200813269 九、發明說明： · 【發明所屬之技術領域】 作為 【先前技術】 導執結i Si結晶的結合能強’絕緣破壞電場大，而且 ί有除::;為:;:巧常用= 常數/此料⑽的晶格 内使^的製造合成，包括：在石墨_ 瑞里法（ileigh 晶化的 攜產熱後$sic種單結晶上並=== ^便/、產生化子反應，一邊進行蠢日#旦从广·^ 考非專利文件晶成長為蠢晶的昇華接近法等（請參 si^ C。，但是心 形狀控制以及結晶面控制的困難，==種進行 徑晶圓的問題。 及用此種方式I法侍到大口 得到可因：百-姐 蟲晶成長，因此會有在結晶内有許多微細管方式進行 5 200813269 質單結ί=成高純度且低缺陷密度的良 長晶速細i 因此其 單結晶SiC鑄錠。 卜之私度因而燕法得到長形的 高純度的SK遙晶成長雖的結構，而實現 眺種單結晶表面並i其：; 行蠢晶成長（請參考專種，晶上Jt 獲得一高品質的單钤曰ς〗Γ，θ甘 、°方式中’可以用鬲速 。在專利文件1所揭露的單結晶缺陷。 S晶:ί的3原料之二氧化彻粒:碳超微粒: 獲得之此_恤，係_、_級粒传徑、(平 以下）’因此體積密度小，而且形狀並非呈略球开^=在1， 試將此等原^直接以惰性攜載氣_送到训種/ ^ ’，p使鲁 有易於在配管中途發生堵塞的傾向。、、、"曰曰、，仍y 【專利文件1】日本專利第3505597號公報 '非f利文件1】編著，「半導體s 刊工業新聞社（2003年3月初版發行） T/、應用」曰 【發明内容】 發明所欲解決之誤顳 本發明係為，決上義課題所構思而成。本發明之目於 提供.在SiC種單結晶上’可良好地進行輸送而不會堵夷的妹 晶SiC製造用原料；其製造方法；使用該原料而使高^之單= 6 200813269 晶的方法；以及因此所獲得之高品質單結晶況。 六述的課，可用以下所記載的方式而解決。 M :種單結晶沉製造用原料’係由二氧化軸α夂、 級粒子所實質地構成的次級粒 與％的各初 狀係呈直徑1_〜9_的略I t錢級粒子的形 (2) 種製造如（1)的單結晶SiC製造用原料的制、生古、土甘 以Γ由二氧化雜子、碳粒手以及溶；構成的 有二；二漿 (3) —種單結晶Sic的製造方法，其 堝内，設置固定有Sic種結晶的基座二i“ 用原料的原料 用氣體的=禍内，將依⑴所得的單結晶 一’、斗戈依（2 )的製造方法而製造的罩社曰ς彳ρ彻、生田 原料，經由原料供應管供應到該沉 f曰曰二，士 晶沉成長的成長步驟。 痕，上，猎此方式使早結 麵種早結晶SiC，以（3)之製造方法所製造而成。 體穩明之單結晶SlC製造用原料的話，即可藉由攜載氣 方ί疋可原料。又’藉由使用此原料以製造單結晶SiC的 回π口貝之早結晶Sic的方式。 【實施方式】 j下將參舨圖式詳細說明依據本發明的較佳施开。 造用肩^明^第=相（第1發明）’係有關於-種單結晶Sic製 ’、〃、，/、由二氧化矽與碳的各初級粒子所實質地構成的次級 7 200813269 ^子。其中，該次級粒子的形狀係呈直徑為〜卯卵的略球 料本發明之單結晶SiC製造用原料的構成物而言，較 好與雜子。轉二氧姆粒子與碳 击二杜ΛΑ运刀別"^田砥擇”種類。而無論是二氧化矽粒子或碳粒子， 2兩者的初級粒子的平均粒徑係在100nm以下的微粒 ί下係下的微粒子;特佳的情況係在20咖 J5 情況係在5〜20nm的超微粒子。又，就 、，、屯5而s ’兩者較佳的情況皆係盡可能為高純度者。就二氣化欲 ^: S (flame hydrolysis> :屯j二减梦（燻梦，fumed silica)。又，而々 佳的纽_高驗⑽黑（㈣細e =k。）專。此外，贿粒子的平均粒徑可藉由電子顯微鏡觀察而 並不了二氧切及碳之外， 集的===粒子與碳粒子共同凝 下，其形狀為略球形。仫其直仏々為1㈣上90_以 所明的直径「約為1 K以卜, 級粒子的100重量部之中，复吉庐/ f 乂下」’係指所製造的次 佔9。重量部以上二下，子， ，量部而言。而所謂的U上：=的= 師子進行的分級等而決定。 沾“ 乂下」，可猎由 直徑在巧以二銷售的粒度計等，藉二Si重量平均 形狀除；:長；形在_形之 外，也包括球形表面‘部I下，=„之旋轉橢圓體之 表面有鬚狀突起之形狀。77曰 陷球，或是在球體的 8 200813269 由（2)的制！古冰品/粒子之初級粒子事先混合之後，再藉 子。起賴’加卫成具有該粒徑及雜之次級粒 因為本發明之單結晶Sic製造用 _下的直徑且呈略球形的次級粒子，因此在=、=A 該原料之料^ ί^ί的故早。另外，就獲得該略球形的 二且獲^可將粒度分布抑制得比較小、純度高、 造過ί中不使用該原料的單結獄的製 ，、末不谷易淑知，而且流動性佳，也不會產生 _^^題；更能製造㈣純紅高品質的單結晶“ 面相（第2發明)’係有關於-種製造如⑴所 σ己載==、、、口曰曰SiC製造用原料的製造方法，包括： 驟·製氧化雜子、餘子以及溶媒所構成的漿料的步 驟i以及ΐ蒸發裝置内將該漿料喷霧乾燥並且使其造粒，以製造 ΐί if氧彳㈣與碳的次級粒子之喷霧乾燥步驟。較佳的情ϋ 洛媒為揮發性溶媒。 “要加工成具有上述粒徑及形狀的次級粒子的方法，只要是使 粒度分布較陡續’而且控制成高純度的方法的話，並無特別的限 制。 ^本务明人檢讨了以下所示的種種造粒的方法，包含：壓碎二 氧t矽與碳的各初級粒子之凝集物的壓碎造粒法；使粉體被嵌入 在旋轉滾筒表面的鑄模後壓縮的壓縮造粒法.；以及使低濕的粒子 混合物以顆粒機予以擠製的擠製造粒法等。在經過比較檢討上述 方式之後’基於希望粒徑範圍較小、粒徑分布較狹窄、尤其是從 200813269 痛 的觀點來看，發明人發現依據噴霧乾焊而、&私… 霧乾爍法較為優里，從 二貝務早乙展而造粒的噴 法的發明。、*而疋成此早結晶Sic製造用原料的製造方 在製的’噴霧乾燥法係基於喷霧乾燥之造粒方法。 -奸：與溶媒所實質地構二ί料 • 間乾燥並造粒，作為芝略##从“^ f1 ^的熱風中使其瞬 的液體即可，= 2成/匕外’「溶媒」只要是揮發性 可以使用水。非谷％二氧化石夕或碳的液體亦可，甚至也 亦包含加μ嘴嘴者。就噴嘴而言，雖然 生磨損的疑慮，因此在私日m贺射端造成漿料堵塞或是產 喷霧器。 χ月中，較佳的情況係使用旋轉圓盤的 供應漿料，益’是對以高速旋轉的圓盤中心部 其負荷的空氣車=3夫由空氣壓使旋轉軸懸浮，而支撐. 旋轉圓盤的旋^么:二=了開平ι〇—118536號公報)。如果使 此種具備可高速旋轉§ &可以使次級粒子的粒徑減小。 乾燥機，例如可以^用大川=〜4〇〇〇〇_)的旋轉圓盤之喷霧 次級粒子，且餐名古％炎Ί j衣化出王略球形的二軋化矽與碳 90重量％以上。位為V™1〜90_的範圍内之次級粒子，佔 粒機使用於第2發明的製造方法中，噴霧乾燥造 成的雜子'雜子《及溶媒所構 育務乾w粒機係自該聚料儲存槽丄，藉由祕輸液 10 200813269 « ，2輸送到作為噴霧裝置 如 中而瞬間乾燥，被造粒成切匕;H贺向⑽室8的熱風 風機12輪送空氣。在太日=務益7的周圍，則由送 喷嘴、碟片式噴嘴、二流^嗜’就贺^^言+’可適當選擇加麗 而使用即可，作以碑片^ +路 11塱一流體噴嘴等的朁知喷嘴 - 方為圓芮邱.t碟片式贺嘴較佳。就乾燥室§而言，俜呈右上 S乾==射-_部的構造。在乾燥；81ΐ 清器6，而藉由送工風^ 4^5相予以加熱，然後，使其通過熱風濾 氣線，齡此外，於麵冑8尚設置有排 集塵機U，且介以及 圖示的取出πίΓ子的產品，可從設置於_部的底部之未 本發明之第3面相（第 S的 製造方法，其特徵在於包含以下兩個步ί種早―日S1C的 盘裝置__ ’設置··基座’固定有Sic種結晶， ^枓供應官，用以從外部供應單結晶Sic製造用原料的步驟； 社曰ΐ.ίΐΐ高溫環境氣體的紐_，將依上述⑴所得的單 =曰曰曰ς1二仏用原料或依上述⑵所記載的製造方法而製造的單 : = ‘造用原料，經由原料供應管供應到SiC種結晶表面， s'C疋成長ίΐί的單趣lG的絲編，藉此方式使單結晶 紝曰單結日日SiC之製造溫度並無特別的限制，可以根據所欲的單 結f Sic。的大亡、形狀、種類而適當設定。較佳的製造溫度係16〇〇: C〜2400 c的範圍内，此溫度可由例如測定坩堝外側的溫度而得。 