200952207 九、發明說明： 【發明所屬之技術領域】 本發明是關於一種氣相沈積系統，尤其是關於一種電漿 氣相沈積系統。 【先前技術】 在半導體頜域中，化學氣相沈積（Chemical VaPor Deposition，簡稱CVD)技術是最基本也是最重要的薄膜成 長方式之一，其基本過程是將反應源以氣體形式通入反應 腔，其利用擴散經過邊界層（boundary layer)到達基板表 面；並藉由基板表面提供的能量在基材表面進行氧化、還 原或與基板反應等化學反應，其生成物則因内擴散作用沈 積於基板表面上。基本上，化學氣相沈積技術又分多種’ 目前産業界廣泛應用的是有機金屬化學氣相沈積 (Metalorganic Chemical Vapor Deposition，MOCVD)，其 廣泛運用於各種不同結構的元件上，尤其是II- V族光電元 ^ 件上。MOCVD可以達到較佳平整度，並且能沈積大部分 的三元化合物及四元化合物，例如InGaAs及AlGalnP，及 長出含鋁化合物，例如應用廣泛的砷化鋁鎵（AlGaAs)。在 一些特別的情況下，如在紅外線方面運用極廣的材料如 InxGai-xASyPi-y四元化合物系統上，只能以MOCVD系統 加以成長。 然現有的MOCVD技術也存在諸多缺點，其製作成本 高，且不易控制計量比與厚度。尤其是在製造氮化物半導 體時，利用MOCVD於發光二極體的基板上成長III-V族 200952207 缓衝層，須使用氨氣（NH3)或聯氨（N2h4)氣體作爲v族 元素的反應源。然而該類氣體需要在高溫才能反應，而升 高成長溫度勢必提高GaxM-χΝ (〇>χ$ι)缓衝層成長時對氮的 飽和蒸汽壓的需求量，相應地將增加反應源的消耗量。因 此’有效的反應氮並不會相應增加，卻反而促使反應源消 耗量增大。另一方面’氨氣作爲反應源還導致成長ΠΙ_ν 族半導體緩衝層時發生氫覆蓋現象’使長成的ΠΙ_ν族氮 ❹ 化物緩衝層呈高絕緣狀態，必須進行額外處理才能獲得較 隹的電性。此外，氨氣對於真空管件、石墨、真空油有極 大的損耗及傷害，易造成系統的損壞和增加維護的困難度 及時間。 爲此，業界又開發出電漿化學氣相沈積系統，其借助電 漿的辅助能量，使得沈積反應的溫度得以降低，且可以直 接使用氮氣作爲反應源而避免氨氣對系統的損害。與傳統 的MOCVD相比，電槳化學氣相沈積系統可長時間操作， ❹ 八有再現性良好，所需溫度低，沈積膜的均勻度與品質較 好等優點。依產生電漿的不同方法，目前主要有微波電漿 C VD法（microwave enhanced CVD)和電子回轉共振微波等 電漿 CVD 法（electron cyclotron res〇nance(ECR))。根據微 波電漿CVD法，反應氣體由反應槽上方通入微波産生器， 經導波管導入反應室；適當調整後微波即在反應室内的基 板上方形成駐波而激發產生紫色的球型電漿。然該方法的 緩衝層成長速率較低、沈積面積小，而且基材的移動對於 電漿的形成有相當敏感的影響。電子回轉共振微波電漿 200952207 CVD法其原理和微波電聚CVD法相@，不同在於其在反 應至週邊放置兩組電磁鐵，上面的電磁鐵可使電子回轉， 大幅提高産生電漿的效率。該方法較微波電漿CVD法有 #乂大的控制空間，能擴大成長範圍，然無法克服基材的移 動對電漿的形成有相當敏感的影響等其他缺點。 如此，現有的氣相沈積技術還存在若干問題，尚需進一 步的改進和完善。 【發明内容】 本發明提供一種氣相沈積系統與方法，其可直接使用氮 氣作爲反應源，獨立控制所沈積薄膜的應力，而不會對其 沈積特性造成重大的影響。 爲達到上述目的，本發明提供下述技術方案：一種氣相 沈積系統，其包含：一電聚産生區、一反應腔，以及一置 於該產生區與該反應腔之間的多孔管。該産生區提供一第 元素的電漿。該多孔管將該第一元素的電聚及—第二元 ❹ 素匯集導入該反應腔。該第一元素的電槳及該第二元素於 該反應腔中於一基板進行化學氣相磊晶使成長一薄膜層。 該電漿產生區解離具有第一元素的氣體分子。該反應腔 爲一中頻加熱器。該中頻加熱器可將該基板及該氣相沈積 系統的溫度控制在室溫至攝氏9〇〇度之間。該第—元素爲 一 V族元素。該V族元素是選自氨（NH3)或氮（N2 )之 一或其混合物。該第二元素爲ΠΙ族有機金屬。該ΙΠ族有 機金屬爲鎵的有機金屬化合物。該ΠΙ族有機金屬來源爲鎵 的有機金屬化合物、銦的有機金屬化合物及鋁的有 屬 200952207 化合物的混合物，例如三曱基鎵（TMGa )、三曱基銦 (TMIn)、三甲基鋁（TMA1)、三乙基鎵（TEGa )、三 乙基銦（TEIn )、三乙基铭（TEA1)。該基板包含選自藍 寳石、GaN、AIN、SiC、GaAs、GaP、Si、ZnO、MgO、200952207 IX. Description of the Invention: [Technical Field] The present invention relates to a vapor deposition system, and more particularly to a plasma vapor deposition system. [Prior Art] Chemical VaPor Deposition (CVD) is one of the most basic and important ways of film growth in the semiconductor mandible. The basic process is to pass the reaction source into the reaction chamber as a gas. And diffusing through the boundary layer to reach the surface of the substrate; and performing chemical reaction such as oxidation, reduction or reaction with the substrate on the surface of the substrate by the energy provided on the surface of the substrate, and the product is deposited on the substrate by internal diffusion. On the surface. Basically, chemical vapor deposition technology is divided into a variety of 'currently widely used in the industry is Metalorganic Chemical Vapor Deposition (MOCVD), which is widely used in various structural components, especially II-V Family photocells. MOCVD can achieve better flatness and can deposit most of the ternary compounds and quaternary