1245820 九、發明說明： 【發明所屬之技術領域】 本發明係有關一種旋轉震動式的單向凝固單晶生長系 統與方法，尤指一種利用不小於0.2赫茲的震動頻率進行 震動、均勻的旋轉加熱，達到增進單晶品質與強化界面穩 定性的單晶生長系統與方法。 【先前技術】 在單晶製造技術領域中，生長單晶的材料包括半導 體、有機物、無機物（氧化物）、金屬、超導體等。而目 前生長這些單晶的方式主要包括柴氏法（Czochralski Method)、布氏法（Bridgman Method)以及與布氏法極相 似的凝固溫度梯度法（Gradient Freeze Method)。 一般而言，柴氏法的產率（yield)比凝固溫度梯度法 高，但是柴氏法因為熱應力所引起的缺陷（defect)也較 高。因此，近年來，除了石夕單晶外，化合物的單晶生長以 布氏法與凝固溫度梯度法來製造較為普遍。 以布氏法與凝固溫度梯度法而論，其差別在於布氏法 是將坩堝（crucible )在具有高溫部與低溫部的爐管 (furnace)中移動以改變掛禍中溶融態（melt)的溫度， 而凝固溫度梯度法乃是直接降低坩堝的溫度而不移動坩堝 以改變坩堝中熔融態（melt)的溫度。不論是布氏法或是 凝固溫度梯度法，其皆能夠提供穩定的環境溫度來進行穩 定的單晶生長，所以能夠以一種較適當的單晶生長條件來 製造高品質、低缺陷的單晶。然而，由於單晶生長時會釋 1245820 放出凝固熱，所以，如第一圖所示，係習知技術單晶生長 之熔融態與固態之界面示意圖。在固態的單晶11與熔融態 12的界面13常呈中央凹陷，其中熔融態12可以是前述任 何一種生長單晶的材料，而由重力所引起的自然對流 (convective flow)會造成、熔融態12中的摻雜14之分布 集中在界面13的中央處，亦即是造成摻雜14的轴向偏析 (segregation)與徑向偏析，進而造成界面13的過冷及 界面崩潰的現象，其中，重力方向如箭號G所示，自然對 流方向如箭號C所示。如上所述，即使在單晶生長時能夠 精確地控制熱量傳遞（heat transfer)，但是依然無法完 全消除呈熔融態的對流現象。因此，所生長的單晶會有缺 陷。因此，要減少摻雜的軸向偏析與徑向偏析以有效控制 摻雜的軸向與徑向分布，有效控制對流是十分重要的。 在習知技術中，為了有效減少對流現象對單晶生長的 影響，採用了外加磁場（magnetic field)的方式來減少 局部的摻雜累積。然而，利用外加磁場之單晶生長系統與 方法不但製造不易、成本高，而且無法有效地提供磁場至 單晶生長的區域以控制單晶生長，並且其只能應用於溶液 為電導體的情況。 請參照第二圖所示，係習知技術離心式單晶生長系統 示意圖。近年來發展出一種利用離心的方式來減少局部的 對流，進而改善轴向偏析，其係利用一大型離心機21來離 心掛禍（crucible) 22，在大多數的情況下，其係以自由 旋轉來操作，即離心力與重力的合成加速度與坩堝軸平 1245820 行。然而’依據上述的操作方式迷未善加利用離心力與科 氏力，而且會造成溶融態23的三維流動，以及增㈣雜 24的徑向偏析。利用同軸旋轉也可達到相同的效果。此外， 加速 轉技術（accelerated crucible rotation technique，簡稱ACRT)，則利用緩慢的變更旋轉，利用界 面處的埃克曼流（Eckman f low)及管璧處的泰勒流（Tai〇r flow)來增加混合，會產生長周期的生長不穩與雜質波動分 布佈。為了有效形成邊界層，旋轉變動方向週期長，多在 數秒到數分鐘左右。 以中華民國專利公告號500839之專利，名稱為旋轉式 單向凝固單晶生長系統及方法，其中揭露了一爐管、 禍與一旋轉支撐裝置，該旋轉支撐裝置支撐並旋轉該掛 堝，而該柑堝旋轉的切速度為不小於5ττ/3公分/秒。因 此’可以得知其中的旋轉支撑裝置係進行旋轉式77地旋轉^ 塥’希望達到某種提供與重力方向垂直的離心力與科氏力 給原料物質及其中的摻雜’進而消除介面中央因換雜累 引起的凹陷、強化介面穩定性，並且產生與自然對、充方白 相反的對流來消除自然對流以便改善摻雜分布〈輛2及三 向〉、增進單晶品質、然而’單純的1旋轉方向旋3 在難以達到足夠的效率。因此，如何提俾_ 、 ^種忐夠有效減 t對流現象（即可減少轴向偏析）並消除界面的中央凹陷 崩潰，以便減少摻雜之軸向偏析與徑向偏析，進而避曰 面的過冷及界面崩潰，正是當前亟待解決的課題之一 1245820 【發明内容】 本發明之主要目的，乃在於提供一種旋轉震動式的單 向凝固單晶生長系統與方法，以能夠對抗因重力產生之自 然對流，進而改善摻雜分布，增進單晶品質。 本發明之另一目的為提供一種旋轉震動式的單向凝固 單晶生長系統與方法，以能夠消除界面中央因溶質或摻雜 累積引起的凹陷，並強化界面穩定性。 本發明之一種旋轉震動式的單向凝固單晶生長系統， 包含：一爐管，係垂直設置，以提供不同溫度的環境；一 坩堝，係位於該爐管内，並呈與爐管同轴心的垂直排列； 以及一旋轉震動裝置，係包括一支撐台、一馬達與一震動 裝置，且連接該坩堝，並對坩堝進行旋轉震動；其中，該 爐管更包含一高溫部、一絕熱部與一低溫部，該高溫部提 供一高溫狀態，該低溫部提供一低溫狀態，高溫狀態提供 大於原料物質之熔點的溫度，以進行加熱的程序，低溫狀 態提供小於原料物質之溶點的溫度，以進行結晶的程序， 因此，得以提供不同溫度的環境，以進行不同的程序。 本發明之一種旋轉震動式單向凝固單晶生長方法步驟 ，包括： si.提供一内部具有坩堝的爐管，且該坩堝内部係裝盛有一 晶種與原料物質， 52. 利用該爐管對坩堝加熱，以熔化該原料物質，達到均勻 擾摔的目的， 53. 提供一旋轉震動裝置，係對坩堝進行旋轉震動，且再度 1245820 利用爐管對掛禍冷卻。 需注意者，在習知的單晶生長系統與方法中，熟習該 項技藝者為增加掛禍受熱的均勻性，可能會低速旋轉掛堝 ，並用停止坩堝旋轉與反向坩堝旋轉來增加混合的ACRT方 法有明顯的不同。換言之，在習知技術中，旋轉坩堝或是 改變轉動方向之頻率極低（遠低於0. 2赫茲），且其目的是 為了增加坩堝受熱的均勻性，與雜質的混合，與本發明之 目的明顯不同，而且坩堝旋轉或改變方向的頻率會遠小於 本發明所宣稱的0. 2赫茲。 由於依本發明之旋轉震動式單向凝固單晶生長系統與 方法係於單晶生長的過程中，以不小於0.2赫茲的頻率在旋 轉方向來回震動原料物質及其中的摻雜，所以能夠提供與 足與抗衡的界面處的史托克流動，來抗衡重力引起的不均 對流給原料物質及其中的摻雜，進而消除界面中央因摻雜 累積引起的凹陷、強化界面穩定性，並且產生的史托克流 與自然對流方向相反，可用來消除自然對流以便改善摻雜 分布（軸向及徑向）、增進單晶品質。 【實施方式】 請參閱第三圖，係本發明之一種旋轉震動式的單向凝 固單晶生長系統的一較佳實施例圖式。本發明之一種旋轉 震動式的單向凝固單晶生長系統3，包含：一爐管31，係 垂直設置，以提供不同溫度的環境；一坩堝32，係位於該 爐管31内，並呈與爐管31同軸心的垂直排列；以及 一 旋轉震動裝置33，係包括一支撐台331、一馬達333與一 1245820 震動裝置335 ’且連接該㈣32，並對_犯進行旋 動，其中’ 5亥爐官31更包含一高溫部3U、一絕熱部 與一低溫部312，該高溫部311提供―高溫㈣，該· 部312提供一低溫狀態，高溫狀態提供大於原料物質之ς f的溫度’以進行加熱的程序，低溫狀態提供小於原料物 質之熔點的溫度’以進行結晶的程序，因此，得以提供不 同溫度的環境’以進行不同的程序，該絕熱部313係設置 部311與低溫部312之間，以隔絕爐管3i的高溫部 311與低溫部312之溫度差；該频32具有-晶種井32; 及一生長區322 ’該晶種井321中係容納有-晶種72，該 ^區322中係容納有原料物質71及分布於該原料物質 =摻雜711’原料物f 71可為有機材料、氧化物材料、 t .、金屬材料或半導體材料，如有機材料中的笨 、(BenZl1 ) ’氧化材料中的銳鐘（LiNbOO，或壓 包材料（例如 ’超體材料中的紀鋇銅氧化物 u〇6+x) A屬材料中的鋁（Aluminum)，以及半導 中的_化鎵（Gap)、坤化鎵（GaAs)、石夕鍺化合物 择·1Χθ1-χ)、鎊化鎘（CdTe)，以作為本發明可應用的範 掛尚32更包括—掛禍軸332，以與旋轉震動裝置犯 " 達到旋轉晨動的穩定效果，精確地說，旋轉震動襞 _ 〃掛禍32 @日守貫質上為同軸旋轉震動；本發明更有 的，承!34 ’设置於掛禍32的—端，以方便掛禍於爐管中 *二轉震動’方疋轉辰動裝置33係以震動頻率不小於〇· 2赫 餘的方式震動，且震動振幅依需要可調整。