TW201429870A - Process for deposition of polycrystalline silicon - Google Patents

Process for deposition of polycrystalline silicon Download PDF

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TW201429870A
TW201429870A TW103103136A TW103103136A TW201429870A TW 201429870 A TW201429870 A TW 201429870A TW 103103136 A TW103103136 A TW 103103136A TW 103103136 A TW103103136 A TW 103103136A TW 201429870 A TW201429870 A TW 201429870A
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containing gas
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Dieter Knerer
Piotr Filar
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Wacker Chemie Ag
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/02—Silicon
    • C01B33/021—Preparation
    • C01B33/027—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material
    • C01B33/035—Preparation by decomposition or reduction of gaseous or vaporised silicon compounds other than silica or silica-containing material by decomposition or reduction of gaseous or vaporised silicon compounds in the presence of heated filaments of silicon, carbon or a refractory metal, e.g. tantalum or tungsten, or in the presence of heated silicon rods on which the formed silicon is deposited, a silicon rod being obtained, e.g. Siemens process
    • B—PERFORMING OPERATIONS; TRANSPORTING
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    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
    • B01J23/50—Silver
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/48—Silver or gold
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/86—Chromium

Abstract

The invention relates to a process for depositing polycrystalline silicon, by introducing a silicon-containing gas into a reactor and depositing polycrystalline silicon on a support body heated by direct passage of current to a temperature of at least 550 DEG C by reducing the silicon-containing gas, wherein, during the reduction of the silicon-containing gas, at least one first metal selected from the group consisting of titanium, chromium, manganese, iron, cobalt, nickel, copper and zinc is present, which acts as a first catalyst, and at least one second metal which is different than the first metal and is selected from the group consisting of copper, silver and gold is additionally present, which acts as a second catalyst.

Description

沉積多晶矽之方法 Method of depositing polycrystalline germanium

本發明關於沉積多晶矽的方法。 The invention relates to a method of depositing polycrystalline germanium.

高純度多晶體矽(多晶矽)用作透過柴可拉斯基(Czochralski，CZ)法或區域熔融(zone melting，FZ)法以製造用於半導體的單晶矽、以及透過不同的提拉(pulling)和澆注(casting)方法以製造單晶或多晶矽以製造光伏打(photovoltaic)太陽能電池的起始材料，以及用作鋰離子電池的電極中的組分。 High-purity polycrystalline germanium (polycrystalline germanium) is used to pass through the Czochralski (CZ) method or the zone melting (FZ) method to produce single crystal germanium for semiconductors, and to pass through different pulls (pulling) And a casting method to fabricate single crystal or polycrystalline germanium to make a starting material for a photovoltaic solar cell, and as a component in an electrode of a lithium ion battery.

多晶矽通常利用西門子法製造。在此，將包含一種或多種含矽組分及視需要存在的氫的反應氣體導入包含經直接流通電流進行加熱的支撐體的反應器中，其中矽以固體形式沉積在支撐體上。 Polycrystalline germanium is usually manufactured by the Siemens method. Here, a reaction gas comprising one or more ruthenium-containing components and optionally hydrogen is introduced into a reactor comprising a support heated by direct flow of current, wherein ruthenium is deposited as a solid on the support.

所使用含矽組分較佳為矽烷(SiH4)、單氯矽烷(SiH3Cl)、二氯矽烷(DCS，SiH2Cl2)、三氯矽烷(TCS，SiHCl3)、四氯矽烷(SiCl4)或該等物質的混合物。 The rhodium-containing component used is preferably decane (SiH 4 ), monochlorodecane (SiH 3 Cl), dichlorodecane (DCS, SiH 2 Cl 2 ), trichlorodecane (TCS, SiHCl 3 ), tetrachlorodecane ( SiCl 4 ) or a mixture of such substances.

西門子法通常在沉積反應器(又稱作“西門子反應器”)中進行。在最常用的具體實施態樣中，該反應器包含金屬底板和安裝在底板上的可冷卻的鐘形罩，從而在鐘形罩內部形成 反應空間。底板設置有一或多個氣體進料開口以及一或多個用於排出反應氣體的廢氣開口，以及設置有保持裝置其協助保持支撐體在反應空間中並供應電流。EP 2 077 252 A2說明在製造多晶矽時使用的反應器類型的一般構造。 The Siemens process is usually carried out in a deposition reactor (also known as a "Siemens reactor"). In the most common embodiment, the reactor comprises a metal bottom plate and a coolable bell jar mounted on the bottom plate to form inside the bell jar Reaction space. The bottom plate is provided with one or more gas feed openings and one or more exhaust gas openings for discharging the reaction gases, and a holding device is provided which assists in maintaining the support in the reaction space and supplying current. EP 2 077 252 A2 describes the general construction of the type of reactor used in the manufacture of polycrystalline germanium.

每個支撐體通常由兩根細的細絲棒和一橋接(bridge)組成，該橋接通常將相鄰的棒在其自由端連接。在最通常的情況下，細絲棒由單晶或多晶矽製成，較罕見地使用金屬、合金或碳。細絲棒垂直地***位於反應器底部的電極中，經由電極而與電源連接。在加熱的細絲棒及水平的橋接上沉積高純度多晶矽，由此使其直徑隨時間而增大。在達到所期望的直徑之後，藉由停止送入含矽組分而結束該過程。 Each support typically consists of two thin filament rods and a bridge that typically connects adjacent rods at their free ends. In the most general case, the filament rods are made of single crystal or polycrystalline germanium, and metals, alloys or carbon are used sparingly. The filament rod is inserted vertically into the electrode at the bottom of the reactor and connected to the power source via the electrode. High purity polycrystalline germanium is deposited on the heated filament rods and horizontal bridges, thereby increasing its diameter over time. After the desired diameter is reached, the process is terminated by stopping the feed of the ruthenium containing component.

