TWI482736B - Manufacture of high purity silicon micropowder - Google Patents
Manufacture of high purity silicon micropowder Download PDFInfo
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本發明係關於一種製造裝置，其係用以製造高純度且具有微細結晶之矽微粉末，該矽微粉末主要用作鋰離子電池用負極材料或高純度氮化矽用原料。又，該矽之微細結晶可用作太陽電池用、或其他矽化合物用原料。The present invention relates to a manufacturing apparatus for producing a fine powder of high purity and fine crystals, which is mainly used as a negative electrode material for lithium ion batteries or a raw material for high purity tantalum nitride. Further, the fine crystal of the crucible can be used as a raw material for a solar cell or other antimony compound.
關於高純度矽，在電子裝置用途中，單結晶矽晶圓等11 nine程度之超高純度品已為人所知，又，即使在最近急速擴展的太陽電池用途中，雖因雜質元素之種類而異，但仍至少需要6 nine程度之高純度。為達上述目的，某些手段已被實施，以使在製造矽時儘量使生成之矽的結晶成長且不含雜質。亦即，已知一種所謂西門子法的典型矽製程，該方法係以氫還原三氯矽烷，並使生成之矽在基材上成長一段時間。然而，此技術雖為獲得超高純度矽之極佳方法，但其消耗能源極大，且生成速度較慢，因此必然需要較大設備，製造成本變得極大。Regarding high-purity germanium, in the use of electronic devices, ultra-high-purity products such as single-crystal germanium wafers of 11 nine degrees are known, and even in the recently rapidly expanding solar cell applications, the types of impurity elements are used. Different, but still need at least 6 nine degrees of high purity. In order to achieve the above object, certain means have been implemented so that the crystals of the formed crucible are grown as much as possible in the manufacture of crucibles and contain no impurities. That is, a typical crucible process known as the Siemens method is known which reduces trichloromethane with hydrogen and allows the formed crucible to grow on the substrate for a period of time. However, although this technique is an excellent method for obtaining ultra-high purity crucibles, it consumes a large amount of energy and has a slow generation rate, so that a large equipment is inevitably required, and the manufacturing cost becomes enormous.
另一方面，已提出有改變了原料、或改變了條件的多種矽製造方法(非專利文獻1)。然而，就現況而言，該等方法存在原料較為特殊、或作為原料之矽化合物較不安定且具爆發性等問題，廣泛實用化之製程極度受限。On the other hand, various types of crucible manufacturing methods have been proposed in which the raw materials are changed or the conditions are changed (Non-Patent Document 1). However, as far as the current situation is concerned, these methods have problems in that the raw materials are relatively special, or the ruthenium compound as a raw material is relatively unstable and explosive, and the widely used process is extremely limited.
另外，已知一種稱為冶金法的方法，其係將4 nine程度的高純度矽作為原料，進行電漿熔解或進行電子束熔解，藉此使雜質揮發而高純度化。又提出有一種獲得高純度矽的方法，其係於經此種高純度化之矽的凝固過程中施加單方向凝固技術，僅使雜質向端部移動。此方法雖可獲得超高純度矽，但由於原料矽純度高而昂貴、適當矽源稀少等問題，故並未進一步擴展其實用化。Further, a method called a metallurgical method is known in which high-purity yttrium of about 4 to 9 is used as a raw material, and plasma melting or electron beam melting is performed, whereby impurities are volatilized and purified. Further, there has been proposed a method for obtaining high-purity lanthanum which is applied to a unidirectional solidification technique during solidification of such a highly purified ruthenium, and only causes impurities to move toward the ends. Although this method can obtain ultra-high purity ruthenium, it is not further expanded in practical use due to problems such as high purity of the raw material cesium, high cost, and insufficient source.
更不用說，由於上述矽皆係用以獲得塊狀且緻密質之高純度矽而進行，因此不符本案發明之目的。Needless to say, since the above-mentioned crucibles are used to obtain a block-like and dense high-purity crucible, the object of the present invention is not attained.
近來，主要從節省能源的觀點來看，以鋅還原四氯化矽的方法已多有研究。也就是說，在1950年前後，藉由此種四氯化矽之鋅還原法所進行的矽之製造首度被提出，其後出現許多技術提案，一部分已被商品化。然而，另一方面，卻有係高溫製程而難以保持其運作條件、及難以處理副生氯化鋅的問題等。Recently, from the viewpoint of energy saving, there have been many studies on the method of reducing antimony tetrachloride by zinc. That is to say, before and after 1950, the manufacture of ruthenium by the zinc reduction method of ruthenium tetrachloride was first proposed, and many technical proposals appeared later, and some of them were commercialized. However, on the other hand, there are problems such as high-temperature processes that are difficult to maintain operating conditions, and problems in handling by-product zinc chloride.
為此已施行過各種手段，例如專利文獻1及專利文獻2中曾提出「將四氯化矽吹入液狀鋅表面以獲得矽」的方法。此方法雖有能以相對較低溫度製造矽的特徵，但實際上卻有如下問題：「屬於固相的矽」與「屬於液層鋅及氣相反應生成物的氯化鋅」之分離並不容易、無論如何液層鋅中的雜質終究會混入矽中因而極難將其分離。Various methods have been used for this purpose. For example, Patent Document 1 and Patent Document 2 have proposed a method of "blowing ruthenium tetrachloride into a liquid zinc surface to obtain ruthenium". Although this method has the characteristics of producing niobium at a relatively low temperature, in reality, there is a problem in that "the crucible belonging to the solid phase" is separated from the "zinc chloride belonging to the liquid layer zinc and the gas phase reaction product". It is not easy, no matter how the impurities in the liquid layer zinc will eventually be mixed into the crucible and it is extremely difficult to separate them.
此外，已提出有數個「以鋅氣體還原四氯化矽氣體，使生成之矽生成於反應爐的爐壁」之方法。專利文獻3中，限定氣體之混合比以控制析出，並促進結晶之成長。進一步，專利文獻4中曾提出將離型材施於反應槽內之壁，以作為一種更容易提取矽於爐壁之析出的方法。然而，卻有「由於成為一種批次程序，因此雜質混入生成矽中的機會增多」、「難以去除、分離作為反應氣體的四氯化矽」之問題。再者，該等皆著眼於儘量使生成之矽結晶成長。Further, there have been proposed a method of "reducing ruthenium tetrachloride gas with zinc gas to form a ruthenium formed in the furnace wall of the reactor". In Patent Document 3, the mixing ratio of the gases is limited to control the precipitation and promote the growth of the crystal. Further, in Patent Document 4, it is proposed to apply the release material to the wall in the reaction tank as a method for extracting the precipitation on the furnace wall more easily. However, there is a problem that "there is an increase in the chance of impurities being mixed into the crucible due to being a batch procedure" and "it is difficult to remove and separate the antimony tetrachloride as a reaction gas". Furthermore, these are all focused on maximizing the growth of the resulting crystals.
進一步，為了使生成矽結晶成長得更大，專利文獻5中揭示了：在惰性載體氣體環境中限定條件，來進行四氯化矽氣體與鋅氣體的反應。此外，專利文獻6中進行了：將矽種晶板置於反應爐內或是製作此種壁，以使針狀矽於該處成長。然而，因該等亦為批次程序故無法抽離，即便加以改良，亦極難防止雜質混入。該等皆著眼於為了達成高純度化而使粒子變大。Further, in order to make the generated ruthenium crystal grow larger, Patent Document 5 discloses that a reaction between the ruthenium tetrachloride gas and the zinc gas is carried out under conditions defined in an inert carrier gas atmosphere. Further, in Patent Document 6, it is carried out by placing a seed crystal plate in a reaction furnace or making such a wall so that the needle-shaped crucible grows there. However, since these are also batch procedures, they cannot be removed, and even if they are improved, it is extremely difficult to prevent impurities from entering. These are all aimed at making the particles larger in order to achieve high purity.
專利文獻7中揭示了：將作為原料之四氯化矽氣體從噴嘴吹出至位於下部之鋅氣體環境中，藉此於四氯化矽氣體噴嘴周圍使矽形成為筒狀。雖然實質上限定了氣體流速，但實施例中揭示了：藉由輸送稀薄的氣體以一面控制反應一面進行製造。使用相對大型設備製造較大結晶，並於噴嘴周圍使結晶成長，藉此，可使生成結晶在不接觸反應塔內面的情形下進行成長。透過該手段雖能得到未摻有雜質的高純度結晶，但是並未在短時間內大量地合成微細結晶，即便是相同的鋅還原法，反而會相反地促進結晶成長。Patent Document 7 discloses that ruthenium tetrachloride gas as a raw material is blown out from a nozzle to a zinc gas atmosphere located in a lower portion, whereby ruthenium is formed into a cylindrical shape around a helium tetrachloride gas nozzle. Although the gas flow rate is substantially limited, it is disclosed in the examples that the production is carried out while controlling the reaction side by transporting a thin gas. Large crystals are produced using relatively large equipment, and crystals are grown around the nozzles, whereby the produced crystals can be grown without contacting the inner surface of the reaction column. Although high-purity crystals which are not doped with impurities can be obtained by this means, fine crystals are not synthesized in a large amount in a short time, and even the same zinc reduction method promotes crystal growth in the opposite direction.
