TWI825959B - Manufacturing method of nitrogen-doped P-type single crystal silicon - Google Patents

Manufacturing method of nitrogen-doped P-type single crystal silicon Download PDF

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TWI825959B
TWI825959B TW111132604A TW111132604A TWI825959B TW I825959 B TWI825959 B TW I825959B TW 111132604 A TW111132604 A TW 111132604A TW 111132604 A TW111132604 A TW 111132604A TW I825959 B TWI825959 B TW I825959B
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silicon
single crystal
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TW202300717A (en
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徐鵬
蘭洵
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大陸商西安奕斯偉材料科技股份有限公司
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    • C30CRYSTAL GROWTH
    • C30BSINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B15/00Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C30B15/02Single-crystal growth by pulling from a melt, e.g. Czochralski method adding crystallising materials or reactants forming it in situ to the melt
    • C30B15/04Single-crystal growth by pulling from a melt, e.g. Czochralski method adding crystallising materials or reactants forming it in situ to the melt adding doping materials, e.g. for n-p-junction
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B15/00Single-crystal growth by pulling from a melt, e.g. Czochralski method
    • C30B15/20Controlling or regulating
    • CCHEMISTRY; METALLURGY
    • C30CRYSTAL GROWTH
    • C30BSINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02Elements
    • C30B29/06Silicon

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  • Crystallography & Structural Chemistry (AREA)
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Abstract

本發明實施例公開了一種氮摻雜P型單晶矽製造方法,包括:將高摻雜氮單晶與多晶矽投入坩堝並加熱拉晶爐,得到第一矽熔體;向該第一矽熔體加入高摻雜硼單晶,得到第二矽熔體;在該第二矽熔體中以直拉法拉制氮摻雜P型單晶矽。The embodiment of the invention discloses a method for manufacturing nitrogen-doped P-type single crystal silicon, which includes: putting highly nitrogen-doped single crystal and polycrystalline silicon into a crucible and heating the crystal pulling furnace to obtain a first silicon melt; Highly doped boron single crystal is added into the second silicon melt to obtain a second silicon melt; nitrogen-doped P-type single crystal silicon is drawn in the second silicon melt by Czochralski method.

Description

氮摻雜P型單晶矽製造方法Manufacturing method of nitrogen-doped P-type single crystal silicon

本發明屬於半導體矽片生產領域,尤其關於一種氮摻雜P型單晶矽製造方法。The invention belongs to the field of semiconductor silicon wafer production, and in particular relates to a method for manufacturing nitrogen-doped P-type single crystal silicon.

伴隨資訊化的全球發展,矽片應用領域的器件尺寸持續減小,同時在器件集成度逐漸提高的情況下,功率器件的應用領域越來越廣,功率器件的主要特徵是耐高壓,基底的電阻對於器件性能的影響極大,因此要求基底的電阻率高且電阻率變化小。由於摻雜元素與矽元素晶格不匹配,在單晶矽生長過程中存在分凝現象,即摻雜元素結晶於單晶矽晶錠中的濃度小於熔體(原料)中的濃度,使得摻雜元素在坩堝中的濃度不斷升高,從而使單晶矽晶錠中摻雜元素的濃度也不斷升高,致使單晶矽晶錠生長末期摻雜元素濃度急劇升高,載流子密度隨之顯著升高,晶錠電阻率急劇下降,晶錠軸向電阻率變化梯度較大。近年來伴隨著電子元器件尤其是功率器件要求電阻率變化率梯度越來越小,通過改變摻雜方式來減小電阻率的變化變得非常重要。另外,若在上述矽晶片上存在重金屬雜質,會引起器件的特性不良,因此減少重金屬雜質也值得引起注意。作為降低重金屬雜質的技術之一,吸雜技術的重要性越來越高,因此使用吸雜效果高的低電阻率的P型矽晶片是很有利的。同時在器件集成度逐漸提高的情況下,矽片所受到的應力會顯著提高,由於矽材料的機械強度低,會影響加工和製造過步驟參數的設定,並且在產品組裝過程中矽片損傷、破碎的情況極其容易發生,從而導致矽片生產成本的增加,因此改善矽片的機械強度具有重要意義。With the global development of informatization, the size of devices in silicon chip applications continues to decrease. At the same time, with the gradual increase in device integration, the application fields of power devices are becoming wider and wider. The main characteristics of power devices are high voltage resistance and low substrate resistance. Resistance has a great impact on device performance, so the substrate is required to have high resistivity and small resistivity change. Due to the lattice mismatch between the doping elements and the silicon element, segregation occurs during the growth process of single crystal silicon. That is, the concentration of the doping elements crystallized in the single crystal silicon ingot is less than the concentration in the melt (raw material), causing the doping The concentration of impurity elements in the crucible continues to increase, so that the concentration of doping elements in the single crystal silicon ingot also continues to increase, resulting in a sharp increase in the concentration of doping elements at the end of the growth of the single crystal silicon ingot, and the carrier density increases with It increases significantly, the resistivity of the crystal ingot drops sharply, and the gradient of the axial resistivity of the crystal ingot is large. In recent years, as electronic components, especially power devices, require smaller and smaller resistivity change rate gradients, it has become very important to reduce the change in resistivity by changing the doping method. In addition, if heavy metal impurities are present on the above-mentioned silicon wafer, it will cause poor device characteristics. Therefore, reducing heavy metal impurities is also worthy of attention. As one of the technologies for reducing heavy metal impurities, gettering technology is becoming more and more important. Therefore, it is very advantageous to use low-resistivity P-type silicon wafers with high gettering effects. At the same time, as the degree of device integration gradually increases, the stress on the silicon wafer will increase significantly. Due to the low mechanical strength of the silicon material, it will affect the setting of processing and manufacturing step parameters, and the silicon wafer will be damaged during the product assembly process. Breakage is extremely easy to occur, which leads to an increase in the production cost of silicon wafers. Therefore, it is of great significance to improve the mechanical strength of silicon wafers.

用於生產上述積體電路等半導體電子元器件的矽片,主要通過將直拉(Czochralski)法拉制的單晶矽棒切片而製造出。Czochralski法包括使由石英製成的坩堝中的多晶矽熔化以獲得矽熔體,將單晶晶種浸入矽熔體中,以及連續地提升晶種移動離開矽熔體表面,由此在移動過程中在相介面處生長出單晶矽棒。Silicon wafers used to produce semiconductor electronic components such as the above-mentioned integrated circuits are mainly produced by slicing single crystal silicon rods drawn by the Czochralski method. The Czochralski method involves melting polycrystalline silicon in a crucible made of quartz to obtain a silicon melt, immersing a single crystal seed crystal into the silicon melt, and continuously lifting the seed crystal to move away from the surface of the silicon melt, whereby during the movement Single crystal silicon rods grow at the phase interface.

