TW546850B - Manufacturing method for crystallization of group III nitride semiconductor, manufacturing method for gallium nitride compound semiconductor, gallium nitride compound semiconductor, gallium nitride compound semiconductor light emitting elements and light - Google Patents

Manufacturing method for crystallization of group III nitride semiconductor, manufacturing method for gallium nitride compound semiconductor, gallium nitride compound semiconductor, gallium nitride compound semiconductor light emitting elements and light Download PDF

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TW546850B
TW546850B TW090119766A TW90119766A TW546850B TW 546850 B TW546850 B TW 546850B TW 090119766 A TW090119766 A TW 090119766A TW 90119766 A TW90119766 A TW 90119766A TW 546850 B TW546850 B TW 546850B
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Taiwan
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gallium nitride
manufacturing
based compound
compound semiconductor
substrate
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TW090119766A
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Chinese (zh)
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Yasuhito Urashima
Mineo Okuyama
Tetsuo Sakurai
Hisayuki Miki
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Showa Denko Kk
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/005—Processes
    • H01L33/0062—Processes for devices with an active region comprising only III-V compounds
    • H01L33/0075—Processes for devices with an active region comprising only III-V compounds comprising nitride compounds
    • 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
    • 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
    • H01L21/02436—Intermediate layers between substrates and deposited layers
    • H01L21/02439—Materials
    • H01L21/02455—Group 13/15 materials
    • H01L21/02458—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
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02538—Group 13/15 materials
    • H01L21/0254—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
    • H01L21/02612—Formation types
    • H01L21/02617—Deposition types
    • H01L21/0262—Reduction or decomposition of gaseous compounds, e.g. CVD

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)

Abstract

Generally speaking, gallium nitride compound semiconductor crystallization film which is utilized to manufacture semiconductor elements is formed, through low temperature buffering method, on a sapphire substrate. Through the method, a layer which is formed on the sapphire substrate is called the low temperature buffering layer, on which there is formed a gallium nitride compound semiconductor. The low temperature buffering layer which is formed by the method results in, during temperature ramp up, sublimation and re-crystallization, then is obtained, and then becomes a construction of a crystallization core which consists of GaN that is rarely spread on the sapphire substrate. However, through such a method, it is very difficult to freely control a density, shape, and size of the crystallization core which is formed. The said construction consisting, through the low temperature buffering method, of carrier gas when temperature ramp up, thermal history or growing gallium nitride is accidentally determined. The present invention manufactures group III nitride semiconductor crystallization film through a process that stacks group III metal particles on the substrate in an ambient that does not contain nitrogen source, and through a process that nitrifies the metal material in an nitrogen source ambient that does not contain metal material and through a process that grows group III nitride semiconductor crystallization on the substrate that is stacked with the metal particles. Moreover, the MO material is introduced on the substrate and after the metal core is attached to the sapphire, which is annealed later, and NH3 is introduced so as to nitrify the metal core that is formed. Furthermore, a mask layer is formed on the substrate so as to form areas that have different growing speeds in order to from a better crystallization property of the gallium nitride compound semiconductor. Through such a method, it is possible to freely control the density, shape and size of the growing core. Through controlling conditions, the shape of growing core that is finally formed can be achieved, and the growing core has ladder-shaped sectional view that is parallel to the substrate and has a flat top surface.

