TW201222866A - Method of producing GaN-type compound semiconductor - Google Patents

Method of producing GaN-type compound semiconductor Download PDF

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TW201222866A
TW201222866A TW100108309A TW100108309A TW201222866A TW 201222866 A TW201222866 A TW 201222866A TW 100108309 A TW100108309 A TW 100108309A TW 100108309 A TW100108309 A TW 100108309A TW 201222866 A TW201222866 A TW 201222866A
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gas
ammonia
container
phase portion
liquid phase
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Yasuyuki Hoshino
Tatsuharu Arai
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Showa Denko Kk
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
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    • H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/301—AIII BV compounds, where A is Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • C23C16/303—Nitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/448—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for generating reactive gas streams, e.g. by evaporation or sublimation of precursor materials
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
    • C30B25/02—Epitaxial-layer growth
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • C30B29/403—AIII-nitrides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02367—Substrates
    • H01L21/0237—Materials
    • H01L21/0242—Crystalline insulating materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02538—Group 13/15 materials
    • H01L21/0254—Nitrides

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Abstract

The present invention provides a method of producing a GaN-type compound semiconductor having an excellent light-emitting property in a large scale. The present invention relates to a method of producing a GaN-type compound semiconductor, in which liquefied ammonia is filled in a charging container, in which one portion of the liquefied ammonia in the charging container is in a liquid phase, the other portion is in a gas phase and in which vapor of the liquefied ammonia is used. The liquefied ammonia in the charging container is continuously or intermittently cycled into the gas phase part or the liquid phase part within the charging container from the liquid phase part within the charging container by a pipe. One end of the pipe is communicated with the liquid phase part within the charging container, and the other end of the pipe is communicated with the gas phase part or the liquid phase part within the charging container. The liquefied ammonia is cycled and at least a part of the liquefied ammonia is vaporized by being heated in the cycle, and then the cycled liquefied ammonia is sent back to the other end of the pipe communicated with the gas phase part or the liquid phase part within the charging container. The vapor of the liquefied ammonia is supplied by a method which includes being sent back. The vapor of the ammonia is taken out from the charging container as a gas, and is introduced as a gas into a reaction chamber housing a substrate therein. A layer comprising a GaN-type compound semiconductor is formed on the substrate using the ammonia as a raw material.

Description

201222866 六、發明說明： 【發明所屬之技術領域】 本發明係關於使用氨之氮化鎵（GaN )系化合物半導 體之製造方法。 【先前技術】 以往，以氮化鎵系化合物半導體元件而言，已知有例 如第5圖所示者。在此所示之氮化鎵系化合物半導體元件 係在藍寶石基板1上依序層積：由屬於氮化鎵系化合物的 GaxAl^N (其中OSxS 1 )所構成的緩衝層2、屬於摻雜 有Si的η型包覆層的Si摻雜η型GaxAl^N層（η型包 覆層）3、屬於摻雜有Ζη且發光的活性層的Ζη摻雜 GaxAlhN層（活性層）4、屬於摻雜有Mg的ρ型包覆層 的Mg摻雜p型GaxAl^N層（p型包覆層）5，在η型包 覆層3及ρ型包覆層5設有電極6、7所構成。在此所示 之氮化鎵系化合物半導體元件係作爲例如藍色發光二極體 (藍色LED )加以利用。 第1圖係顯示製造上述氮化鎵系化合物半導體元件所 使用的製造裝置之例。在此所示之製造裝置係有機金屬化 學氣相沈積（MOCVD )裝置，具備有：收容藍寶石基板 的反應室11;支持該反應室11內的藍寶石基板的支持部 1 2 ;將被支持部1 2所支持的藍寶石基板加熱的加熱器1 3 :作爲有機金屬供給源的有機金屬用容器14、15;將由 該等容器1 4、1 5所被供給的有機金屬氣體導入至反應室 -5- 201222866 11內的有機金屬氣體導入管16、17;作爲氨氣供給源的 塡充容器18;將由該塡充容器18所被供給的氨氣導入至 反應室11內的導入管19;將反應室11內的氣體排出至 室外的排出管20 ; Si化合物用容器23 ; Zn化合物用容器 24 ; Mg化合物用容器25 ;及將由該等容器23、24、25 所被供給的化合物導入至反應室1 1內的導入管26、27、 28 ° 製造上述氮化鎵系化合物半導體元件所使用的磊晶晶 圓係使用上述製造裝置，如以下所示藉由MOCVD法予以 製作。在製造上述元件時，首先在將藍寶石基板1收容在 反應室11內之後，將收容在容器14內的有機鎵、及收容 在容器15內的有機鋁，使用管21、22而以H2氣體進行 起泡，將所得的有機鎵氣體、有機鋁氣體通過導入管16 、17而連同^氣體一起導入至反應室11內，同時，將 由塡充容器18所被供給的氨氣通過導入管19而導入至反 應室11內，以該等有機鎵氣體、有機鋁氣體、氨氣爲原 料’將由GaxAh.XN所構成的緩衝層2形成在藍寶石基板 1的表面。 接著’連同上述有機鎵、有機鋁、氨氣一起將由容器 23所被供給的Si化合物通過管26而供給至反應室1 1內 ’在緩衝層2上形成n型包覆層3。接著，連同上述有機 鎵、有機鋁、氨氣一起將由容器24所被供給的Ζη化合物 通過管27而供給至反應室n內，在η型包覆層3上形成 活性層4。接著，連同上述有機鎵、有機鋁、氨氣一起將 -6- 201222866 由容器25所被供給的Mg化合物通過管28而供給至反應 室11內，在活性層4上形成p型包覆層5。之後，將如 上述所製作的磊晶晶圓由反應室11取出，在n型及p型 包覆層3、5設置電極6、7而得上述氮化鎵系化合物半導 體元件。 在專利文獻1中係揭示作爲原料所使用的氨中所含有 的水分濃度會對氮化鎵系化合物半導體元件的亮度等發光 特性造成大幅影響。在該專利文獻1係揭示在塡充容器內 以至少一部分成爲液相的方式予以塡充，使用前述塡充容 器內的液相氨中的水分濃度以傅立葉轉換紅外光譜法（ FT-IR)進行測定爲〇.5volppm以下的氣作爲原料，在收 納基板的反應室內導入氣體狀態的氨，將由氮化鎵系化合 物半導體所構成的層形成在前述基板上的氮化鎵系化合物 半導體之製造方法。尤其，相對氨爲高沸點成分的含有水 分係大部分被分配在液相側，因此在將由塡充有液化氨的 容器直接在氣體狀態下所取出的氨氣導入至MOCVD裝置 的方法中係會發揮藉由單蒸發所致的精製效果，與將液化 氨在保持液體狀態下直接取出而在之後予以氣體化的氨氣 導入至MOCVD裝置的方法相比，可使用含有水分濃度低 的氨氣作爲原料，因此可製造亮度等發光特性優異的高品 質的氮化鎵系化合物半導體元件。 藍色LED係以低消耗電力獲得高亮度，而且壽命長 ，因此作爲省能量型液晶背光用光源或照明用光源的需求 急速擴大。目前在製造氮化鎵系化合物半導體元件的工廠 201222866 中，有效率且廉價地大量生產高性能的氮化鎵系化合物半 導體的技術不斷在開發，關於作爲主原料的氨氣的供給， 以大流量安定供給氨氣的新穎系統已被提出。在如氨般的 液化氣體中，若將塡充容器內的氣相部的氣體放出至外部 時，氣相部的壓力會減少，同時由液相部，液化氣體會蒸 發而被供給至氣相部。該蒸發所需的大部分熱量係由位於 塡充容器內的液相部的液化氣體所奪取，因此若在容器未 設置加熱手段時，液化氣體的溫度會降低，而變得無法因 蒸氣壓降低來維持所希望的氣體流量。雖然會有塡充容器 藉由由外氣所接收到的熱量來維持液化氣體的溫度的情形 ，但是其熱量係有限定。因此，爲了將塡充容器內的氨直 接在氣體狀態下取出，而以數100L/min的大流量安定供 給，藉由由塡充容器的外面使用加熱手段來對容器加熱， 以使液化氣體的蒸發量增加的方法已被提出幾種。若可使 可由氨塡充容器安定取出的平均1台的氣體流量增加，則 可使昂貴的氨氣供給設備的設置台數減少，而可大幅減低 氮化鎵系化合物半導體的製造成本。 例如’在專利文獻2係揭示一種對氨塡充容器噴吹溫 水淋洗而加溫，在恒溫裝置內以常溫維持氨塡充容器的方 法。此外’在專利文獻3係揭示一種以鹵素燈加熱器將塡 充有特殊材料氣體的容器加溫，而將容器內氣相壓力保持 爲一定的方法。在專利文獻4係揭示一種以I η加熱器將 塡充有液化氣體的容器加熱而將液化氣體氣化的方法。 但是，在如上述習知技術所示之將氨塡充容器直接加 -8 - 201222866 溫的方法中，基於確保安全的理由’必須將容器本身的溫 度常時抑制在40 °C左右以下，因此會有無法將較大熱量直 接施加於容器的問題。此外，施加於氨塡充容器表面的熱 係通過鐵等容器材料而被傳至容器內的液化氨’但是在殘 留於塡充容器內的液化氨量減少的狀態下，係會有傳熱效 率極端降低的問題。因此，在習知技術中，係僅可確保 300至500L/min左右的氨氣流量。 [先前技術文獻] [專利文獻] [專利文獻1]日本特開2000-9 1 23 5號公報 [專利文獻2]日本特開2003-2293 64號公報 [專利文獻3]日本特開2006- 1 83 863號公報 [專利文獻4]日本特開2008-95809號公報 【發明內容】 (發明所欲解決之課題） 在上述習知技術中，用以將氮化鎵系化合物半導體元 件大量生產所需的氨氣供給設備的設置台數明顯變多。如 此一來’所製造的氮化鎵系化合物半導體元件的發光特性 ，尤其亮度會易於變得不充分，而迫切期望一種以低成本 且確實大量生產發光特性優異者的技術。 本發明係鑑於上述情形而硏創者，目的在提供一種可 有效率地大量生量發光特性優異之氮化鎵系化合物半導體 201222866 的氮化鎵系化合物半導體之製造方法。 (解決課題之手段） 本發明人等發現在塡充有高純度液化氣體的容器，設 置其中一端與容器內的液相部相連通、另一端與容器內的 氣相部或液相部相連通的配管，使容器內的液化氣體由其 中一端的液相部朝另一端的氣相部或液相部連續性或間歇 性作循環，而且在循環中加熱，在使液化氣體的至少一部 分氣化後即送回至另一端的氣相部或液相部，藉此可進行 大流量氨氣的安定供給，可製造亮度等發光特性優異的氮 化鎵系化合物半導體元件，而完成本發明。 亦即本發明係摘要如以下所示。 (1) 一種氮化鎵系化合物半導體之製造方法，係使 用以一部分成爲液相的方式而被塡充在塡充容器的液化氨 的氣相部的氨，該氮化鎵系化合物半導體之製造方法之特 徵爲：前述氣相部的氨係藉由包含以下工程的方法予以供 給：藉由其中一端與前述塡充容器內的液相部相連通、另 一端與前述塡充容器內的氣相部或液相部相連通的配管， 使前述塡充容器內的液化氨由前述其中一端的液相部朝前 述另一端的氣相部或液相部連續性或間歇性作循環，而且 在循環中將前述液化氨加熱，藉此在使液化氨的至少一部 分氣化後，送回至前述另一端的氣相部或液相部，將由前 述塡充容器直接在氣體狀態下所取出的氨’在氣體狀態下 導入至收納有基板的反應室內，以前述氨爲原料’將由氮 -10- 201222866 化鎵系化合物半導體所構成之層形成在前述基板上。 (2) —種氮化鎵系化合物半導體之製造方法，係前 述配管的另一端與前述塡充容器內的氣相部相連通之如（ 1)所記載之氮化鎵系化合物半導體之製造方法，其特徵 爲：在藉由在前述塡充容器內設置區隔板，將前述塡充容 器內的前述氣相部分斷爲：與被抽出至外部的氣體相連通 的氣相部、及與前述配管的另一端相連通的氣相部的狀態 下，由前述氣相部抽出氣體來進行供給。 (3) 如（1)所記載之氮化鎵系化合物半導體之製造 方法，其中，前述配管的另一端與前述塡充容器內的液相 部相連通。 (發明之效果） 藉由本發明，可效率佳地大量生產亮度等發光特性優 異的氮化鎵系化合物半導體’且可兼顧製造良率的提升與 生產成本的減低。 【實施方式】 以下以使用第2圖所示之製造裝置’製造第5圖所示 之氮化鎵系化合物半導體元件的情形爲例’來說明本發明 之氮化鎵系化合物半導體之製造方法。 第2圖所示之製造裝置係有機金屬化學氣相沈積（ MOCVD )裝置，具備有：收容藍寶石基板的反應室11; 支持該反應室11內的藍寶石基板的支持部12;將被支持 -11 - 201222866 在支持部12的藍寶石基板加熱的加熱器13;作爲有機金 屬供給源的有機金屬用容器14、15:將由該等容器14、 15所被供給的有機金屬氣體導入至反應室11內的有機金 屬氣體導入管16、17:作爲氨氣供給源的氣體供給裝置 A ;將由氣體供給裝置A所被供給的氨氣導入至反應室11 內的氨氣導入管19;將反應室11內的氣體排出至室外的 排出管20 ; Si化合物用容器23 : Zn化合物用容器24 ; Mg化合物用容器25;及將由該等容器23、24、25所被 供給的化合物導入至反應室1 1內的導入管26、27、28。 在氣體的供給裝置A係配備有：塡充有液化氨的塡 充容器18;由塡充容器18使液化氨在氣相狀態下導出至 外部的導出配管48 ;及設在導出配管48中途的閥49。 塡充容器1 8中的液化氨係在液相及氣相的狀態下存 在。如第2圖所示，在塡充容器18係共存氨的液相部41 與氣相部42。 此外，在供給裝置A係配備有：與塡充容器1 8的液 相部41相連通的取出配管43;與氣相部42相連通的返 回配管44 ;將取出配管43及返回配管44相連結的循環 配管45、46;設在取出配管43與循環配管45之間的閥 40 :在循環配管45、46彼此的連結部中設在比塡充容器 18爲更低的位置的熱交換器47;及設在循環配管40與返 回配管4 4之間的閥5 0。 在第2圖所示之供給裝置A中’藉由取出配管43、 返回配管44及循環配管45、46，構成使塡充容器18內 -12- 201222866 的液化氨由液相部41朝氣相部42連續性或間歇性作循環 的配管。 塡充容器1 8內的氨係以至少一部分成爲液體的方式 予以塡充。液相氨的水分濃度較佳爲以例如傅立葉轉換紅 外光譜法（FT-IR)進行測定爲〇.5volppm以下。若液相 氨的水分濃度超過〇.5 volPPm ’氮化鎵系化合物半導體的 亮度等發光特性容易降低。 以塡充容器18而言’可使用第2圖所示之圓筒形塡 充容器18，尤其以使用在容器內面施行鍍敷處理或硏磨 處理者爲宜。此外’以該塡充容器18的材質而言’係可 使用猛鋼或錫合金。 導出配管48係其中一端被配置在塡充容器18內的氣 相部42，使塡充容器18內的液化氨在氣相狀態下取出至 外部。導出配管48的另一端係與CVD裝置的氣導入管 1 9相連接。 取出配管43係其中一端43a (配管的其中--端）被 配置在液相部41內’使液化氨在液相狀態下取出至塡充 容器18的外部。此外，藉由打開閥40、50，使液化氨在 循環配管45、46流通。 此外，返回配管44係其中一端（配管的另一端）被 配置在氣相部42內，將藉由熱交換器47所被加熱的液化 氨送回至塡充容器18。 閥40、50係爲了維持液化氨的純度而可使用氣密性 能良好、可抑制發生金屬微粒等雜質的隔膜閥。