如圖所示，掛 1245820 堝32係可垂直移動，以便坩堝32在爐管31中為可旋轉震 動地自高溫部移動至低溫部，因此，可以進行高溫部311 加熱以產生與熱對流相反的運動，才能夠對抗因重力產生 之自然對流，進而改善摻雜分布，與消除界面中央因溶質 或摻雜累積引起的凹陷，並強化界面穩定性，並在移動後 可利用低溫部312的冷卻與晶種井3 21中的晶種7 2進行單 晶生長的程序，因此，本實施例可以更包括一馬達（圖中未 示）及一線性滑執（圖中未示），以便驅動並控制坩禍32的 上下移動；另一實施例係爐管31可垂直移動，以便掛禍 ^ 32在爐管31中可旋轉震動並自高溫部311移動至低溫部 312，同樣地進行上述的加熱、融化、冷卻、結晶的過程。 如第三圖所示，本較佳實施例所揭露的旋轉震動裝置33係 設置於坩堝32下方；另一方面，旋轉震動裝置33亦可設 置於坩堝32上方或其他方位。# 上述原料物質71所有相對的摻雜711，例如於笨偶酉贫 中為鈥（Neodymium)，於銳酸鋰中為氧化鎂（处〇)或是 鐵（Iron)，於鋁中為銅（Copper )，於石申化鎵中為石夕或 ^ 硒（Selenium)，於鎊化鎘中為磷（phosphorus )，需注 意者’在上述的紀鋇銅氧化物與石夕錯化合物中，係以不同 · 元素組成作為掺雜，例如，含6個氧的釔鋇銅氧化物 · (Yba2Cu3〇6)與含7個氧的紀鋇銅氧化物（Yba2cU3〇7)。另 外’也可生長化學計量比為1 : 1的鈮酸鋰或钽酸鐘 (LiTaOs)。 以半導體材料為例’當原料物質71為半導體材料中的 12 1245820 HA族元素中的鎵（Gallium)與VA族元素中的坤 (Arsenic )時，高溫部311必須提供高於珅化鎵（gal 1 ium arsenide，GaAs)之熔點的溫度，而低溫部則提供低於砷 化鎵之炫點的溫度。 請參閱附件之附圖一與附圖二，係本發明之實驗室二 實施例照片，其顯示於丁二腈（Succinonitrile)中加入 少量丙酮作為摻雜時的單晶生長情形，其中單晶生長速k 皆為2. 5pm/s，而附圖一顯示掛禍32無旋轉震動時的單晶 生長結果，附圖二顯示坩堝32以60赫茲旋轉震動（角度振 幅約0. 01徑度）時的單晶生長結果，由附圖一與附圖二中 可以清楚瞭解當坩堝32無旋轉震動時，丙酮會累積在界面 中心處，因此會加速發生界面崩潰，當坩堝32旋轉震動 時，則界面崩潰不發生。 請參閱第四圖，係本發明之一種旋轉震動式單向凝固 單晶生長方法步驟圖式，包括： S1 :提供一内部具有坩堝的爐管，且該坩堝内部係裝 盛有一晶種與原料物質：由於該坩堝具有一晶種井及 一生長區，因此，該晶種井中係容納該晶種，該生長 區中係容納該原料物質及分布於該原料物質中的摻 雜；在本發明中，原料物質可採用皿-V族半導體的磷 化鎵，摻雜可採用矽； S2 :利用該爐管對坩堝加熱，以熔化該原料物質，達到均 勻攪拌的目的：由於爐管包含一高溫部，該高溫部提 供一高溫狀態，高溫狀態提供大於原料物質之熔點的 13 1245820 溫度，因此可以融化原料物質；在本發明中，由於所 使用的原料物質為磷化鎵，所以必須將坩堝加熱至 1465°C以上，以便熔化磷化鎵；1245820 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to a rotary vibration type unidirectional solidification single crystal growth system and method, especially a kind of vibration and uniform rotary heating using a vibration frequency of not less than 0.2 Hz To achieve a single crystal growth system and method that enhances the quality of the single crystal and enhances the stability of the interface. [Prior art] In the field of single crystal manufacturing technology, materials for growing single crystals include semiconductors, organics, inorganics (oxides), metals, superconductors, and the like. The current methods for growing these single crystals include the Czochralski Method, the Bridgman Method, and the Gradient Freeze Method, which is very similar to the Brinell Method. In general, the yield of the Chai's method is higher than that of the solidification temperature gradient method, but the defects of the Chai's method due to thermal stress are also higher. Therefore, in recent years, in addition to Shi Xi single crystals, single crystal growth of compounds by Brinell method and solidification temperature gradient method has become more common. The difference between the Brinell method and the solidification temperature gradient method is that the Brinell method moves a crucible in a furnace having a high temperature portion and a low temperature portion to change the melt state in the event of a disaster. Temperature, and the solidification temperature gradient method is to directly reduce the temperature of the crucible without moving the crucible to change the temperature of the melt in the crucible. Both the Brinell method and the solidification temperature gradient method can provide stable ambient temperature for stable single crystal growth, so a single crystal with high quality and low defects can be manufactured under a suitable single crystal growth condition. However, since 1245820 is released during the growth of a single crystal, the heat of solidification is released, so as shown in the first figure, it is a schematic diagram of the interface between the molten state and the solid state of single crystal growth in the conventional technology. The interface 13 