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546850 五、發明說明（1 ) 【技術領域】 本發明係有關一種製作發光二極體（LED)、雷射二極體 (L· D )、電t裝置等所使用的I I I族氮化物半導體結晶之製 xa方法、热化鎵系化合物半導體之製造方法、氮化鎵系化 合物半導體、氮化鎵系化合物半導體發光元件及使用該半 導體發光元件之光源。 【先前技術】 I I I族氮化物半導體，係具有自可視光相當於紫外線區 域之能量直接遷移型之帶隙可爲高效率的發光，故可作成 LED或LD之製品化。又，氮化鋁鎵（AlGaN)與氮化鎵（GaN) 之異質接合界面，係在Π I族氮化物半導體由特徵性的壓 電效果發現2次元電子層等，作爲電子裝置時具有獲得先 前之11 I -V族化合物半導體不能得到的潛在特性。 然而，I II族氮化物半導體，因在單結晶之育成溫度有 及於2 0 0 0氣壓的氮之解離壓力，故不易育成單結晶，如 其他的I I卜V族化合物半導體作爲外延成長使用的基板， 欲利用其111族氮化物半導體之單結晶基板在現狀實爲困 難。於是，作爲外延成長所使用的基板，係採用藍寶石 (A 1 203 )單結晶或碳化矽（S i C )單結晶等不同種類材質所成 的基板。 此等之異種基板、與在其上作外延成長的I I I族氮化物 半導體結晶之間存在有大的格子不整合。例如藍寶石 (A 1 203 )與氮化鎵（GaN)之間存在有16%、SiC與氮化鎵之間 546850 五、 發明說明（2) 存 在 有 6%之格子不整合。一般在存在有如此該 大 的 格 子 不 整 合 時 ，不易使結晶在基板上直 接外延成長， 即 使 有 成 長 仍 姐 夕、N、 法得到結晶性良好的結晶。 於是，由有機 金 屬 化 學 氣 相 成 長 (M0CVD)法將I I I族氮化 物半導體結晶 以 外 延 成 長 於 藍 寶 石單結晶基板或S i C單結 晶基板上時， 如 曰 本 專 利 第 3 0 26087號公報或特開平4-: 297023號公報 所 揭 示 ， 首 先 以 氮 化鋁（A1N)或AlGaN構成 稱爲低溫緩衝 層 之 層 堆 積 於 基 板 上，一般在高溫下使I I I 族氮化物半導 體 結 晶 進 行 外 延 成 長的方法。 使 用 藍寶石作爲基板時，上述 低溫緩衝層大 約 以 如 下 形 成 〇 首 先 ，使藍寶石基板在MOCVD法之成長裝 置 內 加 熱 至 1 0 0 0 °c 〜1 200°C之高溫，除去表 面之氧化膜等 〇 其 後 降 低 成 長 裝置之溫度以400〜60〇°C 左右之溫度同 時 供 辉 人LU、 給 有 機 金 屬 原料與氮源於基板上來堆 積低溫緩衝層 0 其 後 停 止 供 應 有機金屬原料、再度提高 成長裝置之溫 度 進 行 稱 爲 低 溫 緩 衝層之結晶化的熱處理， 如此後以外延 成 長 S 的 之 II I : 族： ®化物半導體結晶。 在 低 溫緩衝層之堆積溫度爲z 400 〜600 〇C， 作 爲 原 料使 用 的 有 機金屬原料或氮源、尤其 是作爲氮源使 用 的 氨 之 熱 分 解 不 充分。因此如在此之低溫 下堆積的低溫 緩 衝 層 中 含 有 很 多 缺陷。又由於以低溫下反 應原料，故在 原 料 之 有 機 金 屬 的 院基或未分解的氮源間産 -4 - 生聚合反應、 此 等 之 反 應 546850 五、發明說明（3) 物等雜質大量含於低溫緩衝層之結晶中。 而用以解消此等缺陷或雜質來進行，但係稱爲上述低溫 緩衝層之結晶化的熱處理製程。緩衝層之結晶化製程在含 有很多雜質與缺陷的低溫緩衝層、在接近I I I族氮化物半 導體結晶之外延成長溫度下以高溫進行熱處理，用來除去 此等雜質與缺陷。 如上述欲形成低溫緩衝層時，需要有在低溫之緩衝層堆 積製程與在高溫結晶化之製程，欲得高品質之緩衝層時， 就需要此寺製程之相關製造條件之最合適化。列舉有關低 溫之緩衝層的堆積製程，有機金屬原料與氮源之比、堆積 時之溫度、載運氣體之流量等會予影響低溫緩衝層之特性 。又，在結晶化之製程則高溫熱處理的溫度或時間、昇溫 率等會予影響低溫緩衝層之特性。例如T . I t 〇等人檢討 有關此等使用氮化鋁之低溫緩衝層的條件。（Journal of Crystal Growth 205(1999)、 20-24) 欲獲得筒品質之低溫緩衝層時，對上述各個製造條件加 以仔細硏究、需要謀求最合適化。而且通常此等條件，係 必須對由MOC VD法使用於外延成長的每成長裝置調整，在 不同的成長裝置間移植最合適的條件，經常需要很多的時 間與勞力。 低温緩衝層係用以結晶化於熱處的昇溫時，引起昇華與 再結晶作變成在藍寶石基板上變成稀疏地散佈有由氮化鎵 所成的結晶核構造。並以散佈於該基板上的結晶核爲核成 546850 五、發明說明（4) 長氮化鎵系化合物半導體、以適度的密度產生的結晶結合 成結晶膜。亦即，製作良好結晶性之氮化鎵系化合物半導 體層’可由適當地控制散佈的結晶核密度達成。 可是，於上述低溫緩衝層中結晶核之散佈構造，係依昇 溫時之熱經歷或成長氮化鎵系半導體層時之載運氣體之組 成，僅於偶發的決定，不易自由地控制結晶核之密度或形 狀、大小等，所得的氮化鎵系化合物半導體結晶之結晶性 有限。 本發明係代替需要使太多製造條件最合適化採用上述低 溫緩衝層的方法，提供一種簡單的方法可形成高品質之 I I I族氮化物半導體結晶的I I I族氮化物半導體結晶之製 造方法爲目的。尤其是提供一種在藍寶石基板上以簡單的 方法可使高品質之I I I族氮化物半導體結晶外延成長的 I I I族氮化物半導體結晶之製造方法者（以下I I I族氮化物 半導體係以 InxGayAlzN 表不，x + y + z = 0、、OSy S 1、OS z S 1 )。 又，本發明係提供一種予以自如地控制構成設於基板上 的層之結晶核密度或形狀、大小等、可使其結晶性良好、 可使疊層於其上的結晶層之結晶性良好者之氮化鎵系化合 物半導體之製造方法及氮化鎵系化合物半導體爲目的。。 更於本發明，係提供一種發光效率優異、惡化速度遲緩 、省電力化、低成本化、低更換頻率化之發光元件及光源 爲目的。 546850 五、發明說明（5) 【發明之揭示】 依本發明I I I族氮化物半導體結晶之製造方法的第丨構 成’係由在基板表面上堆積I I I族金屬之微粒子的第1製 程；在其後包含氮源之環境中氮化該微粒子的第2製程； 及其後在堆積該微粒子的基板表面上由氣相成長法形成 I I I族氮化物半導體結晶之第3製程所成。 上述基板包含爲藍寶石（A1 203 )。 上述 I I I 族金屬包含 InuGavAlw(惟 u + v + w=l、0 S u S 1、 上述ΠI族金屬的微粒子係包含由有機金屬原料之熱分 解所堆積。 上述第1製程包含在不含氮源之環境中，以上述III族 金屬之熔點以上的溫度下進行。 上述第2製程，包含在不含金屬原料之環境中、以第1 製程之溫度以上的溫度下進行。 上述第3製程係包含在第2製程之溫度以上的溫度進行 〇 由有機金屬化學氣相成長法該I I I族氮化物半導體結晶 ’包含由有機金屬化學氣相成長法形成。 再者，於第2製程中氮化I π族金屬微粒子者係由I 1 I 方矢莉化物之多結晶及/或非晶質所成、且含未反應之金屬 〇 又，依本發明I I I族氮化物半導體結晶之製造方法的第 546850 五、發明說明（6) 2構成，在不含氮源之環境中使用至少含有一種類1 η與 G a與Α1之金屬元素的有機金屬原料熱分解，在藍寶石基 板上至少使用由一種類I η與G a與A 1所成以I n u G a v A 1 w所 示金屬 1(惟 u + v + w= l、O^uSl、〇Sv€l、〇gw€l)，在 該金屬1之熔點以上的溫度T1來堆積之第1製程；在不 含有機金屬原料、含氮源之環境中、以溫度T2(惟T2- T1 ) 推積的金屬1氮化的第2製程；以及與在堆積有金屬1之 藍寶石基板上、以溫度Τ3(惟Τ3-Τ2)由有機金屬化學氣 相成長法外延成長Π I族氮化物半導體結晶的第3製程。 上述藍寶石基板具有（0001)面、該（0 00 1)面之垂直軸自 &lt;〇〇0 1 &gt;方向傾斜於特定方向。 上述藍寶石基板之特定方向爲&lt;1-1〇〇&gt;方向、且自 &lt;〇〇01&gt;方向之傾斜角度爲〇 . 2°〜1 5° 。 上述溫度Τ1爲900°C以上、溫度Τ3爲1000°c以上。 於第1製程中有機金屬原料之熱分解係在氫氣環境中進 行。 堆積於上述藍寶石基板上之金屬1不成爲層狀、係成粒 狀，上述粒狀金屬1之高度爲50A〜1 000A以下。 於第2製程氮化金屬1者由多結晶所成、且其多結晶含 氮與金屬化學量論比不爲1 : 1之區域（InuGavAlwNk、惟 u+v+w=l、〇$ u、v、w$l、〇〈k&lt;l)。 又，依本發明I I I族氮化物半導體結晶之製造方法第3 構成，將I I I族金屬原料供應於加熱的基板、堆積Π I族 546850 五、發明說明（7) 金屬原料及/或其分解生成物於該基板上之第1製程；其 後以該基板在含有氮源之環境中熱處理的第2製程，以及 其後使用I I I族金屬原料與氮源以氣相法成長I I I族氮化 物半導體於該基板上的第3製程。 上述成長在基板上的I I I族氮化物半導體結晶之表面具 成（0001)面之面方位、且該表面之垂直軸自&lt;〇〇〇1&gt;方向傾 斜於特定的方向。 上述傾斜的特定方向爲&lt;1 1 -20&gt;方向、且自&lt;〇〇〇1 &gt;方向 的傾斜角度爲0 . 2 °〜1 5 ° 。 再者，依本發明在基板上成長氮化鎵系化合物半導體結 晶層所成的氮化鎵系化合物半導體之製造方法第1構成， 係由附著金屬核在基板上的第1製程；退火該金屬核之第 2製程，氮化退火後之金屬核形成成長核的第3製程；以 及在具成長核的基板上成長氮化鎵系化合物作爲氮化鎵系 化合物半導體結晶層的第4製程所成。 上述基板包含爲藍寶石基板。又，上述第1製程係在經 加熱的基板上，流通含有機金屬原料之蒸氣且不含氮源的 氣體使金屬核附著。 又，有機金屬原料之蒸氣，至少一種含鎵之有機金屬原 料、含鋁之有機金屬原料、及含銦之有機金屬原料的有機 金屬原料之蒸氣。 再者，第2製程亦不含氮源與有機金屬原料之蒸氣、僅 流通載運氣體來進行退火金屬核處理。 546850 五、發明說明（8) 又，第3製程流通含有氮源且不含有機金屬原料之蒸氣 的氣體用來進行氮化金屬核。 又，第4製程流通含有氮源與有機金屬原料兩者之氣體 、由有機金屬氣相成長法來成長氮化鎵系化合物半導體。 又，第2製程以第1製程之溫度以上的溫度進行，第3 製程以第2製程之溫度以上的溫度進行，第4製程以第3 製程之溫度以上的溫度進行。 再者，使第1製程與第2製程交互進行2次以上後進行 第3製程，或反覆進行第1製程與第2製程與第3製程2 次以上後、進行第4製程。 