隔膜閥的 -13- 201222866201222866 VI. Description of the Invention: [Technical Field of the Invention] The present invention relates to a method for producing a gallium nitride (GaN)-based compound semiconductor using ammonia. [Prior Art] Conventionally, a gallium nitride-based compound semiconductor device has been known as shown in Fig. 5. The gallium nitride-based compound semiconductor device shown here is sequentially laminated on the sapphire substrate 1 : the buffer layer 2 composed of GaxAl^N (where OSxS 1 ) belonging to the gallium nitride-based compound is doped with a Si-doped ZnO-type GaxAl^N layer (n-type cladding layer) of the n-type cladding layer of Si, a Ζn-doped GaxAlhN layer (active layer) 4 belonging to an active layer doped with Ζη and emitting light, a Mg-doped p-type GaxAl N layer (p-type cladding layer) 5 mixed with a Mg p-type cladding layer, and electrodes 6 and 7 are provided in the n-type cladding layer 3 and the p-type cladding layer 5 . The gallium nitride-based compound semiconductor device shown here is used as, for example, a blue light-emitting diode (blue LED). Fig. 1 shows an example of a manufacturing apparatus used for manufacturing the above-described gallium nitride-based compound semiconductor device. The manufacturing apparatus shown here is an organic metal chemical vapor deposition (MOCVD) apparatus, comprising: a reaction chamber 11 for accommodating a sapphire substrate; a support portion 1 2 supporting the sapphire substrate in the reaction chamber 11; and a supported portion 1 2 supported sapphire substrate-heated heaters 13: organic metal containers 14 and 15 as organic metal supply sources; and organic metal gases supplied from the containers 14 and 15 are introduced into the reaction chamber-5- The organometallic gas introduction pipes 16 and 17 in 201222866 11; the sump container 18 as an ammonia gas supply source; the ammonia gas supplied from the sump container 18 is introduced into the introduction pipe 19 in the reaction chamber 11; The gas in 11 is discharged to the outdoor discharge pipe 20; the Si compound container 23; the Zn compound container 24; the Mg compound container 25; and the compound supplied from the containers 23, 24, 25 to the reaction chamber 1 The introduction tube 26, 27, and 28 in 1 The epitaxial wafer used for manufacturing the gallium nitride-based compound semiconductor device was produced by the MOCVD method as described below using the above-described manufacturing apparatus. In the production of the above-described element, first, after the sapphire substrate 1 is housed in the reaction chamber 11, the organic gallium contained in the container 14 and the organic aluminum contained in the container 15 are subjected to H2 gas using the tubes 21 and 22. The foaming is carried out, and the obtained organic gallium gas and organoaluminum gas are introduced into the reaction chamber 11 together with the gas through the introduction pipes 16 and 17, and the ammonia gas supplied from the charging container 18 is introduced through the introduction pipe 19. In the reaction chamber 11, a buffer layer 2 composed of GaxAh.XN is formed on the surface of the sapphire substrate 1 using the organic gallium gas, the organoaluminum gas, and the ammonia gas as raw materials. Then, the Si compound supplied from the container 23 is supplied into the reaction chamber 1 through the tube 26 together with the above-mentioned organogallium, organoaluminum, and ammonia gas. The n-type cladding layer 3 is formed on the buffer layer 2. Next, the Ζn compound supplied from the container 24 is supplied into the reaction chamber n through the tube 27 together with the above-mentioned organogallium, organoaluminum, and ammonia gas, and the active layer 4 is formed on the n-type cladding layer 3. Next, together with the above-mentioned organogallium, organoaluminum, and ammonia gas, the Mg compound supplied from the container 25 to the -6-201222866 is supplied into the reaction chamber 11 through the tube 28, and the p-type cladding layer 5 is formed on the active layer 4. . Thereafter, the epitaxial wafer prepared as described above is taken out from the reaction chamber 11, and the electrodes 6 and 7 are provided on the n-type and p-type cladding layers 3 and 5 to obtain the gallium nitride-based compound semiconductor element. In Patent Document 1, it is disclosed that the concentration of water contained in the ammonia used as a raw material greatly affects the light-emitting characteristics such as the brightness of the gallium nitride-based compound semiconductor device. Patent Document 1 discloses that the at least one portion of the retort container is filled with a liquid phase, and the water concentration in the liquid phase ammonia in the retort container is subjected to Fourier transform infrared spectroscopy (FT-IR). A method of producing a gallium nitride-based compound semiconductor in which a gas in a gaseous state is introduced into a reaction chamber in which a substrate is accommodated, and a layer made of a gallium nitride-based compound semiconductor is formed on the substrate is used as a raw material. In particular, since most of the water-containing phase in which ammonia is a high-boiling component is distributed on the liquid phase side, the method of introducing ammonia gas taken out from a vessel filled with liquefied ammonia directly into a gas state into an MOCVD apparatus is By using the purification effect by single evaporation, it is possible to use ammonia gas having a low water concentration as a method of introducing ammonia gas which is directly taken out of the liquefied ammonia in a liquid state and then gasified into the MOCVD apparatus. Since the raw material is used, it is possible to produce a high-quality gallium nitride-based compound semiconductor element having excellent light-emitting characteristics such as brightness. The blue LED is high in brightness and low in power consumption, and has a long life. Therefore, the demand for a light source for a power-saving liquid crystal backlight or a light source for illumination has rapidly increased. At present, in the factory 201222866 for manufacturing a gallium nitride-based compound semiconductor device, a technology for mass-producing a high-performance gallium nitride-based compound semiconductor in an efficient and inexpensive manner is being developed, and a large flow rate is required for supply of ammonia gas as a main raw material. A novel system for the stabilization of ammonia gas has been proposed. In the liquefied gas such as ammonia, when the gas in the gas phase portion in the sump container is released to the outside, the pressure in the gas phase portion is reduced, and at the same time, the liquefied gas is evaporated from the liquid phase portion and supplied to the gas phase. unit. Most of the heat required for the evaporation is taken up by the liquefied gas in the liquid phase portion in the charging container. Therefore, if the heating means is not provided in the container, the temperature of the liquefied gas is lowered, and the vapor pressure is not lowered. To maintain the desired gas flow. Although there is a case where the retort container maintains the temperature of the liquefied gas by the heat received by the outside air, the heat is limited. Therefore, in order to take out the ammonia in the sump container directly in a gaseous state, the supply is stabilized at a large flow rate of several hundred L/min, and the container is heated by heating means from the outside of the sputum container to make the liquefied gas Several methods of increasing the amount of evaporation have been proposed. If the average gas flow rate of one of the ammonia-filled containers can be increased, the number of expensive ammonia gas supply devices can be reduced, and the manufacturing cost of the gallium nitride-based compound semiconductor can be greatly reduced. For example, Patent Document 2 discloses a method of heating an ammonia-filled container by spraying with warm water and rinsing it, and maintaining the ammonia-filled container at a normal temperature in a thermostat. Further, Patent Document 3 discloses a method of heating a container filled with a special material gas by a halogen lamp heater to maintain a constant gas phase pressure in the container. Patent Document 4 discloses a method of heating a container filled with a liquefied gas by an I η heater to vaporize the liquefied gas. However, in the method of directly adding the ammonia crucible container to the temperature of -8 - 201222866 as shown in the above-mentioned prior art, based on the reason for ensuring safety, the temperature of the container itself must be constantly suppressed to about 40 ° C or less. There is a problem that it is impossible to apply a large amount of heat directly to the container. Further, the heat applied to the surface of the ammonia-filled container is transferred to the liquefied ammonia in the container by a container material such as iron. However, in the state where the amount of liquefied ammonia remaining in the charging