between the single crystal 11 and the molten state 12 in the solid state often has a central depression. The molten state 12 can be any of the foregoing materials for growing single crystals, and the natural convective flow caused by gravity will cause the molten state. The distribution of dopant 14 in 12 is concentrated at the center of interface 13, that is, it causes axial segregation and radial segregation of dopant 14, and then causes supercooling and interface collapse of interface 13, among which The direction of gravity is shown by arrow G, and the direction of natural convection is shown by arrow C. As described above, even if heat transfer can be accurately controlled during single crystal growth, the convection phenomenon in a molten state cannot be completely eliminated. Therefore, the grown single crystal is defective. Therefore, to reduce the axial segregation and radial segregation of doping to effectively control the axial and radial distribution of doping, it is very important to effectively control convection. In the conventional technology, in order to effectively reduce the effect of convection on the growth of a single crystal, an external magnetic field method is used to reduce local doping accumulation. However, a single crystal growth system and method using an external magnetic field is not only difficult to manufacture and costly, but also cannot effectively provide a magnetic field to a single crystal growth region to control single crystal growth, and it can only be applied when the solution is an electrical conductor. Please refer to the second figure, which is a schematic diagram of a conventional centrifugal single crystal growth system. In recent years, a centrifugal method has been developed to reduce local convection and thereby improve axial segregation. It uses a large centrifuge 21 to centrifuge crucible 22. In most cases, it uses free rotation. To operate, that is, the combined acceleration of centrifugal force and gravity and the crucible axis are 1245820 rows. However, according to the above-mentioned operation method, the centrifugal force and Coriolis force are not properly used, and the three-dimensional flow of the molten state 23 and the radial segregation of the doped 24 are increased. The same effect can be achieved with coaxial rotation. In addition, the accelerated crucible rotation technique (ACRT) uses slow change rotation, using Eckman f low at the interface and Taior flow at the tube to increase Mixing will produce long-term growth instability and impurity fluctuation distribution. In order to effectively form the boundary layer, the period of the rotation variation direction is long, which is usually several seconds to several minutes. According to the patent of the Republic of China Patent Publication No. 500839, the name is a rotary unidirectional solidification single crystal growth system and method, which discloses a furnace tube, a rotary support device, and a rotary support device that supports and rotates the hanging pot, and The cutting speed of the mandarin pot rotation is not less than 5ττ / 3 cm / sec. Therefore, 'It can be known that the rotary support device is rotated in a rotating manner of 77 ^ 塥' I hope to achieve some kind of centrifugal force and Coriolis force perpendicular to the direction of gravity to the raw material substance and its doping ', thereby eliminating the central interface change. Depression caused by miscellaneous, to strengthen the stability of the interface, and to generate convection opposite to natural convection, to eliminate natural convection in order to