對於前述問題，本發明人等對利用旋回熔融法的高溫製程進行了研究，以作為在矽不生成於反應爐爐壁之情形下連續地使矽生成的方法。關於該等方法，已進行過專利文獻8、專利文獻9、專利文獻10、專利文獻11、專利文獻12等之發明。藉由該等方法，能夠不受反應爐爐壁之影響且連續運作，並可賦予製品矽良好性能。然而，由於必須為1200℃以上、通常為矽熔點1410℃附近之高溫，因此，雖為少許但仍有存在於系統內之雜質容易混入生成矽中，6 nine程度的純度已是極限。又有「反應裝置本身為了形成旋風而大型化」之問題。此外，由於反應溫度極高，構成反應爐之材料的耐久性容易發生問題，雖然短時間內問題較少，但是卻有難以找到長期穩定之裝置材料的問題。The inventors of the present invention have studied the high-temperature process using the spiral melting method as a method of continuously forming ruthenium in the case where ruthenium is not generated in the furnace wall of the reactor. In the above methods, the inventions of Patent Document 8, Patent Document 9, Patent Document 10, Patent Document 11, and Patent Document 12 have been carried out. By these methods, it is possible to operate continuously without being affected by the wall of the reactor, and to impart good performance to the article. However, since it is necessary to have a high temperature of 1200 ° C or higher and usually a melting point of 1410 ° C, the impurities existing in the system are easily mixed into the formation enthalpy, and the purity of 6 nine is the limit. There is also the problem that the reaction device itself is enlarged in order to form a cyclone. Further, since the reaction temperature is extremely high, the durability of the material constituting the reactor tends to be problematic, and although there are few problems in a short period of time, it is difficult to find a long-term stable device material.
為了解決該等問題，本發明人等與專利文獻13相同地進行了氣相反應法，藉由限定條件，成功地以單結晶纖維的形態提取矽。進一步，藉此一面謀求高純度化，一面以熔體提取之而謀求更加效率化。然而，卻發現以下新問題：為了形成此種纖維狀單結晶，必須於高溫中使高濃度的鋅與四氯化矽反應，由於反應場所之壓力變化相對較大，若要實用化則條件控制變得嚴格。此外，亦發現「由於係高溫反應，故有時雜質等級容易變高」之問題。In order to solve such problems, the inventors of the present invention performed a gas phase reaction method in the same manner as in Patent Document 13, and succeeded in extracting ruthenium in the form of a single crystal fiber by a limited condition. Further, in order to achieve high purity, it is more efficient in terms of melt extraction. However, the following new problems have been discovered: in order to form such a fibrous single crystal, it is necessary to react a high concentration of zinc with ruthenium tetrachloride at a high temperature, since the pressure at the reaction site changes relatively, and if it is to be put into practical use, condition control Become strict. In addition, it has also been found that "the level of impurities tends to be high due to the high temperature reaction."
再者，該等皆為「為了使結晶成長優先而不引起微粉末之形成」的條件，且從該等無法提取矽之微粉末。In addition, these are all conditions for "predicting the growth of crystals without causing the formation of fine powders", and the fine powder of bismuth cannot be extracted from these.
另外，雖然藉由如此在反應裝置內生成矽結晶後進行熔體化而能夠連續運作，但是另一方面，為了生成結晶，可能溫度、環境等條件較為嚴格而在裝置之耐久性方面會有問題。此外，生成之結晶容易產生不均，在與氣體之分離步驟中有時成長不充分之結晶會混入排氣的情形時有所聞。再者，如專利文獻6所示，將種晶置於內部的方式曾被考慮作為一種以大致一定之狀態使生成之結晶成長的方法，然而，卻變得難以連續運作，並且不符獲得微細結晶之本目的。In addition, although it is possible to continuously operate by forming a ruthenium crystal in the reaction apparatus and then performing melt reaction, on the other hand, in order to generate crystals, conditions such as temperature and environment may be strict and there may be problems in durability of the apparatus. . Further, the crystals to be formed tend to be uneven, and in the case where the crystals which are insufficiently grown in the gas separation step are mixed with the exhaust gas, they are sometimes smelled. Further, as shown in Patent Document 6, the method of placing the seed crystals in the inside has been considered as a method of growing the crystals formed in a substantially constant state, however, it has become difficult to operate continuously, and it is inconsistent with obtaining fine crystals. The purpose of this.
本發明者之一發現，作為進一步推進該等之技術，利用鋅進行之四氯化矽還原反應極為快速，而對使用更小型裝置並能大幅擴大製造能力的製造條件或裝置進行了研究。亦即實現了：將液狀四氯化矽供給至高濃度氣體狀鋅中來進行極高度之會合的矽製造條件(專利文獻15，專利文獻16，專利文獻17)。發現到，該等之反應部變得小型，而作為反應生成物之矽，則一面從成為完全之矽之前的中間體變成矽結晶一面進行成長(非專利文獻2)。One of the inventors of the present invention has found that as a technique for further advancing these, the ruthenium tetrachloride reduction reaction by zinc is extremely fast, and the production conditions or devices which use a smaller device and can greatly expand the manufacturing ability have been studied. In other words, the crucible production conditions in which the liquid hafnium tetrachloride is supplied to the high-concentration gaseous zinc to achieve an extremely high degree of convergence (Patent Document 15, Patent Document 16, Patent Document 17). It is found that these reaction units are small, and the reaction product is grown as a reaction product, and the intermediate is formed into a ruthenium crystal (Non-Patent Document 2).
在該等程序中，會藉由因結晶成長部、旋風等引起之反應氣體與矽的分離，並進一步視需要經過熔體化程序，來獲得矽結晶。在此種程序中，以物理方式進行氣相與固相矽之分離程序的結果，其間必須促進至少某種程度的結晶成長，因此，存在即使不進行溶解生成之矽亦會伴隨某種程度之粒子成長的問題。然而，若作為太陽電池用途，由於會將純度視為問題，因此粒子變大反而較理想。In these procedures, ruthenium crystals are obtained by separation of the reaction gas and ruthenium caused by the crystal growth portion, cyclone, and the like, and further subjected to a melt process as necessary. In such a procedure, the result of the separation process of the gas phase and the solid phase is physically performed, and at least a certain degree of crystal growth must be promoted therebetween. Therefore, there is a certain degree of enthalpy even if no dissolution is formed. The problem of particle growth. However, if it is used as a solar cell, since the purity is regarded as a problem, it is preferable that the particles become larger.
作為唯一連續地在種晶上生成矽之方法，有一種所謂使用流動層的方法(非專利文獻1)。然而，作為反應氣體之氯化鋅存在於系統中的情形時，會有反應氣體之分離回收變得困難而流動層本身之形成較為困難的問題。As a method of continuously forming ruthenium on a seed crystal, there is a method of using a fluidized layer (Non-Patent Document 1). However, when zinc chloride as a reaction gas is present in the system, separation and recovery of the reaction gas become difficult, and formation of the fluidized bed itself is difficult.
再者，上述之目的皆為獲得高純度/超高純度之矽，卻幾乎沒有一面保持高純度一面獲得微細之結晶。Furthermore, the above-mentioned objects are all for obtaining high purity/ultra-high purity ruthenium, but almost no one side maintains high purity while obtaining fine crystals.