container is reduced, there is heat transfer efficiency. Extremely low problem. Therefore, in the prior art, it is only possible to ensure an ammonia gas flow rate of about 300 to 500 L/min. [PRIOR ART DOCUMENT] [Patent Document 1] Japanese Laid-Open Patent Publication No. 2000-9 1-23 (Patent Document 2) Japanese Laid-Open Patent Publication No. 2003-2293 No. [Patent Document 4] Japanese Unexamined Patent Publication (KOKAI) No. JP-A No. 2008-95809 (Invention) The above-mentioned prior art is required for mass production of a gallium nitride-based compound semiconductor device. The number of installed ammonia supply devices has significantly increased. As a result, the light-emitting characteristics of the gallium nitride-based compound semiconductor device produced by the above-mentioned, in particular, the brightness tends to be insufficient, and a technique which is excellent in light-emitting characteristics at a low cost and in a large amount is desired. The present invention has been made in view of the above circumstances, and an object of the invention is to provide a method for producing a gallium nitride-based compound semiconductor which can efficiently and efficiently produce a gallium nitride-based compound semiconductor 201222866 having excellent light-emitting characteristics. (Means for Solving the Problem) The present inventors have found that a container filled with a high-purity liquefied gas is provided with one end communicating with a liquid phase portion in the container and the other end communicating with a gas phase portion or a liquid phase portion in the container. The piping allows the liquefied gas in the vessel to be continuously or intermittently circulated from the liquid phase portion at one end toward the gas phase portion or the liquid phase portion at the other end, and is heated in the circulation to vaporize at least a portion of the liquefied gas. Then, it is returned to the gas phase portion or the liquid phase portion at the other end, whereby stable supply of a large-flow ammonia gas can be performed, and a gallium nitride-based compound semiconductor device having excellent light-emitting characteristics such as luminance can be produced, and the present invention has been completed. That is, the summary of the present invention is as follows. (1) A method for producing a gallium nitride-based compound semiconductor, which is a method of producing a gallium nitride-based compound semiconductor by using ammonia which is charged in a gas phase portion of liquefied ammonia in a retort container in a part of a liquid phase. The method is characterized in that the ammonia in the gas phase portion is supplied by a method comprising the following steps: one end is in communication with the liquid phase portion in the charging vessel, and the other end is in the gas phase in the charging vessel a pipe in which the liquid phase is connected to the liquid phase, and the liquefied ammonia in the charging vessel is continuously or intermittently circulated from the liquid phase portion of the one end portion toward the gas phase portion or the liquid phase portion of the other end portion, and is circulated. The liquefied ammonia is heated to neutralize at least a portion of the liquefied ammonia, and then returned to the gas phase portion or the liquid phase portion at the other end, and the ammonia taken out from the above-mentioned sump container in a gaseous state directly The gas is introduced into the reaction chamber in which the substrate is housed, and a layer made of a nitrogen-douger-10-201222866 gallium-based compound semiconductor is formed on the substrate using the ammonia as a raw material. (2) A method for producing a gallium nitride-based compound semiconductor, wherein the other end of the pipe is in communication with a gas phase portion in the charging container, and the method for producing the gallium nitride-based compound semiconductor according to (1) The gas phase portion in the charging container is broken into a gas phase portion that communicates with the gas extracted to the outside, and the foregoing, by providing a partition plate in the charging container. In a state in which the other end of the pipe is in the gas phase portion, the gas is extracted from the gas phase portion and supplied. (3) The method for producing a gallium nitride-based compound semiconductor according to the above aspect, wherein the other end of the pipe is in communication with a liquid phase portion in the retort container. (Effect of the Invention) According to the present invention, a gallium nitride-based compound semiconductor ′ having excellent light-emitting characteristics such as brightness can be efficiently produced in a large amount, and both the improvement in production yield and the reduction in production cost can be achieved. [Embodiment] Hereinafter, a method for producing a gallium nitride-based compound semiconductor of the present invention will be described by taking a case where the gallium nitride-based compound semiconductor device shown in Fig. 5 is produced by using the manufacturing apparatus shown in Fig. 2 as an example. The manufacturing apparatus shown in Fig. 2 is an organic metal chemical vapor deposition (MOCVD) apparatus, and includes a reaction chamber 11 for accommodating a sapphire substrate, and a support portion 12 for supporting the sapphire substrate in the reaction chamber 11; - 201222866 The heater 13 heated by the sapphire substrate of the support portion 12; the organic metal containers 14 and 15 serving as the organic metal supply source: the organic metal gas supplied from the containers 14 and 15 is introduced into the reaction chamber 11 The organic metal gas introduction pipes 16 and 17 are: a gas supply device A as an ammonia gas supply source; the ammonia gas supplied from the gas supply device A is introduced into the ammonia gas introduction pipe 19 in the reaction chamber 11; The gas discharge to the outdoor discharge pipe 20; the Si compound container 23: the Zn compound container 24; the Mg compound container 25; and the compound supplied from the containers 23, 24, 25 into the reaction chamber 1 1 The tubes 26, 27, 28 are introduced. The gas supply device A is equipped with a charging container 18 filled with liquefied ammonia, a lead-out pipe 48 for discharging the liquefied ammonia to the outside in a gas phase state by the charging container 18, and a middle of the lead-out pipe 48. Valve 49. The liquefied ammonia in the sump container 18 is present in the liquid phase and the gas phase. As shown in Fig. 2, in the charging container 18, the liquid phase portion 41 and the gas phase portion 42 in which ammonia is present are present. Further, the supply device A is provided with a take-out pipe 43 that communicates with the liquid phase portion 41 of the sump container 18, a return pipe 44 that communicates with the gas phase portion 42, and a take-up pipe 43 and a return pipe 44 that are connected. The circulation pipes 45 and 46; the valve 40 provided between the take-out pipe 43 and the circulation pipe 45: the heat exchanger 47 provided at a lower position than the sump container 18 in the connection portion between the circulation pipes 45 and 46 And a valve 50 provided between the circulation pipe 40 and the return pipe 44. In the supply device A shown in Fig. 2, by taking out the pipe 43, the return pipe 44, and the circulation pipes 45 and 46, the liquefied ammonia in the retort container 18-12-22222 is formed from the liquid phase portion 41 toward the gas phase portion. 42 continuous or intermittent piping for circulation. The ammonia in the retort container 18 is charged so that at least a part of the ammonia becomes a liquid. The water concentration of the liquid phase ammonia is preferably 〇. 5 volppm or less as measured by, for example, Fourier transform infrared spectroscopy (FT-IR). When the water concentration of the liquid ammonia exceeds 〇.5 volppm, the light-emitting characteristics such as the brightness of the gallium nitride-based compound semiconductor are liable to lower. In the case of the tamping container 18, the cylindrical retort container 18 shown in Fig. 2 can be used, and it is particularly preferable to use a plating treatment or a honing treatment on the inner surface of the container. Further, in the case of the material of the sump container 18, it is possible to use a steel or a tin alloy. The lead-out pipe 48 is a gas phase portion 42 in which one end is disposed in the sump container 18, and the liquefied ammonia in the sump container 18 is taken out to the outside in a gas phase state. The other end of the lead-out pipe 48 is connected to the gas introduction pipe 19 of the CVD apparatus. The take-out pipe 43 is one end 43a (the end of the pipe is disposed in the liquid phase portion 41), and the liquefied ammonia is taken out to the outside of the sump container 18 in a liquid phase state. Further, by opening the valves 40 and 50, the liquefied ammonia is circulated through the circulation pipes 45 and 46. Further, one end of the return pipe 44 (the other end of the pipe) is disposed in the gas phase portion 42, and the liquefied ammonia heated by the heat exchanger 47 is returned to the sump container 18. In order to maintain the purity of liquefied ammonia, the valves 40 and 50 can use a diaphragm valve which is excellent in airtightness and can suppress generation of impurities such as metal fine particles. Diaphragm valve -13- 201222866