improve the doping distribution (vehicle 2 and three-way), improve the quality of single crystal, but 'simple 1 Turning in the direction of rotation 3 is difficult to achieve sufficient efficiency. Therefore, how to improve the 俾 _ and ^ species can effectively reduce the t-convection phenomenon (that is, reduce axial segregation) and eliminate the collapse of the central depression of the interface, so as to reduce the axial segregation and radial segregation of the doping, and thus avoid the surface Undercooling and interface collapse are just one of the issues that need to be solved 1245820 [Summary of the invention] The main purpose of the present invention is to provide a rotating vibration type unidirectional solidification single crystal growth system and method, which can counteract the generation due to gravity The natural convection improves the doping distribution and the quality of the single crystal. Another object of the present invention is to provide a rotary vibration type unidirectional solidification single crystal growth system and method, which can eliminate depressions caused by solute or dopant accumulation in the center of the interface, and enhance the stability of the interface. A rotary vibration type unidirectional solidification single crystal growth system of the present invention includes: a furnace tube, which is vertically arranged to provide different temperature environments; a crucible, which is located in the furnace tube and is coaxial with the furnace tube And a rotary vibration device, which includes a support table, a motor and a vibration device, and is connected to the crucible and rotates the crucible; wherein the furnace tube further includes a high-temperature portion, an adiabatic portion and A low temperature part, which provides a high temperature state. The low temperature part provides a low temperature state. The high temperature state provides a temperature greater than the melting point of the raw material substance to perform the heating process. The low temperature state provides a temperature less than the melting point of the raw material substance. The crystallization process is performed, so that different temperature environments can be provided to perform different processes. The steps of a method for rotating and vibrating a unidirectional solidified single crystal according to the present invention include: si. Providing a furnace tube with a crucible inside, and the crucible contains a seed crystal and a raw material, 52. using the furnace tube pair The crucible is heated to melt the raw material to achieve the purpose of uniform scatter. 53. A rotary vibration device is provided to rotate the crucible, and once again 1245820 uses the furnace tube to cool the accident. It should be noted that, in the known single crystal growth system and method, in order to increase the uniformity of heating and heating, the skilled person may rotate the hanging pot at a low speed, and stop the crucible rotation and reverse the crucible rotation to increase the mixing. The ACRT method is significantly different. In other words, in the conventional technology, the frequency of rotating the crucible or changing the direction of rotation is extremely low (well below 0.2 Hz), and the purpose is to increase the uniformity of the crucible heating, the mixing with impurities, and the invention 2Hz。 