在通過上述直拉法製備吸雜效果高的低電阻率的P型矽晶片的過程中,通常選擇硼作為控制電阻率的摻雜劑,通過摻氮去除Void缺陷增強機械強度。然而在摻硼、摻氮的過程中,由於作為硼摻雜劑的硼單質易揮發且與氮會形成難融化的氮化硼(BN)使得製成的低電阻率的P型矽晶片硼含量低,或者造成位錯導致拉晶失敗。同時,硼摻雜劑和氮摻雜劑的熔化溫度高,使得石英坩堝軟化,導致氧析出不可控,影響製成的吸雜效果、低電阻率低的P型矽晶片的品質。In the process of preparing P-type silicon wafers with high gettering effect and low resistivity through the above-mentioned Czochralski method, boron is usually selected as the dopant to control the resistivity, and void defects are removed by nitrogen doping to enhance the mechanical strength. However, during the process of boron doping and nitrogen doping, since the boron element as a boron dopant is easily volatile and forms refractory boron nitride (BN) with nitrogen, the resulting low resistivity P-type silicon wafer has a boron content of Low, or causing dislocations leading to crystal pulling failure. At the same time, the high melting temperatures of boron dopants and nitrogen dopants soften the quartz crucible, leading to uncontrollable oxygen precipitation and affecting the quality of the produced P-type silicon wafers with gettering effects and low resistivity.

為解決上述技術問題,本發明實施例期望提供一種氮摻雜P型單晶矽的製造方法,能夠克服硼易揮發的問題,且能避免氮化硼生成,從而以高生產率、低成本製造高品質的具有高吸雜能力的氮摻雜P型單晶矽。In order to solve the above technical problems, embodiments of the present invention are expected to provide a method for manufacturing nitrogen-doped P-type single crystal silicon, which can overcome the problem of boron volatilization and avoid the generation of boron nitride, thereby manufacturing high-performance silicon with high productivity and low cost. High-quality nitrogen-doped P-type single crystal silicon with high gettering ability.

本發明的技術方案是這樣實現的,包括: 將高摻雜氮單晶與多晶矽投入坩堝並加熱拉晶爐,得到第一矽熔體; 向該第一矽熔體加入高摻雜硼單晶,得到第二矽熔體; 在該第二矽熔體中以直拉法拉制氮摻雜P型單晶矽。 The technical solution of the present invention is implemented in this way, including: Put the highly doped nitrogen single crystal and polycrystalline silicon into the crucible and heat the crystal pulling furnace to obtain the first silicon melt; Adding highly doped boron single crystal to the first silicon melt to obtain a second silicon melt; Nitrogen-doped P-type single crystal silicon is drawn in the second silicon melt by Czochralski method.

可選地,該將高摻雜氮單晶與多晶矽投入坩堝並加熱拉晶爐,得到第一矽熔體包括: 將該高摻雜氮單晶定量計算後與該多晶矽一起投入坩堝; 將該拉晶爐抽真空並通入保護氣體; 打開加熱器,提升爐室溫度並保溫一段時間,直至該高摻雜氮單晶與該多晶矽完全熔化,得到該第一矽熔體。 Optionally, putting the highly doped nitrogen single crystal and polycrystalline silicon into the crucible and heating the crystal pulling furnace to obtain the first silicon melt includes: After quantitative calculation, the highly doped nitrogen single crystal is put into the crucible together with the polycrystalline silicon; Evacuate the crystal pulling furnace and introduce protective gas; Turn on the heater, raise the temperature of the furnace chamber and keep it warm for a period of time until the highly doped nitrogen single crystal and the polycrystalline silicon are completely melted to obtain the first silicon melt.

可選地,該第一矽熔體為低摻氮矽熔體; 可選地,該保護氣體為氬氣。 Optionally, the first silicon melt is a low nitrogen-doped silicon melt; Optionally, the protective gas is argon.

可選地,該向該第一矽熔體加入高摻雜硼單晶,得到第二矽熔體包括: 將該第一矽熔體靜置一段時間; 向靜置後的該第一矽熔體加入該高摻雜硼單晶; 提高爐室溫度,使得該高摻雜硼單晶完全融化至該第一矽熔體,得到該第二矽熔體。 Optionally, adding highly doped boron single crystal to the first silicon melt to obtain the second silicon melt includes: Let the first silicon melt stand for a period of time; Add the highly doped boron single crystal to the first silicon melt after standing; The temperature of the furnace chamber is increased so that the highly doped boron single crystal is completely melted into the first silicon melt to obtain the second silicon melt.

可選地,該第二矽熔體為低摻硼氮矽熔體。Optionally, the second silicon melt is a low boron-doped silicon nitride melt.

可選地,該在該第二矽熔體中以直拉法拉制氮摻雜P型單晶矽包括:調節爐室溫度;向該第二矽熔體中緩慢放置籽晶,經過引晶、縮頸、放肩、等徑生長、收尾階段完成晶體的生長過程;製成該氮摻雜P型單晶矽。Optionally, the step of pulling nitrogen-doped P-type single crystal silicon in the second silicon melt by Czochralski method includes: adjusting the furnace temperature; slowly placing a seed crystal into the second silicon melt, and after seeding, The crystal growth process is completed in the necking, shouldering, equal-diameter growth, and finishing stages; the nitrogen-doped P-type single crystal silicon is produced.

可選地,該高摻雜氮單晶和該高摻雜硼單晶為顆粒或粉末。Optionally, the highly doped nitrogen single crystal and the highly doped boron single crystal are particles or powders.

為利 貴審查委員了解本發明之技術特徵、內容與優點及其所能達到之功效,茲將本發明配合附圖及附件,並以實施例之表達形式詳細說明如下,而其中所使用之圖式,其主旨僅為示意及輔助說明書之用,未必為本發明實施後之真實比例與精準配置,故不應就所附之圖式的比例與配置關係解讀、侷限本發明於實際實施上的申請範圍,合先敘明。In order to help the review committee understand the technical features, content and advantages of the present invention and the effects it can achieve, the present invention is described in detail below in the form of embodiments with the accompanying drawings and attachments, and the drawings used therein are , its purpose is only for illustration and auxiliary description, and may not represent the actual proportions and precise configurations after implementation of the present invention. Therefore, the proportions and configuration relationships of the attached drawings should not be interpreted or limited to the actual implementation of the present invention. The scope shall be stated first.