compounds, such as InGaAs and AlGalnP, and grow aluminum-containing compounds, such as widely used aluminum gallium arsenide (AlGaAs). In some special cases, such as the InxGai-xASyPi-y quaternary compound system, which is widely used in infrared light, it can only be grown by MOCVD system. However, the existing MOCVD technology also has many disadvantages, and its manufacturing cost is high, and it is difficult to control the metering ratio and thickness. Especially in the manufacture of nitride semiconductors, the III-V 200952207 buffer layer is grown on the substrate of the light-emitting diode by MOCVD, and ammonia (NH3) or hydrazine (N2h4) gas is used as the reaction source of the v-group element. . However, such gases need to be reacted at high temperatures, and increasing the growth temperature tends to increase the demand for saturated vapor pressure of nitrogen during the growth of the GaxM-χΝ(〇>χ$ι) buffer layer, which in turn increases the reaction source. consumption. Therefore, the effective reaction nitrogen does not increase correspondingly, but instead causes the reaction source to consume more. On the other hand, 'ammonia gas as a reaction source also causes hydrogen clogging phenomenon when growing ΠΙ ν group semiconductor buffer layer', so that the grown ΠΙ_ν group nitrogen hydride buffer layer is highly insulated, and additional processing is necessary to obtain a relatively low electrical property. . In addition, ammonia gas has great loss and damage to vacuum pipe fittings, graphite and vacuum oil, which is easy to cause damage to the system and increase the difficulty and time of maintenance. To this end, the industry has developed a plasma chemical vapor deposition system that uses the auxiliary energy of the plasma to reduce the temperature of the deposition reaction, and can directly use nitrogen as a reaction source to avoid damage to the system by ammonia. Compared with the conventional MOCVD, the electric paddle chemical vapor deposition system can be operated for a long time, and has good reproducibility, low required temperature, uniformity and quality of the deposited film. According to different methods of generating plasma, there are mainly microwave plasma CVD and electron cyclotron res (n) (electron cyclotron res〇nance (ECR)). According to the microwave plasma CVD method, the reaction gas is introduced into the microwave generator from above the reaction tank, and is introduced into the reaction chamber through the waveguide; after proper adjustment, the microwave forms a standing wave above the substrate in the reaction chamber to excite the purple spherical plasma. . However, the buffer layer of this method has a low growth rate and a small deposition area, and the movement of the substrate has a relatively sensitive influence on the formation of plasma. Electronic gyro-resonant microwave plasma 200952207 The principle of CVD method and microwave electro-polymerization CVD method phase @, the difference is that it is placed in the vicinity of the two sets of electromagnets, the upper electromagnet