The purpose is significantly different, and the frequency of crucible rotation or change direction will be far less than claimed in the present invention 0.2 Hz. Since the rotating vibration type unidirectional solidification single crystal growth system and method according to the present invention are in the process of single crystal growth, the raw material substance and its doping are vibrated back and forth in the rotation direction at a frequency of not less than 0.2 Hz, so it can provide the same The Stokes flow at the interface between the foot and the counterbalance counteracts the uneven convection caused by gravity to the raw material substance and its doping, thereby eliminating the depression caused by the accumulation of doping in the center of the interface and strengthening the stability of the interface. Toke flow is opposite to natural convection. It can be used to eliminate natural convection in order to improve the doping distribution (axial and radial) and improve the quality of single crystal. [Embodiment] Please refer to the third figure, which is a schematic diagram of a preferred embodiment of a rotary vibration type unidirectional solidified single crystal growth system of the present invention. A rotary vibration type unidirectional solidification single crystal growth system 3 of the present invention includes: a furnace tube 31 which is vertically arranged to provide different temperature environments; a crucible 32 which is located in the furnace tube 31 and presents the same The furnace tube 31 is coaxially arranged vertically; and a rotary vibration device 33 includes a support table 331, a motor 333, and a 1245820 vibration device 335 ', and is connected to the cymbal 32, and the guilty is rotated, among which' 5HAI The furnace officer 31 further includes a high-temperature portion 3U, an adiabatic portion, and a low-temperature portion 312. The high-temperature portion 311 provides `` high temperature '', and the portion 312 provides a low-temperature state, and the high-temperature state provides a temperature greater than the raw material substance f '. The process of heating, the low-temperature state provides a temperature lower than the melting point of the raw material 'to perform the crystallization process, so that different temperature environments can be provided to perform different processes. The thermal insulation part 313 is a set part 311 and the low-temperature part 312. In order to isolate the temperature difference between the high temperature part 311 and the low temperature part 312 of the furnace tube 3i; the frequency 32 has a -seed well 32; and a growth zone 322 'the seed well 321 contains -the seed 72, the ^ area 322 The raw material substance 71 is contained in and distributed in the raw material substance = doping 711 '. The raw material f 71 may be an organic material, an oxide material, t., A metal material, or a semiconductor material, such as benzene, (BenZl1) in organic materials. Sharp bell (LiNbOO in oxidized materials, or lamination materials (such as' barium copper oxide in supermaterials u〇6 + x) Aluminum in material A, and gallium carbide in semiconductors (Gap), gallium gallium (GaAs), Shi Xi germanium compound selection · 1 × θ1-χ), and cadmium cadmium (CdTe), which are applicable as the present invention can be linked to 32. Includes-hanging axis 332, and The rotary vibration device achieves the stabilization effect of the rotating morning motion. To be precise, the rotary vibration 襞 _ 〃 hanging woes 32 @ 日 守 consistent quality is coaxial rotary vibration; the invention is even more, Cheng! 