又，上述第1製程係由含流通至少一種含鋁之有機金屬 原料、含鎵之有機金屬原料及含銦之有機金屬原料的有機 金屬原料蒸氣之氣體的前期製程、含有與該前期製程不同 的有機金屬原料之蒸氣的氣體流通之後期製程2製程所成 〇 再者，上述第1製程係以前期製程與後期製程交互進行 2次以上之製程、其後進行第2製程。 又，成長核爲具與基板平行的平坦頂面與平坦側面之大 致梯形狀的氮化物半導體結晶。 又，在第4製程形成的氮化鎵系化合物半導體結晶層上 ，依序成長其他的氮化鎵系化合物半導體結晶層。 又，依本發明在基板上成長氮化鎵系化合物半導體結晶 層所成的氮化鎵系化合物半導體之製造方法第2構成，係 -10- 546850 五、發明說明（9) 由流通含至少一種含鋁之有機金屬原料、含鎵之有機金屬 原料及含銦之有機金屬原料的有機金屬原料之蒸氣的氣體 之前期製程、及含流通與該前期製程不同的有機金屬原料 之蒸氣的氣體流通之後期製程2個製程所成、在基板上附 著金屬核的第1製程，與氮化該金屬核形成成長核的第2 製程，與在具成長核之基板上成長氮化鎵系化合物作成氮 化鎵系化合物半導體結晶層之第3製程所成。 上述基板爲藍寶石基板。 又，上述第1製程係進行前期製程與後期製程交互2次 以上之製程、其後進行第2製程，或第1製程與第2製程 交互進行2次以上後、進行第3製程。 再者，上述第1製程在加熱的基板上、流通含有有機金 屬原料之蒸氣且不含氮源之氣體用來附著金屬核。 又，上述第2製程，係流通含有氮源且不含有機金屬原 料蒸氣的氣體進行氮化金屬核。 又，上述第3製程，係流通含有氮源與有機金屬原料兩 者的氣體、由金屬氣相成長法成長氮化鎵系化合物半導體 〇 又，使第2製程在第1製程之溫度以上的溫度進行，使 第3製程在第2製程之溫度以上的溫度進行。 又，上述成長核，爲具與基板平行的平坦頂面與平坦側 面之大致梯形狀的I I I族氮化物半導體結晶。 又，在上述第3製程形成的氮化鎵系化合物半導體結晶 -1 1 - 546850 五、發明說明（1 〇 ) 層上依序成長其他的氮化鎵系化合物半導體結晶層。 再者，本發明，係由上述第1構成、第2構成及第3構 成之II化録系化合物半導體之製造方法所製造的氮化鎵系 化合物半導體。 又’本發明，係使用上述氮化鎵系化合物半導體所製作 的氮化鎵系化合物半導體發光元件。 又，本發明，係使用上述氮化鎵系化合物半導體發光元 件所製作的光源。 又，本發明，於上述氮化鎵系化合物半導體之製造方法 的第1及第2構成，在上述基板上，包含形成氮化鎵系化 合物半導體之成長速度慢的光罩層之製程，包含選擇性成 長氮化鎵系化合物半導體。 上述光罩層之形成製程係在與成長氮化鎵系化合物半導 體相同的裝置內進行。 上述光罩層之形成，係在加熱的基板上流通含S !之氣 體原料之氣體來進行。 上述光罩層之形成，係在經加熱的基板上同時流通含S 1 之氣體原料氨來進行。 上述形成的光罩層’包含構成光罩層之材料覆蓋基板面 之部分與露出基板面之部分。 於上述第1製程中光罩層之形成係同時使含有I I I族元 素之原料氣體氣體與S i之原料氣體流通。 再於上述氮化鎵系化合物半導體成長前的基板表面上， -12- 546850 五、發明說明（11) 形成使氮化鎵系化合物半導體之成長速度慢的材料被覆基 板面的部分與由氮化鎵系化合物半導體之成長速度快的材 料被覆基板面的部分。 【圖式之簡單說明】 【第1圖（a)〜（e)】 係爲本發明在基板上形成氮化鎵系化合物半導體層時於 各製程（步驟）中成長機構的說明圖。 【第2圖】 係爲本發明在基板上形成氮化鎵系化合物半導體時加熱 形式例圖。 【第3圖】 係爲本發明實施例6之製程圖。 【第4圖】 係爲本發明實施例7之製程圖。 【第5圖】 係爲本發明實施例8及實施例9之製程圖。 【第6圖】 係爲本發明實施例4、實施例1 0及實施例1 1所製作的 半導體發光元件之截面構造模態圖。 【第7圖】 係爲第6圖之半導體發光元件的平面圖。 【第8圖】 係爲本發明實施例1 2及實施例1 5所製作的半導體發光 546850 五、發明說明（12) 元件之截面構造模態圖。 【第9(a)〜（g)圖】 係爲本發明在基板上形成光罩層以形成氮化鎵系化合物 半導體層時各製程之成長狀態例說明圖。 【第10圖（a)〜（f)】 係爲本發明在基板上形成光罩層以形成氮化鎵系化合物 半導體層時各製程之成長狀態的其他例說明圖。 [用以實施發明之最佳形態] 首先，說明本發明I I I族氮化物半導體結晶之製造方法 的第1構成。 本第1構成之I I I族氮化物半導體結晶的製造方法係具 備在基板表面上堆積II I族金屬之微粒子的第1製程、其 後在含有氮源之環境中使該微粒子氮化的第2製程、與在 堆積有該微粒子之基板表面上藉由氣相成長法形成I I I族 氮化物半導體結晶之第3製程。 藉由上述具備第1、第2、第3製程之IΠ族氮化物半 導體結晶之製造方法，可在基板上形成結晶性佳的Π I族 氮化物半導體結晶。而且，該方法與習知使用低溫緩衝層 之方法相比，不需嚴密控制製造條件、可容易地製造高品 質的111族氮化物半導體結晶。而且，本說明書中1 1 1族 氮化物半導體以InxGayAl ZN表示U + y + z = l、OS X ‘ 1、〇$ y $ 1、OS z $ 1 )。 於上述製造方法中，基板可使用玻璃、S i C、S i、G a A s -14-546850 V. Description of the Invention (1) [Technical Field] The present invention relates to a group III nitride semiconductor crystal used in the manufacture of light-emitting diodes (LEDs), laser diodes (L · D), and electrical devices. Xa method, method for manufacturing gallium-based compound semiconductor, gallium nitride-based compound semiconductor, gallium nitride-based compound semiconductor light-emitting element, and light source using the semiconductor light-emitting element. [Prior art] I I I group nitride semiconductors have a band gap with a self-visible light equivalent to the energy in the ultraviolet region and a direct-gap band gap that can emit light with high efficiency, so it can be made into LEDs or LDs. In addition, the heterojunction interface between aluminum gallium nitride (AlGaN) and gallium nitride (GaN) is a two-dimensional electron layer discovered by a characteristic piezoelectric effect in a group I nitride semiconductor. The potential characteristics that 11 I-V compound semiconductors cannot get. However, single-crystal nitride semiconductors are difficult to grow into single crystals due to the temperature at which the single-crystals grow at a temperature lower than the nitrogen dissociation pressure of 2000 atmospheres. For example, other group II-V semiconductors are used for epitaxial growth. As a substrate, it is difficult to make use of a single crystal substrate of a group 111 nitride semiconductor. Therefore, as a substrate for epitaxial growth, a substrate made of different types of materials such as sapphire (A 1 203) single crystal or silicon carbide (S i C) single crystal is used. There is a large lattice mismatch between these heterogeneous substrates and the I I I nitride semiconductor crystals that are epitaxially grown thereon. For example, there is 16% between sapphire (A 1 203) and gallium nitride (GaN), and between SiC and gallium nitride 546850. V. Description of the invention (2) There is 6% grid unconformity. Generally, when there is such a large lattice mismatch, it is not easy to make crystals directly epitaxially grow on the substrate, and even if there is growth, crystals with good crystallinity can be obtained. Therefore, when a Group III nitride semiconductor crystal is epitaxially grown on a sapphire single crystal substrate or a Si C single crystal substrate by an