在本發明實施例的描述中,需要理解的是,術語“長度”、“寬度”、“上”、“下”、“前”、“後”、“左”、“右”、“垂直”、“水平”、“頂”、“底”“內”、“外”等指示的方位或位置關係為基於附圖所示的方位或位置關係,僅是為了便於描述本發明實施例和簡化描述,而不是指示或暗示所指的裝置或元件必須具有特定的方位、以特定的方位構造和操作,因此不能理解為對本發明的限制。In the description of the embodiments of the present invention, it should be understood that the terms "length", "width", "upper", "lower", "front", "back", "left", "right", "vertical" The orientations or positional relationships indicated by "horizontal", "top", "bottom", "inner", "outer", etc. are based on the orientations or positional relationships shown in the drawings, and are only for the convenience of describing the embodiments of the present invention and simplifying the description. , rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operate in a specific orientation, and therefore cannot be construed as a limitation of the present invention.

此外,術語“第一”、“第二”僅用於描述目的,而不能理解為指示或暗示相對重要性或者隱含指明所指示的技術特徵的數量。由此,限定有“第一”、“第二”的特徵可以明示或者隱含地包括一個或者更多個所述特徵。在本發明實施例的描述中,“多個”的含義是兩個或兩個以上,除非另有明確具體的限定。In addition, the terms “first” and “second” are used for descriptive purposes only and cannot be understood as indicating or implying relative importance or implicitly indicating the quantity of indicated technical features. Thus, features defined as “first” and “second” may explicitly or implicitly include one or more of the described features. In the description of the embodiments of the present invention, "plurality" means two or more than two, unless otherwise explicitly and specifically limited.

在本發明實施例中,除非另有明確的規定和限定,術語“安裝”、“相連”、“連接”、“固定”等術語應做廣義理解,例如,可以是固定連接,也可以是可拆卸連接,或成一體;可以是機械連接,也可以是電連接;可以是直接相連,也可以通過中間媒介間接相連,可以是兩個元件內部的連通或兩個元件的相互作用關係。對於本領域的具通常知識者而言,可以根據具體情況理解上述術語在本發明實施例中的具體含義。In the embodiments of the present invention, unless otherwise expressly stipulated and limited, the terms "installation", "connection", "connection", "fixing" and other terms should be understood in a broad sense. For example, it can be a fixed connection or a removable connection. Disassembly and connection, or integration; it can be a mechanical connection or an electrical connection; it can be a direct connection or an indirect connection through an intermediate medium; it can be an internal connection between two elements or an interaction between two elements. For those with ordinary knowledge in the art, the specific meanings of the above terms in the embodiments of the present invention can be understood according to specific circumstances.

下面將對本發明實施例中的技術方案進行清楚、完整地描述。The technical solutions in the embodiments of the present invention will be described clearly and completely below.

本發明的氮摻雜P型單晶矽製造方法是以柴氏拉晶法(又稱為直拉法)為基礎,同時配合固相摻雜的方式進行氮摻雜P型單晶矽的製備。也就是說,將多晶矽和摻雜劑一起放置在坩堝內加熱形成熔體,並提拉該熔體生長成單晶矽。在本發明中,將高摻雜氮單晶與多晶矽投入坩堝並加熱拉晶爐,得到第一矽熔體;向該第一矽熔體加入高摻雜硼單晶,得到第二矽熔體;在該第二矽熔體中以直拉法拉制氮摻雜P型單晶矽。The manufacturing method of nitrogen-doped P-type single crystal silicon of the present invention is based on the Czochralski crystallization method (also known as Czochralski method) and is combined with solid-phase doping to prepare nitrogen-doped P-type single crystal silicon. . That is to say, polycrystalline silicon and dopants are placed together in a crucible, heated to form a melt, and the melt is pulled to grow into single crystal silicon. In the present invention, highly doped nitrogen single crystal and polycrystalline silicon are put into a crucible and heated in a crystal pulling furnace to obtain a first silicon melt; a highly doped boron single crystal is added to the first silicon melt to obtain a second silicon melt ; Nitrogen-doped P-type single crystal silicon is drawn in the second silicon melt by Czochralski method.

為了通過改變摻雜方式減小電阻率的變化這一技術問題,相關技術中一般通過摻雜兩種或更多種微量元素作為雜質,可使得單晶的導電性發生顯著變化。摻入的雜質主要是三價或五價元素,根據摻雜劑不同所帶來的導電性能上的差異一般可分為N型單晶矽片和P型單晶矽片。在單晶矽片中摻入微量雜質時,雜質原子附近的週期勢場受到干擾並形成附加的束縛狀態,在禁帶中產生附加的雜質能級。能提供電子載流子的雜質稱為施主(Donor)雜質,相應能級稱為施主能級,位於禁帶上方靠近導帶底附近。例如四價元素矽晶體中摻入五價元素磷、砷、銻等雜質原子時,雜質原子作為晶格的一分子,其五個價電子中有四個與周圍的矽原子形成共價鍵,多餘的一個電子被束縛於雜質原子附近,產生類氫淺能級—施主能級。施主能級上的電子躍遷到導帶所需能量比從價帶激發到導帶所需能量小得多,很易激發到導帶成為電子載流子,因此對於摻入施主雜質的單晶矽片,導電載流子主要是被激發到導帶中的電子,屬電子導電型,稱為N型單晶矽片。由於單晶矽片中總是存在本征激發的電子電洞對,所以在N型單晶矽片中電子是多數載流子,電洞是少數載流子。In order to reduce the technical problem of resistivity change by changing the doping method, in related technologies, two or more trace elements are generally doped as impurities, which can significantly change the conductivity of a single crystal. The doped impurities are mainly trivalent or pentavalent elements. According to the differences in conductive properties caused by different dopants, they can generally be divided into N-type single-crystal silicon wafers and P-type single-crystal silicon wafers. When trace amounts of impurities are doped into a single crystal silicon wafer, the periodic potential field near the impurity atoms is disturbed and additional bound states are formed, creating additional impurity energy levels in the forbidden band. Impurities that can provide electron carriers are called donor impurities, and the corresponding energy level is called the donor energy level, which is located above the forbidden band and near the bottom of the conduction band. For example, when impurity atoms of pentavalent elements such as phosphorus, arsenic, and antimony are mixed into a silicon crystal with a tetravalent element, the impurity atom acts as a molecule in the crystal lattice, and four of its five valence electrons form covalent bonds with the surrounding silicon atoms. The extra electron is bound near the impurity atom, creating a hydrogen-like shallow energy level - the donor energy level. The energy required for electrons at the donor energy level to transition to the conduction band is much smaller than the energy required to excite them from the valence band to the conduction band. They are easily excited to the conduction band and become electron carriers. Therefore, for single crystal silicon doped with donor impurities The conductive carriers are mainly electrons excited into the conduction band, which belongs to the electronic conductivity type and is called N-type single crystal silicon wafer. Since there are always intrinsically excited electron-hole pairs in single-crystal silicon wafers, electrons are majority carriers and holes are minority carriers in N-type single-crystal silicon wafers.