34 'Set in hanging The end of the disaster 32, for the convenience of accidents in the furnace tube * two revolution vibration 'Fang Chen Zhunchen moving device 33 is vibrated with a vibration frequency of not less than 0.2 Hz, and the vibration amplitude can be adjusted as needed. As shown in the figure, the hanging 1245820 pot 32 can be moved vertically, so that the crucible 32 can rotate in the furnace tube 31 from the high-temperature part to the low-temperature part in a rotatable vibration. Therefore, the high-temperature part 311 can be heated to generate the opposite of thermal convection Movement can counteract natural convection due to gravity, thereby improving doping distribution, and eliminating depressions caused by solute or dopant accumulation in the center of the interface, and strengthening the stability of the interface. After the movement, the cooling and The seed crystal 7 2 in the seed well 3 21 performs a single crystal growth process. Therefore, this embodiment may further include a motor (not shown) and a linear slider (not shown) in order to drive and control the crucible. The up and down movement of the calamity 32; another embodiment is that the furnace tube 31 can be moved vertically to hang the calamity ^ 32 in the furnace tube 31 can be rotated and vibrated and moved from the high temperature portion 311 to the low temperature portion 312, and the above heating and melting are performed similarly. , Cooling, crystallization process. As shown in the third figure, the rotary vibration device 33 disclosed in the preferred embodiment is disposed below the crucible 32; on the other hand, the rotary vibration device 33 can also be disposed above the crucible 32 or in other orientations. # All the above-mentioned raw material substances 71 have a relative doping 711, such as “(Neodymium) in stupidity”, “magnesium oxide (at 0)” or “iron” (in iron sharp), and “copper” (in aluminum) Copper) is Shi Xi or Selenium in gallium sulfide, and phosphorous in cadmium cadmium. It should be noted that in the above-mentioned barium copper oxide and Shi Xico compounds, Different dopants are used as the dopants, for example, yttrium barium copper oxide (Yba2Cu306) containing 6 oxygen and barium copper oxide (Yba2cU307) containing 7 oxygen. In addition, lithium niobate or tantalate bells (LiTaOs) having a stoichiometric ratio of 1: 1 can be grown. Take the semiconductor material as an example. When the raw material 71 is 12 1245820 Gallium in the HA group element and Arsenic in the VA group element, the high temperature portion 311 must provide higher than gallium halide (gal 1 ium arsenide (GaAs), and the low temperature part provides a temperature below the dazzling point of gallium arsenide. Please refer to the attached drawings 1 and 2 of the appendix, which are photos of the second embodiment of the laboratory of the present invention, which show the single crystal growth situation when a small amount of acetone is added to succinonitrile as a doping. The speed k is 2. 5 pm/s, and the attached figure 1 shows the single crystal growth results when the rotating crater 32 has no rotational vibration, and the attached figure 2 shows the crucible 32 rotating at 60 Hz (the angular amplitude is about 0.01 diameter). The results of the single crystal growth can be clearly understood from Figures 1 and 2 that when the crucible 32 has no rotational vibration, acetone will accumulate at the center of the interface, so the interface collapse will accelerate. When the crucible 32 rotates and vibrates, the interface The crash did not happen. Please refer to the fourth figure, which is a schematic diagram of a method for growing a single crystal solidification method by rotating vibration type, including: S1: Provide a furnace tube with a crucible