使用於本發明的單結晶SiC的製造方法之製造裝置，其結構 11 200813269 ，…、4寸別驗制。也就是說，·錄結晶的大小、獅加 ^職材質、原料供應方式、環境氣體調整方式、長晶壓^、、 溫度f制方式等’可以根據所欲的單結晶SiC的大小、形狀、種 結晶SlC製造用原料之種類與數量等適當選擇而得。例如， 在溫度測定與溫度控制中，可使用piD溫度控制技術。 =本發明所使關掛塌之形狀，關於其外形並無特別的限 去以配合所欲的單結曰曰日SlC的大小與形狀而適當選擇。此外， 考慮到使用溫度的範圍，該掛竭的材質較佳為石墨製。 欲的的f座之形狀並無特別的限制’可以根據所 SiC的大小與形狀而適當選擇。然， 度的範圍，該基錢材質較佳為石難。 Μ職用咖 供應單結晶Sic製騎_料供應f =制2以根據所欲的單結晶S1C的大小與形狀而適當 f慮=使用溫度的範® ’該供應f的材質較佳為石墨製。 少□疋有；^化⑦（SiG)種單結晶的基座巾，可使原料^岸瞢 在掛禍中與其相對設置，亦可使其呈直角或斜向言2_供應吕 時，造用原料而製造單結晶沉 大小、加熱方式、材質、原料供應方ί、S 大:;狀式種;度式等，可以根據所欲的單結晶Sic的 =等錄、觀，而適當獅單結晶Sic製造闕料之種類與 的方單結B!Sic製造用原料而製造單結晶sic 吕iif ’在掛褐之中呈相對設置，亦可使其呈直 略平行，制最大呈45。_斜為止均可讀絲颜錯直方向 12 200813269 訪+外，在採用上述的基座與原料供應管的設置狀態下，加熱 ，使坩堝内充填有高溫環境氣體，並將該單結晶Sic製造 、車锋ϊϊ造該單結晶SiC時，作騎結晶sic製造用原料，而且 的二氧化矽粒子與碳粒子的混合比，以及（連續）供應 〜特別的限制。原則上二氧化雜子與碳粒子的比以1. Γ ΐ的混表性。然而，可依據製造條件適當選擇所希 他成=外’該單結晶Sic製造用原料也可以視必要而微量添加其 該單結晶Sic製造用原料供應到Sic種結晶上的方 !隹：:2用：間斷地連續供應的方法。例如，可使用市面上200813269 IX. Description of the invention: · [Technical field to which the invention pertains] As a prior art, the bonding energy of the iSi crystal is strong, the dielectric breakdown electric field is large, and ί has the following::; /In the crystal lattice of this material (10), the synthesis of ^, including: in the graphite_Rayleigh method (the ileigh crystallization of the heat generated by the $sic single crystal and === ^, /, the generation of the reaction, Doing a stupid day #旦从广·^ The non-patent document crystal grows into a sublimation approach to the stupid crystal. (Please refer to si^ C. However, the difficulty of heart shape control and crystal face control, == kind of wafer The problem is that I can get a good cause by using the I method: the growth of the hundred-sister insect crystal, so there will be many micro-tubes in the crystal. 5 200813269 singular knot ί=high purity and low defect density The good crystal length of the fine i is therefore its single crystal SiC ingot. Therefore, the private method of the swallow method obtains the long-form structure of the high-purity SK crystal growth, and realizes the single crystal surface and realizes its Stupid crystal growth (please refer to the special species, Jt. Jt to get a high quality single 钤曰ς Γ) In the θ Gan, ° mode, 'can be used for idle speed. The single crystal defect disclosed in Patent Document 1. S crystal: ί 3 raw material of oxidized crystal: carbon ultrafine particles: obtained this _ shirt, _, _ The size of the granules, (below the flat) 'so the bulk density is small, and the shape is not slightly open ^ = at 1, try to send the original ^ directly to the inert carrier gas _ to the training / ^ ', p Lu has a tendency to block in the middle of piping.,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, In the first edition of SiC, the application of the invention is based on the concept of the present invention. a raw material for the production of a sister crystal SiC which can be transported without being blocked, a method for producing the same, and a method for producing a high-quality single = 6 200813269 crystal using the raw material; and thus a high-quality single crystal condition obtained thereby The six lessons can be solved in the manner described below. M: Single crystal sink manufacturing The raw material 'is made up of the secondary particles of the α-axis and the primary particles, and the primaries of the % are in the form of a diameter of 1_~9_. a method for producing a raw material for producing