相應地,能提供電洞載流子的雜質稱為受主(Acceptor)雜質,相應能級稱為受主能級,位於禁帶下方靠近價帶頂附近。例如在矽晶體中摻入微量三價元素硼、鋁、鎵等雜質原子時,雜質原子與周圍四個矽原子形成共價結合時尚缺少一個電子,因而存在一個空位,與此空位相應的能量狀態就是受主能級。由於受主能級靠近價帶頂,價帶中的電子很容易激發到受主能級上填補這個空位,使受主雜質原子成為負電中心。同時價帶中由於電離出一個電子而留下一個空位,形成自由的電洞載流子。因此這時電洞是多數載流子,雜質單晶矽片主要靠電洞導電,即電洞導電型,稱為p型單晶矽片。在P型單晶矽片中電洞是多數載流子,電子是少數載流子。在半導體器件的各種效應中,少數載流子常扮演重要角色。其特點在於摻入的雜質越多,多子(電洞)的濃度就越高,導電性能就越強。Correspondingly, impurities that can provide hole carriers are called acceptor impurities, and the corresponding energy level is called the acceptor energy level, which is located below the forbidden band and near the top of the valence band. For example, when trace amounts of trivalent elements boron, aluminum, gallium and other impurity atoms are mixed into a silicon crystal, the impurity atom lacks an electron when it forms a covalent bond with the four surrounding silicon atoms, so there is a vacancy, and the energy state corresponding to this vacancy It is the acceptor energy level. Since the acceptor energy level is close to the top of the valence band, electrons in the valence band can easily be excited to the acceptor energy level to fill the vacancy, making the acceptor impurity atom a negative center. At the same time, a vacancy is left in the valence band due to the ionization of an electron, forming a free hole carrier. Therefore, the holes are the majority carriers at this time, and the impurity single crystal silicon wafer mainly conducts electricity through holes, that is, the hole conductivity type is called p-type single crystal silicon wafer. In P-type single crystal silicon wafers, holes are majority carriers and electrons are minority carriers. Minority carriers often play an important role in various effects of semiconductor devices. Its characteristic is that the more impurities are incorporated, the higher the concentration of electrons (holes) and the stronger the conductivity.

在實際使用過程中,通常使用硼作為控制電阻率的摻雜劑。因此,提供這樣的一種P型矽片是非常有利的,該P型矽片具有從正面開始向體內延伸的無晶體缺陷區域(Denuded Zone,DZ)以及與DZ鄰接並且進一步向體內延伸的含有體微缺陷(Bulk Micro Defect,BMD)的區域,這裡的正面指的是P型矽片的需要形成電子元器件的表面。上述的DZ是重要的,因為為了在P型矽片上形成電子元器件,要求在電子元器件的形成區域內不存在晶體缺陷,否則會導致電路斷路等故障的產生,使電子元器件形成在DZ中便可以避免晶體缺陷的影響;而上述的BMD的作用在於,能夠對金屬雜質產生內在吸雜(Intrinsic Getter,IG)作用,使P型矽片中的金屬雜質保持遠離DZ,從而避免金屬雜質導致的漏電電流增加、柵極氧化膜的膜質下降等不利影響。In practical applications, boron is often used as a dopant to control resistivity. Therefore, it is very advantageous to provide a P-type silicon wafer that has a crystal defect-free zone (Denuded Zone, DZ) extending from the front side toward the body and a containing body adjacent to the DZ and extending further toward the body. The area of Bulk Micro Defect (BMD), the front side here refers to the surface of the P-type silicon wafer that needs to form electronic components. The above-mentioned DZ is important because in order to form electronic components on P-type silicon wafers, it is required that there are no crystal defects in the formation area of the electronic components, otherwise it will lead to circuit breakage and other faults, causing the electronic components to be formed in The influence of crystal defects can be avoided in the DZ; and the function of the above-mentioned BMD is to produce an intrinsic getter (IG) effect on metal impurities, keeping the metal impurities in the P-type silicon wafer away from the DZ, thereby avoiding metal impurities. There are adverse effects such as an increase in leakage current caused by impurities and a decrease in the film quality of the gate oxide film.

然而,在生產上述的具有BMD區域的P型矽片的過程中,在P型矽片中摻雜有氮是非常有利的。在P型矽片中摻雜有氮的情況下,能夠促進以氮作為核心的BMD的形成,從而使BMD達到一定的密度,使BMD作為金屬吸雜源有效地發揮作用,而且還能夠對BMD的密度分佈產生有利影響,比如使BMD的密度在P型矽片的徑向上的分佈更為均勻,比如使BMD的密度在臨近DZ的區域更高而朝向矽片的體內逐漸降低等。在CZ法制P型矽片中摻雜氮雜質還可以減小Voids的尺寸,使其在高溫下退火得到消除,氮還能改善位錯提高P型矽片的機械性能。另外,在CZ法拉制P型矽片中摻雜氮雜質,氮和氧會發生相互作用,形成淺熱施主性能的氮氧複合體,進一步改善P型矽片的電學性能。However, in the process of producing the above-mentioned P-type silicon wafer with a BMD region, it is very advantageous to dope the P-type silicon wafer with nitrogen. When the P-type silicon wafer is doped with nitrogen, it can promote the formation of BMD with nitrogen as the core, so that the BMD reaches a certain density, allowing the BMD to effectively function as a metal getter source, and it can also The density distribution has a beneficial effect, such as making the BMD density more uniformly distributed in the radial direction of the P-type silicon wafer, such as making the BMD density higher in the area adjacent to the DZ and gradually decreasing toward the body of the silicon wafer. Doping nitrogen impurities in P-type silicon wafers produced by the CZ method can also reduce the size of Voids, eliminating annealing at high temperatures. Nitrogen can also improve dislocations and improve the mechanical properties of P-type silicon wafers. In addition, when nitrogen impurities are doped into P-type silicon wafers drawn by CZ method, nitrogen and oxygen will interact to form a nitrogen-oxygen complex with shallow thermal donor properties, further improving the electrical properties of P-type silicon wafers.