Cv値（表示閥的流量特性的値）大部分小 形閥等，在本發明之方法中，係以選擇Cv 的閥爲佳，以選擇Cv値爲0.5以上的閥爲 Cv値爲未達0.3的閥時，閥的流路中的壓 而抑制液化氨循環，因此會有難以維持液化 氣壓的情形。 熱交換器47係將在液相狀態下流通的 使至少其一部分或全部氣化。熱交換器4 7 爲了進行與外氣的熱交換而具有多數傳熱片 溫水等熱媒來進行熱交換者等。 熱交換器47之中，以液化氨所接觸的 言，以選擇抗蝕性優異的不銹鋼爲佳。此外 微粒等雜質發生的目的下，以表面粗糙度以 示平滑度的値）計爲25 μηι以下爲佳。 以熱交換器47而言，可使用電氣加熱 等熱媒的熱交換器等，但是以使用高頻感應 。被使用在製造半導體等之用的高純度液化 性，因此使用加熱器本身未被加熱的高頻感 藉此可在萬一漏洩時立即緊急停止。此外’ ，因此可抑制運轉成本並且使裝置精簡化。 在第2圖之氣體供給裝置Α中，若將 配管48的閥49開放時，由塡充容器18直 下取出液化氨，且對CVD裝置的反應室1 1 於組件閥或球 値爲〇. 3以上 更佳。若使用 力損失會影響 氨的溫度及蒸 液化氨加熱， 係可任意選擇 者、或者藉由 部位的材質而 ，在抑制金屬 Rmax値（表 器、採用溫水 加熱裝置爲佳 氨係呈現強毒 應加熱裝置， 由於熱效率高 被設置在導出 接在氣體狀態 供給前述氣體 -14- 201222866 此時，塡充容器1 8內的液化氨蒸發所需熱量由液相 部4 1所被奪取的結果，液相部4 1的溫度會降低。在此， 若閥40及閥50呈開放，藉由虹吸原理，由與液相部41 相連通的取出配管43,塡充容器18內的液化氨在保持液 相的狀態下通過循環配管45而流入至位於比塡充容器1 爲更低位置的熱交換器47而被加熱。以熱交換器47所被 加溫的液化氨係一部分或全部發生氣化，透過循環配管 46而由返回配管44被送回至塡充容器18內的氣相部42 。此時，藉由根據液化氨的密度差的自然循環，來維持塡 充容器18內的液化氨的溫度及蒸氣壓。將閥49開放而連 續供給氣體狀的氨時，液化氨係被連續性作循環。另一方 面，氣體狀的氨的供給間歇性進行時，液化氨的循環係成 爲間歇性。 如上所示，由於防止液相部4 1溫度降低，因此在塡 充容器1 8內，液相部4 1的液化氨會氣化而安定形成氣相 部42，可將氣體狀的氨安定地供給至外部。 接著，說明氣體供給裝置的變形例。 在第3圖中顯示其他例之氣體供給裝置B。第3圖所 示之氣體供給裝置B的構成要素之中，與第2圖所示之氣 體供給裝置A的構成要素爲相同的構成要素係標註相同 的元件符號且省略其說明。 在第3圖所例示的氣體供給裝置B係在塡充容器i 8 內的氣相部42設置有區隔板53。區隔板53係被配置在 返回配管44與導出配管48之間，而且其下端部被浸漬在 -15- 201222866 液相部41。藉由該區隔板53，氣相部42係被分斷 管側氣相部42a與配管側氣相部42b。在此，導出 相部42a係與被抽出至外部的氣體相連通的氣相部 側氣相部42b係與返回配管46的其中一端（配管 端）相連通的氣相部。 在第3圖所示之供給裝置b中，藉由返回配管 被送回至塡充容器18內的氨係在藉由導出配管48 給至外部之前確實經由液相部4 1。在氨經由液相部 ’氨中所含有的水分等高沸點成分容易殘留在液牛! °經由液相部4 1的氨係經由導出管側氣相部4 2 a 水分等高沸點成分的含有量較少的高純度氣體而被 接著，說明氣體供給裝置的其他變形例。 在第4圖中顯示其他例的供給裝置c。第4圖 氣體供給裝置C的構成要素之中，與第2圖所示之 給裝置A的構成要素爲相同的構成要素係標註相 件符號且省略其說明。 在第4圖所例示的供給裝置c中，配備有與液 相連通的返回配管51來取代第2圖的返回配管44 熱交換器47所被加熱的液化氨係透過返回配管51 至塡充容器1 8內的液相部4 1。 在第4圖所例示的供給裝置中，取出配管43 —端43 a與返回配管51的其中一端51a的距離 100mm以上爲佳。與液相部41相連通的各配管 的其中一端彼此的距離未達l〇〇mm時，液化氨的 爲導出 管側氣 ，配管 的另一 f 44而 而被供 ;41時 目部41 ，作爲 取出。 所示之 氣體供 同的元 相部3 。藉由 而返回 的其中 以分離 43、51 密度差 -16- 201222866 會變小而抑制循環，會有難以維持液化氨的溫度及蒸氣壓 的情形。 此外，在返回配管5 1設有閥5 2。閥5 2係使用與第2 圖的閥5 0爲相同者。 在第4圖所示之供給裝置C中，若將被設置在導出配 管48的閥49開放時，由塡充容器18直接在氣體狀態下 取出氨等氣體，對CVD裝置的反應室11供給氣體。 此時，塡充容器18內的液化氨蒸發所需熱量由液相 部41被奪取，液相部41的溫度會降低。因此，若閥40 及閥50呈開放，藉由虹吸原理，由與液相部41相連通的 取出配管43，塡充容器18內的液化氨通過循環配管45 而流入至熱交換器47。以熱交換器47所被加溫的氨係通 過循環配管46而由返回配管44被送回至塡充容器18內 的液相部41。藉由根據液化氨的密度差的自然循環，來 維持塡充容器18內的氨的溫度及蒸氣壓。 藉由第4圖所示之供給裝置C，藉由配管51而被送 回至塡充容器18內的氨被直接送回至液相部41，因此在 藉由導出配管48而被供給至外部之前，確實會經由液相 部41。藉此，當氨經由液相部41時，氨中所含有的水分 等高沸點成分容易殘留在液相部4 1。經由液相部4 1的氨 係經由氣相部42，作爲水分等高沸點成分的含有量較少 的氣體而被取出。 此外’在第2圖至第4圖所示之例中，以塡充在塡充 容器1的液化氨而言，例如可藉由使粗製氨與合成沸石、 -17- 201222866 氧化锆等吸附材相接觸而使粗製氨中的水分吸附在該吸附 材，或進行精密蒸餾，將吸附或蒸餾處理後的氨塡充在塡 充容器18的方法來製造。此時，在將上述吸附或蒸餾處 理後的氨塡充至塡充容器18爲止的各工程中’以採取儘 量使水分不會混入，而且預先以經精製的氨來洗淨塡充容 器、或進行真空抽吸等方策爲宜。液相氨中的水分濃度係 以藉由例如傅立葉轉換紅外光譜法（FT-IR )所爲之測定 爲O.Olvolppm以上、0.5volppm以下爲佳。 在本實施形態之製造方法中，使用由氣體供給裝置A 、B、C所被供給的氨，如以下所示製造氮化鎵系化合物 半導體。 例如第2圖所示，首先，將藍寶石基板1收容在反應 室11內且支持在支持部12’將反應室11進行真空排氣 後，使用加熱器1 3將藍寶石基板1加熱至較佳爲約400°c 〇 接著，將收容在容器14內的三甲基鎵（TMGa)等有 機鎵、及收容在容器15內的三甲基鋁（TMA1)等有機鋁 ，使用管2 1、22而以H2氣體進行起泡’將所得的有機鎵 氣體、有機鋁氣體通過導入管16、17而連同1^2氣體一起 導入至反應室11內◊同時，將由塡充容器18所被供給的 氨氣，通過導入管19而導入至反應室11內’將該等有機 鎵氣體、有機鋁氣體、氨氣作爲原料而將由0^Α1ι·χΝ所 構成的緩衝層2形成在藍寶石基板1的表面。在供給氨氣 時，打開閥40、50 ’藉由熱交換器47將液體氨加熱，俾 -18· 201222866 以不會發生液相部的溫度降低。以下供給氨氣時係進行相 同的操作。 接著’將基板1的溫度升溫至約1 1 5 0 °c，連同上述有 機鎵、有機鋁、氨氣一起將由容器23所被供給的矽烷等 Si化合物通過管26而供給至反應室11內，而在緩衝層2 上形成η型包覆層3。 接著，連同上述有機鎵、有機鋁、氨氣一起將由容器 24所被供給的二甲基鋅等Ζη化合物通過管27而供給至 反應室11內，而在η型包覆層3上形成活性層4。 接著’連同上述有機鎵、有機鋁、氨氣一起將由容器 25所被供給的雙環戊二烯鎂等Mg化合物通過管28而供 給至反應室1 1內，而在活性層4上形成p型包覆層5。 之後，由反應室1 1取出如上所述所製作的磊晶晶圓 ，在η型及p型包覆層3、5上設置電極6、7而得上述氮 化鎵系化合物半導體元件。 藉由上述實施形態之製造方法，所得的氮化鎵系化合 物半導體元件成爲亮度等發光特性優異者。因此，可達成 製造良率的提升》 藉由上述製造方法所製作的氮化鎵系化合物半導體元 件之所以成爲發光特性優異者，係因爲藉由將上述氨的水 分濃度形成爲上述範圍，可將混入在以該氨爲原料所形成 的η型及ρ型包覆層3、5、活性層4內的氧量抑制爲較 低，可防止由該等氮化鎵系化合物半導體所構成的層的結 晶性發生劣化的情形之故。 -19- 201222866 此外，在氣體供給裝置A、B、C中’由於防止液相 部41的溫度降低，因此在塡充容器18內，液相部41的 液化氨會氣化而安定形成氣相部42，可將氣體狀的氨安 定供給至外部，藉此可大量生產氮化鎵系化合物半導體元 件。 此外，在循環配管45、46的中途設置熱交換器47’ 在塡充容器18的外部對液化氨加熱’藉此可對液化氨有 效率地進行熱傳達。此外，取出液相狀態的液化氨而加熱 ，藉此在熱交換前後的液化氨密度變化會變大，液化氨的 膨脹成爲驅動源而可使液化氨自然循環，變得不需要泵等 動力源。循環泵等係成爲油或外部空氣的混入源，因此藉 由該方法，可避免因異物混入至液化氨所造成的污染而可 維持純度。藉此達成氮化鎵系化合物半導體元件的製造設 備的簡化。 藉由使用第2圖至第4圖所示之供給裝置A、B、C 的氨的供給方法，一面將高純度的氨氣，尤其將含有水分 濃度維持在低濃度，一面可進行以習知技術並無法對應的 大流量的安定供給，因此可大量生產高品質的氮化鎵系化 合物半導體元件。 在上述實施形態中，係例示以上述氨爲原料而形成以 GaxAh.xN爲主成分的η型及p型包覆層3、5、活性層4 的方法’但是本發明並非侷限於此，可將上述氨使用在製 造將由 GaN、InGaN、InGaAIN、AlGaN等氮化鎵系化合 物所構成之層形成在基板上的氮化鎵系化合物半導體。 -20- 201222866 [實施例] 以下顯示具體例，詳加說明本發明 (實施例1 ) 使用第2圖所示之供給裝置A，如 出實驗。使用第2圖所示之圓柱形狀且 充有980kg之液化氨的塡充容器18。 置放於室溫（24°C )條件下來加以使用 使用具備有多數傳熱片者，將氨氣加熱 溫度。氨氣係由第2圖所示之閥49直 出，在閥49的近旁設置未圖示的壓力 充容器18內的氣相氨的壓力變化。 接著，使氣體取出流量由300slm( 階段性增加至800slm (每隔一小時增j] 出使氣相部的壓力不會降低而可供給的 結果可知，即使在使氣體取出流量 800slm的大流量的情形下亦同樣地， 0.7MPa-G，可安定地連續供給氨氣。 (比較例1 ) 除了關閉第2圖所示之閥40及50 圍內常時溫度調整後的溫水浴槽浸漬塡 下供給氨氣以外，係與實施例1同樣地 驗。 下所示進行氨氣取 容量爲I 8 6 0 L、塡 此外’塡充容器係 ，熱交換器4 7係 至常溫或其以上的 接在氣體狀態下取 測定器，來測定塡 〔standard 1/min.) 口 1 0 0 s 1 m )，調查 氨氣流量。 由 300slm增加至 氛氣壓力係維持 ，在3 7〜3 9 t：的範 充容器1 8的狀態 進行氨氣的取出實 .21 - 201222866 結果，在使氣體取出流量由300slm增加至400slm的 情形下發現氨氣的壓力降低，接著在增加至500slm的情 形下，氨氣壓力降低至未達〇.4MPa-G，而變得無法連續 供給氛氣。 (實施例2 ) 使用第2圖所示之製造裝置來製作第6圖所示之氮化 鎵系化合物半導體元件。以氨的供給裝置A而言，使用 第2圖所示之圓筒形狀且容量爲1860L，塡充有980kg的 液化氨的塡充容器1 8。塡充容器1 8係置放在室溫（24°C )條件下加以使用，熱交換器47係使用設置有多數傳熱 片者。氨氣係由第2圖所示之閥49直接在氣體狀態下取 出，將氣體取出流量在800slm( standard Ι/min.)成爲一 定而連續取出24小時，將其一部分供給至第1圖所示之 反應室1 1，將剩餘排出至吹氣線（未圖示）。連續24小 時取出氨氣後的液化氨的剩餘重量爲105kg。同時，在氨 氣導入管部設置壓力測定器（未圖示），來測定出塡充容 器18內的氨氣的壓力變化。 藍寶石基板1係使用爲圓形、直徑50mm、厚度 0.3mm，且將表面進行鏡面硏磨者。首先，使以經有機洗 淨的c面爲主面的單結晶的上述藍寶石基板1支持在反應 室11內的支持部。接著，在將反應室11的壓力減壓至 lxl(T3t〇rr以下之後，將H2導入至反應室內而使反應室 1 1內的壓力恢復到大氣壓（760torr )。接著，一面將H2 -22- 201222866 以 5slm( standard l/min.)導入至反應室內，一面將基板 1的溫度設爲1 1 5 0 °C而將藍寶石基板1進行熱清洗。 接著使基板溫度降低至4 5 0 °C，將由Η 2及N 2所構成 的載子氣體以6slm、將氨氣以isim、將含有三甲基鋁（ TMA1)蒸氣的 H2 以 20sccm( standard cc/min.)供給 1.5 分鐘至反應室內。此時’ TMA1的莫耳供給量爲3.8χ 1 0_5mol/min。在該過程中，在藍寶石基板1上形成有由 A1N所構成之厚度約20nm的緩衝層31。在供給氨氣時， 打開閥40、50 ’藉由熱交換器47將液體氨加熱，使得不 會發生液相部的溫度降低。以下，供給氨氣時係進行相同 的操作。 接著，停止供給TMA1，將藍寶石基板1的溫度升溫 至1 l〇〇°C且保持在該溫度。接著，將上述載子氣體以 6slm、將氣氣以2.5slm、將以H2稀釋成lvolppm的二砂 烷（Si2H6)以 5sccm、將含有三甲基鎵（TMGa)蒸氣的 H2以15sccm供給90分鐘至反應室內。此時，TMGa的莫 耳供給量爲5.8xl(T5m〇l/mirv。在該過程中形成有膜厚約 1.5μιη、載子濃度約3xl017/cm3的η型GaN層32。 接著，停止供給TMGa之後，將藍寶石基板1的溫度 降溫至85 0 °C而保持在該溫度。接著，將載子氣體以6slm 、將氨氣以2.5slm、將以氫稀釋成l〇〇v〇lppm的二乙基鋅 (DEZn )以 lOsccm、將以 H2 稀釋成 lvolppm 的 Si2H6 以 lOsccm、將含有TMGa蒸氣的H2以5sccm、將含有三甲 基銦（TMIn)蒸氣的H2以13sccm供給15分鐘至反應室 -23- 201222866 內。此時，TMGa及TMIn的莫耳供給量分別爲1.9χ l(T5mol/min及7.6xl0_6mol/min。在該過程中形成有含有 膜厚約100nm的Si及Zn雜質的InGaN活性層33。 接著，在將藍寶石基板1的溫度保持在與上述InGaN 活性層形成時爲相同的溫度的情況下直接停止供給TMIn ，將載子氣體以6slm、將氨氣以4.5slm、將含有TMGa 蒸氣的H2以1 seem供給2分鐘至反應室內。此時，TMGa 的莫耳供給量爲3.8xl0_6mol/min。在該過程中形成有膜 厚約3nm的GaN層34。 接著，停止供給TMGa，將藍寶石基板1的溫度升溫 至1150°C且保持在該溫度，將載子氣體以6slm、將氨氣 以 3slm、將含有TMA1蒸氣的 H2以 4.3sccm、將含有 TMGa蒸氣的H2以5sccm、將含有雙環戊二烯鎂（Cp2Mg )蒸氣的H2以135sccm供給10分鐘至反應室內。此時， TMA1、TMGa、及Cp2Mg的莫耳供給量分S!J爲2.3χ 1 (T6mol/min、1 · 5 X 1 (K5mol/min、及 1 · 1 χ 1 0-4mol/min。在 該過程中形成有膜厚約70nm、載子濃度約lxl〇17/cm3的 p 型 AlGaN 層 35。 接著，停止供給TMA1、TMGa及Cp2Mg，將藍寶石 基板1的溫度降溫至1 1 oo°c而保持在該溫度。接著，將載 子氣體以6slm、將氨氣以2.5slm、將含有TMGa蒸氣的 H2以15sccm、將含有Cp2Mg蒸氣的H2以135sccm供給 10分鐘至反應室內。此時，TMGa及Cp2Mg的莫耳供給 量爲 5.7xl(T5mol/min 及 l.lxl(T4mol/miii。在該過程中形 -24- 201222866 成有膜厚約300nm、載子濃度約3xl〇17/cm3的p型GaN 層3 6 〇 將如上述所得的磊晶晶圓由反應室11取出’使用周 知的元件化技術而在η型GaN層32及p型GaN層36分 別設置η電極3 7及p電極3 8而得第6圖所示之元件。在 所得元件的上述η電極3 7、ρ電極3 8間通過順向的電流 2 0 m A，測定出使該元件發光時的亮度。將結果顯示於表1 〇 此外，將塡充容器內的液相部41的氨中的水分濃度 (試驗開始前）及由塡充容器18所取出的氨氣中的水分 濃度的値一倂顯示於表1。液相部的氨的水分濃度係將塡 充容器18內的液化氨作取樣而使其氣化，使用FT-IR ( NICOLET公司製，MAGNA5 60 )來測定出所得的氣體中 的水分量。此外，由塡充容器18所取出的氨氣中的水分 濃度係以與上述相同的方法來測定所取樣的氣體中的水分 量。 此外，同時所測定出的塡充容器18內的氨氣壓力的 値亦一倂顯不於表1。 (實施例3 ) 以氨的墳充容器18而言，除了使用第3圖所示者以 外，係與實施例2同樣地製作出氮化鎵系化合物半導體元 件。將該等氮化鎵系化合物半導體元件發光時的亮度、由 塡充容器所取出的氨氣中的水分濃度、及塡充容器18內 -25- 201222866 的氨氣壓力一倂顯示於表1。 (實施例4) 以所使用的氨的塡充容器18而言，除了使用第 所示之形狀者以外，係與實施例2同樣地製作出氮{! 化合物半導體元件。將該等氮化鎵系化合物半導體3 光時的亮度、由塡充容器所取出的氨氣中的水分濃g 塡充容器18內的氨氣壓力一倂顯示於表1。 (比較例2) 除了關閉第2圖所示之閥40及50之後，在37 -的範圍內常時溫度調整後的溫水浴槽浸漬塡充容器 狀態下供給氨氣以外，嘗試與實施例2同樣地製作囊 系化合物半導體元件。 但是，若將氨氣的取出流量設爲800slm時，在 時以內發生急劇的壓力降低，而無法安定供給氨氣， 法製造氮化鎵系化合物半導體元件。 (比較例3) 由氨的塡充容器18直接取出液化氨，使用習矢丨 發器將所取出的液化氨進行氣化而形成爲氨氣以外， 實施例2同樣地製作氮化鎵系化合物半導體元件。 將所製作出的氮化鎵系化合物半導體元件發光闲 度、由塡充容器所取出的氨氣中的水分濃度、及塡货 4圖 鎵系 件發 、及 -39〇C 18的 ，化鎵 1小 而無 的蒸 係與 的亮 容器 -26- 201222866 18內的氨氣壓力~倂顯系於表^ 在該方法中，氨氣的大量供給雖爲可能，但是被供給 含有大量水分等高沸點成分的氨氣，因此無法製造出亮度 超過1.5cd的發光特性優異的氮化鎵系化合物半導體。 -27- 201222866 [表i] 液相中水分濃度 氣相中水分濃度 亮度 壓力 (volppm) (volppm) (cd) (MPa-G) &lt;0.01 0.6 經過吹出8h時 經過吹出8h時 實施例2 0.01 (試驗開始前） &lt;0.01 經過吹出16h時 2.8 0.6 經過吹出16h時 &lt;0.01 0.6 經過吹出24h時 經過吹出24h時 &lt;0.01 0.6 經過吹出8h時 經過吹出8h時 實施例3 0.01 (試驗開始前） &lt;0.01 經過吹出16h時 3.0 0.6 經過吹出16h時 &lt;0.01 0.6 經過吹出24h時 經過吹出24h時 &lt;0.01 0.6 經過吹出8h時 經過吹出8h時 實施例4 0.01 (試驗開始前） &lt;0.01 經過吹出16h時 3.0 0.6 經過吹出16h時 &lt;0.01 0.6 經過吹出24h時 經過吹出24h時 比較例2 0.01 (試驗開始前） 未測定 (無法供給氣體） 無法製作 (無法供給氣體） &lt;0.4 經過吹出lh時 (無法供給氣體） 0.01 0.6 經過吹出8h時 經過吹出8h時 比較例3 0.01 (試驗開始前） 0.01 經過吹出16h時 1.0 0.6 經過吹出16h時 0.01 0.6 經過吹出24h時 經過吹出24h時 -28- 201222866 由上述結果可知，若使用本發明之方法，在將氨氣的 供給流量設定爲800slm之大流量時，塡充容器內的氨氣 壓力會維持長時間，而且可進行水分濃度低的氨氣的大流 量的安定供給，可製造出亮度超過1.5cd的發光特性優異 的氮化鎵系化合物半導體。 [產業上可利用性] 藉由本發明，可效率佳地大量生產亮度等發光特性優異 的氮化鎵系化合物半導體，可兼顧製造良率的提升與生產 成本的減低，因此在產業上極爲有用。 【圖式簡單說明】 第1圖係顯示製造習知之氮化鎵系化合物半導體時所 使用的製造裝置的槪略構成圖。 第2圖係顯示本發明之氮化鎵系化合物半導體之製造 方法所使用的製造裝置的槪略構成圖。 第3圖係顯示第2圖所示之製造裝置所使用之氨氣供 給裝置的其他例的槪略構成圖。 第4圖係顯示第2圖所示之製造裝置所使用之氨氣供 給裝置的其他例的槪略構成圖。 第5圖係顯示氮化鎵系化合物半導體元件之例的局部 剖面圖。 第6圖係顯示藉由本發明之氮化鎵系化合物半導體之 製造方法之一例所製造出的氮化鎵系化合物半導體元件之 -29- 201222866 例的局部剖面圖。 【主要元件符號說明】 1 :藍寶石基板 2 :緩衝層 3 : η型包覆層 4 :活性層 5 : ρ型包覆層 6 :電極 7 :電極 1 1 :反應室 1 2 :支持部 1 3 :加熱器 14、15:有機金屬用容器 16、17:有機金屬氣體導入管 18 :塡充容器 19 :導入管 20 :排出管 21 : Η2氣體導入管 22 : Η2氣體導入管 2 3 : S i化合物用容器 24 : Zn化合物用容器 25 : Mg化合物用容器 26 : Si化合物導入管 -30- 201222866 27 : Zn化合物導入管 28 : Mg化合物導入管 3 1 :緩衝層 32: η 型 GaN 層 3 3 :活性層 3 4 : G aN 層 35 : p 型 AlGaN 層 36: p 型 GaN 層 3 7 : η電極 38 : ρ電極 40 :閥 41 :液相部 42 :氣相部 43 :取出配管 43a :配管的其中一端 44 :返回配管 44a :配管的其中一端 45、46:循環配管 47 :熱交換器 48 :導出配管 49 、 50 :閥 51 :返回配管 52 :閥 5 3 :區隔板 -31 201222866 A :氣體供給裝置 -32Cv値 (表示 indicating the flow characteristic of the valve) Most of the small valves, etc., in the method of the present invention, it is preferable to select a valve of Cv, and to select a valve having a Cv値 of 0.5 or more as Cv値 is less than 0.3. At the time of the valve, the pressure in the flow path of the valve suppresses the circulation of the liquefied ammonia, so that it is difficult to maintain the liquefied gas pressure. The heat exchanger 47 vaporizes at least a part or all of it in a liquid phase state. The heat exchanger 47 has a heat medium such as a plurality of heat transfer sheets and a heat medium for heat exchange with the outside air to perform heat exchange. Among the heat exchangers 47, it is preferable to select stainless steel having excellent corrosion resistance in contact with liquefied ammonia. Further, in the case where impurities such as fine particles are generated, it is preferable that the surface roughness is 25 μηι or less in terms of smoothness. In the heat exchanger 47, a heat exchanger such as a heat medium such as electric heating can be used, but high frequency induction is used. Since it is used for high-purity liquefaction for manufacturing semiconductors and the like, a high-frequency feeling that the heater itself is not heated can be used, so that an emergency stop can be immediately performed in case of leakage. In addition, the running cost can be suppressed and the device can be simplified. In the gas supply device 第 of Fig. 2, when the valve 49 of the pipe 48 is opened, the liquefied ammonia is taken out directly from the sump container 18, and the reaction chamber 1 1 of the CVD apparatus is set to the component valve or the ball. The above is better. If the loss of force affects the temperature of ammonia and the heating of distilled ammonia, it can be selected arbitrarily or by the material of the part, and the metal Rmax 抑制 can be suppressed (the table device and the warm water heating device are highly toxic to the ammonia system). The heating device should be installed, and the heat is efficiently supplied to the gas to supply the gas-14-201222866. At this time, the heat required for the evaporation of the liquefied ammonia in the charging container 18 is captured by the liquid phase portion 41. The temperature of the liquid phase portion 41 is lowered. Here, if the valve 40 and the valve 50 are opened, the liquefied ammonia in the charging container 18 is maintained by the take-out pipe 43 communicating with the liquid phase portion 41 by the siphon principle. In the liquid phase, it flows through the circulation pipe 45 and is heated to the heat exchanger 47 located at a lower position than the sump vessel 1. The liquefied ammonia heated by the heat exchanger 47 is partially or completely vaporized. The return pipe 44 is returned to the gas phase portion 42 in the retort container 18 through the circulation pipe 46. At this time, the liquefied ammonia in the retort container 18 is maintained by natural circulation according to the density difference of the liquefied ammonia. Temperature and vapor When the valve 49 is opened and the gaseous ammonia is continuously supplied, the liquefied ammonia is continuously circulated. On the other hand, when the supply of the gaseous ammonia is intermittently performed, the circulation of the liquefied ammonia is intermittent. Since the temperature of the liquid phase portion 41 is prevented from decreasing, the liquefied ammonia in the liquid phase portion 41 is vaporized in the retort container 18 to form the gas phase portion 42 in a stable manner, and the gaseous ammonia can be stably supplied to Next, a modification of the gas supply device will be described. Fig. 3 shows a gas supply device B of another example. Among the components of the gas supply device B shown in Fig. 3, the gas shown in Fig. 2 The constituent elements of the supply device A are denoted by the same reference numerals, and the description thereof will not be repeated. The gas supply device B illustrated in Fig. 3 is provided with a partition in the gas phase portion 42 in the charging container i 8 . The partition plate 53 is disposed between the return pipe 44 and the lead-out pipe 48, and the lower end portion thereof is immersed in the liquid phase portion -15 - 201222866. With the partition plate 53, the gas phase portion 42 The gas phase portion 42a and the pipe side gas phase are separated 42b. Here, the lead-in phase portion 42a is a gas phase portion in which the gas phase portion side gas phase portion 42b that communicates with the gas extracted to the outside is in communication with one end (pipe end) of the return pipe 46. In the supply device b shown in the drawing, the ammonia which is returned to the inside of the charging container 18 by the return pipe is surely passed through the liquid phase portion 41 before being supplied to the outside through the outlet pipe 48. The high-boiling point component such as water contained in the ammonia is likely to remain in the liquid bovine! ° The ammonia via the liquid phase portion 4 1 passes through the outlet tube side gas phase portion 4 2 a High-purity gas having a small content of high-boiling components such as moisture Next, another modification of the gas supply device will be described. The supply device c of another example is shown in Fig. 4. In the components of the gas supply device C, the same components as those of the device A shown in Fig. 2 are denoted by the same reference numerals, and their description is omitted. In the supply device c illustrated in Fig. 4, a return pipe 51 that communicates with the liquid phase is provided instead of the returning pipe 44 of Fig. 2, and the liquefied ammonia-based transmission return pipe 51 heated to the heat exchanger 47 is supplied to the charging container. The liquid phase portion 4 1 in 18. In the supply device illustrated in Fig. 4, it is preferable that the distance between the end 43a of the pipe 43 and the one end 51a of the return pipe 51 is 100 mm or more. When the distance between one end of each of the pipes communicating with the liquid phase portion 41 is less than 10 mm, the liquefied ammonia is supplied to the side of the pipe, and the other f 44 of the pipe is supplied; Take it out. The gas shown is supplied to the same phase portion 3 . By returning from the separation, the density difference of -43 to 201222866 is reduced, and the cycle is suppressed, and it is difficult to maintain the temperature and vapor pressure of the liquefied ammonia. Further, a valve 52 is provided in the return pipe 51. The valve 52 is the same as the valve 50 of Fig. 2 . In the supply device C shown in Fig. 4, when the valve 49 provided in the outlet pipe 48 is opened, the gas is supplied from the reaction chamber 11 to the reaction chamber 11 of the CVD apparatus by directly extracting the gas such as ammonia from the condensing container 18 in a gaseous state. . At this time, the heat required for evaporation of the liquefied ammonia in the sump container 18 is taken up by the liquid phase portion 41, and the temperature of the liquid phase portion 41 is lowered. Therefore, when the valve 40 and the valve 50 are opened, the liquefied ammonia in the retort container 18 