organometallic chemical vapor growth (M0CVD) method, such as Japanese Patent No. 3026087 or a special feature Kaiping 4-: 297023 discloses a method in which a layer called a low-temperature buffer layer composed of aluminum nitride (A1N) or AlGaN is first deposited on a substrate, and a III-nitride semiconductor crystal is generally epitaxially grown at a high temperature. When sapphire is used as the substrate, the above-mentioned low-temperature buffer layer is formed as follows. First, the sapphire substrate is heated to a high temperature of 100 ° C to 1200 ° C in a growth apparatus of the MOCVD method, and the surface oxide film is removed. After that, the temperature of the growing device was reduced to 400-600 ° C. At the same time, Huiren LU was supplied, and the organic metal raw materials and nitrogen source were deposited on the substrate to deposit a low-temperature buffer layer. Then the supply of organic metal materials was stopped and the growing device was raised again. At this temperature, a heat treatment called crystallization of a low-temperature buffer layer is performed, and then epitaxial growth of the II I: Group: ® compound semiconductor crystals. The stacking temperature in the low-temperature buffer layer is z 400 ~ 600 ° C. The organic metal raw material or nitrogen source used as the raw material, especially the ammonia used as the nitrogen source, has insufficient thermal decomposition. Therefore, the low-temperature buffer layer deposited at this low temperature contains many defects. Since the raw materials are reacted at a low temperature, the -4-biopolymerization reaction between the organometallic base of the raw materials or the undecomposed nitrogen source is produced, and these reactions are 546850. V. Description of the Invention (3) Crystallization of the low-temperature buffer layer. It is performed to eliminate these defects or impurities, but it is a heat treatment process called crystallization of the above-mentioned low-temperature buffer layer. The crystallization process of the buffer layer is performed at a high temperature at a low-temperature buffer layer containing a lot of impurities and defects, and at a temperature close to the epitaxial growth temperature of the group I I nitride semiconductor to remove these impurities and defects. As described above, when a low-temperature buffer layer is to be formed, a buffer layer stacking process at a low temperature and a process of crystallization at a high temperature are required. When a high-quality buffer layer is to be obtained, an optimization of the manufacturing conditions related to this temple process is required. The enumeration process of the low-temperature buffer layer is listed, and the ratio of the organometallic raw material to the nitrogen source, the temperature during the stacking, and the flow rate of the carrier gas will affect the characteristics of the low-temperature buffer layer. In addition, during the crystallization process, the temperature or time of the high-temperature heat treatment, the heating rate, and the like may affect the characteristics of the low-temperature buffer layer. For example, T. Itto et al. Reviewed the conditions for these low temperature buffer layers using aluminum nitride. (Journal of Crystal Growth 205 (1999), 20-24) In order to obtain a tube-quality low-temperature buffer layer, each of the above-mentioned manufacturing conditions must be carefully studied, and it is necessary to optimize them. Moreover, these conditions usually need to be adjusted for each growth device used by the MOC VD method for epitaxial growth. The most suitable conditions for transplanting between different growth devices often require a lot of time and labor. The low-temperature buffer layer is used to cause sublimation and recrystallization when crystallization is performed in a hot place, and the crystal core structure made of gallium nitride is sparsely dispersed on the sapphire substrate. The crystal nucleus scattered on the substrate is used as a core to form 546850. 