沉積過程通常藉由設定棒溫度和反應氣體的流量或組成加以控制。利用輻射高溫計通常在朝向反應器壁的棒表面上測量棒溫度。棒溫度以定額的方式設定或取決於棒直徑而藉由控制或調節電功率而加以設定。反應氣體的量和組成取決於時間或棒直徑而加以設定。 The deposition process is usually controlled by setting the rod temperature and the flow rate or composition of the reaction gas. The rod temperature is typically measured on the surface of the rod towards the reactor wall using a radiant pyrometer. The rod temperature is set in a fixed manner or is determined by controlling or adjusting the electric power depending on the rod diameter. The amount and composition of the reaction gas are set depending on the time or the diameter of the rod.

通常在900與1100℃之間的棒溫度下，以在每1平方公尺棒表面上(總計)0.5至10千莫耳/小時(kmol/h)的一或多種含矽組分的進料速率，利用TCS或其與DCS和/或STC的混合物進行沉積，其中在進料氣體流中該一或多種組分的莫耳比率(總計)在10%與50%之間(剩餘的90%至50%通常是氫)。 Typically at a rod temperature between 900 and 1100 ° C, one or more feeds containing one or more rhodium-containing components on a total of 0.5 to 10 kilomoles per hour (kmol/h) per 1 square meter of rod surface Rate, using TCS or its deposition with a mixture of DCS and/or STC, wherein the molar ratio (total) of the one or more components in the feed gas stream is between 10% and 50% (the remaining 90%) Up to 50% is usually hydrogen).

US 4,481,232公開了一種製造高純度矽的方法，該方 法包含形成矽化銅合金及將所述合金放置在容器內；相對於該合金放置一細絲；送入適合於輸送矽的輸送氣體；將該細絲和該合金加熱至使該氣體在該合金表面上與矽反應並且使矽沉積在該細絲上的溫度，其中該合金在該溫度下能夠藉由擴散而捕獲雜質。使用銅以促進矽生成矽烷的反應。由所形成的矽烷又立即沉積成矽。 US 4,481,232 discloses a method of making high purity bismuth, the party The method comprises forming a copper telluride alloy and placing the alloy in a container; placing a filament relative to the alloy; feeding a transport gas suitable for transporting the crucible; heating the filament and the alloy to cause the gas to be in the alloy A temperature at which the surface reacts with cerium and deposits cerium on the filament, wherein the alloy is capable of trapping impurities by diffusion at this temperature. Copper is used to promote the reaction of hydrazine to form decane. The decane formed is immediately deposited into ruthenium.

US 4,759,830和US 4,773,973涉及在適合作為電極的導電材料上由一包含鹵化矽、鹵化鋁、鹼金屬鹵化物或鹵化銨及過渡金屬鹵化物的鹽熔體藉由電解沉積矽而製造元素矽薄層的方法，其中電解是在100至350℃的溫度下在惰性氣體(atmosphere)中及視情況加壓進行的。所揭露之過渡金屬的鹵化物為碘化鉻(II)(CrI2)、碘化錳(II)(MnI2)、碘化鐵(II)(FeI2)、碘化銅(I)(CuI)、碘化鉿(IV)(HfI4)、碘化鎳(NiI2)、碘化釩(II)(VI2)或這些碘化物的混合物。 US 4,759,830 and US 4,773,973 relate to the production of a thin layer of elemental tantalum by electrolytic deposition of tantalum on a conductive material suitable as an electrode from a salt melt comprising a hafnium halide, an aluminum halide, an alkali metal halide or an ammonium halide and a transition metal halide. The method wherein the electrolysis is carried out at a temperature of 100 to 350 ° C in an inert atmosphere and optionally under pressure. The halides of the disclosed transition metals are chromium (II) iodide (CrI 2 ), manganese (II) iodide (MnI 2 ), iron (II) iodide (FeI 2 ), copper (I) iodide (CuI). ), cerium (IV) iodide (HfI 4 ), nickel iodide (NiI 2 ), vanadium (II) iodide (VI 2 ) or a mixture of these iodides.

矽的電解沉積可在陰極進行，其中使用由銅、鉻、鉬、鎳、鉑、鐵或不銹鋼、較佳由鋁、矽或石墨組成的材料作為陰極材料，使用由鉑、矽或石墨組成的材料作為陽極材料。 The electrolytic deposition of germanium can be carried out at the cathode, using a material consisting of copper, chromium, molybdenum, nickel, platinum, iron or stainless steel, preferably of aluminum, ruthenium or graphite, as the cathode material, using platinum, rhodium or graphite. The material acts as an anode material.

矽的電解沉積可在陽極由一包含鹵化矽、鹵化鋁、鹼金屬鹵化物或鹵化銨的熔體進行，其中所使用的陽極材料是由鋁組成，所使用的陰極材料是由矽或石墨組成。電解沉積矽係可由一，例如，包含四碘化矽、三碘化鋁和碘化鋰的熔體進行。 Electrodeposition of ruthenium may be carried out at the anode from a melt comprising ruthenium halide, aluminum halide, alkali metal halide or ammonium halide, wherein the anode material used is composed of aluminum and the cathode material used is composed of ruthenium or graphite. . The electrolytically deposited lanthanide can be carried out by, for example, a melt comprising cerium tetraiodide, aluminum triiodide and lithium iodide.