single crystal SiC, a raw material for the production of samarium, a samarium dioxide, a carbon granule, and a solvent; and a method for producing a single crystal Sic; In the inside of the crucible, a slab that is fixed with a singular crystal of Sic crystals, a slab of a raw material, and a method of producing a single crystal of the singularity of (1)曰ς彳ρ彻, raw materials, through the raw material supply pipe to the sinking, the growth step of Shijing Shen. The method of marking, topping, hunting, and early crystallization of early surface SiC is produced by the manufacturing method of (3). If the raw material for the production of single crystal SlC is stable, it can be obtained by carrying the gas. Further, by using this raw material, a method of producing the early crystalline Sic of the π-mouth of the single-crystal SiC is produced. [Embodiment] A preferred embodiment of the present invention will be described in detail with reference to the drawings. The shoulders of the first phase (the first invention) are related to the single crystal Sic made of 'Single', 〃, /, and the secondary 7 composed of the primary particles of cerium oxide and carbon. ^子. Among them, the shape of the secondary particles is a slightly spherical material having a diameter of ~ 卯 eggs. The composition of the raw material for producing single crystal SiC of the present invention is preferably a heterogeneous material. The dioxin particles and the carbon hit two rhododendrons are different from the "^ Tian 砥" type. Regardless of the cerium oxide particles or carbon particles, the primary particles of both of them have an average particle diameter of 100 nm or less.微粒The lower particles are fine; the best case is the ultrafine particles of 5~20nm in the case of 20 coffee J5. Also, the best case of both, ,5 and s ' is high purity as much as possible. The second gasification desire ^: S (flame hydrolysis>: 屯j two dreams (fumed silica). Also, and the best New _ high test (10) black ((four) fine e = k.). In addition, the average particle size of the bribe particles can be observed by an electron microscope without the dioxin and carbon, and the set === particles and carbon particles are coagulated together, and the shape is slightly spherical. 1(4) The upper 90_ is the diameter of the specified "about 1 K, the weight of the 100-weight portion of the grade particles, the complex weight of the 庐 / 乂 」 」 ” ” ” ” ” ” ” ” Sub, the volume, and the so-called U:=== The division of the division is determined by the division. Dip "乂下", you can hunt the grain by the diameter of the two Calculate, by the weight average shape of the two Si division;: long; shape in addition to the _ shape, also includes the spherical surface 'part I, = „the surface of the spheroid has a shape of a whisker-like protrusion. 77 曰, Or in the sphere 8 200813269 by the system of (2)! The ancient particles of the ancient ice / particles are pre-mixed, and then borrowed. The tribute 'adds the secondary particles with the particle size and impurities because of the invention Single crystal Sic is manufactured with a diameter of _ under the shape of a slightly spherical secondary particle, so at =, = A the raw material of the material ^ ί ^ ί early. In addition, the slightly spherical second and obtained The particle size distribution is suppressed to be relatively small, the purity is high, and the single-hail system that