can make the electrons turn, greatly improving the efficiency of plasma generation. Compared with the microwave plasma CVD method, this method has a large control space and can expand the growth range, but it cannot overcome other disadvantages such as the influence of substrate movement on the formation of plasma. As such, there are still some problems with the existing vapor deposition technology, and further improvements and improvements are needed. SUMMARY OF THE INVENTION The present invention provides a vapor deposition system and method that directly uses nitrogen gas as a reaction source to independently control the stress of a deposited film without significantly affecting its deposition characteristics. In order to achieve the above object, the present invention provides the following technical solution: a vapor deposition system comprising: an electropolymerization generating zone, a reaction chamber, and a porous tube disposed between the generating zone and the reaction chamber. The production zone provides a plasma of the first element. The porous tube introduces the electropolymerization of the first element and the second elemental collection into the reaction chamber. The electric paddle of the first element and the second element are subjected to chemical vapor epitaxy on a substrate in the reaction chamber to grow a thin film layer. The plasma generating zone dissociates gas molecules having a first element. The reaction chamber is an intermediate frequency heater. The intermediate frequency heater controls the temperature of the substrate and the vapor deposition system between room temperature and 9 degrees Celsius. The first element is a V group element. The group V element is one selected from the group consisting of ammonia (NH3) or nitrogen (N2) or a mixture thereof. The second element is a lanthanide organometallic. The steroid has an organic metal compound in which the organic metal is gallium. The lanthanide organometallic source is an organometallic compound of gallium, an organometallic compound of indium, and a mixture of aluminum compounds of the group 200952207, such as trimethylgallium (TMGa), trimethylindium (TMIn), trimethylaluminum (TM). TMA1), triethylgallium (TEGa), triethylindium (TEIn), triethylamine (TEA1). The substrate comprises sapphire, GaN, AIN, SiC, GaAs, GaP, Si, ZnO, MgO,
Mg Al2〇2、及玻璃所構成的材料組群中的至少一種材料或其 他可代替的材料。 本發明的高頻電漿化學沈積系統較現有技術，具有一般 電漿氣相沈積系統的優點’而且能夠獨立地控制所沈積薄 膜的應力，不會對其他的沈積特性造成重大的影響。此外， 因V族元素電漿産生區和ΙΠ族元素的有機金屬源爲呈一 線型排列’可以提高起使物的有效使用率。 【實施方式】 高頻電漿CVD是以線圈式及電容式形成高頻率電場，以 在反應室中激發反應氣體，産生化學活性較高的離子，同 時基板表面受到離子的撞擊其化學活性也得以提高。如此 共同作用使得基板表面的化學反應速率提高，在較低的溫 度下即可在基板附近産生高濃度自由基，使薄膜沈積於其 上。該沈積系統在用於沈積合成類鑽薄臈時，具有可大面 積沈積的優點。其可應用的基板包含選自藍寶石、GaN、 AIN、SiC、GaAs、GaP、Si、ZnO、MgO、MgAl2〇2、及玻 璃所構成的材料組群中的至少一種材料或其他可代替的材 料。 如圖1所示，根據本發明一實施例的高頻電裝氣相沈積 系統100，包含並排而置的一電漿産生區i、反應腔2，以 200952207 及一個多孔管3。