過渡金屬的鹵化物是所謂的催化劑，其明顯改善在 例如銅、鉻、鉬、鎳、鐵和鉻鋼或者無機玻璃(例如由二氧化錫或二氧化錫/氧化銦混合物所組成者)上的矽沉積及矽層的品質，且實際上使在該方法的條件下能夠在矽載體上形成矽層。若不使用該催化劑，則實際上觀察不到矽的沉積。 The halide of the transition metal is a so-called catalyst which is significantly improved in For example, the quality of tantalum deposits and tantalum layers on copper, chromium, molybdenum, nickel, iron and chromium steel or inorganic glass (for example composed of a mixture of tin dioxide or tin dioxide/indium oxide), and actually Under the conditions of the method, a layer of germanium can be formed on the tantalum support. If the catalyst is not used, no deposition of ruthenium is actually observed.

Müller-Rochow合成法是一種供工業規模製造甲基氯矽烷的方法。所使用的催化劑為銅，其是以元素形式或例如以銅的氧化物的形式使用。此外，鋅、錫、磷及其他元素也作為促進劑。該反應在約300℃及0.5至2巴(錶壓)下進行。 The Müller-Rochow synthesis is a process for the manufacture of methyl chlorodecane on an industrial scale. The catalyst used is copper, which is used in elemental form or in the form of, for example, an oxide of copper. In addition, zinc, tin, phosphorus and other elements are also used as promoters. The reaction is carried out at about 300 ° C and 0.5 to 2 bar (gauge).

EP 2 036 117 A1公開了根據慣用的技術藉由使用催化金屬層在基材上生長矽奈米線。該金屬例如可以是在基材上沉積的金。此形成催化金屬島(catalytic metal island)。隨後，使用來自矽源的矽以達成在金屬島上生長矽奈米線。 EP 2 036 117 A1 discloses the growth of a nanowire on a substrate by using a catalytic metal layer according to conventional techniques. The metal can be, for example, gold deposited on a substrate. This forms a catalytic metal island. Subsequently, helium from the source was used to achieve the growth of the nanowires on the metal island.

EP 2 082 419 A2公開了一種金屬催化生長奈米線的方法，其中有效的金屬催化劑為元素週期表的過渡金屬，包括銅、銀、金、鎳、鈀、鉑、鈷、銠、銥、銦、鐵、釕、錫、鋨、錳、鉻、鉬、鎢、釩、鈮、鉭、鈦、鋯和鎵，包括一或多種此等金屬的混合物。 EP 2 082 419 A2 discloses a process for the catalytic growth of nanowires by metal, wherein the effective metal catalyst is a transition metal of the periodic table, comprising copper, silver, gold, nickel, palladium, platinum, cobalt, rhodium, ruthenium, indium. , iron, bismuth, tin, antimony, manganese, chromium, molybdenum, tungsten, vanadium, niobium, tantalum, titanium, zirconium and gallium, including mixtures of one or more of these metals.

將矽應用於半導體技術中的現有技術在使用粗製矽時，對材料純度提出越來越高的要求。 The prior art in which germanium is used in semiconductor technology places increasing demands on material purity when using coarse crucibles.

本發明的目的在於提供更經濟地沉積多晶矽的方法。 It is an object of the present invention to provide a method for depositing polycrystalline germanium more economically.

該目的是藉由沉積多晶矽的方法達成的，其中將含矽氣體導入反應器中，藉由使含矽氣體還原而在經直接流通電流而加熱到至少為550℃的溫度的支撐體上沉積多晶矽，其中，在使含矽氣體還原期間係存在至少一種選自以下群組作為第一催化劑的第一金屬：鈦、鉻、錳、鐵、鈷、鎳、銅和鋅，並另外存在有至少一種選自以下群組、不同於第一金屬、作為第二催化劑的第二金屬：銅、銀和金。 This object is achieved by a method of depositing polycrystalline germanium in which a helium-containing gas is introduced into a reactor, and polycrystalline germanium is deposited on a support heated to a temperature of at least 550 ° C by direct current flow by reducing the gas containing helium. Wherein at least one first metal selected from the group consisting of titanium, chromium, manganese, iron, cobalt, nickel, copper, and zinc is present during the reduction of the helium-containing gas, and at least one of A second metal selected from the group consisting of copper, silver, and gold that is different from the first metal as the second catalyst.

該含矽氣體較佳為鹵矽烷，更佳為三氯矽烷。 The helium-containing gas is preferably halodecane, more preferably trichlorodecane.

較佳地，在存在有氫的情況下係使用三氯矽烷。 Preferably, trichloromethane is used in the presence of hydrogen.

進行兩個部分反應。必須斷開Si-H鍵和Si-Cl鍵。如下文所述，需要兩類催化劑，以促進這兩個部分反應。 Perform two partial reactions. The Si-H bond and the Si-Cl bond must be disconnected. As described below, two types of catalysts are needed to facilitate the reaction of the two parts.

以下組合被發現是特別合適的：銅和鈦/鐵/鎳；銀和鉻/錳/鐵/鋅；金和鈦/鉻/錳/鐵/鈷/鎳/鋅。 The following combinations have been found to be particularly suitable: copper and titanium/iron/nickel; silver and chromium/manganese/iron/zinc; gold and titanium/chromium/manganese/iron/cobalt/nickel/zinc.

特別較佳為金和鈦、以及金和鉻的組合。 Particularly preferred are gold and titanium, and combinations of gold and chromium.

尤其特別較佳為使用銅和鎳。 It is especially preferred to use copper and nickel.