inside, and the crucible contains a seed and raw material Substance: Since the crucible has a seed well and a growth zone, the seed well contains the seed crystal, and the growth zone contains the raw material substance and doping distributed in the raw material substance; in the present invention The raw material can use gallium-V semiconductor gallium phosphide, and silicon can be used for doping. S2: Use the furnace tube to heat the crucible to melt the raw material to achieve the purpose of uniform stirring: because the furnace tube contains a high temperature part The high temperature part provides a high temperature state. The high temperature state provides a temperature of 13 1245820 greater than the melting point of the raw material material, so the raw material material can be melted. In the present invention, since the raw material material used is gallium phosphide, the crucible must be heated to Above 1465 ° C to melt gallium phosphide;
S3 :提供一旋轉震動裝置，係對坩堝進行旋轉震動，且再 度利用爐管對坩堝冷卻：該旋轉震動裝置係設置於該 坩堝上方或下方，且配合著一軸承與一坩堝轴，以便 旋轉震動裝置與坩堝同時實質上為同轴旋轉震動與達 到旋轉震動的穩定效果，並且以不小於0.2赫茲之震 動頻率震動，震動之振幅得依需要可調整；另一方面， 由於坩堝可上下移動，因此，坩堝在爐管中為可旋轉 震動地自高溫部移動至低溫部，該低溫部提供一低溫 狀態，低溫狀態提供小於原料物質之熔點的溫度，因 此可以利用晶種井中的晶種結晶化原料物質，且爐管 可包含一絕熱部，其係設置於該高溫部與該低溫部之 間，以隔絕爐管的南溫部與低溫部之溫度差，致使結 晶化後的原料物質不受加熱部分的影響；相對地，另 一個實施例中，該爐管係可垂直移動，以便坩堝在爐 管中為可旋轉震動並相對於爐管自高溫部移動至低溫 部；在本發明中，由於所使用的原料物質為磷化鎵， 所以必須將坩堝冷卻至1465°C以下，以便凝固磷化鎵。 本發明所採用的原料物質可為有機材料、氧化物材料、超 導體材料、金屬材料和半導體材料等’如有機材料中的苯 偶酿（Benzil)，氧化材料中的銳酸鋰（LiNb03 )，或壓 電材料（例如PZNT)，超導體材料中的釔鋇銅氧化物 14 1245820 (Yba2Cu3〇6+x)，金屬材料中的紹（Aluminum)，以及半 導體材料中的磷化鎵（GaP)、砷化鎵（GaAs)、石夕錯化 合物（SixGeKx)、鎊化鎘（CdTe)。因此，本發明可芒、、乏 地運用於半導體界和其相關產業。 綜上所述 田％伋本發明之靛轉震動式單向凝固單晶 生長系統與方法係於單晶生長的過程中，掛竭係以不低於 0· 2赫茲的頻率旋轉震動，所以能夠提供足夠的界面處漭 動（史托克流）給坩堝中的原料物質，因此，原料物質^ 生方向與如圖1所示之自然對流方向（如箭號乂）相^ 對流’結果可以消除界面中央因摻㈣起的凹陷 白 然對流、減少反應物之軸向偏析與徑向偏析，進而避: 雜局部累積引起的組成過冷及界面崩潰。 多 以上所述僅為舉例性’而非為限制性者。例如，濟 :度設計可以ί依據溫度梯度法或是布氏法，而二的 皿度分布也可猎由多段式加熱來 ^置 :::震:r任何未脫離本發明 ;請專利範圍更’均應包含於後附之 ^ 疋故本發明已符合發明專利標的的 :二μ進^&與產業利用性，爰依法申請發明專利， 亚"鈞局惠料審料專利1感德便。 【圖式簡單說明】 第一圖係習知技術單晶生异於 ^ 生長之垃以怨與固態之界面示意 15 1245820 第二圖係習知技街離心式單晶生長系統 . 第三圖係本發明之—機轉震動柄單向凝^ 統的一較佳實施例圖式； ^ 早晶生長系 第四圖係本發明之一 步驟圖式； 種旋轉震動式單向 疑固單晶生長方法 附圖一與關二，係本發k實驗室二實施例照片。 【主要元件符號說明】 c自然對流 G重力 U單晶 12融溶態 13界面 14摻雜 21大型離心機 22掛禍 2 3融炼態 2 4換雜 3單向凝固單晶生長系統 31爐管 311高溫部 312低溫部 313絕熱部 1245820 32坩堝 321晶種井 322生長區 33旋轉震動裝置 331支撐台 332坩堝軸 333馬達 334轴承 335震動裝置 71原料物質 711摻雜 72晶種 S1至S3係步驟編號S3: Provide a rotary vibration device to rotate the crucible and use the furnace tube to cool the crucible again: the rotary vibration device is set above or below the crucible and is matched with a bearing and a crucible shaft to rotate and shake At the same time, the device and the crucible are substantially coaxial with the rotational vibration and achieve the stabilization effect of the rotational vibration, and vibrate at a vibration frequency of not less than 0.2 Hz, and the amplitude of the vibration can be adjusted as needed; on the other hand, because the crucible can move up and down, so The crucible moves in the furnace tube from the high temperature part to the low temperature part in a rotatable vibration. The low temperature part provides a low temperature state. The low temperature state provides a temperature lower than the melting point of the raw material. Therefore, the seed can be used to crystallize the raw material. Material, and the furnace tube may include an adiabatic part, which is arranged between the high temperature part and the low temperature part to isolate the temperature difference between the south temperature part and the low temperature part of the furnace tube, so that the crystallized raw material substance is