does not use the raw material is produced, and the end is not easy to know, and the fluidity is good, and the problem is not produced _^^; The red high-quality single crystal "face phase (second invention)" is a method for producing a raw material for producing 曰曰 曰曰, which is produced by (1), and includes: oxidizing impurities And the step i of the slurry composed of the remainder and the solvent, and the slurry is spray-dried in the helium evaporation device and Granulation to produce a spray drying step of 彳 if 彳 彳 四 四 四 与 与 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 There is no particular limitation as long as it is a method of making the particle size distribution steeper and further controlled to high purity. ^The present inventors reviewed the various methods of granulation shown below, including: crushing dioxins a crush granulation method for agglomerates of primary particles of bismuth and carbon; a compression granulation method for compressing a powder after being embedded in a mold on a surface of a rotating drum; and extruding a mixture of low-humidity particles by a pellet machine The extrusion method of making pellets, etc. After a comparative review of the above methods, 'based on the desire to have a smaller particle size range and a narrower particle size distribution, especially from 200813269, the inventors found that according to spray dry welding, & private... Youli, the invention of the spray method of granulation from the second bake. *, and the production of raw materials for the production of this early crystal Sic. The spray drying method is a granulation method based on spray drying. - 奸: With the solvent, the material is solid and granulated, as the Zhiluo ## from the hot air of "^ f1 ^, it can be instantaneous liquid, = 2% / 匕" "Solvent" Water can be used as long as it is volatile. Non-valid% dioxide dioxide or carbon liquids may also be included, even including the addition of a mouth. As far as the nozzle is concerned, although there is a concern of wear and tear, the slurry is blocked or the sprayer is produced at the private day. In the middle of the month, it is better to use the supply slurry of the rotating disc, which is the air vehicle that loads the center of the disc at a high speed, and the air is compressed by the air pressure to support the suspension. The rotation of the disc: 2 = Kaiping ι〇 - 118536 bulletin). If such a high-speed rotation is enabled, the particle size of the secondary particles can be reduced. For the dryer, for example, you can use the sprayed secondary particles of the rotating disc of Okawa = ~4〇〇〇〇_), and the name of the dish is 古 % Ί Ί 衣 衣 衣 王 王 王 王 王 王 王 王More than weight%. The secondary particles in the range of VTM1 to 90_ are used in the manufacturing method of the second invention, and the heterozygous miscellaneous and the solvent-structured dry w-grain machine are produced by spray drying. From the aggregate storage tank, by the secret infusion 10 200813269 « , 2 is sent to the spray device as a medium to be instantaneously dried, granulated into a cut; H He Xiang (10) room 8 hot air blower 12 rounds the air. In the vicinity of Tairi = Shiyi 7, the nozzle, the disc nozzle, the second stream, the hobby, and the ^^言+' can be selected and used appropriately. A nozzle for a fluid nozzle, etc. - is a round 芮 .. In the case of the drying chamber §, 俜 is the structure of the