特別較佳還可以組合使用銅和銀、以及銅和金。 It is particularly preferable to use copper and silver in combination, as well as copper and gold.

在使含矽氣體還原期間，至少一種第一金屬和至少一種第二金屬存在的量應當使得在沉積的多晶矽中包含至少一種選自以下群組的元素：鈦、鉻、錳、鐵、鈷、鎳、銅和鋅，其濃度為18pptw至40ppbw鈦、0.2pptw至5ppbw鉻、0.5pptw至15ppbw 錳、7pptw至50ppbw鐵、0.012pptw至25ppbw鈷、0.9pptw至8ppbw鎳、3pptw至12ppbw銅和/或0.6pptw至11ppbw鋅；並且包含至少一種選自以下群組的不同於第一元素的第二元素：銅、銀和金，其濃度為3pptw至12ppbw銅、0.15pptw至21ppbw銀和0.001pptw至0.3ppbw金。 During the reduction of the ruthenium containing gas, the at least one first metal and the at least one second metal are present in an amount such that at least one element selected from the group consisting of titanium, chromium, manganese, iron, cobalt, is included in the deposited polycrystalline germanium. Nickel, copper and zinc in concentrations from 18 pptw to 40 ppbw titanium, 0.2 pptw to 5 ppbw chrome, 0.5 pptw to 15 ppbw Manganese, 7 pptw to 50 ppbw iron, 0.012 pptw to 25 ppbw cobalt, 0.9 pptw to 8 ppbw nickel, 3 pptw to 12 ppbw copper and/or 0.6 pptw to 11 ppbw zinc; and comprising at least one second different from the first element selected from the group consisting of Elements: copper, silver and gold in concentrations of 3 pptw to 12 ppbw copper, 0.15 pptw to 21 ppbw silver and 0.001 pptw to 0.3 ppbw gold.

因此，本發明還關於多晶矽，其包含至少一種選自以下群組的第一金屬：鈦、鉻、錳、鐵、鈷、鎳、銅和鋅；以及至少一種選自以下群組的不同於第一金屬的第二金屬：銅、銀和金；其中至少兩種所選擇的金屬在多晶矽中以如下的量存在：18pptw至40ppbw鈦、0.2pptw至5ppbw鉻、7pptw至50ppbw鐵、0.012pptw至25ppbw鈷、0.9pptw至8ppbw鎳、3pptw至12ppbw銅、0.6pptw至11ppbw鋅、0.15pptw至21ppbw銀、0.001pptw至0.3ppbw金、0.5pptw至15ppbw錳。 Accordingly, the present invention is also directed to a polycrystalline germanium comprising at least one first metal selected from the group consisting of titanium, chromium, manganese, iron, cobalt, nickel, copper, and zinc; and at least one selected from the group consisting of a second metal of a metal: copper, silver, and gold; at least two of the selected metals are present in the polycrystalline silicon in an amount of 18 pptw to 40 ppbw titanium, 0.2 pptw to 5 ppbw chromium, 7 pptw to 50 ppbw iron, 0.012 pptw to 25 ppbw Cobalt, 0.9 pptw to 8 ppbw nickel, 3 pptw to 12 ppbw copper, 0.6 pptw to 11 ppbw zinc, 0.15 pptw to 21 ppbw silver, 0.001 pptw to 0.3 ppbw gold, 0.5 pptw to 15 ppbw manganese.

表1所示為在所沉積的多晶矽中金屬的最小和最大濃度。 Table 1 shows the minimum and maximum concentrations of metals in the deposited polycrystalline germanium.

較佳地，該一或多種金屬係連同碳一起使用。 Preferably, the one or more metal systems are used in conjunction with carbon.

最佳是存在有銅、鎳和碳。 The best is copper, nickel and carbon.

為此，含矽氣體中甲烷的濃度應當為2至18ppm。 For this purpose, the concentration of methane in the helium-containing gas should be 2 to 18 ppm.

該方法涉及龐大的經濟益處。在研究具有第1圖所示設計的反應器中的沉積速率時發現，與傳統方法(不使用金屬)相比，由於存在這兩種催化劑金屬而達成了至少50%的多晶矽厚度增長。金屬作為催化劑。這是在更低的操作溫度下使用更短的操作時間，因此節約相當大的能量。即使在550℃的溫度下，也顯示出有效的沉積速率。 This approach involves enormous economic benefits. When investigating the deposition rate in a reactor having the design shown in Figure 1, it was found that a polycrystalline germanium thickness increase of at least 50% was achieved due to the presence of the two catalyst metals compared to conventional methods (no metal). Metal acts as a catalyst. This results in shorter operating times at lower operating temperatures, thus saving considerable energy. Even at a temperature of 550 ° C, an effective deposition rate was exhibited.

尤其是在光伏打和電池技術中的應用，所製的多晶矽具有優異的適用性。關於微電子的應用，因為對於多晶矽純度的要求可能過高，所製的多晶矽的使用並非那麼較佳。 Especially in the application of photovoltaic and battery technology, the polycrystalline silicon produced has excellent applicability. Regarding the application of microelectronics, the use of polycrystalline germanium produced is not so preferred because the purity requirements for polycrystalline germanium may be too high.

但是發現，即使存在有極少量的對於多晶矽品質不具有負面影響的金屬，也顯示出正面的作用(positive effect)。 However, it has been found that even if there is a very small amount of metal which does not have a negative influence on the quality of the polysilicon, it exhibits a positive effect.