該電崎在居戸·ι-ρ/At least one of a material group consisting of Mg Al2 2 and glass, or another material that can be substituted. The high frequency plasma chemical deposition system of the present invention has the advantages of a conventional plasma vapor deposition system as compared with the prior art, and is capable of independently controlling the stress of the deposited film without significantly affecting other deposition characteristics. Further, since the organic metal source of the group V plasma generating region and the lanthanum element is in a linear arrangement, the effective use rate of the resultant can be improved. [Embodiment] High-frequency plasma CVD is to form a high-frequency electric field in a coil type and a capacitor type to excite a reaction gas in a reaction chamber to generate ions with high chemical activity, and at the same time, the surface of the substrate is subjected to ion impact and chemical activity thereof is also obtained. improve. Such a combination acts to increase the rate of chemical reaction on the surface of the substrate, and at a lower temperature, a high concentration of free radicals can be generated in the vicinity of the substrate to deposit a thin film thereon. The deposition system has the advantage of large area deposition when used to deposit synthetic diamond-like tantalum. The substrate to which it is applied comprises at least one material selected from the group consisting of sapphire, GaN, AIN, SiC, GaAs, GaP, Si, ZnO, MgO, MgAl2 2, and glass, or other alternative materials. As shown in Fig. 1, a high frequency electrical vapor deposition system 100 according to an embodiment of the present invention comprises a plasma generating zone i, a reaction chamber 2, and a porous tube 3, which are arranged side by side. The electric akisaki in Kluang·ι-ρ/
电漿産生& 1可經由一種主管4輸入V 族氣體並解離産生電漿，田於担讲 电水用於楗供V族元素的電漿，該v 族氣體由主管4輸入雷將卢迚斤！ 电漿産生區丨。該V族氣體是選自氨 (3)或氮(N2)之—或其混合物’本實施例中使用氮氣。 該反應腔2是用於使該v族元素以及—或多種m族元素 於其中與基板進行化學氣相薄膜層的長成，該第二元素胃 ΙΠ族有機金屬’如鎵的有機金屬化合物，或其與麵的有機 ❿The plasma generation & 1 can be converted into a plasma via a main body 4 input V gas and dissociated, and the field is used to conduct electric water for the plasma of the V group element, which is input by the supervisor 4 jin! The plasma generation zone is defective. The Group V gas is selected from the group consisting of ammonia (3) or nitrogen (N2) - or a mixture thereof. In the present embodiment, nitrogen gas is used. The reaction chamber 2 is an organic metal compound for causing the v-group element and/or a plurality of m-group elements to undergo a chemical vapor phase thin film layer with the substrate, the second element of the stomach-organic organometallic such as gallium. Or its organic
金屬化合物及鋁的有機金屬化合物的混合物。該多孔管3 位於電漿産生㊣1與反應腔2之間，用來導入一或多種的 ΠΙ族元素源及由電聚産生區1所形成的V族元素電漿氣體 至反應腔2從而在基材表面上形成薄膜層。經調整電漿產 生區卜主管4及多孔管3的相對位置，可減少高頻電漿激 發的氮氣經由自由碰撞回復穩定分子態。基材由晶片傳送 至6傳送至反應腔2經過其内部中頻加熱器加熱至反應溫 度後沈積薄膜。該中頻加熱器可將該基板及該氣相沈積系 統的溫度控制在室溫至攝氏9〇〇度之間。 V族氣體的氨（NH3)或氮（N2)儲存於氣體櫃5中，同 時ΙΠ族III族有機金屬來源也儲存於氣體櫃5中不同的氣 室内。該III族有機金屬爲鎵的有機金屬化合物。該111族 有機金屬來源爲鎵.的有機金屬化合物、銦的有機金屬化合 物及鋁的有機金屬化合物的混合物，例如三曱基錄 (TMGa)、三甲基銦（TMIn)、三甲基銘（TMA1)、三 乙基鎵（TEGa)、三乙基銦（ΤΕΙη)、三乙基鋁^^丨）。 氣體櫃5中V族氣體及ΙΠ族有機金屬來源由氣體流量控 200952207 制Is 9控制輸送的流量，並分別供應至主管4及多孔管3 的入口 2。另外’反應腔2内的真空度是由真空抽氣系統7 控制，真空抽氣系統7和氣體流量控制器9的壓力是由壓 力控制器8控制。 