5. Description of the invention (4) A long gallium nitride compound semiconductor and crystals generated at a moderate density are combined to form a crystalline film. That is, production of a gallium nitride-based compound semiconductor layer 'having good crystallinity can be achieved by appropriately controlling the density of the dispersed crystal nuclei. However, the distribution structure of the crystal nuclei in the above-mentioned low-temperature buffer layer depends on the thermal history at the time of temperature rise or the composition of the carrier gas when growing the gallium nitride-based semiconductor layer, and it is difficult to freely control the density of the crystal nuclei only by occasional decision. In terms of shape, size, etc., the crystallinity of the obtained gallium nitride-based compound semiconductor crystal is limited. The present invention aims to provide a manufacturing method of an I I I nitride semiconductor crystal which can form a high-quality I I I nitride semiconductor crystal in a simple method instead of the method using the above-mentioned low-temperature buffer layer in order to optimize too many manufacturing conditions. In particular, a method for manufacturing a group III nitride semiconductor crystal that can epitaxially grow a high-quality group III nitride semiconductor crystal on a sapphire substrate by a simple method (the following group III nitride semiconductor is represented by InxGayAlzN, x + y + z = 0, OSy S 1, OS z S 1). In addition, the present invention provides a person who can freely control the density, shape, size, and the like of the crystal nuclei constituting a layer provided on a substrate so that the crystallinity can be made good and the crystallinity of a crystal layer laminated thereon can be made good. The purpose is to produce a gallium nitride-based compound semiconductor and a gallium nitride-based compound semiconductor. . Furthermore, the present invention aims to provide a light-emitting element and a light source which are excellent in light-emitting efficiency, have a slow deterioration rate, save power, reduce cost, and have low replacement frequency. 546850 V. Description of the invention (5) [Disclosure of the invention] The first constitution of the method for manufacturing a group III nitride semiconductor crystal according to the present invention is a first process of depositing particles of a group III metal on a substrate surface; thereafter, A second process of nitriding the microparticles in an environment containing a nitrogen source; and a third process of forming a group III nitride semiconductor crystal by a vapor phase growth method on a substrate surface on which the microparticles are deposited. The substrate is made of sapphire (A1 203). The group III metal includes InuGavAlw (but u + v + w = 1, 0 S u S 1, and the fine particles of the group III metal are deposited by thermal decomposition of an organic metal raw material. The first process described above includes no nitrogen source In the environment, the temperature is higher than the melting point of the group III metal. The second process is performed in an environment containing no metal raw materials and at a temperature higher than the temperature of the first process. The third process includes Performed at a temperature equal to or higher than the temperature of the second process. The group III nitride semiconductor crystals including the organometallic chemical vapor growth method are formed by the organometallic chemical vapor growth method. Furthermore, in the second process, the nitride is I π. Group metal microparticles are made of polycrystalline and / or amorphous crystalline materials of I 1 I, and contain unreacted metals. In addition, according to Article 546850 of the method for producing a group III nitride semiconductor crystal according to the present invention. Explanation (6) 2 composition, using an organic metal raw material containing at least one kind of 1 η and G a and A1 metal elements in a nitrogen-free environment for thermal decomposition, and using at least one Kind I η and G a and A 1 form I 1 nu G av A 1 w metal 1 (but u + v + w = l, O ^ uSl, 〇Sv € l, 〇gw € l), here The first process of stacking at a temperature T1 above the melting point of metal 1; the second process of nitriding metal 1 at a temperature T2 (but T2-T1) in an environment containing no organic metal raw materials and a nitrogen source; And a third process for epitaxially growing a group I nitride semiconductor crystal by an organometallic chemical vapor growth method at a temperature T3 (but T3-T2) on a sapphire substrate on which metal 1 is deposited. The sapphire substrate has (0001) The vertical axis of the plane and the (00 1) plane is inclined to a specific direction from the &lt; 〇000 1 &gt; direction. The specific direction of the above sapphire substrate is the &lt; 1-1〇〇 &gt; direction and from &lt; 〇 〇01 &gt; The inclination angle of the direction is 0.2 ° ~ 15 °. The above-mentioned temperature T1 is 900 ° C or higher, and the temperature T3 is 1000 ° c or