[專利文獻1]特開平11-060228公報[Patent Document 1] Japanese Patent Publication No. 11-060228
[專利文獻2]特開平11-092130公報[Patent Document 2] Japanese Patent Publication No. 11-092130
[專利文獻3]特開2003-095633公報[Patent Document 3] JP-A-2003-095633
[專利文獻4]特開2003-095632公報[Patent Document 4] JP-A-2003-095632
[專利文獻5]特開2004-196643公報[Patent Document 5] JP-A-2004-196643 Bulletin
[專利文獻6]特開2003-095634公報[Patent Document 6] JP-A-2003-095634
[專利文獻7]特開2003-095634公報[Patent Document 7] JP-A-2003-095634
[專利文獻8]特開2004-210594公報[Patent Document 8] JP-A-2004-210594
[專利文獻9]特開2003-342016公報[Patent Document 9] Special Open 2003-342016 Gazette
[專利文獻10]特開2004-010472公報[Patent Document 10] JP-A-2004-010472
[專利文獻11]特開2004-035382公報[Patent Document 11] JP-A-2004-035382
[專利文獻12]特開2004-099421公報[Patent Document 12] Japanese Patent Publication No. 2004-099421
[專利文獻13]特開2006-290645公報[Patent Document 13] JP-A-2006-290645
[專利文獻14]特開2006-298740公報[Patent Document 14] JP-A-2006-298740
[專利文獻15]特開2008-81387公報[Patent Document 15] JP-A-2008-81387 Bulletin
[專利文獻16]特開2008-115066公報[Patent Document 16] JP-A-2008-115066
[專利文獻17]特開2008-115455公報[Patent Document 17] JP-A-2008-115455 Bulletin
[專利文獻18]特開2009-13042公報[Patent Document 18] JP-A-2009-13042 Bulletin
[非專利文獻1]矽24(1994)培風館[Non-Patent Document 1] 矽 24 (1994) Breeze Hall
[非專利文獻2]名古屋工業大學，陶瓷基盤工學研究中心年報、vol7 17(2007)[Non-Patent Document 2] Annual Report of Ceramics Engineering Research Center, Nagoya Institute of Technology, vol7 17 (2007)
本發明之課題在於提供一種矽製造裝置，其可解決上述問題，並能夠以最小能源高效率且大量地獲得矽，該矽具有超高純度、微細、且粒狀一致。An object of the present invention is to provide a crucible manufacturing apparatus which can solve the above problems and which can obtain crucibles with high efficiency and high efficiency with a minimum of high purity, fineness, and uniformity of particles.
本發明係一種高純度矽微粉末之製造裝置，其特徵在於含有如下機構而成：(1)將金屬鋅加熱蒸發至鋅之沸點以上以供給鋅氣體的機構、(2)將液狀四氯化矽供給至該鋅氣體中的機構、(3)混合攪拌上述鋅氣體與上述四氯化矽使其反應以生成含矽粒子之反應氣體的機構、(4)將上述反應氣體之溫度降至300℃～800℃以使生成之矽粒子成長並且與氣體成分之一部分一起沈澱的機構、(5)保持上述沈澱物並且將該沈澱物加溫至950℃以上使蒸發物揮發以獲得固體矽的機構、(6)將含有上述蒸發物、含有未反應氣體等之排氣排出至系統外的排氣機構，藉由鋅還原四氯化矽來製造矽時，無關乎不均化反應，均可達到極高濃度下之反應，在矽核選擇性地生成之條件下進行矽生成，結果，可大量生成微粉末矽，並且使該矽部分地與原料鋅以及未反應鋅一起發生沈澱，藉此可有效率地獲得微粉矽。The present invention relates to a device for producing a high-purity bismuth micropowder characterized by comprising: (1) a mechanism for heating and evaporating metallic zinc to a boiling point of zinc or more to supply zinc gas, and (2) a liquid tetrachloride. a mechanism for supplying hydrazine into the zinc gas, (3) mixing and stirring the zinc gas and the ruthenium tetrachloride to generate a reaction gas containing ruthenium particles, and (4) reducing the temperature of the reaction gas 300 ° C to 800 ° C to grow the ruthenium particles and precipitate together with a part of the gas component, (5) to maintain the above precipitate and warm the precipitate to 950 ° C or higher to volatilize the vapor to obtain a solid ruthenium (6) an exhaust mechanism that discharges the exhaust gas containing the vaporized material and the unreacted gas to the outside of the system, and when the crucible is reduced by zinc to produce antimony, irrespective of the unevenness reaction, The reaction at a very high concentration is reached, and ruthenium formation is carried out under conditions in which the ruthenium nucleus is selectively formed. As a result, a fine powder ruthenium can be formed in a large amount, and the ruthenium is partially precipitated together with the raw material zinc and unreacted zinc. Effective To obtain silicon powder.
如本案發明般之氣相反應中，一般來說，已知藉由增大原料氣體濃度來促進反應生成物之核生成，因此生成之結晶粒變小。本發明人等所實用化之將液狀四氯化矽供給至鋅氣體中以使其反應的方法，就常壓下進行之反應而言為最高濃度，是用以獲得微細結晶的最理想形態。因此，為了活用該條件，並以高效率、高產率獲得高純度矽之微細粒子結晶，而完成本發明。In the gas phase reaction as in the case of the present invention, it is generally known that the nucleation of the reaction product is promoted by increasing the concentration of the material gas, so that the crystal grains formed are small. The method of supplying liquid ruthenium tetrachloride to the zinc gas to be reacted by the inventors of the present invention is the highest concentration in the reaction under normal pressure, and is the most preferable form for obtaining fine crystals. . Therefore, in order to utilize this condition and obtain high-purity fine particle crystals of high purity in high efficiency and high yield, the present invention has been completed.
亦即，關於鋅氣體，可在供給鋅氣體之機構(1)中，直接加熱液狀或固體之鋅金屬，使其沸騰、蒸發，藉此獲得大致僅由鋅氣體構成之沸騰溫度的鋅氣體。進一步，將其加熱至必要之反應溫度1050℃～1300℃。此時，雖然亦可無環境氣體，然而，為了使系統內氣體之流動順暢並防止中途的堵塞，亦可添加氬氣，可藉此稍微加壓。而其氣體量或加壓只要少許即可，例如壓力最大到10000Pa左右(水柱1m左右)即足夠。若反應管粗度為25mm左右，則氬量約在50ml/分～1000ml/分即適當。That is, with regard to the zinc gas, in the mechanism (1) for supplying the zinc gas, the liquid metal or the solid zinc metal is directly heated to boil and evaporate, thereby obtaining a zinc gas having a boiling temperature substantially composed only of zinc gas. . Further, it is heated to a necessary reaction temperature of 1050 ° C to 1300 ° C. At this time, although there is no ambient gas, in order to make the flow of the gas in the system smooth and prevent clogging in the middle, argon gas may be added, and the pressure may be slightly pressurized. The amount of gas or pressure may be as small as a little, for example, a pressure of up to about 10,000 Pa (about 1 m of water column) is sufficient. When the reaction tube has a thickness of about 25 mm, the amount of argon is preferably about 50 ml/min to 1000 ml/min.
在此種加熱鋅氣體之中，利用下個步驟之供給四氯化矽的機構(2)，直接以液態供給沸點約為56.4℃之四氯化矽。供給可利用重力從上部滴下至鋅氣體氣流中，亦可噴霧至鋅氣體氣流中。再者，四氯化矽與鋅氣體氣流之會合部分的溫度較理想為1050℃～1300℃，更理想為1100℃～1200℃。然而，此部分之實際溫度或許較此低一些。此部分之溫度若低於1050℃，則因反應而生成之矽或矽前驅物變得容易析出，矽或矽前驅物會在鋅與四氯化矽之會合部分析出，可能對連續運作造成阻礙。因此，雖然會合部分之溫度較高較理想，但若為1300℃以上，則由於在一般使用之反應裝置材質石英玻璃或碳化矽燒結體之耐久性方面產生問題，消耗能源變得太大，因此雖為可行但仍有實用上之問題。Among such heated zinc gas, ruthenium tetrachloride having a boiling point of about 56.4 ° C is directly supplied in a liquid state by means of a mechanism (2) for supplying ruthenium tetrachloride in the next step. The supply can be dropped from the upper portion into the zinc gas stream by gravity or sprayed into the zinc gas stream. Further, the temperature at which the arsenic tetrachloride and the zinc gas stream meet is preferably from 1050 ° C to 1300 ° C, more preferably from 1100 ° C to 1200 ° C. However, the actual temperature in this section may be lower. If the temperature of this part is lower than 1050 ° C, the ruthenium or osmium precursor formed by the reaction will be easily precipitated, and the ruthenium or osmium precursor will be analyzed at the junction of zinc and ruthenium tetrachloride, which may cause continuous operation. Obstruction. Therefore, although the temperature of the meeting portion is relatively high, if the temperature is 1300 ° C or higher, the energy consumption of the quartz glass or the tantalum carbide sintered body of the reactor material used in general is problematic, and the energy consumption is too large. Although feasible, there are still practical problems.