upper right S = = = shot - _ section. In the dry; 81 ΐ cleaner 6, and by heating the wind ^ 4 ^ 5 phase to be heated, and then through the hot air filter gas line, in addition, in the face 胄 8 is still equipped with a dust collector U, and the map The product of the π Γ 取出 取出 取出 取出 取出 取出 取出 π π π ( ( ( ( π ( π π π π π π π π π π π π π π π π π π π π π π π π π π π π π π π π π 'Settings··Base' is fixed with Sic crystals, ^枓supply officer, the step of supplying raw materials for single crystal Sic production from the outside; 曰ΐ. High temperature ambient gas 纽, will be obtained according to (1) above. Single = 曰曰曰ς 1 仏 原料 原料 或 或 = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = = In the meantime, the manufacturing temperature of the SiC of the single crystal is not particularly limited, and can be appropriately set according to the desired death, shape, and type of the single knot f Sic. The manufacturing temperature is in the range of 16 〇〇: C 2400 c, which can be, for example, The apparatus for producing a single crystal SiC according to the present invention has a structure 11 200813269, ..., 4 inch inspection. That is, the size of the crystal is recorded, and the lion is added. The material, the raw material supply method, the ambient gas adjustment method, the long crystal pressure, the temperature f system, etc. can be appropriately selected depending on the size and shape of the desired single crystal SiC, and the type and amount of the raw material for the production of the seed crystal SlC. For example, in temperature measurement and temperature control, piD temperature control technology can be used. = The shape of the suspension of the invention is not limited to the shape of the single knot. The size and shape are appropriately selected. Further, in consideration of the range of the use temperature, the material to be exhausted is preferably made of graphite. The shape of the desired seat is not particularly limited 'may depend on the size and shape of the SiC. Appropriate choice. However, the range of the degree, the base money material is preferably stone difficult. The service of the coffee supply single crystal Sic riding _ material supply f = 2 to suit the size and shape of the desired single crystal S1C f =The temperature of the use of the standard 'The material of the supply f is preferably made of graphite. Less 疋 疋; ^ 7 (SiG) single crystal pedestal towel, can make the raw material ^ 瞢 in the disaster It can also be made at right angles or obliquely. When supplying Lv, the raw material is used to make a single crystal sink size, heating method, material, raw material supply, ί, S:: type; degree, etc. According to the desired single crystal Sic = the same, the view, and the appropriate lion single crystal Sic to make the type of the material and the square single knot B! Sic manufacturing raw materials to produce a single crystal sic Lu iif 'in the brown Relative setting, it can also be made straight and parallel, the maximum is 45. _ oblique to read the silk straight wrong direction 12 200813269 visit + outside, in the above state of the base and raw material supply pipe, heating When the crucible is filled with a high-temperature ambient gas, and the single crystal Sic is manufactured and the single crystal SiC is produced by the single crystal, the raw material for the production of the crystal sic is used, and the mixing ratio of the