higher. In the first process, the thermal decomposition of the organic metal raw material is in a hydrogen environment. The metal 1 deposited on the sapphire substrate is not layered or granular, and the height of the granular metal 1 is 50A to 1,000A or less. The second process is a region in which the metal nitride 1 is formed by polycrystals, and the polycrystalline nitrogen content and the stoichiometric ratio of the metal are not 1: 1 (InuGavAlwNk, but u + v + w = 1, 〇 $ u, v , W $ l, 0 <k &lt; l). In addition, according to the third configuration of the method for manufacturing a group III nitride semiconductor crystal according to the present invention, a group III metal raw material is supplied to a heated substrate, and the group I 546850 is deposited. 5. Description of the invention (7) The first process of metal raw materials and / or their decomposition products on the substrate; the second process of heat treating the substrate in an environment containing a nitrogen source, and the subsequent use of group III metal raw materials and nitrogen sources The third process of growing a group III nitride semiconductor on the substrate by a vapor phase method. The surface of the I I I nitride semiconductor crystal grown on the substrate has a plane orientation of the (0001) plane, and the vertical axis of the surface is inclined from the &lt; 0.001 &gt; direction to a specific direction. The specific direction of the above-mentioned inclination is the &lt; 1 1 -20 &gt; direction, and the inclination angle from the &lt; 00〇1 &gt; direction is 0.2 ° to 15 °. Furthermore, according to the present invention, the first method of manufacturing a gallium nitride compound semiconductor formed by growing a gallium nitride compound semiconductor crystal layer on a substrate is a first process of attaching a metal core to a substrate; annealing the metal The second process of the nucleus, the third process of forming the metal nucleus after the nitride annealing and the growth of the nucleus; and the fourth process of growing the gallium nitride-based compound on the substrate with the growth nucleus as the crystal layer of the gallium nitride-based compound semiconductor . The substrate includes a sapphire substrate. In the first process, a metal substrate is attached to a heated substrate by passing a vapor containing organic metal raw materials and a nitrogen-free gas. In addition, the vapor of the organic metal raw material includes at least one vapor of the organic metal raw material containing gallium, the organic metal raw material containing aluminum, and the organic metal raw material containing indium. In addition, the second process does not include vapors of nitrogen sources and organic metal materials, and only carries a carrier gas for annealing metal core treatment. 546850 V. Description of the invention (8) In the third process, a gas containing a nitrogen source and containing no organic metal raw material vapor is used to nitride the metal core. In the fourth process, a gas containing both a nitrogen source and an organic metal raw material is passed, and a gallium nitride-based compound semiconductor is grown by an organic metal vapor phase growth method. The second process is performed at a temperature higher than the temperature of the first process, the third process is performed at a temperature higher than the temperature of the second process, and the fourth process is performed at a temperature higher than the temperature of the third process. Furthermore, the third process is performed after the first process and the second process are performed twice or more, or the fourth process is performed after the first process, the second process, and the third process are performed twice or more. In addition, the first process is a preliminary process including a gas containing an organic metal raw material vapor containing at least one organic metal raw material containing aluminum, an organic metal raw material containing gallium, and an organic metal raw material containing indium. The gas flow of the organometallic raw material vapor is completed in the second stage of the second process. Furthermore, the first process described above is a process in which the previous process and the later process are performed twice or more, and then the second process is performed. The growth nuclei are nitride semiconductor crystals having a substantially trapezoidal shape with a flat top surface and a flat side surface parallel to the substrate. Further, on the gallium nitride-based compound semiconductor crystal layer formed in the fourth process, other gallium nitride-based compound semiconductor crystal layers are sequentially grown. In addition, according to the present invention, the second method of manufacturing a gallium nitride compound semiconductor formed by growing a gallium nitride compound semiconductor crystal layer on a substrate is a system of -10- 546850. 