此處，鋅與四氯化矽以氣-液或氣-氣之方式會合，至少部分地進行反應，含有部分生成之矽或矽前驅物的氣體，在內部受到具有攪拌手段之生成反應氣體的機構(3)之引導而繼續反應並完結。此處使用之攪拌手段，除了能使鋅與四氯化矽之會合完全，充分地進行攪拌之外，只要能將反應管內之壓力損失抑制到最小限度，並且不會因生成之矽固體導致堵塞，則任何機構皆可。例如，可使用無規設置之擋板、或商品名稱為SQUARE MIXER之機構，該SQUARE MIXER會將流動於管內之氣體分為兩份，其中一份以縱波方式曲折地流動，另一份以横波方式流動，以1個週期會合，藉由反覆進行該會合來加以攪拌混合。藉由該等，可在幾乎無壓力損失之情形下獲得完全的混合。Here, zinc and ruthenium tetrachloride meet in a gas-liquid or gas-gas manner, at least partially react, and a gas containing a partially formed ruthenium or osmium precursor is internally reacted with a reaction gas having a stirring means. The guidance of the institution (3) continues to react and end. The stirring means used here can completely reduce the pressure loss in the reaction tube, and can not minimize the pressure loss caused by the formation of zinc and ruthenium tetrachloride. If it is blocked, it can be used by any institution. For example, a baffle with a random setting or a mechanism called SQUARE MIXER can be used. The SQUARE MIXER divides the gas flowing in the tube into two parts, one of which flows in a zigzag manner and the other in a The transverse wave method flows and joins in one cycle, and the mixture is stirred and mixed to repeat the mixing. By this, complete mixing can be obtained with almost no pressure loss.
如此生成之含有矽前驅物、矽的反應氣體，在機構(3)中流動的同時，進一步進行反應。接著，來自該等之反應物質，被送至溫度被保持在300～800℃之「使矽粒子成長並且與氣體成分之一部分一起沈澱的機構(4)」，作為反應氣體之未反應鋅氣體與氯化鋅之至少一部分與生成之矽成為一體而析出。藉此，結晶成長前之非常微細的矽粒子與氯化鋅或鋅氣體一起沈澱。The reaction gas containing the ruthenium precursor and ruthenium thus generated is further flowed while flowing through the mechanism (3). Then, the reaction materials from the above are sent to a mechanism (4) in which the cerium particles are grown and precipitated together with a part of the gas component at a temperature of 300 to 800 ° C, and unreacted zinc gas as a reaction gas At least a part of the zinc chloride is integrated with the formed crucible and precipitated. Thereby, very fine cerium particles before crystal growth are precipitated together with zinc chloride or zinc gas.
如此生成之沈澱，或許由於成為與氯化鋅或鋅之共沈澱，因此為含有生成之非常微細之粒子的狀態。該因溫度而造成之矽的沈澱，會在極短時間內進，只要於被保持在300～800℃之部分保持0.5秒至2秒左右即可，只要通過保持在該溫度之垂直管，即可大致完全使矽沈澱。通過此種溫度部分而沈澱之矽，到達作為「使被保持在950℃以上之蒸發物揮發以獲得固體矽之機構(5)」之保持槽，鋅或氯化鋅之類的揮發物被分離去除，僅留下高純度之矽微粒子。此處，鋅或氯化鋅之類或未反應之四氯化矽，被從排氣機構排出，一般會對排氣成分進行處理並回收。The precipitate thus formed may be in a state of containing very fine particles formed because it is coprecipitated with zinc chloride or zinc. The precipitation due to the temperature will be carried out in a very short time, as long as it is kept at 300 to 800 ° C for 0.5 seconds to 2 seconds, as long as the vertical tube is maintained at this temperature, that is, The hydrazine can be precipitated substantially completely. The enthalpy precipitated by such a temperature portion reaches a holding tank which is a mechanism ("the mechanism for volatilizing the evaporate held above 950 ° C to obtain a solid enthalpy (5)", and volatiles such as zinc or zinc chloride are separated. Remove, leaving only high purity ruthenium particles. Here, zinc or zinc chloride or the unreacted antimony tetrachloride is discharged from the exhaust mechanism, and the exhaust gas component is generally treated and recovered.
再者，視需要可將「使矽粒子成長並且與氣體成分之一部分一起沈澱的機構(4)」設為傾斜管而非垂直管，藉此，可謀求進一步的安定化。若相對於水平傾斜30～90度，預先將傾斜部分之溫度保持在300～800℃、較理想為500～750℃，則在該部分矽與氯化鋅以及鋅成為一體，大致瞬間沈澱，並且生成物緩慢地花一些時間在傾斜部分滑動，落下至矽保持槽，於該處使揮發物揮發，成為純矽而被保持。傾斜部之斜度相對於水平為30度至90度左右即可，可藉由角度改變保持時間。In addition, the "mechanism (4) which grows the cerium particles and precipitates together with one part of the gas component" can be used as the inclined pipe instead of the vertical pipe, and further stabilization can be achieved. When the temperature of the inclined portion is maintained at 300 to 800 ° C, preferably 500 to 750 ° C, in advance, the portion of the crucible is integrated with zinc chloride and zinc, and precipitates substantially instantaneously, and The resultant slowly took some time to slide on the inclined portion and dropped to the crucible holding tank where the volatile matter was volatilized and became pure crucible and held. The inclination of the inclined portion may be about 30 to 90 degrees with respect to the horizontal, and the holding time can be changed by the angle.
此處，傾斜管之斜度若小於30度，則生成矽之落下容易變得不完全，有時會發生停滯而成為堵塞的原因。然而，隨著接近垂直會使保持時間變短，根據條件會變得容易產生不均，因此，必須配合用途與生產量來決定傾斜角度。Here, if the inclination of the inclined pipe is less than 30 degrees, the falling of the generated sag is likely to be incomplete, and the stagnation may occur and the clogging may occur. However, as the approaching time is short, the holding time is shortened, and unevenness is likely to occur depending on the conditions. Therefore, it is necessary to determine the tilt angle in accordance with the use and the amount of production.
以液狀將四氯化矽供給至高溫高濃度之鋅氣體中，一面於高溫狀態充分攪拌一面使其反應，藉此由四氯化矽生成矽，使其與作為反應氣體之鋅以及作為反應生成物之氯化鋅的一部分一起於300℃～800℃進行凝聚，藉此，能夠安定地且以高產率獲得微細矽粒子。此外，如此凝聚之生成物，於保持槽內以鋅之沸點以上的溫度使以鋅與氯化鋅為主之揮發物蒸發分離，藉此能夠以高產率獲得微粒之高純度矽。The ruthenium tetrachloride is supplied to the zinc gas having a high temperature and a high concentration in a liquid state, and is stirred while being stirred at a high temperature to form ruthenium tetrachloride, which is reacted with zinc as a reaction gas and reacted. A part of the zinc chloride of the product is agglomerated together at 300 to 800 ° C, whereby the fine cerium particles can be obtained stably and in high yield. Further, the thus-aggregated product is obtained by evaporating and separating the volatile matter mainly composed of zinc and zinc chloride at a temperature equal to or higher than the boiling point of zinc in the holding tank, whereby high-purity cerium of fine particles can be obtained in high yield.
藉由圖式對本發明進行說明。亦即，圖1係將含矽之反應氣體的溫度降至300℃～800℃以使生成之矽粒子成長並且與氣體成分之一部分一起沈澱的機構為垂直管之情形，圖2係將該沈澱機構設為傾斜之管體的情形。此外，圖3係為了控制該沈澱機構之溫度而具有冷卻扇的情形。此外，展示了排氣處理機構之示意圖的構想。圖4中，使「保持沈澱物並加溫至950℃以上使蒸發物揮發以獲得固體矽之機構」的底部傾斜，一面使生成之矽移動一面進行處理，而可進行連續運作。The invention is illustrated by the drawings. That is, Fig. 1 is a case where the temperature of the reaction gas containing ruthenium is lowered to 300 ° C to 800 ° C to cause the generated ruthenium particles to grow and precipitate together with a part of the gas component as a vertical tube, and Fig. 2 is the precipitate. The case where the mechanism is set to the inclined pipe body. Further, Fig. 3 is a case where a cooling fan is provided in order to control the temperature of the sedimentation mechanism. In addition, the concept of a schematic diagram of the exhaust gas treatment mechanism is shown. In Fig. 4, the bottom of the "mechanism that maintains the precipitate and warms to 950 ° C or higher to volatilize the evaporate to obtain a solid crucible" is tilted, and the generated crucible is moved while being processed to perform continuous operation.
圖1中，從鋅供給部1供給鋅線或熔體鋅。此處，只要能定量供給鋅，則從鋅熔融槽利用泵等輸送定量之鋅即可，至於供給鋅線之方式，小型裝置由於操作容易、容易定量輸送，因此是特別理想之方法。另外，可配合此處之輸送進行加壓，並可視需要混合供給用以調整環境的環境氣體。In Fig. 1, a zinc wire or molten zinc is supplied from the zinc supply unit 1. Here, as long as the zinc can be supplied quantitatively, a predetermined amount of zinc can be supplied from a zinc melting tank by a pump or the like. As for the method of supplying the zinc wire, the small device is easy to handle and is easy to be quantitatively transported, which is a particularly preferable method. In addition, it can be pressurized in conjunction with the transportation here, and the ambient gas for adjusting the environment can be mixed and supplied as needed.