flows into the heat exchanger 47 through the circulation pipe 45 by the take-out pipe 43 that communicates with the liquid phase portion 41 by the siphon principle. The ammonia heated by the heat exchanger 47 is sent back to the liquid phase portion 41 in the retort container 18 through the return pipe 44 through the circulation pipe 46. The temperature and vapor pressure of ammonia in the retort container 18 are maintained by natural circulation according to the difference in density of liquefied ammonia. By the supply device C shown in Fig. 4, the ammonia sent back to the sump container 18 by the pipe 51 is directly returned to the liquid phase portion 41, and therefore is supplied to the outside by the outlet pipe 48. Before, it does pass through the liquid phase portion 41. As a result, when ammonia passes through the liquid phase portion 41, high-boiling components such as moisture contained in the ammonia tend to remain in the liquid phase portion 41. The ammonia that has passed through the liquid phase portion 41 is taken out through the gas phase portion 42 as a gas containing a small amount of a high-boiling component such as moisture. Further, in the examples shown in Figs. 2 to 4, the liquefied ammonia which is filled in the retort container 1 can be, for example, a crude ammonia and a synthetic zeolite, -17-201222866 zirconia or the like. The water in the crude ammonia is adsorbed to the adsorbent material by contact, or is subjected to precision distillation, and the ammonia crucible after adsorption or distillation is charged in the charging vessel 18. At this time, in each of the processes of charging the ammonia or the ammonia after the adsorption or distillation treatment to the charging container 18, the water is not mixed as much as possible, and the purified container is washed with purified ammonia in advance. It is advisable to carry out vacuum pumping and other methods. The water concentration in the liquid ammonia is preferably 0.Olvolppm or more and 0.5 volppm or less as measured by, for example, Fourier transform infrared spectroscopy (FT-IR). In the production method of the present embodiment, the ammonia supplied from the gas supply devices A, B, and C is used to produce a gallium nitride-based compound semiconductor as follows. For example, as shown in FIG. 2, first, the sapphire substrate 1 is housed in the reaction chamber 11, and after the reaction chamber 11 is vacuum-vented in the support portion 12', the sapphire substrate 1 is heated by the heater 13 to preferably. About 400° C. Next, organic gallium such as trimethylgallium (TMGa) contained in the container 14 and organoaluminum such as trimethylaluminum (TMA1) contained in the container 15 are used, and the tubes 2 1 and 22 are used. Foaming with H 2 gas 'The obtained organic gallium gas and organoaluminum gas are introduced into the reaction chamber 11 together with the 1 2 gas through the introduction pipes 16 and 17, and the ammonia gas supplied from the charging container 18 is simultaneously supplied. The introduction layer 19 is introduced into the reaction chamber 11 to form a buffer layer 2 composed of 0 Α 1 χΝ χΝ on the surface of the sapphire substrate 1 using the organic gallium gas, the organoaluminum gas, and the ammonia gas as raw materials. When ammonia gas is supplied, the valves 40, 50' are opened to heat the liquid ammonia by the heat exchanger 47, 俾 -18 201222866 so that the temperature drop of the liquid phase portion does not occur. The same operation is performed when the ammonia gas is supplied below. Then, 'the temperature of the substrate 1 is raised to about 1 150 ° C, and the Si compound such as decane supplied from the container 23 is supplied into the reaction chamber 11 through the tube 26 together with the above-mentioned organogallium, organoaluminum, and ammonia gas. On the buffer layer 2, an n-type cladding layer 3 is formed. Next, the Ζ 化合物 compound such as dimethyl zinc supplied from the container 24 is supplied into the reaction chamber 11 through the tube 27 together with the above-described organogallium, organoaluminum, and ammonia gas, and an active layer is formed on the n-type cladding layer 3. 4. Then, together with the above-mentioned organogallium, organoaluminum, and ammonia gas, Mg compound such as dicyclopentadienyl magnesium supplied from the container 25 is supplied into the reaction chamber 1 through the tube 28, and a p-type package is formed on the active layer 4. Cladding 5. Thereafter, the epitaxial wafer prepared as described above is taken out from the reaction chamber 1 1 , and the electrodes 6 and 7 are provided on the n-type and p-type cladding layers 3 and 5 to obtain the gallium nitride-based compound semiconductor device. According to the production method of the above embodiment, the obtained gallium nitride-based compound semiconductor device is excellent in light-emitting characteristics such as brightness. Therefore, the gallium nitride-based compound semiconductor device produced by the above-described production method is excellent in light-emitting characteristics because the water concentration of the ammonia is in the above range. The amount of oxygen contained in the n-type and p-type cladding layers 3 and 5 and the active layer 4 formed by using the ammonia as a raw material is suppressed to be low, and a layer composed of the gallium nitride-based compound semiconductor can be prevented. The case where the crystallinity deteriorates. -19-201222866 In addition, in the gas supply devices A, B, and C, since the temperature of the liquid phase portion 41 is prevented from decreasing, the liquefied ammonia in the liquid phase portion 41 is vaporized in the sump container 18 to form a gas phase. In the portion 42, the gaseous ammonia can be supplied to the outside, whereby the gallium nitride-based compound semiconductor device can be mass-produced. Further, the heat exchanger 47' is provided in the middle of the circulation pipes 45, 46 to heat the liquefied ammonia outside the sump container 18, whereby heat can be efficiently transferred to the liquefied ammonia. Further, the liquefied ammonia in the liquid phase is taken out and heated, whereby the change in the density of the liquefied ammonia before and after the heat exchange is increased, and the expansion of the liquefied ammonia becomes a driving source, and the liquefied ammonia can be naturally circulated, and a power source such as a pump is not required. . Since the circulation pump or the like is a source of mixing of oil or outside air, the method can prevent the contamination caused by the incorporation of foreign matter into the liquefied ammonia to maintain the purity. Thereby, the simplification of the manufacturing apparatus of the gallium nitride-based compound semiconductor device is achieved. By using the ammonia supply method of the supply devices A, B, and C shown in FIGS. 2 to 4, it is possible to carry out high-purity ammonia gas, in particular, to maintain the water concentration at a low concentration. Since the technology cannot supply a stable supply of a large flow rate, a high-quality gallium nitride-based compound semiconductor element can be mass-produced. In the above-described embodiment, the method of forming the n-type and p-type cladding layers 3 and 5 and the active layer 4 containing GaxAh.xN as a main component using the above-mentioned ammonia as a raw material is exemplified, but the present invention is not limited thereto. The above-mentioned ammonia is used to produce a gallium nitride-based compound semiconductor in which a layer made of a gallium nitride-based compound such as GaN, InGaN, InGaAIN, or AlGaN is formed on a substrate. -20-201222866 [Examples] Specific examples will be described below, and the present invention will be described in detail (Example 1) Using the supply device A shown in Fig. 2, an experiment was carried out. A retort container 18 having a cylindrical shape as shown in Fig. 2 and filled with 980 kg of liquefied ammonia was used. Use at room temperature (24 ° C) and use ammonia gas to heat the temperature. The ammonia gas is directed from the valve 49 shown in Fig. 2, and a pressure change of the vapor phase ammonia in the pressure-filling container 18 (not shown) is provided in the vicinity of the valve 49. Then, it is known that the gas take-out flow rate is increased from 300 slm (in increments of 800 slm (every hour), and the pressure in the gas phase portion is not lowered, and it is possible to supply the gas at a flow rate of 800 slm. In the same manner, in the same manner, at 0.7 MPa-G, ammonia gas can be continuously supplied in a stable manner. (Comparative Example 1) In addition, the temperature of the warm water bath after the temperature