根據本發明的一實施例，在電漿産生區1中高頻電漿産 生器的兩個電極板間外加一個高頻電壓，如13.56MHz的射 頻電壓，使兩個電極之間産生輝光放射。v族氣體由主管4 ❹ 處導入，並以徑向流動方式通過輝光放射區域。在兩個相 對應的金屬電極板上施加一高頻電壓，當兩電極板間的氣 體分子濃度在某一特定的區間（特定區間的要求或標準），電 極板表面因離子轟擊（I〇n Bombardment)所産生的二次電子 (Secondary Electrons) ’在電極板所提供的電場下將獲得足 夠的能量，而與電極板間的氣體分子因撞擊而進行所謂的 解離（Dissociation)，離子化（I〇nization)，及激發（Excitati〇n) 等反應，相應的産生離子、原子、原子團（Radicals)，及更 ❹ 多的電子，以維持離子内各粒子間的濃度平衡，而在反應 腔内沈積於基材表面上。以V族元素中的氮爲例，其反應 方程式可表示爲： e_· + N — N + + 2 e“ 高頻電漿氣相沈積系統具有一般電漿氣相沈積系統的普 遍優點，如工作溫度低、低成本、低污染等，還可獨立控 制所沈積薄膜的應力’且不會對其他的沈積特性造成重大 的影響’例如沈積速率和薄膜均勻性。另外，根據本發明 •10- 200952207 的一實施例，因v族元素電漿産生區和ΙΠ族元素的有機 金屬源爲一線型排列，可以提高ν族元素和ΙΠ族元素源 有效使用率。另一方面，由於基板可以利用中頻加熱器加 熱到反應溫度，有利於薄膜層的結晶性和品質。在成長發 光二極體或是雷射二極體等的固態發光元件，可利用此薄 膜層做爲原件的緩衝層，以增加元件的結晶質量。 本發明之技術内容及技術特點已揭示如上，然而熟悉本 項技術之人士仍可能基於本發明之教示及揭示而作種種不 煮離本發明精神之替換及修飾。因此，本發明之保護範圍 應不限於實施例所揭示者，而應包括各種不背離本發明之 替換及修飾’並為以下之申請專利範圍所涵蓋。 【圖式簡單說明】 圖1根據本發明一實施例的高頻電漿氣相沈積系統。 【主要元件符號說明】 1電漿産生區 φ 3多孔管 5氣體櫃 7真空抽氣系統 9 氣體流量控制器 2 反應腔 4 主管 6晶片傳送室 8壓力控制器 1〇〇高頻電漿氣相沈積系統 -11 -A mixture of a metal compound and an organometallic compound of aluminum. The porous tube 3 is located between the plasma generating positive 1 and the reaction chamber 2, and is used for introducing one or more steroid source materials and a group V element plasma gas formed by the electropolymerization generating region 1 to the reaction chamber 2 so as to A film layer is formed on the surface of the substrate. By adjusting the relative positions of the main electrode 4 and the porous tube 3 in the plasma generating region, the high-frequency plasma-excited nitrogen can be reduced to restore the stable molecular state via free collision. The substrate is transferred from the wafer to 6 and transferred to the reaction chamber 2 to be heated by its internal intermediate frequency heater to a reaction temperature to deposit a film. The intermediate frequency heater controls the temperature of the substrate and the vapor deposition system between room temperature and 9 degrees Celsius. Ammonia (NH3) or nitrogen (N2) of the Group V gas is stored in the gas cabinet 5, and the source of the Group III organometallic metal is also stored in a different gas chamber in the gas cabinet 5. The Group III organic metal is an organometallic compound of gallium. The Group 111 organometallic source is a mixture of an organometallic compound of gallium, an organometallic compound of indium, and an organometallic compound of aluminum, such as tricarbyl (TMGa), trimethylindium (TMIn), trimethylamine (TM) TMA1), triethylgallium (TEGa), triethylindium (ΤΕΙη), triethylaluminum^^). The V group gas and the lanthanide organic metal source in the gas cabinet 5 are controlled by the gas flow control 200952207, and the flow rate is controlled to be supplied to the inlet 4 of the main pipe 4 and the perforated pipe 3, respectively. Further, the degree of vacuum in the reaction chamber 2 is controlled by the vacuum pumping system 7, and the pressures of the vacuum pumping system 7 and the gas flow controller 9 are controlled by the pressure controller 8. According to an embodiment of the present invention, a high-frequency voltage, such as an RF voltage of 13.56 