以上述方式輸送之鋅線或鋅熔體會從鋅供給口1供給，利用供給鋅氣體之機構的鋅蒸發槽2將其加熱、蒸發，產生鋅蒸氣。此處直接藉由加熱器以鋅之沸點以上使鋅成為蒸氣。藉此，雖含有少許氬氣，但實質上成為只有鋅氣體之環境。利用同機構之氣體加熱部3，將該鋅氣體加熱至所要的溫度。通常1050℃至1300℃即可，1100～1200℃尤其適當。以此方式受到加熱並送至經控制之供給四氯化矽的機構4。The zinc wire or the zinc melt conveyed in the above manner is supplied from the zinc supply port 1, and is heated and evaporated by the zinc evaporation tank 2 of the mechanism for supplying the zinc gas to generate zinc vapor. Here, the zinc is made into a vapor directly by the heater above the boiling point of zinc. Therefore, although it contains a little argon gas, it is an environment which is only a zinc gas. The zinc gas is heated to a desired temperature by the gas heating unit 3 of the same mechanism. Usually, it is 1050 ° C to 1300 ° C, and 1100 ~ 1200 ° C is particularly suitable. In this way it is heated and sent to a controlled mechanism 4 for supplying ruthenium tetrachloride.
由於四氯化矽之沸點為57.6C，一般的平衡狀態下會成為氣體，但此處是從四氯化矽供給口41滴下，以液狀供給。當然可直接以液滴狀態供給，亦可以噴霧或噴淋狀供給。供給之方法並無特別指定，較理想為藉由管式泵或隔膜泵來定量供給，大部分的情形係對四氯化矽保持部施加壓力，通過流量計而流動，藉由閥來調整流量。該等均從該部分以液狀供給四氯化矽。Since the boiling point of ruthenium tetrachloride is 57.6 C, it is a gas in a normal equilibrium state, but it is dropped from the ruthenium tetrachloride supply port 41 and supplied as a liquid. Of course, it can be supplied directly in the form of droplets, or it can be supplied by spraying or spraying. The method of supply is not specifically specified, and it is preferable to quantitatively supply by a tube pump or a diaphragm pump. In most cases, pressure is applied to the crucible crucible holding portion, flow is performed through the flow meter, and flow is adjusted by the valve. . These are all supplied with ruthenium tetrachloride in liquid form from this portion.
被供給之四氯化矽從該部分起立刻與鋅氣體開始反應，開始生成矽前驅物以及矽，並且於生成含矽粒子之反應氣體的機構5，藉由位於其中之將氣體亂流化之要素51，一面充分攪拌一面繼續反應並移動，於使矽粒子成長並且與氣體成分之一部分一起沈澱的機構6降低溫度，生成矽與一部分未反應鋅以及生成之氯化鋅成為一體而沈澱，移動至獲得固體矽之機構7。再者，對於該沈澱機構6之溫度保持，不僅是加熱器加熱，亦會藉由設置導入外部空氣等進行冷卻之冷卻要素(例如圖3之300)來保持溫度。The supplied ruthenium tetrachloride starts to react with the zinc gas from this portion, starts to form a ruthenium precursor and ruthenium, and a mechanism 5 for generating a reaction gas containing ruthenium particles, by which the gas is turbulently flowed The element 51 continues to react and move while stirring sufficiently, and the mechanism 6 which grows the cerium particles and precipitates together with a part of the gas component lowers the temperature, and forms hydrazine and a part of unreacted zinc and the formed zinc chloride as a whole, and precipitates and moves. To the institution 7 that obtained solid enthalpy. Further, the temperature of the sedimentation mechanism 6 is maintained not only by the heater but also by the cooling element (for example, 300 in Fig. 3) which is cooled by introducing external air or the like.
藉此，使在一般的旋風方式中難以沈澱之10微米以下尤其是達到次微米之微粒子的矽沈澱於獲得固體矽之機構7。此處，將底面加熱至1000℃以上，壁部較其低一些，然而，由於保持為高於鋅之沸點，因此會使為揮發物之鋅或氯化鋅揮發蒸發，又幾乎沒有矽之粒成長，生成矽被以高純度保持。再者，雖然有時該加熱會一直進行，但亦可視需要先將溫度保持得較低，間歇性地將溫度加熱至上述1000℃以上。再者，若使該機構之底面以外的溫度成為1000℃以上，則一部分之微粒的矽會與氯化鋅等之蒸發一起從排氣機構8逸失，因此，從這方面來看，周圍溫度較理想為1000℃以下。Thereby, the crucible of 10 micrometers or less, particularly submicron particles, which is difficult to precipitate in a general cyclone mode, is precipitated in the mechanism 7 for obtaining a solid crucible. Here, the bottom surface is heated to above 1000 ° C, and the wall portion is lower than it. However, since it is kept higher than the boiling point of zinc, the zinc or zinc chloride which is a volatile substance is volatilized and evaporated, and there is almost no granule. Growing, the generated mites are maintained in high purity. Further, although the heating may be continued at all times, the temperature may be kept low as needed, and the temperature may be intermittently heated to 1000 ° C or higher. In addition, when the temperature other than the bottom surface of the mechanism is 1000 ° C or more, the enthalpy of a part of the fine particles will escape from the exhaust mechanism 8 together with the evaporation of zinc chloride or the like. Therefore, from this point of view, the ambient temperature is higher. Ideally below 1000 °C.
排氣機構8並無特別指定，此處，雖保持為高於鋅之沸點以免於氣體管內之途中引起沈澱，但其後之排氣處理部9將溫度充分降低而使其以固體析出，或者，使其與氯化鋅水溶液接觸，於存在未反應四氯化矽之情形下，使其以SiCl4 +2H2 O→SiO2 +4HCl的方式以氧化矽沈澱，又，亦可將氯化鋅與鋅溶解於氯化鋅水溶液，再連續地取出至外部進行處理。The exhaust mechanism 8 is not particularly specified. Here, although it is kept higher than the boiling point of zinc to prevent precipitation in the middle of the gas pipe, the exhaust gas treatment unit 9 thereafter sufficiently lowers the temperature to precipitate solids. Alternatively, it is brought into contact with an aqueous solution of zinc chloride, and in the presence of unreacted hafnium tetrachloride, it is precipitated as cerium oxide in the form of SiCl 4 + 2H 2 O → SiO 2 + 4 HCl, and chlorine may also be used. Zinc and zinc are dissolved in an aqueous solution of zinc chloride, and are continuously taken out to the outside for treatment.
圖2與圖1原則上相同，但圖1中，使矽粒子成長並且與氣體成分之一部分一起沈澱的機構6被設為垂直管，圖2中則換成傾斜管61，此處，為了使由矽與氯化鋅及/或鋅構成之沈澱物確實地在傾斜部析出，可延長低溫之期間，以更確實地進行冷卻、沈澱，並且使矽粒適當地成長，以更加提高產率。又，藉由保持於該中間之溫度某個程度的時間，在此處進行沈澱之同時可去除以氯化鋅為主之揮發物的至少一部分，因此，位於使蒸發物揮發以獲得固體矽之機構7之鋅、氯化鋅的揮發較少，伴隨其之矽微粒子向排氣部的逸失更為減少，在效率提升方面甚為有效。此外，當然能確實地獲得更為微粒之矽。2 is basically the same as FIG. 1, but in FIG. 1, the mechanism 6 for growing the ruthenium particles and depositing together with a part of the gas component is set as a vertical pipe, and in FIG. 2, it is replaced with a slant pipe 61, here, Since the precipitate composed of cerium chloride and/or zinc is surely precipitated in the inclined portion, the period of low temperature can be prolonged, the cooling and precipitation can be more surely performed, and the cerium particles can be appropriately grown to further improve the yield. Further, by maintaining the temperature in the middle for a certain period of time, at least a part of the volatile matter mainly composed of zinc chloride can be removed while precipitating there, and therefore, the evaporating substance is volatilized to obtain a solid ruthenium. The zinc and zinc chloride of the mechanism 7 are less volatile, and the loss of the fine particles to the exhaust portion is further reduced, which is effective in improving the efficiency. In addition, of course, it is possible to surely obtain more particles.