adjustment of the valves 40 and 50 shown in FIG. The test was carried out in the same manner as in Example 1 except for the ammonia gas. The ammonia gas take-up capacity was I 8 60 L as shown below, and the heat exchanger was connected to a normal temperature or higher. The gas meter was taken to measure the standard[standard 1/min.) port 1 0 0 s 1 m ), and the ammonia gas flow rate was investigated. From 300slm to the pressure of the atmosphere is maintained, in the state of 3 7~3 9 t: the filling of the tank is carried out in the state of the ammonia gas. 21 - 201222866 The result is that the gas withdrawal flow rate is increased from 300slm to 400slm. It was found that the pressure of the ammonia gas was lowered, and then, in the case of increasing to 500 slm, the ammonia gas pressure was lowered to less than .4 MPa-G, and it became impossible to continuously supply the atmosphere. (Example 2) A gallium nitride-based compound semiconductor device shown in Fig. 6 was produced by using the production apparatus shown in Fig. 2 . In the supply device A for ammonia, a cylindrical container having a cylindrical shape and a capacity of 1860 L and filled with 980 kg of liquefied ammonia was used. The retort container 18 is used at room temperature (24 ° C), and the heat exchanger 47 is provided with a plurality of heat transfer sheets. The ammonia gas is taken out directly from the valve 49 shown in Fig. 2, and the gas take-off flow rate is continuously set at 800 slm (standard Ι/min.) for 24 hours, and a part thereof is supplied to the first figure. The reaction chamber 1 1 is discharged to a blow line (not shown). The remaining weight of the liquefied ammonia after taking out ammonia gas for 24 hours was 105 kg. At the same time, a pressure measuring device (not shown) is provided in the ammonia introducing pipe portion to measure the pressure change of the ammonia gas in the helium charging container 18. The sapphire substrate 1 is a circular shape, a diameter of 50 mm, a thickness of 0.3 mm, and the surface is mirror-honed. First, the sapphire substrate 1 having a single crystal having a c-plane which is organically cleaned is supported by a support portion in the reaction chamber 11. Next, after the pressure of the reaction chamber 11 is reduced to 1×1 (T3t〇rr or less, H2 is introduced into the reaction chamber to return the pressure in the reaction chamber 1 to atmospheric pressure (760 torr). Next, H2-22- 201222866 Introduced into the reaction chamber at 5 slm (standard l/min.), and the sapphire substrate 1 was thermally cleaned while setting the temperature of the substrate 1 to 1150 ° C. Then, the substrate temperature was lowered to 405 ° C. The carrier gas composed of Η 2 and N 2 was supplied to the reaction chamber at 6 slm, ammonia was used as isim, and H 2 containing trimethylaluminum (TMA1) vapor was supplied at 20 sccm (standard cc/min.) for 1.5 minutes. The molar supply amount of TMA1 is 3.8 χ 10 0 5 mol/min. In this process, a buffer layer 31 composed of A1N and having a thickness of about 20 nm is formed on the sapphire substrate 1. When ammonia gas is supplied, the valve 40 is opened. 50' is heated by the heat exchanger 47 so that the temperature of the liquid phase does not decrease. Hereinafter, the same operation is performed when the ammonia gas is supplied. Next, the supply of the TMA1 is stopped, and the temperature of the sapphire substrate 1 is raised. To 1 l ° ° C and keep at this temperature. Then, The carrier gas was supplied to the reaction chamber at 6 slm, with an atmosphere of 2.5 slm, diluted with H2 to 1 volppm of di-salane (Si2H6) at 5 sccm, and H3 containing trimethylgallium (TMGa) vapor at 15 sccm for 90 minutes. At this time, the molar supply amount of TMGa was 5.8 x 1 (T5 m〇l/mirv. In the process, an n-type GaN layer 32 having a film thickness of about 1.5 μm and a carrier concentration of about 3×10 17 /cm 3 was formed. Then, the supply was stopped. After TMGa, the temperature of the sapphire substrate 1 is lowered to 85 ° C and maintained at this temperature. Then, the carrier gas is diluted at 6 slm with ammonia at 2.5 slm, and diluted with hydrogen to l〇〇v〇lppm. Ethyl zinc (DEZn) was diluted at 10°C, Si2H6 diluted to 1volppm with H2 at 10sccm, H2 containing TMGa vapor at 5sccm, and H2 containing trimethylindium (TMIn) vapor was supplied at 13sccm for 15 minutes to the reaction chamber- 23-201222866. At this time, the molar supply of TMGa and TMIn is 1.9 χ l (T5mol/min and 7.6x10_6mol/min respectively). InGaN activity containing Si and Zn impurities with a film thickness of about 100 nm is formed in the process. Layer 33. Next, the temperature of the sapphire substrate 1 is maintained to form with the above-mentioned InGaN active layer The same as the temperature of stopping the supply of direct TMIn, the carrier gas 6slm, the ammonia gas 4.5slm, containing the vapor of H2 for supplying TMGa 1 seem 2 min to the reaction chamber. At this time, the molar supply amount of TMGa was 3.8 x 10 6 mol/min. A GaN layer 34 having a film thickness of about 3 nm is formed in the process. Next, the supply of TMGa is stopped, the temperature of the sapphire substrate 1 is raised to 1,150 ° C, and the temperature is maintained at this temperature, and the carrier gas is 6 slm, the ammonia gas is 3 slm, and the H2 containing TMA1 vapor is 4.3 sccm, and the TMGa vapor is contained. H2 was supplied at 5 sccm, and H2 containing dicyclopentadienyl magnesium (Cp2Mg) vapor was supplied at 135 sccm for 10 minutes into the reaction chamber. At this time, the molar supply amount of TMA1, TMGa, and Cp2Mg was S!J of 2.3χ 1 (T6mol/min, 1 · 5 X 1 (K5mol/min, and 1·1 χ 1 0-4mol/min. In this process, a p-type AlGaN layer 35 having a film thickness of about 70 nm and a carrier concentration of about lxl 〇 17/cm 3 is formed. Next, supply of TMA1, TMGa, and Cp2Mg is stopped, and the temperature of the sapphire substrate 1 is lowered to 1 1 oo °c. The temperature was maintained at this temperature. Then, the carrier gas was supplied to the reaction chamber at 6 slm, ammonia gas at 2.5 slm, H2 containing TMGa vapor at 15 sccm, and H2 containing Cp2Mg vapor at 135 sccm for 10 minutes. The molar supply of Cp2Mg is 5.7xl (T5mol/min and l.lxl (T4mol/miii. In the process, shape-24-201222866 has a p-type with a film thickness of about 300 nm and a carrier concentration of about 3xl〇17/cm3). The GaN layer 3 6 取出 extracts the epitaxial wafer obtained as described above from the reaction chamber 11 'The n-type GaN layer 32 and the p-type GaN layer 36 are respectively provided with the n-electrode 3 7 and the p-electrode 3 8 using a well-known device technology. The element shown in Fig. 6 was obtained, and when the element was illuminated by the forward current of 20 m A between the n-electrode 37 and the p electrode 38 of the obtained device, The results are shown in Table 1. In addition, the water concentration in the ammonia in the liquid phase portion 41 in the liquid container (before the start of the test) and the water concentration in the ammonia gas taken out from the helium container 18 are the same.倂 is shown in Table 1. The water concentration of ammonia in the liquid phase portion was sampled and vaporized by liquefied ammonia in the charging container 18, and the obtained gas was measured using FT-IR (MAGNA5 60 manufactured by NICOLET Co., Ltd.). In addition, the moisture concentration in the ammonia gas taken out from the sump container 18 is measured in the same manner as described above in the gas sampled. Further, the measured sump container 18 is simultaneously measured. The enthalpy of the ammonia gas pressure in the inside was also not shown in Table 1. (Example 3) A grave filling container 18 containing ammonia was produced in the same manner as in Example 2 except that the one shown in Fig. 3 was used. The gallium nitride-based compound semiconductor device, the luminance when the gallium nitride-based compound semiconductor device emits light, the concentration of water in the ammonia gas taken out from the retort container, and the ammonia gas pressure in the retort 18 - 201222866 The force is shown in Table 1. (Example 4) In the same manner as in the second embodiment, the nitrogen-containing compound semiconductor device was produced in the same manner as in the second embodiment. The brightness of the gallium nitride-based compound semiconductor was 3 The water in the ammonia gas taken out from the sump container is concentrated. The pressure of the ammonia gas in the retort container 18 is shown in Table 1. (Comparative Example 2) The same as in the second embodiment, except that the valves 40 and 50 shown in Fig. 2 were closed, and the ammonia water was supplied in the state where the temperature was