5. Description of the invention (9) At least one A gas previous process of vapor containing an organometallic raw material containing aluminum, a gallium-containing organometallic raw material, and an organometallic raw material containing indium-containing organometallic raw material, and a gas flow containing vapor containing a vapor of an organometallic raw material different from the previous process The first process, which is made by two processes of post-processing, and the metal core is attached to the substrate, and the second process, which forms a growing core by nitriding the metal core, and the nitride is formed by growing a gallium nitride-based compound on a substrate with a growing core. The third process of the gallium-based compound semiconductor crystal layer. The substrate is a sapphire substrate. In addition, the first process is a process in which a pre-process and a post-process are interacted more than two times, and then a second process is performed, or a first process and a second process are interacted more than two times, and then a third process is performed. Furthermore, in the first process described above, a gas containing an organic metal raw material and a nitrogen-free gas is passed on the heated substrate to adhere the metal core. In the second process, a metal core is nitrided by flowing a gas containing a nitrogen source and containing no organic metal raw material vapor. In the third process, a gas containing both a nitrogen source and an organometallic material is flowed, and a gallium nitride-based compound semiconductor is grown by a metal vapor phase growth method. The second process is performed at a temperature equal to or higher than the temperature of the first process. This is performed so that the third process is performed at a temperature equal to or higher than the temperature of the second process. The growth nuclei are I I I group nitride semiconductor crystals having a substantially trapezoidal shape with a flat top surface and a flat side surface parallel to the substrate. In addition, other gallium nitride-based compound semiconductor crystal layers are sequentially grown on the gallium nitride-based compound semiconductor crystal formed in the third process -1 1-546850 5. Description of the Invention (10) layer. In addition, the present invention is a gallium nitride-based compound semiconductor manufactured by the method for manufacturing an II chemical compound-based compound semiconductor having the first configuration, the second configuration, and the third configuration described above. The present invention also relates to a gallium nitride-based compound semiconductor light-emitting device manufactured using the gallium nitride-based compound semiconductor. The present invention is a light source manufactured using the above-mentioned gallium nitride-based compound semiconductor light-emitting device. In the present invention, in the first and second configurations of the method for manufacturing a gallium nitride-based compound semiconductor, the substrate includes a process for forming a photomask layer with a slow growth rate of the gallium nitride-based compound semiconductor, including selection. Growth of GaN-based compound semiconductor. The formation process of the photomask layer is performed in the same device as that for growing a gallium nitride-based compound semiconductor. The formation of the above-mentioned photomask layer is performed by flowing a gas containing a gaseous raw material on the heated substrate. The formation of the above-mentioned photomask layer is performed by simultaneously flowing a gas source ammonia containing S 1 on a heated substrate. The photomask layer formed as described above includes a portion of the material constituting the photomask layer that covers the substrate surface and a portion that exposes the substrate surface. The formation of the photomask layer in the above-mentioned first process is to simultaneously circulate the source gas containing the I I I group elements and the source gas of Si. On the surface of the substrate before the above-mentioned gallium nitride-based compound semiconductor grows, -12-546850 