圖3係使處理水通過排氣處理部之情形的示意圖。亦即，藉由使氯化鋅水溶液於排氣處理部之底部循環，使從上部進入之排氣成分氯化鋅溶解於該水溶液。又，存在未反應之鋅以及四氯化矽之情形時，四氯化矽會立即與水反應，變成鹽酸與氧化矽，又，由於該水溶液會因生成之鹽酸而成為酸，因此，鋅亦會溶解而成為氯化鋅水溶液。再者，只要預先對該循環之水添加少許鹽酸，即使沒有未反應四氯化矽，亦可將鋅完全溶解，可使排氣完全成為氯化鋅溶液。亦可將其純化以獲得氯化鋅，亦可直接送至隔膜法電解槽，以金屬鋅的形態回收鋅。Fig. 3 is a schematic view showing a state in which treated water is passed through an exhaust treatment unit. That is, by circulating the zinc chloride aqueous solution at the bottom of the exhaust treatment portion, the exhaust component zinc chloride entering from the upper portion is dissolved in the aqueous solution. Further, in the case of unreacted zinc and antimony tetrachloride, antimony tetrachloride immediately reacts with water to become hydrochloric acid and cerium oxide, and since the aqueous solution becomes acid due to the formed hydrochloric acid, zinc is also It will dissolve and become an aqueous solution of zinc chloride. Further, by adding a little hydrochloric acid to the circulating water in advance, even if there is no unreacted antimony tetrachloride, the zinc can be completely dissolved, and the exhaust gas can be completely made into a zinc chloride solution. It can also be purified to obtain zinc chloride, or it can be directly sent to a diaphragm electrolysis cell to recover zinc in the form of metal zinc.
圖4中，到使矽粒子成長並且與氣體成分之一部分一起沈澱的機構6為止與圖1相同，而位於其下方之用以獲得固體矽之機構7的底部則設為傾斜，會因為從6落入之沈澱物而受壓並移動，同時使揮發物揮發，亦可僅使矽移至設於中途且位於更下部的容器或溶解機構400，從該處連續地取出、或者熔解而以熔體之形態取出。In Fig. 4, the mechanism 6 which grows the ruthenium particles and precipitates together with a part of the gas component is the same as Fig. 1, and the bottom of the mechanism 7 below which is used to obtain the solid 矽 is set to be inclined, because it is from 6 The sediment falling into the deposit is pressed and moved, and at the same time, the volatile matter is volatilized, and only the crucible can be moved to the container or dissolution mechanism 400 which is located in the middle and located at a lower portion, from which it is continuously taken out or melted to be melted. The shape of the body is taken out.
以下表示藉由實驗性地建構而成之試驗裝置來進行的實施例。The following is an example of an experimental apparatus constructed by experimental construction.
再者，實施例之裝置大部分是以石英玻璃作成，但隨著大型化，當然亦可使用碳化矽等陶瓷材料。Further, most of the devices of the examples are made of quartz glass, but of course, ceramic materials such as tantalum carbide may be used as the size increases.
【實施例】[Examples]
「實施例1」"Example 1"
試作圖1所示之裝置。亦即，鋅蒸發槽(氣化部)係具有「於直徑150mm高度35mm且上下被封塞之圓筒形的一端，相對於圓筒朝高度方向45度設置之內徑4mm的鋅供給口」與「於該圓筒之相反側與圓筒水平地設置之外徑30mm的氣體流路」的石英玻璃管製，將「在與氣體流路凸緣連接之單側50mm的部分具有內徑10mm之垂直管，且外徑30mm長度600mm的石英玻璃管」作為鋅氣體加熱用(調整部)，於其另一端設立垂直管而設置成四氯化矽供給機構。進一步，於水平方向設置外徑30mm長度1000mm之石英玻璃製反應管，成為生成反應氣體之機構。於該反應管中，將4台碳化矽製長度125mm直徑23mm之SQUARE MIXER置入四氯化矽供給機構側。進一步，於該石英玻璃製反應管之四氯化矽供給機構的相反側，通過以直角落下之外徑35mm高度600mm的石英玻璃製垂直管，於其下側安裝外徑160mm x高度200mm之同為石英玻璃製的容器(矽保持容器)。於該石英玻璃容器之蓋部分，設置來自上述垂直管之接受口(接受氣體之要素)與排氣管安裝口(排出排氣之要素)，對其安裝外徑25mm之石英玻璃製排氣管，將其另一端連接於不鏽鋼(SUS304)製之桶(drum)。於該桶內充滿氬氣，作為排氣處理用。其中，不施加壓力，不產生背壓。Try the device shown in Figure 1. In other words, the zinc evaporation tank (vaporization unit) has a cylindrical supply end having a diameter of 35 mm and a height of 35 mm and is closed up and down, and a zinc supply port having an inner diameter of 4 mm which is provided at a height of 45 degrees with respect to the cylinder. The quartz glass control of the "gas flow path of 30 mm outer diameter provided horizontally on the opposite side of the cylinder from the cylinder" has an inner diameter of 10 mm on the one side of the 50 mm side connected to the gas flow path flange. The vertical tube and the quartz glass tube having an outer diameter of 30 mm and a length of 600 mm are provided as a zinc gas heating (adjustment unit), and a vertical tube is provided at the other end thereof to provide a crucible tetrachloride supply mechanism. Further, a reaction tube made of quartz glass having an outer diameter of 30 mm and a length of 1000 mm was provided in the horizontal direction to form a reaction gas. In the reaction tube, four SQUARE MIXERs having a length of 125 mm and a diameter of 23 mm made of tantalum carbide were placed on the side of the crucible tetrachloride supply mechanism. Further, on the opposite side of the ruthenium tetrachloride supply mechanism of the quartz glass reaction tube, an outer diameter of 160 mm x a height of 200 mm is attached to the lower side by a vertical tube made of quartz glass having an outer diameter of 35 mm and a height of 600 mm under a straight corner. It is a container made of quartz glass (矽 keeps the container). In the cover portion of the quartz glass container, a receiving port (a component that receives a gas) and an exhaust pipe mounting port (an element that discharges the exhaust gas) from the vertical pipe are provided, and a quartz glass exhaust pipe having an outer diameter of 25 mm is attached thereto. Connect the other end to a stainless steel (SUS304) drum. The barrel is filled with argon gas for use as an exhaust gas treatment. Among them, no pressure is applied and no back pressure is generated.
鋅蒸發槽係以密合於玻璃圓筒之上下的方式設置由鐵鉻線發熱體構成的發熱板。又，石英玻璃容器之下面，亦同樣地以發熱面密合之方式來設置。又，其他部分係以包圍該等圓筒之方式設置加熱器來進行溫度之控制。The zinc evaporation tank is provided with a heat generating plate composed of an iron-chromium wire heating element so as to be in close contact with the glass cylinder. Further, the lower surface of the quartz glass container is similarly provided in such a manner that the heat generating surface is in close contact with each other. Further, the other portion is provided with a heater so as to surround the cylinders to control the temperature.
關於供給之鋅，係以10mm/秒連續地輸送直徑2mm之純鋅(鋅成分99.995質量%)線。又，四氯化矽係從上部藉由管式泵以0.25g/秒連續地供給。又，運作開始係先開始供給鋅，30秒後再開始四氯化矽之供給。再者，從鋅線部分之支管以200ml/分的速度供給氬氣。Regarding the supplied zinc, a line of pure zinc (zinc component 99.995 mass%) having a diameter of 2 mm was continuously conveyed at 10 mm/sec. Further, ruthenium tetrachloride was continuously supplied from the upper portion by a tube pump at 0.25 g/sec. At the beginning of the operation, the supply of zinc was started first, and the supply of antimony tetrachloride was started 30 seconds later. Further, argon gas was supplied from the branch of the zinc wire portion at a rate of 200 ml/min.
關於各部之溫度，鋅蒸發槽：1100℃，鋅氣體加熱部1100℃，四氯化矽供給機構(鋅氣體通過部)1200℃，關於反應管之溫度，SQUARE MIXER***部設為1100℃，反應管之剩餘部分(後半)設為1050℃。垂直管為700～750℃，關於矽保持容器，底部為1050℃，側壁部為950℃。四氯化關於矽供給中，在計算上，鋅為17%程度過剩。進行20分鐘之連續運作的結果，獲得褐色且微粉末之矽45.2g。計測該矽之粒度分布的結果，粒度5微米與15微米之處具有波峰，可知由平均粒度10微米以下之矽微粒子構成。又，矽之收獲量相對於理論值為91%。由於在排氣部分有鹽酸氣味，因此，即便於此種條件下未反應部分亦殘留少許，並可見部分地脫逸至排氣中，又可見一部分儲存於管內。The temperature of each part, zinc evaporation tank: 1100 ° C, zinc gas heating unit 1100 ° C, ruthenium tetrachloride supply mechanism (zinc gas passage) 1200 ° C, the temperature of the reaction tube, SQUARE MIXER insertion part set to 1100 ° C, reaction The remainder of the tube (second half) was set to 1050 °C. The vertical tube is 700 to 750 ° C, and the crucible holding container has a bottom portion of 1050 ° C and a side wall portion of 950 ° C. In the case of tetrachlorination, in the supply of niobium, in terms of calculation, zinc is excessively 17%. As a result of continuous operation for 20 minutes, 45.2 g of a brownish and fine powder was obtained. As a result of measuring the particle size distribution of the crucible, peaks were formed at a particle size of 5 μm and 15 μm, and it was found that the fine particles having an average particle size of 10 μm or less were composed. In addition, the yield of cockroaches is 91% relative to the theoretical value. Since there is a hydrochloric acid odor in the exhaust portion, even under such conditions, the unreacted portion remains a little, and it is seen that it partially escapes into the exhaust gas, and a part of it is stored in the tube.
