℃下烘烤晶圓達大約1分鐘。在矽晶圓上達成薄如50 μm之摻雜劑線寬度。 In a 2 L beaker, 10 parts of hydroxyethyl cellulose, 2 parts of titanate coupling agent TC-WT available from Anhui TaiChang Chemical, 39 parts of Aerosil R812, and 136 parts of 85% phosphoric acid aqueous solution were combined using mechanical stirring. And 398 parts of glycerol. The suspension was stirred at 500 rpm for 20 minutes and heated to 100 °C for 1 hour. The suspension became sticky and 130 parts of deionized water and 60 parts of aqueous ammonia were added to reduce the viscosity. Next, 39 parts of Aerosil 150 were added to adjust the final viscosity. The speed was adjusted to 1500 rpm and the suspension was stirred for 3 hours. The phosphorous-containing dopant is deposited on the bare P-type germanium wafer using screen printing. The wafer was baked at 300 ° C for approximately 1 minute. A dopant line width as thin as 50 μm is achieved on the germanium wafer.
在2 L管形反應器中，用198份25% TMAH水溶液中和136份85%磷酸水溶液。將溶液與190份去離子水及398 g丙三醇組合並以300 rpm將其機械攪拌達15分鐘。逐漸地，將37份Aerosil 380發煙二氧化矽、30份Aerosil R972及9份Aerosil R816添加至溶液。以500 rpm攪拌懸浮液達3小時。使用網版印刷將含磷摻雜劑沈積在裸P型矽晶圓上。在300℃下烘烤晶圓達大約1分鐘。在矽晶圓上達成薄如50 μm之摻雜劑線寬度。 In a 2 L tubular reactor, 136 parts of an 85% aqueous solution of phosphoric acid was neutralized with 198 parts of a 25% TMAH aqueous solution. The solution was combined with 190 parts of deionized water and 398 g of glycerol and mechanically stirred at 300 rpm for 15 minutes. Gradually, 37 parts of Aerosil 380 fuming cerium oxide, 30 parts of Aerosil R972 and 9 parts of Aerosil R816 were added to the solution. The suspension was stirred at 500 rpm for 3 hours. The phosphorous-containing dopant is deposited on the bare P-type germanium wafer using screen printing. The wafer was baked at 300 ° C for approximately 1 minute. A dopant line width as thin as 50 μm is achieved on the germanium wafer.
因此，已提供在半導體材料中形成磷摻雜區域之實質上無矽烷之含磷摻雜劑、製作此等含磷摻雜劑之方法及使用此等含磷摻雜劑在半導體材料中形成磷摻雜區域之方法。雖然已在上文實施方式中提出至少一個例示性實施例，但是應瞭解存在許多變化。亦應瞭解例示性實施例或諸例示性實施例僅為實例且不旨在以任何方式限制本發明之範疇、適用性或組態。而是，上文實施方式將為熟習此項技術者提供用於實施本發明之例示性實施例之便利途徑，但是應瞭解可對例示性實施例中所描述之元件之功能及配置作出各種改變而不脫離如隨附申請專利範圍及其合法等效物所述之本發明之範圍。 Accordingly, there has been provided a substantially decane-free phosphorus-containing dopant for forming a phosphorus-doped region in a semiconductor material, a method of fabricating such a phosphorus-containing dopant, and the use of such a phosphorus-containing dopant to form phosphorus in a semiconductor material Method of doping regions. While at least one exemplary embodiment has been presented in the above embodiments, it should be appreciated that many variations are possible. It is also to be understood that the exemplified embodiments or the exemplary embodiments are merely illustrative and are not intended to limit the scope, applicability, or configuration of the invention in any manner. Rather, the above-described embodiments will provide those skilled in the art with a convenient way to implement the exemplary embodiments of the present invention, but it is understood that various changes can be made in the function and configuration of the elements described in the exemplary embodiments. The scope of the invention as set forth in the appended claims and their legal equivalents.