在製備氮摻雜P型單晶矽時,相關技術中通常將氮摻雜劑、硼摻雜劑以及多晶矽原料同時加入到石英坩堝中進行加熱,原材料均熔化後得到摻雜有氮和硼的矽熔體,接著,以CZ法拉制氮摻雜P型單晶矽。在該製備過程中,本領域通常使用固態材料進行摻雜劑添加,以精確地控制摻雜劑的添加濃度,如選用Si 3N 4原材料和硼單質作為摻雜劑。在製備氮摻雜P型單晶矽的過程中,需要將石英坩堝內的多晶矽、Si 3N 4原材料以及硼單質加熱為熔融狀態,以獲得摻有氮和硼的矽熔體。在1450℃下多晶矽可完全融化,然而Si 3N 4原材料和硼單晶分別需要在1900℃和2100℃下保溫一段時間才能夠完全融解,未完全融解的摻雜劑會造成晶棒中的位錯缺陷,導致拉晶失敗。 When preparing nitrogen-doped P-type single crystal silicon, in related technologies, nitrogen dopants, boron dopants and polycrystalline silicon raw materials are usually added to a quartz crucible at the same time for heating. After the raw materials are melted, a nitrogen- and boron-doped material is obtained. The silicon melt is then pulled into nitrogen-doped P-type single crystal silicon by CZ method. In this preparation process, solid-state materials are usually used in this field to add dopants to accurately control the concentration of dopants, such as Si 3 N 4 raw materials and boron elements as dopants. In the process of preparing nitrogen-doped P-type single crystal silicon, it is necessary to heat the polycrystalline silicon, Si 3 N 4 raw material and boron elemental substance in the quartz crucible to a molten state to obtain a silicon melt doped with nitrogen and boron. Polycrystalline silicon can be completely melted at 1450°C. However, the Si 3 N 4 raw material and boron single crystal need to be kept at 1900°C and 2100°C for a period of time respectively before they can be completely melted. Incompletely melted dopants will cause bit defects in the crystal rod. Wrong defects lead to crystal pulling failure.

但是,將爐室溫度長時間保持在高溫下會造成石英坩堝的軟化,熔融Si和坩堝原料SiO 2的反應產物為氣態SiO,逸出後與放置坩堝的石墨製品反應形成CO氣體,CO易於進入矽熔體中,將碳和氧引入矽中,使得矽熔體中的氧含量增多。過多的氧原子是形成缺陷的主要起因,過多的氧原子在器件啟動區中的氧沉澱可引起擊穿或漏電,在退火過程中,氧沉澱的產生使得器件成品率下降。同時,作為摻雜劑的硼單質揮發量極大,尤其是在高溫的拉晶爐內硼摻雜劑得以進一步揮發。另外,硼極容易被氧化,環境溫度在1600℃下,硼與氮易形成難熔物氮化硼(BN),氮化硼的耐高溫性能好,化學性質穩定,在高溫下不與矽反映,不與矽浸潤,也不與矽黏連,當矽熔體中出現氮化硼時,容易導致拉晶過程中出現位錯缺陷導致拉晶失敗。 However, keeping the furnace temperature at a high temperature for a long time will cause the quartz crucible to soften. The reaction product between the molten Si and the crucible raw material SiO2 is gaseous SiO. After escaping, it reacts with the graphite product placed in the crucible to form CO gas, which is easy to enter. In the silicon melt, carbon and oxygen are introduced into the silicon to increase the oxygen content in the silicon melt. Excessive oxygen atoms are the main cause of defects. Oxygen precipitation of excessive oxygen atoms in the device startup area can cause breakdown or leakage. During the annealing process, the generation of oxygen precipitation reduces the device yield. At the same time, the boron element as a dopant volatilizes in a huge amount, especially in the high-temperature crystal pulling furnace, where the boron dopant further volatilizes. In addition, boron is easily oxidized. At an ambient temperature of 1600°C, boron and nitrogen easily form the refractory boron nitride (BN). Boron nitride has good high temperature resistance and stable chemical properties and does not react with silicon at high temperatures. , does not wet with silicon or adhere to silicon. When boron nitride appears in the silicon melt, it is easy to cause dislocation defects during the crystal pulling process and lead to crystal pulling failure.

本發明主要在於在製備氮摻雜P型單晶矽的過程中將作為氮源的氮化矽替換為高摻雜氮單晶,將作為硼源的單質硼替換為高摻雜硼單晶,解決了爐室溫度高,加熱時間久的技術問題。另外,改變硼摻雜劑和氮摻雜劑的熔融順序,抑制了氮化硼(BN)的形成。The present invention mainly consists in replacing silicon nitride as a nitrogen source with a highly doped nitrogen single crystal, and replacing elemental boron as a boron source with a highly doped boron single crystal in the process of preparing nitrogen-doped P-type single crystal silicon. It solves the technical problems of high temperature in the furnace chamber and long heating time. In addition, changing the melting order of boron dopants and nitrogen dopants inhibits the formation of boron nitride (BN).

根據本發明的實施例的一種氮摻雜P型單晶矽的製造方法,如圖1所示,該方法包括下述步驟: S101:將高摻雜氮單晶與多晶矽投入坩堝並加熱拉晶爐,得到第一矽熔體; S102:向該第一矽熔體加入高摻雜硼單晶,得到第二矽熔體; S103:在該第二矽熔體中以直拉法拉制氮摻雜P型單晶矽。 A method for manufacturing nitrogen-doped P-type single crystal silicon according to an embodiment of the present invention, as shown in Figure 1, the method includes the following steps: S101: Put the highly doped nitrogen single crystal and polycrystalline silicon into the crucible and heat the crystal pulling furnace to obtain the first silicon melt; S102: Add highly doped boron single crystal to the first silicon melt to obtain a second silicon melt; S103: Pull nitrogen-doped P-type single crystal silicon in the second silicon melt by Czochralski method.