「實施例2」"Example 2"
組裝圖2所示之矽製造裝置。從鋅供給到鋅四氯化矽供給部與圖1相同，將反應管之長度設為600mm，於該部分裝入與實施例1相同之SQUARE MIXER。於反應管之後方，相對於水平將傾斜角度設為45度，安裝以朝石英玻璃製容器落下之方式配置的斜管，連接於石英玻璃製容器。石英玻璃製容器之蓋部分，設置為較水平部分之反應氣體生成機構部分低600mm，因此斜管之長度成為850mm。再者，傾斜管之外徑為35mm，其餘與實施例1相同。此外，材質係使用碳化矽(SiC)。The crucible manufacturing apparatus shown in Fig. 2 was assembled. The zinc supply to the zinc ruthenium tetrachloride was supplied in the same manner as in Fig. 1, and the length of the reaction tube was set to 600 mm. The same SQUARE MIXER as in Example 1 was placed in this portion. After the reaction tube, the inclined angle was set to 45 degrees with respect to the horizontal direction, and a tilting tube disposed so as to fall toward the quartz glass container was attached and connected to a quartz glass container. The cover portion of the quartz glass container was set to be 600 mm lower than the portion of the reaction gas generating mechanism of the horizontal portion, so the length of the inclined tube was 850 mm. Further, the outer diameter of the inclined tube was 35 mm, and the rest was the same as in the first embodiment. In addition, the material is tantalum carbide (SiC).
溫度如下：鋅蒸發槽：1200℃(蒸發槽外側部)，鋅氣體加熱部亦為1200℃，進而，四氯化矽供給機構：1200℃，反應氣體生成機構：1050℃，進而，傾斜管為500℃(於反應後期因熱移動而成為最高650℃左右並安定)。此外，石英玻璃容器與實施例1同樣地，底板部：1050℃，又，壁部：950℃。The temperature is as follows: zinc evaporation tank: 1200 ° C (outside of the evaporation tank), zinc gas heating section is also 1200 ° C, and further, the ruthenium tetrachloride supply mechanism: 1200 ° C, reaction gas generation mechanism: 1050 ° C, and further, the inclined pipe is 500 ° C (below the heat transfer in the late stage of the reaction, it is about 650 ° C and stable). Further, in the same manner as in the first embodiment, the quartz glass container had a bottom plate portion of 1050 ° C and a wall portion of 950 ° C.
鋅之供給與實施例1相同，以15mm/秒供給鋅線。又，四氯化矽為0.4g/秒。鋅供給與四氯化矽供給同時開始。繼續鋅與四氯化矽之供給30分鐘再停止。停止四氯化矽與鋅之供給後，以這樣的溫度保持30分鐘後，使溫度降低。藉此，從石英玻璃容器獲得矽106g。相對於理論量，其為89.2%。再者，相對於四氯化矽，此處鋅供給量約為9%過剩。該差額之一部分肇因於發生未反應之情形，另一方面，生成矽被保持在傾斜部之玻璃表面的一部分。The supply of zinc was the same as in Example 1, and the zinc wire was supplied at 15 mm/sec. Further, ruthenium tetrachloride was 0.4 g/sec. The zinc supply starts simultaneously with the supply of antimony tetrachloride. Continue the supply of zinc and antimony tetrachloride for another 30 minutes. After the supply of ruthenium tetrachloride and zinc was stopped, the temperature was lowered after maintaining at such a temperature for 30 minutes. Thereby, 矽106g was obtained from the quartz glass container. It is 89.2% with respect to the theoretical amount. Further, the amount of zinc supplied here is about 9% excess with respect to antimony tetrachloride. Part of this difference is due to the occurrence of unreacted conditions, and on the other hand, the generated crucible is held at a portion of the glass surface of the inclined portion.
「實施例3」"Example 3"
作為鋅蒸發槽與鋅供給設備、以及反應塔之氣體的亂流化要素，除了將SQUARE MIXER變更為擋板以外，準備與實施例1相同的裝置。亦即，鋅蒸發槽為相同之大小，對鋅供給部分安裝外徑20mm之斜管，於其前端附有閘(trap)之鋅之鋅供給部的外徑設為15mm，安裝附有液閘之鋅液供給器12。此處之鋅供給，係通過液閘，藉由來自鋅供給器之溢流而供給鋅，於該部分，以20mm/秒之速度，供給與實施例1所用者相同之直徑2mm的鋅線。The same apparatus as in the first embodiment was prepared except that the SQUARE MIXER was changed to a baffle as a turbulent fluid element of the zinc evaporation tank, the zinc supply equipment, and the gas of the reaction tower. That is, the zinc evaporation tank is of the same size, and the inclined pipe having an outer diameter of 20 mm is attached to the zinc supply portion, and the outer diameter of the zinc supply portion of the zinc with a trap at the front end thereof is set to 15 mm, and the liquid gate is attached. Zinc liquid supply unit 12. Here, the supply of zinc was supplied to the zinc by overflow from the zinc supply through the liquid gate, and a zinc wire having a diameter of 2 mm which was the same as that used in the first embodiment was supplied at a rate of 20 mm/sec.
如上所述，於反應管中，以遍及機構內之長度1000mm整體的方式，放入以無規間隔、無規角度設置半圓形狀石英玻璃板而成的擋板，以作為氣體之亂流化要素。再者，該裝置係以石英玻璃為主體。As described above, in the reaction tube, a baffle plate having a semicircular quartz glass plate at a random interval and a random angle is placed over the entire length of 1000 mm in the mechanism to serve as a gas fluidization element. . Furthermore, the device is mainly made of quartz glass.
運作條件係將鋅蒸發槽之溫度設為1300℃。此處，實質上成為沸騰溫度之鋅氣體，為了產生充分量之鋅氣體，又為了瞬間成為鋅氣體，而設為該溫度。此外，鋅氣體加熱部設為1200℃，與四氯化矽供給機構溫度相同。置入有擋板之反應管的溫度設為1150℃。另一方面，垂直管部之溫度設為600～650℃，為了保持該溫度，除了加熱器之外，設置用以取入外部空氣之冷卻機構。此外，關於矽保持部溫度，將底板溫度設為1000℃，將壁部溫度設為800℃。The operating conditions were such that the temperature of the zinc evaporation tank was set to 1300 °C. Here, the zinc gas which is substantially at the boiling temperature is set to be a zinc gas in order to generate a sufficient amount of zinc gas. Further, the zinc gas heating unit was set to 1200 ° C, which was the same temperature as the ruthenium tetrachloride supply mechanism. The temperature of the reaction tube in which the baffle was placed was set to 1150 °C. On the other hand, the temperature of the vertical pipe portion is set to 600 to 650 ° C, and in order to maintain the temperature, a cooling mechanism for taking in outside air is provided in addition to the heater. Further, regarding the temperature of the crucible holding portion, the bottom plate temperature was set to 1000 ° C, and the wall portion temperature was set to 800 ° C.
進一步，使用於底部具有來自外部之氯化鋅水溶液之循環機構的SUS304製桶，作為排氣處理/回收機構。於該桶內側塗佈耐酸性塗料以提升耐蝕性。再者，伴隨矽生成之排氣，藉由外徑30mm之石英玻璃管引導至該桶之頂部。再者，直接將加熱器捲於該排氣用石英玻璃管，藉此保持在1100℃，而不引起揮發物之生成。此外，供給至桶之氯化鋅水溶液透過水冷冷凝器與200 l之溶液槽連接，藉由磁力泵進行循環。又，使15%氯化鋅+5%鹽酸水溶液(質量%)進行循環作為循環氯化鋅水溶液。再者，該循環水之水位設為於桶內底部達50mm。Further, an SUS304 drum having a circulation mechanism from an external zinc chloride aqueous solution at the bottom is used as an exhaust gas treatment/recovery mechanism. An acid-resistant coating is applied to the inside of the barrel to improve corrosion resistance. Furthermore, the exhaust gas generated with the helium was guided to the top of the barrel by a quartz glass tube having an outer diameter of 30 mm. Further, the heater was directly wound on the quartz glass tube for exhaust gas, thereby maintaining at 1100 ° C without causing generation of volatiles. In addition, the zinc chloride aqueous solution supplied to the barrel was connected to a 200 l solution tank through a water-cooled condenser, and was circulated by a magnetic pump. Further, 15% zinc chloride + 5% hydrochloric acid aqueous solution (% by mass) was circulated as a circulating zinc chloride aqueous solution. Furthermore, the water level of the circulating water is set to 50 mm at the bottom of the barrel.