cerium oxide particles to the carbon particles is (Continuous) supply ~ special restrictions. In principle, the ratio of dioxins to carbon particles is 1. Γ ΐ mixed. However, it is possible to appropriately select the raw material for the production of the single crystal Sic according to the production conditions, and to add the raw material for the production of the single crystal Sic to the Sic crystal by a small amount as necessary; 隹::2 Use: Intermittent continuous supply method. For example, can be used on the market
Hi 將該單結晶Sic製造用原料從該粉體運送裝置輸送到 該單二發生堵塞的情況’因此較佳的情況係僅使用將 、、、口日曰SiC y造用原料加工成略球形者。 氣體結晶sic製造用原料與攜載 用原料中作為以 aa 佳為晶圓的形狀。SiC種單結晶晶°圓曰曰的^為t 晶^ 選擇。例如，可適當利用將依改良瑞里當 要進行前處理後之酬結晶晶 13 200813269 板、OFF角基板皆可使用。例如 度的OFF角（〇〇〇1)之Si面基板。用面的Si面基板或具備數 結晶制根據所欲的單 =。一的範圍内’此温度；如 本發明之第4面相（第4菸日日、&士 所製造的單結晶Sic。此Sic “ nt於以第3發明的方法 低，為-高品質之SlC單結rraai子沒有微細管，且缺陷密度 【實施例】 以下說明關於本發明之實施例。 (實施例1) 將作為單結晶Sic製造用原料的碳（電氣化學工業股份 公Γ斤HDrkaBlack)與二氧化石夕（日本Aer〇sii公司生i 之to0sll識）兩者混合之後，溶解在純水中使其裝化。以喷I 乾综機（大川觀工機股份雜公司所生產之FGG_16)將所得 的漿料’加工成呈略球形的造粒粉末。此時的粒徑為以上90 /zm以下。此外，在所得到的原料中，金屬雜質的濃度在次 (sub-ppm)以下。將如此所得到的原料填充於自製的粉 (實施例2). 俄 將此粉體輸=機連接到單結晶Sic製造裝置的原料供應管線。 圖2係顯示單結晶siC製造裝置30的結構圖。單結晶Sic製 造裝置30係採用高頻感應加熱方式，在水冷的密閉腔室31内， 设置有石厌製的圓同掛褐32 (直徑100 mm ;高度150 mm)。於該水冷 的德閉腔至31的外側，設置有高頻感應加熱線圈33。在該圓筒掛 堝32内的上方，貫穿插入有基座35，用以固持&C種結晶34。 除此之外，該基座35延伸到該圓筒坩堝32的外側，可藉由未圖 示的旋轉機構，以該基座的中心軸為旋轉軸而轉動。 又，更設置有：供應該單結晶SiC製造用的造粒原料之粉體 14 200813269 輸送機37 ; _ 藉由配管36’與該高頻感應加埶声 36，從與基座35相反方向的該圓'；^的卜;^妾的原料供應管 堝32内部，與該基座35相對^置。°的底面延伸到圓筒掛 面供，6而_應的原料 、 面，於該粉體輸送機37内部，原料表面。另-方 槽39被供應到配管36，；而造粒原料是由| 而從原料儲存 3 (^示)所供應的惰性攜载氣體A，:原：：氣:供 被供應到圓筒卿32内。而補的_量ϋ應而 37内」依調節闕38之流量調節機構^里制的係精由在粉體輪送機 ，結晶SiC製造裝置30的高頻感應加熱爐 的 ^氣錢與壓力調料統進行壓 真 位置關係係呈上下相對，_林改變管的 亦可變更為分獅橫向的摘·，或乾圍内， 種單結ΪίΓ 該基座喊端部固定有沉 ^如圖2所示的單結日日日Sic製造裝置，並使用依 田 ί ^得之單結晶SlC作為狀種單結晶日日日圓。^Ϊΐ 其次，在抽取高頻感應加熱爐内部的空氣使之&氣# 咖（高純度的氬）取代該高頻 阿^後，籍由該高頻感應加熱線圈對其加埶 ^ ^乳 ，掛_外側溫度升高到露c〜2靴的範使^製的 ，狀態下’將固定有Sic種單結晶晶圓之該基f 〇rPm的旋轉速度使其旋轉。在此，使與該粉體輪送〜 高純度的氬）流入，將該單結晶SiC製造用^料， 由該i、應官内部，供應到設置於該圓筒_内的對向部之 15 200813269 ilrr:®的表面上。在維持於此種情況下，—邊使圓筒掛禍 H則，度維持於一定，一邊在使該單結曰曰曰SiC長成至所欲的尺 ^对xl mm)為止，持續的進行該單結晶Sic製造用原料的 連、、、貝供應，以進行該單結晶SiC的製造。 此外，最佳的成長溫度，會隨著環境氣體壓力與單結晶sic 用原料的混合比、Sic種單結晶晶圓的種化。 (比較例1) a =，為了比較起見，將作為單結晶Sic製造用原料的碳（電 2化予工業股份有限公司所生產之DenkaBlack)與二氧化石夕（日 ^ Aerosil公司生產之Aer〇sil 38〇)兩者混合之後，不經過喷霧Hi, the raw material for manufacturing the single crystal Sic is transported from the powder transport device to the case where the single material is clogged. Therefore, it is preferable to use only the raw material of the SiC y material for processing. . The raw material for gas crystal sic production and the raw material for carrying are preferably in the form of aa as a wafer. SiC species single crystal crystal ° round 曰曰 ^ is t crystal ^ selection. For example, it is possible to appropriately use the crystallized crystals which are to be subjected to pretreatment, and the 2008-11269 plate and the OFF corner substrate can be used. For example, a Si surface substrate having an OFF angle (〇〇〇1). The surface of the Si-side substrate or the number of crystals is used according to the desired single =. In the range of one, the temperature is the same as the fourth surface of the present invention (the fourth crystal day, the single crystal Sic produced by the & s). This Sic "nt is low in the method of the third invention, and is - high quality. The SlC single-junction rraai has no fine tube and has a defect density. [Examples] The following describes an example of the present