重要的是，催化活性物質在所沉積的固體多晶矽中具有活性。氣相中的矽烷分解是非期望的。這會導致氣相成核(nucleation)及粉塵形成，這是非期望的。因此，該反應機制必須在多晶矽的表面內仍有效的。這是藉由使該金屬主要係溶解在 固體矽中而不是以自由形式(free form)留在氣相中而加以確保的。 Importantly, the catalytically active material is active in the deposited solid polycrystalline germanium. The decomposition of decane in the gas phase is undesirable. This can lead to gas phase nucleation and dust formation, which is undesirable. Therefore, the reaction mechanism must be effective in the surface of the polycrystalline crucible. This is by dissolving the main metal system in It is ensured in the solid helium rather than in the free form in the free form.

引入的金屬可自由地擴散進入已沉積的多晶矽中。 The introduced metal is free to diffuse into the deposited polycrystalline germanium.

一旦其到達表面並且非對稱地被矽包圍，則與基材形成更強之具有金屬矽化物特性的鍵結。 Once it reaches the surface and is asymmetrically surrounded by the crucible, a stronger bond with metal telluride properties is formed with the substrate.

該金屬矽化物由於其鍵結結構而對周圍的矽烷中的氫及存在的氯具有吸引作用。藉由擬矽化物類(pseudosilicides)的吸質子作用將氫由周圍環境移除，可能是以質子形式移除。 The metal halide has an attractive effect on hydrogen in the surrounding decane and chlorine present due to its bonding structure. Hydrogen is removed from the surrounding environment by the proton-acting action of pseudosilicides, possibly by protons.

含矽氣體，尤其是三氯矽烷，釋放出氫。這是第一部分反應。 Helium-containing gases, especially trichloromethane, release hydrogen. This is the first part of the reaction.

失穩的(destabilized)矽烷因此分解，由此沉積矽。這是第二部分反應。 The destabilized decane is thus decomposed, thereby depositing ruthenium. This is the second part of the reaction.

在不希望被這一假設所束縛之情形下，本發明的發明人認為，藉由催化劑促進這兩個部分反應，其中藉由第一催化劑促進第一部分反應，及藉由第二催化劑促進第二部分反應，雖然無法闡明是藉由鐵類金屬(ferrous metals)還是藉由貴金屬各自促進第一和第二部分反應。銅顯然能夠在這兩個部分反應中都作為催化劑。 Without wishing to be bound by this hypothesis, the inventors of the present invention believe that the two partial reactions are promoted by the catalyst, wherein the first partial reaction is promoted by the first catalyst, and the second partial reaction is promoted by the second catalyst. Partial reactions, although it is not possible to clarify whether the first and second partial reactions are promoted by ferrous metals or by noble metals, respectively. Copper is clearly capable of acting as a catalyst in both partial reactions.

若使三氯矽烷還原，則產生氯。這確保將金屬以易揮發的金屬氯化物類由反應器排出。同時確保活性催化劑在沉積室內均勻分佈。 When trichloromethane is reduced, chlorine is produced. This ensures that the metal is discharged from the reactor as a volatile metal chloride. At the same time, it is ensured that the active catalyst is uniformly distributed in the deposition chamber

出人意料地發現，這些元素的組合比單一元素更加有效，特別是碳，其在單純形式是無效的，但與金屬組合則顯示 出特別的特性，例如影響多晶矽的表面品質。若粉塵形成，即發生氣相成核，則粉塵顆粒同樣吸收金屬。於是在粉塵顆粒中也形成金屬矽化物，並發生矽沉積。這是非期望的。 Surprisingly, it has been found that the combination of these elements is more effective than a single element, especially carbon, which is ineffective in simple form, but is shown in combination with metal. Special properties, such as the surface quality of polycrystalline germanium. If dust forms, that is, gas phase nucleation occurs, the dust particles also absorb the metal. Thus, metal halides are also formed in the dust particles, and germanium deposition occurs. This is not expected.

藉由添加碳，可能有效地抑制氣相成核。 By adding carbon, it is possible to effectively suppress gas phase nucleation.

所使用的碳源為甲烷或其他含碳氣體，例如乙烷、丙烷、丁烷、戊烷、乙烯、溶劑蒸汽、烴類的異構物形式、甲基矽烷等。由於甲烷在所述溫度下的反應性低，所以甲烷是較佳的。其他氣體具有更高的反應性，其甲烷當量可以藉由廢氣流中未消耗的碳量來確定。 The carbon source used is methane or other carbonaceous gases such as ethane, propane, butane, pentane, ethylene, solvent vapors, isomer forms of hydrocarbons, methyl decane, and the like. Methane is preferred because methane has low reactivity at the temperature. Other gases are more reactive and their methane equivalent can be determined by the amount of unconsumed carbon in the exhaust stream.

若將銅作為催化劑之一引入，在其他方面相同的操作條件下，獲得在最大催化劑作用下20倍厚度的多晶矽層。在根據第1圖的實驗反應器中，多晶矽是沉積在矽核上。在此保持不變的操作條件是溫度、壓力、氣體流量和加熱電流。僅改變經第1圖中的催化劑源9添加金屬的情況(詳細示圖參見第2圖)。 If copper is introduced as one of the catalysts, a polycrystalline tantalum layer having a thickness of 20 times under the action of the maximum catalyst is obtained under otherwise identical operating conditions. In the experimental reactor according to Figure 1, polycrystalline germanium is deposited on the nucleus. The operating conditions that remain constant here are temperature, pressure, gas flow and heating current. Only the case where the metal is added by the catalyst source 9 in Fig. 1 is changed (see Fig. 2 for a detailed view).