針對該裝置，進行以下運作。亦即，如上述般，以20mm/秒供給鋅線，確認到鋅投入至鋅蒸發槽起30秒後，開始四氯化矽之滴下。四氯化矽之供給量為0.5g/秒。藉由60分鐘之運作，獲得252g之褐色矽微粉末。再者，供給鋅就理論量而言，係16.7%之過剩。又，排氣處理桶中之氯化鋅水溶液中，部分地含有氧化矽的沈澱物。由此可知，即使過剩地添加鋅，亦會出現某個程度的未反應四氯化矽。再者，由於氧化矽沈澱之粒子較大，因此以100微米左右孔徑之濾布即可輕易分離。For the device, the following operations were performed. That is, as described above, the zinc wire was supplied at 20 mm/sec, and it was confirmed that 30 minutes after the zinc was introduced into the zinc evaporation tank, the dropping of ruthenium tetrachloride was started. The supply of antimony tetrachloride is 0.5 g/sec. 252 g of brown enamel powder was obtained by operation for 60 minutes. In addition, the supply of zinc is 16.7% of the theoretical amount. Further, the zinc chloride aqueous solution in the exhaust treatment tank partially contains a precipitate of cerium oxide. From this, it is understood that a certain degree of unreacted antimony tetrachloride occurs even if zinc is excessively added. Furthermore, since the particles precipitated by cerium oxide are large, the filter cloth having a pore diameter of about 100 μm can be easily separated.
「實施例4」"Example 4"
如實施例2之裝置之矽保持容器的底部圖4所示，將接受氣體之要素部分作為最上部並以角度20度傾斜，於該底部另外安裝直徑60mm之石英玻璃製管。至於傾斜部之長度，該管之長度為600mm，並賦予溫度梯度以使最上部溫度成為1000℃、最下部溫度成為200℃。此外，於最下部安裝有充滿氬氣之石英玻璃製容器。該容器於上部具有蓋，可連續地取出從上部落至此處的矽。以與實施例2相同之條件進行矽製造試驗，結果，從開始15分左右起，沈澱與被認為是矽之褐色噴霧粒子一起少量地開始落下。由於溫度為200℃，故可從上方將該等取出。As shown in Fig. 4 of the apparatus of Example 2, the bottom portion of the container was held as the uppermost portion and inclined at an angle of 20 degrees, and a quartz glass tube having a diameter of 60 mm was additionally attached to the bottom portion. As for the length of the inclined portion, the length of the tube was 600 mm, and a temperature gradient was applied so that the uppermost temperature became 1000 ° C and the lowermost temperature became 200 ° C. Further, a container made of quartz glass filled with argon gas is attached to the lowermost portion. The container has a lid on the upper portion to continuously take out the crucible from the upper tribe to the place. The ruthenium production test was carried out under the same conditions as in Example 2. As a result, from about 15 minutes onwards, the precipitate began to fall in a small amount together with the brown spray particles which were considered to be ruthenium. Since the temperature is 200 ° C, it can be taken out from above.
[產業上之可利用性][Industrial availability]
本發明係一種以目前製矽所需電力的數分之一並且以迄今尚無報告之微粉末狀態來製造微粉末高純度矽的製造裝置，該微粉末高純度矽不但可用於太陽電池，尤其可用於鋰離子電池負極或作為氮化矽原料，此技術可成為解決今後之能源問題、CO2 造成之地球暖化問題等的重要手段。特別是，由於具有能大幅提升現行鋰離子二次電池特性的可能性，因此，可在被認為今後會大為擴展之混成及電動汽車用二次電池原料製造用方面極廣泛地使用。The present invention is a manufacturing apparatus for producing a micropowder high-purity bismuth in a state in which a fraction of the power required for the current bismuth is produced and which has not been reported so far, which is not only useful for solar cells, especially It can be used as a negative electrode for lithium ion batteries or as a raw material for tantalum nitride. This technology can be an important means to solve future energy problems and global warming problems caused by CO 2 . In particular, since it is possible to greatly improve the characteristics of the current lithium ion secondary battery, it can be widely used in the production of secondary battery materials for hybridization and electric vehicles, which are considered to be greatly expanded in the future.
1．．．鋅供給口1. . . Zinc supply port
11．．．氬氣導入口11. . . Argon inlet
12．．．鋅液供給器12. . . Zinc liquid feeder
2．．．鋅蒸發槽2. . . Zinc evaporation tank
3．．．氣體加熱部3. . . Gas heating department
4．．．供給四氯化矽之機構4. . . Mechanism for supplying antimony tetrachloride
41．．．四氯化矽供給口41. . . Helium tetrachloride supply port
42．．．鋅氣體之通過部42. . . Zinc gas passage
5．．．生成含矽反應氣體之機構5. . . Generating a mechanism containing a ruthenium reaction gas
51．．．將氣體亂流化之要素(SQUARE MIXER)51. . . The element of turbulent gas (SQUARE MIXER)
52．．．將氣體亂流化之要素(擋板)52. . . Element for turbulent gas flow (baffle)
6．．．使矽粒子成長並且與氣體成分之一部分一起沈澱的機構(垂直管)6. . . Mechanism for growing cerium particles and depositing together with a part of the gas component (vertical tube)
61．．．使矽粒子成長並且與氣體成分之一部分一起沈澱的機構(傾斜管)61. . . Mechanism for tilting the ruthenium particles and depositing together with a part of the gas component (inclined tube)
7．．．獲得固體矽之機構7. . . Obtaining a solid body
8．．．排氣機構8. . . Exhaust mechanism
9‧‧‧排氣處理部9‧‧‧Exhaust treatment department
91‧‧‧排氣口91‧‧‧Exhaust port
100‧‧‧泵100‧‧‧ pump
200‧‧‧氯化鋅液槽200‧‧‧Zinc chloride tank
300‧‧‧冷卻要素300‧‧‧ Cooling elements
400‧‧‧矽取出機構400‧‧‧矽 removal agency
圖1係本發明之製造裝置的概念圖。Fig. 1 is a conceptual diagram of a manufacturing apparatus of the present invention.
圖2係本發明之製造裝置的概念圖，矽之沈澱部被設為傾斜管。Fig. 2 is a conceptual view of the manufacturing apparatus of the present invention, and the sediment portion of the crucible is set as an inclined tube.
圖3係本發明之製造裝置的概念圖，於排氣處理部設有水之循環機構。Fig. 3 is a conceptual view of a manufacturing apparatus of the present invention, in which a water circulation mechanism is provided in the exhaust treatment unit.
圖4係本發明之製造裝置的概念圖，設有從矽保持容器連續地取出矽之機構。Fig. 4 is a conceptual view of the manufacturing apparatus of the present invention, which is provided with a mechanism for continuously removing the crucible from the crucible holding container.
1．．．鋅供給口1. . . Zinc supply port
11．．．氬氣導入口11. . . Argon inlet
2．．．鋅蒸發槽2. . . Zinc evaporation tank
3．．．氣體加熱部3. . . Gas heating department
4．．．供給四氯化矽之機構4. . . Mechanism for supplying antimony tetrachloride
41．．．四氯化矽供給口41. . . Helium tetrachloride supply port
42．．．鋅氣體之通過部42. . . Zinc gas passage
5．．．生成含矽反應氣體之機構5. . . Generating a mechanism containing a ruthenium reaction gas
51．．．將氣體亂流化之要素(SQUARE MIXER)51. . . The element of turbulent gas (SQUARE MIXER)
6．．．使矽粒子成長並且與氣體成分之一部分一起沈澱的機構(垂直管)6. . . Mechanism for growing cerium particles and depositing together with a part of the gas component (vertical tube)
7．．．獲得固體矽之機構7. . . Obtaining a solid body
8．．．排氣機構8. . . Exhaust mechanism
9．．．排氣處理部9. . . Exhaust treatment unit
91．．．排氣口91. . . exhaust vent
Claims (14)
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| JP2007217262A (en) * | 2006-02-14 | 2007-08-30 | Kinotech Corp | Apparatus for manufacturing silicon |
| JP2009013042A (en) * | 2007-07-03 | 2009-01-22 | Cs Gijutsu Kenkyusho:Kk | Apparatus for manufacturing high purity silicon |
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| JP2007217262A (en) * | 2006-02-14 | 2007-08-30 | Kinotech Corp | Apparatus for manufacturing silicon |
| JP2009013042A (en) * | 2007-07-03 | 2009-01-22 | Cs Gijutsu Kenkyusho:Kk | Apparatus for manufacturing high purity silicon |
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