invention. (Example 1) Carbon which is a raw material for the production of a single crystal Sic (Electric Chemical Industry Co., Ltd. HDrka Black) After mixing with both of the sulphur dioxide (ato〇sii company's to0sll), it is dissolved in pure water to be packaged. The spray I dry machine (FGG_16 produced by Okawa Kanji Machine Co., Ltd.) The obtained slurry is processed into a spheroidal powder having a substantially spherical shape. The particle diameter at this time is 90/zm or more. Further, in the obtained raw material, the concentration of the metal impurities is below (sub-ppm). The raw material thus obtained was filled in the homemade powder (Example 2). The Russian powder was connected to the raw material supply line of the single crystal Sic manufacturing apparatus. Fig. 2 shows the structure of the single crystal siC manufacturing apparatus 30. Figure. Single crystal Sic manufacturing device 30 uses high frequency induction plus In the hot mode, in the water-cooled closed chamber 31, a round-shaped brown 32 (diameter 100 mm; height 150 mm) is provided, and a high-frequency induction is provided on the outer side of the water-cooled German closed chamber 31. The heating coil 33 is inserted above the cylinder hanger 32 with a base 35 inserted therein for holding the & C crystal 34. In addition, the base 35 extends to the outside of the cylinder 32. The rotating shaft of the susceptor can be rotated by a rotating mechanism (not shown). Further, a powder 14 for supplying the granulated raw material for producing the single crystal SiC is provided. _ by the piping 36' and the high-frequency induction twisting 36, from the opposite direction of the base 35, the inside of the material supply tube 32 of the circle is placed opposite to the base 35 The bottom surface of the ° extends to the cylindrical surface of the cylinder, and the raw material and surface of the material are in the interior of the powder conveyor 37, and the surface of the raw material is supplied to the piping 36. The granulated raw material is The inert carrier gas A supplied from the raw material storage 3 (shown): original:: gas: supplied to the cylinder 32. In the high-frequency induction heating furnace of the crystal SiC manufacturing apparatus 30, the high-frequency induction heating furnace of the crystal SiC manufacturing apparatus 30 is pressed by the powder in the powder transfer machine The positional relationship is up-and-down, and the _forest-changing tube can also be changed to the lion's lateral plucking, or the dry sill, and the single Ϊ Γ Γ Γ 基座 Γ Γ 基座 基座 基座 基座 基座 基座 基座 基座 基座On the day of the day, Sic manufactures the device, and uses the single crystal SlC obtained from Yita to obtain the single crystal day and day. ^Ϊΐ Next, after extracting the air inside the high-frequency induction heating furnace and replacing it with the high-frequency argon, the high-frequency induction heating coil is used to add it to the milk. The hanging_outside temperature rises to the state of the exposed c~2 shoe, and the rotation speed of the base f 〇rPm of the Sic single crystal wafer is fixed. Here, the powder of the single crystal SiC is supplied to the powder, and the raw material for the production of the single crystal SiC is supplied to the opposite portion of the cylinder. 