adjusted in the range of 37 - A capsule-based compound semiconductor element is produced. However, when the flow rate of the ammonia gas is set to 800 slm, a rapid pressure drop occurs within the time, and ammonia gas cannot be stably supplied to produce a gallium nitride-based compound semiconductor device. (Comparative Example 3) A GaN-based compound semiconductor device was produced in the same manner as in Example 2 except that the liquefied ammonia was directly taken out from the sputum-filled container 18 of ammonia, and the liquefied ammonia taken out was vaporized by a shovel hair dryer to form ammonia gas. . The luminescence efficiency of the produced gallium nitride-based compound semiconductor device, the concentration of water in the ammonia gas taken out from the sputum container, and the gallium-emitting material of the 4 4 图 、, and the -39〇C 18 1 small and no steaming and bright container -26- 201222866 18 ammonia pressure ~ 倂 系 in the table ^ In this method, a large supply of ammonia gas is possible, but is supplied with a large amount of water Since the ammonia gas of the boiling point component is not able to produce a gallium nitride-based compound semiconductor having excellent light-emitting characteristics of more than 1.5 cd. -27- 201222866 [Table i] Moisture concentration in the liquid phase Moisture concentration in the gas phase Luminous pressure (volppm) (volppm) (cd) (MPa-G) &lt;0.01 0.6 When the air is blown for 8 hours, it is blown for 8 hours. Example 2 0.01 (Before the start of the test) &lt;0.01 When blew out for 16 hours 2.8 0.6 After blowing for 16 hours &lt;0.01 0.6 After blowing for 24 hours, when blowing for 24 hours &lt;0.01 0.6 After blowing for 8 hours, 8 hours after blowing, Example 3 0.01 (Before the test ) &lt;0.01 when 16h is blown for 16h, when it is blown for 16h, &lt;0.01 0.6 when it is blown for 24 hours, when it is blown for 24 hours, &lt;0.01 0.6, when it is blown for 8 hours, when it is blown for 8 hours, Example 4 0.01 (before the start of the test) &lt;0.01 When 16h was blown out, 0.6 0.6 was blown out for 16 hours, <0.01 0.6, and 24 hours after blowing for 24 hours, when it was blown for 24 hours, Comparative Example 2 0.01 (before the start of the test) was not measured (no gas could be supplied). (No gas can be supplied) &lt;0.4 After blowing out Lh (no gas supply) 0.01 0.6 8h after blowing for 8h, comparative example 3 0.01 (before the start of the test) 0.01 after blowing out 1 When it is blown for 16 hours, it is 0.01 0.6. After blowing for 24 hours, when it is blown for 24 hours, it is blown for 24 hours. -28-201222866 From the above results, it can be seen that when the method of the present invention is used, when the supply flow rate of ammonia gas is set to a large flow rate of 800 slm, 塡The ammonia gas pressure in the charging container is maintained for a long period of time, and a stable flow of a large flow rate of ammonia gas having a low water concentration can be performed, and a gallium nitride-based compound semiconductor excellent in light-emitting characteristics with a luminance exceeding 1.5 cd can be produced. [Industrial Applicability] According to the present invention, a gallium nitride-based compound semiconductor having excellent light-emitting characteristics such as brightness can be efficiently produced in a large amount, and the improvement in production yield and the reduction in production cost can be achieved, which is extremely useful industrially. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic block diagram showing a manufacturing apparatus used in the manufacture of a conventional gallium nitride-based compound semiconductor. Fig. 2 is a schematic block diagram showing a manufacturing apparatus used in the method for producing a gallium nitride-based compound semiconductor of the present invention. Fig. 3 is a schematic block diagram showing another example of the ammonia gas supply device used in the manufacturing apparatus shown in Fig. 2. Fig. 4 is a schematic block diagram showing another example of the ammonia gas supply device used in the manufacturing apparatus shown in Fig. 2. Fig. 5 is a partial cross-sectional view showing an example of a gallium nitride-based compound semiconductor device. Fig. 6 is a partial cross-sectional view showing an example of a gallium nitride-based compound semiconductor device manufactured by an example of a method for producing a gallium nitride-based compound semiconductor according to the present invention, -29 to 201222866. [Description of main component symbols] 1 : Sapphire substrate 2 : Buffer layer 3 : η-type cladding layer 4 : Active layer 5 : ρ-type cladding layer 6 : Electrode 7 : Electrode 1 1 : Reaction chamber 1 2 : Support portion 1 3 : heaters 14 and 15 : organic metal containers 16 and 17 : organometallic gas introduction pipe 18 : sump container 19 : introduction pipe 20 : discharge pipe 21 : Η 2 gas introduction pipe 22 : Η 2 gas introduction pipe 2 3 : S i Container for compound 24 : Container for Zn compound 25 : Container for Mg compound 26 : Si compound introduction tube -30 - 201222866 27 : Zn compound introduction tube 28 : Mg compound introduction tube 3 1 : Buffer layer 32 : η type GaN layer 3 3 : Active layer 3 4 : G aN layer 35 : p-type AlGaN layer 36 : p-type GaN layer 3 7 : η electrode 38 : ρ electrode 40 : valve 41 : liquid phase portion 42 : gas phase portion 43 : take-out pipe 43 a : pipe One end 44: return pipe 44a: one end of the pipe 45, 46: circulation pipe 47: heat exchanger 48: outlet pipe 49, 50: valve 51: return pipe 52: valve 5 3: zone partition - 31 201222866 A : gas supply device -32

Claims (1)

201222866 七、申請專利範圍： 1. 一種氮化鎵系化合物半導體之製造方法，係使用以 一部分成爲液相的方式而被塡充在塡充容器的液化氨的氣 相部的氨，該氮化鎵系化合物半導體之製造方法之特徵爲 前述氣相部的氨係藉由包含以下工程的方法予以供給 :藉由其中一端與前述塡充容器內的液相部相連通、另一 端與前述塡充容器內的氣相部或液相部相連通的配管，使 前述塡充容器內的液化氨由前述其中一端的液相部朝前述 另一端的氣相部或液相部連續性或間歇性作循環，而且在 循環中將前述液化氨加熱，藉此在使液化氨的至少一部分 氣化後，送回至前述另一端的氣相部或液相部， 將由前述塡充容器直接在氣體狀態下所取出的氨，在 氣體狀態下導入至收納有基板的反應室內，以前述氨爲原 料，將由氮化鎵系化合物半導體所構成之層形成在前述基 板上。 2. —種氮化鎵系化合物半導體之製造方法，係前述配 管的另一端與前述塡充容器內的氣相部相連通之如申請專 利範圍第1項之氮化鎵系化合物半導體之製造方法，其特 徵爲： 在藉由在前述塡充容器內設置區隔板，將前述塡充容 器內的前述氣相部分斷爲：與被抽出至外部的氣體相連通 的氣相部、及與前述配管的另一端相連通的氣相部的狀態 下，由前述氣相部抽出氣體來進行供給。 -33- 201222866 3 .如申請專利範圍第1項之氮化鎵系化合物半導體之 製造方法，其中，前述配管的另一端與前述塡充容器內的 液相部相連通。 -34-201222866 VII. Patent application scope: 1. A method for producing a gallium nitride-based compound semiconductor, which is an ammonia which is charged in a gas phase portion of liquefied ammonia in a retort container in a part of a liquid phase, which is nitrided The method for producing a gallium-based compound semiconductor is characterized in that the ammonia in the gas phase portion is supplied by a method comprising: one end is connected to a liquid phase portion in the charging container, and the other end is flushed with the foregoing a pipe in which a gas phase portion or a liquid phase portion in the container communicates with each other, and the liquefied ammonia in the retort container is continuously or intermittently formed from a liquid phase portion of one end portion toward a gas phase portion or a liquid phase portion at the other end portion Circulating, and heating the liquefied ammonia in a cycle, thereby vaporizing at least a portion of the liquefied ammonia, and then returning it to the gas phase portion or the liquid phase portion of the other end, and directly charging the container from the gas state The extracted ammonia is introduced into a reaction chamber in which the substrate is housed in a gas state, and a layer made of a gallium nitride-based compound semiconductor is formed on the base using the ammonia as a raw material. On. 2. A method for producing a gallium nitride-based compound semiconductor, wherein the other end of the pipe is in communication with a gas phase portion in the charging container, and the method for producing a gallium nitride-based compound semiconductor according to claim 1 The gas phase portion in the charging container is broken into a gas phase portion that communicates with the gas extracted to the outside, and the foregoing, by providing a partition plate in the charging container. In a state in which the other end of the pipe is in the gas phase portion, the gas is extracted from the gas phase portion and supplied. The method for producing a gallium nitride-based compound semiconductor according to the first aspect of the invention, wherein the other end of the pipe is in communication with a liquid phase portion in the charging container. -34-
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CN112695373A (en) * 2020-12-10 2021-04-23 国镓芯科(深圳)半导体科技有限公司 Ammonia discharge process and growth method of gallium nitride crystal growth system
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