10‧‧‧太陽能電池 10‧‧‧ solar cells
12‧‧‧矽晶圓 12‧‧‧矽 wafer
14‧‧‧光接收前側 14‧‧‧Light receiving front side
16‧‧‧後側 16‧‧‧ Back side
18‧‧‧p-n接面 18‧‧‧p-n junction
20‧‧‧金屬接觸件 20‧‧‧Metal contacts
22‧‧‧金屬接觸件 22‧‧‧Metal contacts
24‧‧‧窄區域 24‧‧‧Narrow area
30‧‧‧太陽能電池 30‧‧‧ solar cells
32‧‧‧金屬接觸件 32‧‧‧Metal contacts
50‧‧‧噴墨印刷機構 50‧‧‧Inkjet printing agency
52‧‧‧印刷頭 52‧‧‧Print head
54‧‧‧噴嘴 54‧‧‧Nozzles
56‧‧‧墨 56‧‧‧Ink
58‧‧‧基板 58‧‧‧Substrate
60‧‧‧噴霧印刷機構 60‧‧‧Spray printing agency
62‧‧‧生霧器/霧化器 62‧‧‧ fogger / atomizer
64‧‧‧流體 64‧‧‧ Fluid
66‧‧‧霧化流體 66‧‧‧Atomizing fluid
68‧‧‧導流沈積頭 68‧‧‧drain deposition head
70‧‧‧噴嘴 70‧‧‧ nozzle
72‧‧‧環流 72‧‧‧Circulation
74‧‧‧導向基板 74‧‧‧guide substrate
76‧‧‧霧化材料流 76‧‧‧Atomized material flow
圖1係具有光側接觸件及背側接觸件之習知太陽能電池之示意圖；圖2係具有背側接觸件之另一習知太陽能電池之示意圖； 圖3係將墨分佈在基板上之噴墨印刷機構之截面圖；圖4係將墨分佈在基板上之噴霧印刷機構之截面圖；圖5係根據本發明之例示性實施例之使用非接觸印刷製程在半導體材料中形成磷摻雜區域之方法之流程圖；圖6係根據本發明之例示性實施例之製作用於圖5之方法之含磷摻雜劑之方法之流程圖；及圖7係根據本發明之另一例示性實施例之製作用於圖5之方法之含磷摻雜劑之方法之流程圖。 1 is a schematic view of a conventional solar cell having a light side contact and a back side contact; FIG. 2 is a schematic view of another conventional solar cell having a back side contact; 3 is a cross-sectional view of an inkjet printing mechanism that distributes ink on a substrate; FIG. 4 is a cross-sectional view of a spray printing mechanism that distributes ink on a substrate; and FIG. 5 is a non-contact use according to an exemplary embodiment of the present invention. Flowchart of a method of forming a phosphorous doped region in a semiconductor material in a printing process; FIG. 6 is a flow diagram of a method of fabricating a phosphorus-containing dopant for use in the method of FIG. 5 in accordance with an illustrative embodiment of the present invention; 7 is a flow diagram of a method of making a phosphorus-containing dopant for use in the method of FIG. 5 in accordance with another exemplary embodiment of the present invention.
10‧‧‧太陽能電池 10‧‧‧ solar cells
12‧‧‧矽晶圓 12‧‧‧矽 wafer
14‧‧‧光接收前側 14‧‧‧Light receiving front side
16‧‧‧後側 16‧‧‧ Back side
18‧‧‧p-n接面 18‧‧‧p-n junction
20‧‧‧金屬接觸件 20‧‧‧Metal contacts
22‧‧‧金屬接觸件 22‧‧‧Metal contacts
24‧‧‧窄區域 24‧‧‧Narrow area
Claims (35)
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| PCT/CN2011/001392 WO2013026177A1 (en) | 2011-08-22 | 2011-08-22 | Phosphorous-comprising dopants, methods for forming phosphorous-doped regions in semiconductor substrates using such phosphorous-comprising dopants, and methods for forming such phosphorous-comprising dopants |
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| CN1301537C (en) * | 1999-04-16 | 2007-02-21 | 国际商业机器公司 | Low temperature reflux dielectric-boron phosphor-silicon fluorine glass |
| JP2003188393A (en) * | 2001-12-18 | 2003-07-04 | Sharp Corp | Manufacturing method for solar cell |
| US20090208668A1 (en) * | 2008-02-19 | 2009-08-20 | Soo Young Choi | Formation of clean interfacial thin film solar cells |
| KR101631711B1 (en) * | 2008-03-21 | 2016-06-17 | 신에쓰 가가꾸 고교 가부시끼가이샤 | Phosphorus paste for diffusion and method for preparing solar cell by using the same |
| US8309446B2 (en) * | 2008-07-16 | 2012-11-13 | Applied Materials, Inc. | Hybrid heterojunction solar cell fabrication using a doping layer mask |
| US8053867B2 (en) * | 2008-08-20 | 2011-11-08 | Honeywell International Inc. | Phosphorous-comprising dopants and methods for forming phosphorous-doped regions in semiconductor substrates using phosphorous-comprising dopants |
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