在此觀察到，由特定含量起無法藉由增加金屬的量而提高最大功效。在供應量過低的情況下僅發現減小的生長情況。 It has been observed here that it is not possible to increase the maximum efficacy by increasing the amount of metal from a specific content. Only a reduced growth condition was found in the case of a low supply.

若將金作為催化劑之一引入，在其他方面相同的操作條件下，在生長區域上獲得在最大催化劑作用下60倍厚度的多晶矽層。 If gold is introduced as one of the catalysts, a polycrystalline germanium layer having a thickness of 60 times under the action of the maximum catalyst is obtained on the growth region under otherwise identical operating conditions.

在此觀察到，由某一含量起無法藉由增加金的量而提高最大功效。該功效無法提高，直至金在矽中的溶解度極限。 It has been observed here that it is not possible to increase the maximum efficacy by increasing the amount of gold from a certain level. This effect cannot be increased until the solubility limit of gold in the sputum.

在製造太陽能電池時，必須避免所引入的元素摻雜 入矽，因為這使p-n接面的複雜化，並且對太陽能電池的有效性有負面影響。 In the manufacture of solar cells, the doping of the elements introduced must be avoided This is because it complicates the p-n junction and has a negative impact on the effectiveness of the solar cell.

在此，鋁發揮特別的作用。在標準太陽能電池的情況下，借助用鋁高量位(level)摻雜的區域實施接觸連接(contact connection)。這發生在p-n接面的p型摻雜側。在此，鋁不會作為雜質造成干擾。但是在n型摻雜側，鋁對摻雜有逆補償作用。 Here, aluminum plays a special role. In the case of standard solar cells, a contact connection is made by means of a region doped with high levels of aluminum. This occurs on the p-doped side of the p-n junction. Here, aluminum does not cause interference as an impurity. However, on the n-doped side, aluminum has a counter-compensation effect on doping.

因此，鋁和第3主族元素(硼族)不合適作為催化劑。 Therefore, aluminum and a third main group element (boron group) are not suitable as a catalyst.

佔據晶格位置的金屬通常具有作為p型或n型摻雜劑的活性。此外，晶格位置具有局部化作用(localizing effect)，即阻止擴散。 The metal occupying the lattice position generally has activity as a p-type or n-type dopant. In addition, the lattice position has a localizing effect, ie, prevents diffusion.

因此，B、C、Mg、Ca、Zn、Pt是不合適的，而Li、O、Cr、Mn、Fe、Ni、Cu、Ag、Au是間隙的異原子(interstitial foreign atom)。 Therefore, B, C, Mg, Ca, Zn, and Pt are not suitable, and Li, O, Cr, Mn, Fe, Ni, Cu, Ag, and Au are interstitial foreign atoms.

為了總是在表面上存在有金屬原子，其應當擴散至表面，因為其只有在此才能與沉積氣體(deposition atmosphere)相互作用。 In order to always have metal atoms on the surface, it should diffuse to the surface because it can only interact with the deposition atmosphere.

這通常是在大於500℃的溫度下的情況。 This is usually the case at temperatures above 500 °C.

銅即使在低的溫度下仍然具有高的擴散係數。 Copper has a high diffusion coefficient even at low temperatures.

為了實現p-n接面的功能，必須將電荷載子分離。電荷載子壽命(lifetime)越長，則這越容易實現。一些金屬發揮作用並作為再結合位點(recombination site)。 In order to realize the function of the p-n junction, the charge carriers must be separated. The longer the charge carrier lifetime, the easier it is to achieve. Some metals act and act as recombination sites.

銅和銀是特別有利的。 Copper and silver are particularly advantageous.

在反應器中較佳地藉由電弧(light arc)將金屬釋放至冷的氣相中，即至矽烷中，較佳至一惰性氣體中。但也可以其他方式將金屬引入反應氣體中。例如，可以在上游過程中已經將金屬引入氯矽烷中，例如三氯矽烷中。也可以在沉積的一上游方法中將金屬添加至氫。 The metal is preferably released into the cold gas phase by means of a light arc in the reactor, i.e. to decane, preferably to an inert gas. However, it is also possible to introduce the metal into the reaction gas in other ways. For example, a metal may have been introduced into chlorodecane, such as trichloromethane, in an upstream process. It is also possible to add metal to the hydrogen in an upstream process of deposition.

較佳地，利用氣密性的、熱穩定的且防止溫度壓力波動的火花塞(spark plug)引入該等金屬。 Preferably, the metals are introduced using a spark plug that is gas tight, thermally stable, and prevents temperature pressure fluctuations.

藉由高壓脈衝在沉積過程的供應氣體中產生電弧。 An electric arc is generated in the supply gas of the deposition process by a high voltage pulse.

該火花塞包含兩個均含有催化劑金屬的電極。 The spark plug comprises two electrodes each containing a catalyst metal.

這兩個電極均可以完全由催化劑金屬組成。或者，可以將一催化劑金屬安裝在電極尖端上，例如焊接或熔焊的方式。 Both of these electrodes can be composed entirely of catalyst metal. Alternatively, a catalyst metal can be mounted on the tip of the electrode, such as by welding or welding.

經點火電壓和電荷(焦耳)控制所釋放的催化劑金屬的量。 The amount of catalyst metal released is controlled by the ignition voltage and charge (Joules).