由於使用高摻雜氮單晶摻雜劑和高摻雜硼單晶摻雜劑,因此在較低溫度(多晶矽的熔化溫度)下也可以向晶棒參雜氮和硼元素,而不需要將爐室溫度提升過高導致用來承載拉晶材料的石英坩堝不可控地析出大量的氧。另外,調整了高摻雜氮單晶摻雜劑和高摻雜硼單晶摻雜劑添加順序,先通過高摻雜氮單晶摻雜劑和多晶矽原料獲得為低摻氮矽熔體的第一矽熔體,再向該第一矽熔體添加高摻雜硼單晶獲得為低摻硼氮矽熔體的第二矽熔體,最終在該第二矽熔體中通過直拉法拉制氮摻雜P型單晶矽,避免了氮化硼(BN)的出現,防止拉晶失敗的情況發生。Due to the use of highly doped nitrogen single crystal dopants and highly doped boron single crystal dopants, nitrogen and boron elements can also be doped into the crystal rod at a lower temperature (the melting temperature of polycrystalline silicon) without the need to The temperature in the furnace chamber increased too high, causing the quartz crucible used to carry the crystal pulling material to uncontrollably precipitate a large amount of oxygen. In addition, the order of adding the highly nitrogen-doped single crystal dopant and the highly doped boron single crystal dopant was adjusted. The low-nitrogen-doped silicon melt was first obtained through the highly nitrogen-doped single crystal dopant and polycrystalline silicon raw materials. A silicon melt, and then adding a highly doped boron single crystal to the first silicon melt to obtain a second silicon melt that is a low boron-doped nitride silicon melt, and finally drawing it in the second silicon melt by the Czochralski method Nitrogen-doped P-type single crystal silicon avoids the appearance of boron nitride (BN) and prevents crystal pulling failure.

根據本發明一個實施例的氮摻雜P型單晶矽製造方法,如圖2所示,將高摻雜氮單晶與多晶矽投入坩堝並加熱拉晶爐,得到第一矽熔體包括下列步驟: S201:將該高摻雜氮單晶定量計算後與該多晶矽一起投入坩堝。首先,提前將高摻雜氮單晶顆粒或粉末與多晶矽原料投放至石英坩堝,由於此處所添加的摻雜劑的氮含量直接決定製成的氮摻雜P型單晶矽中的含氮量,因此只需要根據目標氮摻雜P型單晶矽的氮濃度決定所需的高摻雜氮單晶的品質即可。適量的氮摻雜量可以釘紮位錯從而增強機械強度,抑制間隙生成,增減積體電路器件柵極氧化層的完整性(GOI),而且可以促進氧沉澱,從而增強單晶的內吸雜能力。 According to the manufacturing method of nitrogen-doped P-type single crystal silicon according to one embodiment of the present invention, as shown in Figure 2, putting highly doped nitrogen single crystal and polycrystalline silicon into a crucible and heating the crystal pulling furnace to obtain the first silicon melt includes the following steps : S201: After quantitative calculation, the highly doped nitrogen single crystal is put into the crucible together with the polycrystalline silicon. First, put the highly doped nitrogen single crystal particles or powder and polycrystalline silicon raw materials into the quartz crucible in advance, because the nitrogen content of the dopant added here directly determines the nitrogen content in the produced nitrogen-doped P-type single crystal silicon. , so it is only necessary to determine the quality of the required highly doped nitrogen single crystal based on the nitrogen concentration of the target nitrogen-doped P-type single crystal silicon. An appropriate amount of nitrogen doping can pin dislocations to enhance mechanical strength, inhibit gap generation, increase or decrease the integrity of the gate oxide layer (GOI) of integrated circuit devices, and promote oxygen precipitation, thereby enhancing the internal absorption of single crystals. Miscellaneous abilities.

S202:將該拉晶爐抽真空並通入保護氣體。在拉晶過程中,為了避免矽的氧化,必須在真空環境和保護氣體的作用下進行。向拉晶爐內通入保護氣體(高純度氬氣),從爐頂注入,底部開啟真空泵將氣體抽出,使得爐內的真空值保持在動態平衡,爐內氣體氣流由上而下貫穿晶棒的生長區域,可以即時帶走高溫生產出來的矽氧化物和雜質揮發物。可選地,通過控制進氣流量以及保持真空泵的抽真空效率以維持爐內的真空值穩定。S202: Evacuate the crystal pulling furnace and introduce protective gas. During the crystal pulling process, in order to avoid oxidation of silicon, it must be carried out in a vacuum environment and under the action of protective gas. Pour protective gas (high-purity argon) into the crystal pulling furnace and inject it from the top of the furnace. Turn on the vacuum pump at the bottom to extract the gas so that the vacuum value in the furnace is maintained at a dynamic balance. The gas flow in the furnace penetrates the crystal rod from top to bottom. The growth area can instantly take away the silicon oxide and impurity volatiles produced at high temperatures. Optionally, the vacuum value in the furnace is maintained stable by controlling the inlet air flow and maintaining the evacuation efficiency of the vacuum pump.

S203:打開加熱器,提升爐室溫度並保溫一段時間,直至該高摻雜氮單晶與該多晶矽完全熔化,得到該第一矽熔體。在此過程中,通過加熱器將爐室溫度升高至多晶矽的熔化溫度(約為1450-1550℃)並在此溫度下保持一段時間使得多晶矽充分熔解,由於使用高摻雜氮單晶代替氮化矽原材料作為氮源,所以在該溫度下保持一段時間後高摻雜氮單晶便能夠充分熔解,使得氮元素充分地融入矽熔體當中,獲得為低摻氮矽熔體的第一矽熔體。在此溫度下石英坩堝不存在軟化、開裂等問題,並且元素的析出在可接受的範圍之內,不會造成氧含量過多的技術問題。由於作為氮源的高摻雜氮單晶氮含量高、氧含量低,可以有效防止摻雜劑為第一矽熔體帶去多餘的氧。S203: Turn on the heater, raise the temperature of the furnace chamber and keep it warm for a period of time until the highly doped nitrogen single crystal and the polycrystalline silicon are completely melted to obtain the first silicon melt. During this process, the temperature of the furnace chamber is raised to the melting temperature of polycrystalline silicon (about 1450-1550°C) through the heater and kept at this temperature for a period of time to fully melt the polycrystalline silicon. Since highly doped nitrogen single crystal is used instead of nitrogen The raw material of silicon is used as a nitrogen source, so after being kept at this temperature for a period of time, the highly nitrogen-doped single crystal can be fully melted, so that the nitrogen element is fully integrated into the silicon melt, and the first silicon is obtained as a low nitrogen-doped silicon melt. Melt. At this temperature, the quartz crucible does not have problems such as softening or cracking, and the precipitation of elements is within an acceptable range, without causing technical problems such as excessive oxygen content. Since the highly doped nitrogen single crystal used as the nitrogen source has a high nitrogen content and a low oxygen content, it can effectively prevent the dopant from bringing excess oxygen to the first silicon melt.