MHz, is applied between the two electrode plates of the high-frequency plasma generator in the plasma generating region 1, so that glow emission is generated between the two electrodes. The group v gas is introduced from the main pipe 4 , and passes through the glow emitting region in a radial flow manner. Applying a high-frequency voltage to the two corresponding metal electrode plates. When the concentration of gas molecules between the two electrode plates is within a certain interval (required or standard for a specific interval), the surface of the electrode plate is bombarded by ions (I〇n The secondary electrons generated by the Bombardment will obtain sufficient energy under the electric field provided by the electrode plate, and the gas molecules between the electrode plates undergo so-called dissociation and ionization (I). 〇nization), and excitation (Excitati〇n) reactions, correspondingly generate ions, atoms, radicals, and more electrons to maintain the concentration balance between the particles in the ion, and deposit in the reaction chamber On the surface of the substrate. Taking the nitrogen in the group V element as an example, the reaction equation can be expressed as: e_· + N — N + + 2 e” The high-frequency plasma vapor deposition system has the general advantages of a general plasma vapor deposition system, such as work. Low temperature, low cost, low pollution, etc., can also independently control the stress of the deposited film 'without significant influence on other deposition characteristics' such as deposition rate and film uniformity. In addition, according to the invention • 10-200952207 In one embodiment, since the organic metal source of the v group element plasma generating region and the lanthanum element is arranged in a line, the effective utilization rate of the ν group element and the lanthanum element source can be improved. On the other hand, since the substrate can utilize the intermediate frequency Heating the heater to the reaction temperature is beneficial to the crystallinity and quality of the film layer. In the case of a solid-state light-emitting element such as a light-emitting diode or a laser diode, the film layer can be used as a buffer layer of the original to increase Crystallization quality of the elements. The technical content and technical features of the present invention have been disclosed above, but those skilled in the art may still make various kinds based on the teachings and disclosures of the present invention. The present invention is not limited to the embodiment of the invention, and should be construed as being limited to the scope of the invention. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a high frequency plasma vapor deposition system according to an embodiment of the present invention. [Main component symbol description] 1 plasma generation zone φ 3 porous tube 5 gas cabinet 7 vacuum pumping system 9 gas flow controller 2 Reaction chamber 4 main pipe 6 wafer transfer chamber 8 pressure controller 1 〇〇 high frequency plasma vapor deposition system -11 -