15 200813269 ilrr: on the surface of the ®. In this case, if the cylinder is hung, the degree is maintained constant, and the single-junction SiC is grown to the desired size (xl mm). The raw material for the production of the single crystal Sic is supplied, and the shell is supplied to produce the single crystal SiC. In addition, the optimum growth temperature is based on the mixing ratio of the ambient gas pressure to the single crystal sic raw material, and the Sic single crystal wafer. (Comparative Example 1) a =, for the sake of comparison, carbon as a raw material for the production of single crystal Sic (Denka Black, produced by Koji Chemical Industries Co., Ltd.) and erbium dioxide (Aer produced by Aerosil Co., Ltd.) 〇sil 38〇) After mixing, do not spray
=的程^，而將其直接填充到自製的粉體輸送機。其後的程序 則刼用與貫施例1完,全相同的條件，以製造單結晶SiO 表1即係顯示在上述的各種不同的條件下，所製造的單結晶 J之結果。從表中可知，未施以喷霧乾燥的處理程序之比較例1， k開始原料的供應之後，原料隨即在配管内產 f結晶，W供應成制斷式的不規職態%夂面對f 儒乾燥加工的處理之實關巾，則可無窒礙地製造出雜 二/辰又低，幾乎無微細管（MP)，而且低缺失密度的高品質大型 結晶SiC。 、 〔表1 實施例 (經實施噴霧乾 燥加工） 配管輸送 無問題 單結晶SiC製i 可獲得2英吋χΐ mm 的單結晶= ^, and directly fill it into the homemade powder conveyor. Subsequent procedures were carried out using the same conditions as in Example 1, to produce a single crystal SiO. Table 1 shows the results of the single crystal J produced under the various conditions described above. As can be seen from the table, in Comparative Example 1 in which the spray drying treatment procedure was not applied, k was used to supply the raw material, and the raw material was then crystallized in the piping, and the W was supplied into a broken irregular state. f Confucian dry processing can be used to produce high-quality large-scale crystalline SiC with low impurity density (MP) and low-density density without any hindrance. [Table 1 Example (Performed by spray drying) Pipe transport No problem Single crystal SiC i can obtain a single crystal of 2 inches mm
結晶品質 雜質濃度$次ppm 幾乎無MP 比較例1 (未實施噴霧乾 燥加工） 在供應中發生 堵塞 成長速度慢 MP爹 疊層缺失多 16 200813269 【圖式簡單說明】 圖1係用以顯示本發明中用以製造單結晶SiC製造用原料而 使用的喷霧乾燥裝置的一例之概念圖。 圖2係顯示用以製造本發明之單結晶SiC的製造裝置的一例 之剖面圖。 【主要元件符號說明】 1〜漿料儲存槽 2〜漿料輸液泵 3〜空氣濾清器 4〜送風機 5〜空氣加熱器 6〜熱風濾、清器 7〜喷霧器（碟片或喷嘴） 8〜乾燥室 9〜旋風式分離器 10〜排風機 11〜集塵機（袋式集塵器、洗滌器） 12〜送風機 30〜單結晶SiC製造裝置 31〜密閉腔室 32〜圓筒坩堝 33〜高頻感應加熱線圈 34〜SiC種結晶 35〜基座 36〜原料供應管 36’〜配管 37〜粉體輸送機 17 200813269 38〜調節闊 39〜原料儲存槽 40〜單結晶SiC的成長層 A〜惰性攜載氣體Crystalline quality impurity concentration $ppm ppm Almost no MP Comparative Example 1 (no spray drying process) No clogging growth occurs during supply MP 爹 lamination loss is more than 16 200813269 [Simplified illustration] Fig. 1 is for showing the present invention A conceptual diagram of an example of a spray drying apparatus used for producing a raw material for producing single crystal SiC. Fig. 2 is a cross-sectional view showing an example of a manufacturing apparatus for producing single crystal SiC of the present invention. [Description of main components] 1~ Slurry storage tank 2~ Slurry infusion pump 3~ Air cleaner 4~ Blower 5~ Air heater 6~ Hot air filter, cleaner 7~ Sprayer (disc or nozzle) 8 to drying chamber 9 to cyclone separator 10 to exhaust fan 11 to dust collector (bag dust collector, washer) 12 to blower 30 to single crystal SiC manufacturing device 31 to airtight chamber 32 to cylinder 坩埚 33 to high Frequency induction heating coil 34 to SiC seed crystal 35 to pedestal 36 to raw material supply pipe 36' to pipe 37 to powder conveyor 17 200813269 38 to adjust width 39 to raw material storage tank 40 to single crystal SiC growth layer A to inert Carrying gas