根據本發明一個實施例的氮摻雜P型單晶矽製造方法,如圖3所示,該向該第一矽熔體加入高摻雜硼單晶,得到第二矽熔體包括下列步驟: S301:將該第一矽熔體靜置一段時間。在確認第一矽熔體中的高摻雜氮單晶摻雜劑和多晶矽原材料完全融化之後,降低加熱器功率後靜置一段時間,使得該第一矽熔體的表面固化,以防止後續添加其他摻雜劑時,引起該第一矽熔體飛濺,避免安全事故的發生。 According to the manufacturing method of nitrogen-doped P-type single crystal silicon according to one embodiment of the present invention, as shown in Figure 3, adding highly doped boron single crystal to the first silicon melt to obtain the second silicon melt includes the following steps: S301: Let the first silicon melt stand for a period of time. After confirming that the highly doped nitrogen single crystal dopant and polycrystalline silicon raw material in the first silicon melt are completely melted, reduce the heater power and let it sit for a period of time to solidify the surface of the first silicon melt to prevent subsequent additions. Other dopants will cause the first silicon melt to splash, thus avoiding safety accidents.

S302:向靜置後的該第一矽熔體加入該高摻雜硼單晶。向靜置了一段時間後的第一矽熔體中加入高摻雜硼單晶顆粒或粉末,由於此處所添加的摻雜劑的硼含量直接決定製成的氮摻雜P型單晶矽中的含氮量,因此只需要根據目標氮摻雜P型單晶矽的氮濃度決定高摻雜氮單晶的品質即可。S302: Add the highly doped boron single crystal to the first silicon melt after standing. Add highly doped boron single crystal particles or powder to the first silicon melt that has been allowed to stand for a period of time. The boron content of the dopant added here directly determines the nitrogen-doped P-type single crystal silicon produced. Therefore, it is only necessary to determine the quality of the highly doped nitrogen single crystal based on the nitrogen concentration of the target nitrogen-doped P-type single crystal silicon.

S303:提高爐室溫度,使得該高摻雜硼單晶完全融化至該第一矽熔體,得到該第二矽熔體。在該步驟中,靜置過後的第一矽熔體表面可能凝固,通過加熱器將爐石溫度升高或保持在矽的熔化溫度(約為1450-1550℃),並在此溫度下保持一段時間使得表面凝固的第一矽熔體和摻雜的高摻雜硼單晶充分融化,硼元素充分地融入第一矽熔體當中,得到為低摻硼氮矽熔體的第二矽熔體。在此溫度下石英坩堝不存在軟化、開裂等問題,並且元素的析出在可接受的範圍之內,不會造成氧含量過多的技術問題。由於作為硼源的高摻雜硼單晶硼含量高、氧含量低,可以有效防止摻雜劑為第一矽熔體帶去多餘的氧。S303: Increase the furnace temperature to completely melt the highly doped boron single crystal into the first silicon melt to obtain the second silicon melt. In this step, the surface of the first silicon melt may solidify after standing. The temperature of the furnace stone is raised or maintained at the melting temperature of silicon (approximately 1450-1550°C) through a heater, and maintained at this temperature for a period of time. Time allows the surface-solidified first silicon melt and the doped highly doped boron single crystal to fully melt, and the boron element is fully integrated into the first silicon melt to obtain a second silicon melt that is a low boron-doped nitride silicon melt. . At this temperature, the quartz crucible does not have problems such as softening or cracking, and the precipitation of elements is within an acceptable range, without causing technical problems such as excessive oxygen content. Since the highly doped boron single crystal used as the boron source has high boron content and low oxygen content, it can effectively prevent the dopant from bringing excess oxygen to the first silicon melt.

根據本發明一個實施例的氮摻雜P型單晶矽製造方法,該以直拉法拉制氮摻雜P型單晶矽包括:調節爐室溫度;緩慢放下籽晶至該第二矽熔體中,爐體內的籽晶經過引晶、縮頸、放肩、等徑生長、收尾階段完成晶體的生長過程;製成氮摻雜P型單晶矽。According to a manufacturing method of nitrogen-doped P-type single crystal silicon according to one embodiment of the present invention, the method of drawing nitrogen-doped P-type single crystal silicon by Czochralski method includes: adjusting the temperature of the furnace chamber; slowly lowering the seed crystal into the second silicon melt In the furnace, the seed crystal in the furnace completes the crystal growth process through seeding, necking, shoulder expansion, equal diameter growth, and the finishing stage; nitrogen-doped P-type single crystal silicon is produced.

根據本發明的一種氮摻雜P型單晶矽製造方法,由於其利用高摻雜氮單晶和高摻雜硼單晶作為製備氮摻雜P型單晶矽的摻雜劑,可以在較低的爐室溫度下使得氮原子和硼原子完全融入矽熔體,使得石英坩堝不會析出多餘的氧原子,改善了氧濃度的控制,提高了BMD控制。另外,通過高摻雜氮單晶和高摻雜硼單晶不同的熔融順序,避免了在製備氮摻雜P型單晶矽的過程中,氮化硼(BN)的產生,防止了因難熔解的雜質導致拉晶失敗的情況發生。According to the manufacturing method of nitrogen-doped P-type single crystal silicon of the present invention, since it uses highly doped nitrogen single crystal and highly doped boron single crystal as dopants for preparing nitrogen-doped P-type single crystal silicon, it can be used in relatively The low furnace temperature allows nitrogen atoms and boron atoms to be completely integrated into the silicon melt, so that the quartz crucible does not precipitate excess oxygen atoms, improving the control of oxygen concentration and improving BMD control. In addition, through the different melting sequences of highly doped nitrogen single crystal and highly doped boron single crystal, the production of boron nitride (BN) in the process of preparing nitrogen-doped P-type single crystal silicon is avoided, preventing difficulties due to Molten impurities cause crystal pulling failure to occur.

需要說明的是:本發明實施例所記載的技術方案之間,在不衝突的情況下,可以任意組合。以上僅為本發明之較佳實施例,並非用來限定本發明之實施範圍,如果不脫離本發明之精神和範圍,對本發明進行修改或者等同替換,均應涵蓋在本發明申請專利範圍的保護範圍當中。It should be noted that the technical solutions recorded in the embodiments of the present invention can be combined arbitrarily as long as there is no conflict. The above are only preferred embodiments of the present invention and are not intended to limit the implementation scope of the present invention. If the present invention is modified or equivalently substituted without departing from the spirit and scope of the present invention, the protection shall be covered by the patent scope of the present invention. within the range.