11‧‧‧石墨電源供應器 11‧‧‧Graphic power supply

12‧‧‧電流接線頭 12‧‧‧current terminal

21‧‧‧矽烷進料：SiH4、DCS、TCS 21‧‧‧ decane feed: SiH 4 , DCS, TCS

22‧‧‧輔助氣體進料：氫、HCl、CH4 22‧‧‧Auxiliary gas feed: hydrogen, HCl, CH 4

23‧‧‧廢氣 23‧‧‧Exhaust

3‧‧‧水冷裝置 3‧‧‧Water cooling device

4‧‧‧聚矽氧烷密封件 4‧‧‧Polyoxane seals

5‧‧‧氣箱 5‧‧‧ air box

61、62、63、64‧‧‧耐壓的螺栓連接件 61, 62, 63, 64‧‧‧ Pressure-resistant bolted joints

71‧‧‧IR照射窗 71‧‧‧IR illumination window

72‧‧‧IR加熱燈/高溫計 72‧‧‧IR heating lamp / pyrometer

8‧‧‧反應容器 8‧‧‧Reaction container

81‧‧‧矽核(生長區域) 81‧‧‧矽Nuclear (growth area)

9‧‧‧火花塞/催化劑源 9‧‧‧Spark plug/catalyst source

91‧‧‧金屬 91‧‧‧Metal

92‧‧‧用於調節電弧長度的調節螺栓 92‧‧‧Adjustment bolts for adjusting the length of the arc

第1圖所示為用於實施該方法的設備。 Figure 1 shows the apparatus used to carry out the method.

第2圖所示為火花塞的詳細示圖。 Figure 2 shows a detailed view of the spark plug.

第1圖所圖示為用於實施該方法的設備。 Figure 1 illustrates an apparatus for implementing the method.

反應容器8是壓力容器，於其中保持有矽核81以沉積多晶矽層。 The reaction vessel 8 is a pressure vessel in which a niobium core 81 is held to deposit a polycrystalline germanium layer.

保持裝置由兩個石墨電源供應器11組成，其安裝方 式使其適合於將加熱電流送至矽核。 The holding device is composed of two graphite power supplies 11 and its mounting side It is suitable for sending a heating current to the helium core.

利用電流接線頭12形成電性連接。 Electrical connections are made using current terminals 12.

為了保護電流接線頭和聚矽氧烷密封件4的元件免受高的加工溫度，利用水冷裝置3冷卻石墨電源。 In order to protect the components of the current terminal and the polyoxyalkylene seal 4 from high processing temperatures, the graphite power source is cooled by means of a water cooling device 3.

熱膨脹和在壓力改變時壓力容器的膨脹藉由氣箱5加以平衡抵消。 The thermal expansion and expansion of the pressure vessel as the pressure changes are counterbalanced by the air box 5.

出於維護和清潔的目的，加工室的元件藉由耐壓的螺栓連接件61、62、63以及64而擰接在一起。 For maintenance and cleaning purposes, the components of the processing chamber are screwed together by pressure-resistant bolted joints 61, 62, 63 and 64.

因為矽核81在室溫下不具有導電性，所以其必須利用紅外加熱燈72加熱至能夠由石墨電源供應器11有效地供應加熱電流的溫度。 Since the nucleus 81 does not have electrical conductivity at room temperature, it must be heated by the infrared heating lamp 72 to a temperature at which the heating current can be efficiently supplied by the graphite power supply 11.

為了加熱，反應容器8係設置有紅外照射窗71。 For heating, the reaction vessel 8 is provided with an infrared irradiation window 71.

在將HIR加熱裝置轉出之後，使用IR照射窗71於觀察反應容器內部的過程，更特定的是，利用IR高溫計72監測溫度。 After the HIR heating device is turned out, the IR irradiation window 71 is used to observe the inside of the reaction vessel, and more specifically, the temperature is monitored by the IR pyrometer 72.

沉積多晶矽需要工作氣體(process gases)。 The deposition of polysilicon requires process gases.

在該加工室底部送入矽烷21，同樣地送入輔助氣體22。 The decane 21 is fed to the bottom of the processing chamber, and the auxiliary gas 22 is sent in the same manner.

在該加工室的上部區域內排出廢氣23。 Exhaust gas 23 is exhausted in the upper region of the processing chamber.

將催化劑引入輔助氣體22的流中。 The catalyst is introduced into the stream of auxiliary gas 22.

在此，利用輕微改變的火花塞9以釋放催化活性金屬。 Here, a slightly modified spark plug 9 is utilized to release the catalytically active metal.

火花塞用作為催化劑源。 A spark plug is used as a catalyst source.

第2圖更詳細地顯示了火花塞9。 Figure 2 shows the spark plug 9 in more detail.

經電漿放電，存在於火花塞的多個電極之間的電弧使來自該等電極的金屬91移動(mobilize)。 Upon electrical discharge, the arc existing between the plurality of electrodes of the spark plug mobilizes the metal 91 from the electrodes.

可使用用於調節電弧長度的調節螺栓92，以調節和校正電極之間的距離。 An adjustment bolt 92 for adjusting the length of the arc can be used to adjust and correct the distance between the electrodes.

所釋放的金屬的量和比例係藉由電極距離、點火電壓、電荷及該等電極的尖端角加以調節。 The amount and ratio of metal released is adjusted by electrode distance, ignition voltage, charge, and the tip angle of the electrodes.

若在相同條件下進行放電直至遠遠超出金屬的檢測極限，則可將金屬的量歸因於單次放電，並由此可以調節該等低於檢測極限的比例。 If the discharge is carried out under the same conditions up to the detection limit of the metal, the amount of metal can be attributed to a single discharge, and thus the ratio below the detection limit can be adjusted.