not heated Part of the effect; in contrast, in another embodiment, the furnace tube system can be moved vertically so that the crucible is rotatable in the furnace tube Tube vibration phase and the low-temperature portion from the high temperature portion to move; in the present invention, since the starting material used is gallium phosphide, the crucible was cooled to 1465 ° C or less must be, in order to solidification gallium phosphide. The raw material substances used in the present invention may be organic materials, oxide materials, superconductor materials, metal materials, and semiconductor materials, such as Benzil in organic materials, LiNb03 in oxide materials, or Piezoelectric materials (such as PZNT), yttrium barium copper oxide 14 1245820 (Yba2Cu306 + x) in superconductor materials, aluminum in metal materials, and gallium phosphide (GaP), arsenide in semiconductor materials Gallium (GaAs), Shixi Co compound (SixGeKx), pound cadmium (CdTe). Therefore, the present invention can be applied to the semiconductor industry and related industries. In summary, Tian Tianji, the indigo-vibration-type unidirectional solidification single crystal growth system and method of the present invention is in the process of single crystal growth, and the exhaustion is caused to rotate at a frequency not lower than 0.2 Hz, so it can Provide sufficient interface motion (Stocker flow) to the raw material in the crucible, so the raw material ^ direction of growth and natural convection direction shown in Figure 1 (such as arrow 乂) ^ convection 'result can be eliminated In the center of the interface, the concavity caused by erbium contamination reduces the axial segregation and radial segregation of the reactants, thereby avoiding: undercooling of the composition and interface collapse caused by local accumulation of impurities. The above is merely exemplary and not restrictive. For example, the degree design can be based on the temperature gradient method or the Brinell method, and the two degree distribution can also be set by multi-stage heating. ^ :: tremor: r Anything that does not depart from the present invention; please patent more 'All should be included in the appendix ^ Therefore, the present invention has met the subject of the invention patent: two μ ^ & and industrial applicability, apply for an invention patent according to law, Asia " Jun Bureau Hui materials review patent 1 sense Poop. [Schematic description] The first picture shows that the conventional technology of the single crystal is different from the growth of the solid and solid interface 15 1245820 The second picture shows the centrifugal single crystal growth system of the Xizhiji Street. The third picture The present invention is a schematic diagram of a preferred embodiment of the unidirectional condensing system of a mechanically vibrating handle; ^ The fourth diagram of the early crystal growth system is a step diagram of the present invention; Methods Figures 1 and 2 are photos of the second embodiment of the Lab. [Description of main component symbols] c Natural convection G Gravity U single crystal 12 Melt state 13 Interface 14 Doping 21 Large centrifuge 22 Hanging disaster 2 3 Melt state 2 4 Miscellaneous 3 Unidirectional solidification single crystal growth system 31 Furnace tube 311 high temperature part 312 low temperature part 313 adiabatic part 1245820 32 crucible 321 seed well 322 growth area 33 rotary vibration device 331 support table 332 crucible shaft 333 motor 334 bearing 335 vibration device 71 raw material substance 711 doped 72 seed S1 to S3 series step number