S101-S103:步驟 S201-S303:步驟 S301-S103:步驟 S101-S103: Steps S201-S303: Steps S301-S103: Steps

圖1為根據本發明的實施例的一種氮摻雜P型單晶矽的製造方法的示意圖; 圖2為根據本發明的實施例的一種氮摻雜P型單晶矽的製造方法中將高摻雜氮單晶與多晶矽投入坩堝並加熱拉晶爐,得到第一矽熔體的示意圖; 圖3為根據本發明的實施例的一種氮摻雜P型單晶矽的製造方法中向該第一矽熔體加入高摻雜硼單晶,得到第二矽熔體的示意圖。 Figure 1 is a schematic diagram of a manufacturing method of nitrogen-doped P-type single crystal silicon according to an embodiment of the present invention; Figure 2 is a schematic diagram of a manufacturing method of nitrogen-doped P-type single crystal silicon according to an embodiment of the present invention, in which highly doped nitrogen single crystal and polycrystalline silicon are put into a crucible and heated in a crystal pulling furnace to obtain a first silicon melt; 3 is a schematic diagram of adding a highly doped boron single crystal to the first silicon melt to obtain a second silicon melt in a manufacturing method of nitrogen-doped P-type single crystal silicon according to an embodiment of the present invention.

S101-S103:步驟 S101-S103: Steps

Claims (8)

一種氮摻雜P型單晶矽製造方法,包括:將高摻雜氮單晶與多晶矽投入坩堝並加熱拉晶爐,得到第一矽熔體;其中,得到該第一矽熔體的加熱溫度為1450-1550℃;向該第一矽熔體加入高摻雜硼單晶,得到第二矽熔體;在該第二矽熔體中以直拉法拉制氮摻雜P型單晶矽;其中,得到該第二矽熔體的加熱溫度為1450-1550℃。 A method for manufacturing nitrogen-doped P-type single crystal silicon, which includes: putting highly nitrogen-doped single crystal and polycrystalline silicon into a crucible and heating the crystal pulling furnace to obtain a first silicon melt; wherein, the heating temperature of the first silicon melt is obtained is 1450-1550°C; add highly doped boron single crystal to the first silicon melt to obtain a second silicon melt; pull nitrogen-doped P-type single crystal silicon in the second silicon melt by Czochralski method; Wherein, the heating temperature to obtain the second silicon melt is 1450-1550°C. 如請求項1所述之氮摻雜P型單晶矽製造方法,其中,該將高摻雜氮單晶與多晶矽投入坩堝並加熱拉晶爐,得到第一矽熔體包括:將該高摻雜氮單晶定量計算後與該多晶矽一起投入坩堝;將該拉晶爐抽真空並通入保護氣體;打開加熱器,提升爐室溫度並保溫一段時間,直至該高摻雜氮單晶與該多晶矽完全熔化,得到該第一矽熔體。 The manufacturing method of nitrogen-doped P-type single crystal silicon as described in claim 1, wherein putting the highly doped nitrogen single crystal and polycrystalline silicon into a crucible and heating the crystal pulling furnace to obtain the first silicon melt includes: After quantitative calculation, the heterogeneous nitrogen single crystal is put into the crucible together with the polycrystalline silicon; the crystal pulling furnace is evacuated and a protective gas is introduced; the heater is turned on, the temperature of the furnace chamber is raised and the temperature is kept for a period of time until the highly doped nitrogen single crystal and the polycrystalline silicon are The polycrystalline silicon is completely melted to obtain the first silicon melt. 如請求項2所述之氮摻雜P型單晶矽製造方法,其中,該第一矽熔體為低摻氮矽熔體。 The manufacturing method of nitrogen-doped P-type single crystal silicon according to claim 2, wherein the first silicon melt is a low nitrogen-doped silicon melt. 如請求項2所述之氮摻雜P型單晶矽製造方法,其中,該保護氣體為氬氣。 The method for manufacturing nitrogen-doped P-type single crystal silicon according to claim 2, wherein the protective gas is argon. 如請求項1所述之氮摻雜P型單晶矽製造方法,其中,該向該第一矽熔體加入高摻雜硼單晶,得到第二矽熔體包括:將該第一矽熔體靜置一段時間;向靜置後的該第一矽熔體加入該高摻雜硼單晶; 提高爐室溫度,使得該高摻雜硼單晶完全融化至該第一矽熔體,得到該第二矽熔體。 The manufacturing method of nitrogen-doped P-type single crystal silicon as described in claim 1, wherein adding highly doped boron single crystal to the first silicon melt to obtain the second silicon melt includes: melting the first silicon melt Let the body stand for a period of time; add the highly doped boron single crystal to the first silicon melt after standing; The temperature of the furnace chamber is increased so that the highly doped boron single crystal is completely melted into the first silicon melt to obtain the second silicon melt. 如請求項5所述之氮摻雜P型單晶矽製造方法,其中,該第二矽熔體為低摻硼氮矽熔體。 The manufacturing method of nitrogen-doped P-type single crystal silicon according to claim 5, wherein the second silicon melt is a low boron-doped nitride silicon melt. 如請求項1所述之氮摻雜P型單晶矽製造方法,其中,該在該第二矽熔體中以直拉法拉制氮摻雜P型單晶矽包括:調節爐室溫度;向該第二矽熔體中緩慢放置籽晶,經過引晶、縮頸、放肩、等徑生長、收尾階段完成晶體的生長過程;製成該氮摻雜P型單晶矽。 The manufacturing method of nitrogen-doped P-type single crystal silicon as described in claim 1, wherein the step of drawing nitrogen-doped P-type single crystal silicon in the second silicon melt by Czochralski method includes: adjusting the temperature of the furnace chamber; The seed crystal is slowly placed in the second silicon melt, and the crystal growth process is completed through seeding, necking, shoulder release, equal diameter growth, and finishing stages; the nitrogen-doped P-type single crystal silicon is produced. 如請求項1所述之氮摻雜P型單晶矽製造方法,其中,該高摻雜氮單晶和該高摻雜硼單晶為顆粒或粉末。 The manufacturing method of nitrogen-doped P-type single crystal silicon according to claim 1, wherein the highly doped nitrogen single crystal and the highly doped boron single crystal are particles or powders.
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