9‧‧‧火花塞/催化劑源 9‧‧‧Spark plug/catalyst source

91‧‧‧金屬 91‧‧‧Metal

92‧‧‧用於調節電弧長度的調節螺栓 92‧‧‧Adjustment bolts for adjusting the length of the arc

Claims (8)

一種沉積多晶矽的方法，其中將一含矽氣體導入一反應器中，以及藉由使該含矽氣體還原而在經直接流通電流而加熱到至少為550℃的溫度的一支撐體上沉積多晶矽，其中，在使該含矽氣體還原期間係存在至少一種選自以下群組作為第一催化劑的第一金屬：鈦、鉻、錳、鐵、鈷、鎳、銅和鋅，並另外存在至少一種選自以下群組、不同於該第一金屬、作為第二催化劑的第二金屬：銅、銀和金。 A method of depositing polycrystalline germanium, wherein a helium-containing gas is introduced into a reactor, and polycrystalline germanium is deposited on a support heated to a temperature of at least 550 ° C by direct current flow by reducing the helium-containing gas, Wherein, during the reduction of the ruthenium-containing gas, at least one first metal selected from the group consisting of titanium, chromium, manganese, iron, cobalt, nickel, copper, and zinc is present, and at least one selected From the following group, a second metal different from the first metal as the second catalyst: copper, silver, and gold. 根據請求項1的方法，其中在使該含矽氣體還原期間係存在有鎳和銅。 The method of claim 1, wherein nickel and copper are present during the reduction of the helium-containing gas. 根據請求項1或2的方法，其中在使該含矽氣體還原期間，另外存在有碳。 The method of claim 1 or 2, wherein during the reduction of the helium-containing gas, carbon is additionally present. 根據請求項1或2的方法，其中，在存在氫的情況下，所使用的含矽氣體是三氯矽烷。 The method according to claim 1 or 2, wherein, in the presence of hydrogen, the helium-containing gas used is trichloromethane. 根據請求項1或2的方法，其中該第一金屬或第二金屬或這兩種金屬是藉由電弧(light arc)釋放至該含矽氣體或一惰性氣體中。 The method of claim 1 or 2, wherein the first metal or the second metal or the two metals are released into the helium-containing gas or an inert gas by a light arc. 根據請求項1或2的方法，其中在使該含矽氣體還原期間，該至少一種第一金屬和至少一種第二金屬的存在量是使得在該沉積的多晶矽中包含至少一種選自以下組中的第一元素：鈦、鉻、錳、鐵、鈷、鎳、銅和鋅，其濃度為18pptw至40ppbw鈦、0.2pptw至5ppbw鉻、0.5pptw至15ppbw錳、7pptw至 50ppbw鐵、0.012pptw至25ppbw鈷、0.9pptw至8ppbw鎳、3pptw至12ppbw銅和/或0.6pptw至11ppbw鋅；並且包含不同於該第一元素的至少一種選自以下群組的第二元素：銅、銀和金，其濃度為3pptw至12ppbw銅、0.15pptw至21ppbw銀和0.001pptw至0.3ppbw金。 The method of claim 1 or 2, wherein the at least one first metal and the at least one second metal are present during reduction of the ruthenium-containing gas such that at least one selected from the group consisting of the selected polycrystalline cesium is selected The first element: titanium, chromium, manganese, iron, cobalt, nickel, copper and zinc, the concentration of 18pptw to 40ppbw titanium, 0.2pptw to 5ppbw chromium, 0.5pptw to 15ppbw manganese, 7pptw to 50 ppbw iron, 0.012 pptw to 25 ppbw cobalt, 0.9 pptw to 8 ppbw nickel, 3 pptw to 12 ppbw copper and/or 0.6 pptw to 11 ppbw zinc; and comprising at least one second element selected from the group consisting of: Silver, gold, and a concentration of 3 pptw to 12 ppbw copper, 0.15 pptw to 21 ppbw silver, and 0.001 pptw to 0.3 ppbw gold. 一種多晶矽，其包含至少一種選自以下群組的第一金屬：鈦、鉻、錳、鐵、鈷、鎳、銅和鋅，及至少一種選自以下群組的不同於該第一金屬的第二金屬：銅、銀和金，其中所選擇的該至少兩種金屬在多晶矽中是以如下的量存在：18pptw至40ppbw鈦、0.2pptw至5ppbw鉻、7pptw至50ppbw鐵、0.012pptw至25ppbw鈷、0.9pptw至8ppbw鎳、3pptw至12ppbw銅、0.6pptw至11ppbw鋅、0.15pptw至21ppbw銀、0.001pptw至0.3ppbw金、0.5pptw至15ppbw錳。 a polycrystalline germanium comprising at least one first metal selected from the group consisting of titanium, chromium, manganese, iron, cobalt, nickel, copper, and zinc, and at least one selected from the group consisting of: Dimetal: copper, silver and gold, wherein the at least two metals selected are present in the polycrystalline germanium in an amount of 18 pptw to 40 ppbw titanium, 0.2 pptw to 5 ppbw chromium, 7 pptw to 50 ppbw iron, 0.012 pptw to 25 ppbw cobalt, 0.9 pptw to 8 ppbw nickel, 3 pptw to 12 ppbw copper, 0.6 pptw to 11 ppbw zinc, 0.15 pptw to 21 ppbw silver, 0.001 pptw to 0.3 ppbw gold, 0.5 pptw to 15 ppbw manganese. 根據請求項7的多晶矽，其中存在有0.9pptw至8ppbw鎳和3pptw至12ppbw銅。 According to the polycrystalline silicon of claim 7, there are 0.9 pptw to 8 ppbw of nickel and 3 pptw to 12 ppbw of copper.
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