V. Description of the invention (11) A portion of the surface of the substrate covered with a material that slows the growth rate of the gallium nitride-based compound semiconductor is formed and nitrided. A material having a high growth rate of a gallium-based compound semiconductor covers a portion of the substrate surface. [Brief description of the drawings] [Figures 1 (a) to (e)] are explanatory diagrams of growth mechanisms in each process (step) when a gallium nitride-based compound semiconductor layer is formed on a substrate according to the present invention. [Fig. 2] Fig. 2 is a diagram illustrating an example of a heating method when a gallium nitride-based compound semiconductor is formed on a substrate according to the present invention. [Figure 3] This is a process chart of Embodiment 6 of the present invention. [Fig. 4] Fig. 4 is a process chart of Embodiment 7 of the present invention. [Fig. 5] It is a process chart of Embodiment 8 and Embodiment 9 of the present invention. [Fig. 6] It is a modal view of a cross-sectional structure of a semiconductor light-emitting element manufactured in Embodiment 4, Embodiment 10, and Embodiment 11 of the present invention. [Fig. 7] Fig. 6 is a plan view of the semiconductor light-emitting element of Fig. 6. [Fig. [Figure 8] This is a semiconductor light-emitting device manufactured in Embodiments 12 and 15 of the present invention. 546850 5. Description of the invention (12) Modal diagram of the cross-sectional structure of the device. [Figs. 9 (a) to (g)] This is an explanatory diagram of an example of the growth state of each process when a photomask layer is formed on a substrate to form a gallium nitride-based compound semiconductor layer in the present invention. [Fig. 10 (a) to (f)] This is an explanatory diagram of another example of the growth state of each process when a photomask layer is formed on a substrate to form a gallium nitride-based compound semiconductor layer in the present invention. [Best Mode for Carrying Out the Invention] First, the first configuration of the method for manufacturing a group I nitride semiconductor crystal according to the present invention will be described. The method for producing a group III nitride semiconductor crystal of the first structure includes a first process of depositing particles of a group II metal on a substrate surface, and a second process of nitriding the particles in an environment containing a nitrogen source. And a third process of forming a group III nitride semiconductor crystal by a vapor phase growth method on the surface of the substrate on which the fine particles are deposited. According to the manufacturing method of the group III nitride semiconductor crystal having the first, second, and third processes described above, a group III nitride semiconductor crystal having excellent crystallinity can be formed on the substrate. In addition, this method can easily produce high-quality 111-nitride semiconductor crystals without strictly controlling the manufacturing conditions compared with the conventional method using a low-temperature buffer layer. In the present specification, the group 1 1 1 nitride semiconductor is represented by InxGayAl ZN, U + y + z = 1, OS X ′ 1, 〇 $ y $ 1, OS z $ 1). In the above manufacturing method, glass, S i C, S i, G a A s -14-

L 546850 五、發明說明（13) 、藍寶石％ 。尤其是上述基板爲藍寶石（Al2〇3)時，具有 可得高品質結晶、以及可低價得手的優點。 藍寶石基板之面方位係使用m面、a面、c面，其中以 c面（ 000 1面）較佳、以基板表面之垂直軸自&lt;000 1 &gt;方向傾 斜於特定方向者更佳。而且，本發明所使用的基板於第1 製程使用前進行如有機洗淨或蝕刻之前處理、可保持基板 表面於一定狀態，故爲理想。 該製造方法之第1製程中堆積於基板表面之ΠI族金屬 的微粒子可使用A 1或G a、I η等。此處，本發明之I I I族 金屬之微粒子尤以 InuGavAlw(u + v + w= l、OS 1、OS vS 1 、0 S 1 )更佳。I I I族金屬爲InuGavAlw時，具有與繼 後經成長的I I I族氮化物半導體之親和性高的優點。而且， 於此等III族金屬之微粒子中亦可添加Si、Be、Mg等III 族以外的金屬。另外，藉由金屬化合物之分解以堆積II I 族金屬時，所形成的I I I族金屬之微粒子中含有碳或氫、 鹵素等雜質，惟此等亦可作爲金屬微粒子使用。 該製造方法之I II族金屬微粒子的堆積可藉由有機金屬 原料或金屬鹵化物之熱分解、或蒸鍍或濺射等各種方法進 行。 尤其是藉由有機金屬原料之熱分解以使上述I I I族金屬 之微粒子堆積爲宜。有機金屬原料可使用三甲基鎵（TMG ) 或三乙基鎵（TEG )或三甲基鋁（TMA )或三甲基銦（TM I )或雙 環戊二烯銦（Cp21 η )之化合物。藉由有機金屬原料之熱分 -1 5 - 546850 五、發明說明（14) 解使上述I I I族金屬之微粒子堆積時，具有可以i n s i t U 堆積金屬微粒子的優點。 使上述第1製程在含有氨之氮源環境下進行_時，由於會 產生阻害表面遷移的問題，故以使上述第！製程在不含氮 源之環境下進行較佳。而且，此處不考慮作爲惰性載體氣 體廣爲使用的N2氣體作爲氮源。n2之分解溫度比氨或吡啶 等一般的氮源爲高、作爲氮源時不是很有效。因此，此等 方法於第1製程中環境中含有N2氣體時不會阻害其效果。 具體而言，作爲環境氣體可使用氫、稀有氣體、氮氣等。 本發明以使第1製程在上述I 11族金屬之熔點以上的溫 度下進行較佳。使第1製程在上述I I I族金屬之熔點以上 的溫度進行時，會有基板上之原子容易遷移、形成微粒子 的優點。 在該第1製程中基板表面上堆積的111族金屬之微粒子 係爲在基板表面上不連續分散、堆積的I I I族金屬之粒子 。III族金屬之微粒子亦可相互接合。該堆積於基板表面 之I 11族金屬之微粒子狀態可以使用AFM (原子間力顯微鏡） 之測定方法觀察。以該第1製程形成的主要I Π族金屬之 微粒子自基板面至粒子頂上的高度爲50〜1 000A，由與基 板垂直方向觀察粒子時自粒子一端至另一端的長度爲1 00 〜10000A，表面密度爲 lXl〇6cirT2 〜lXl01QcnT2。 第2製程在含金屬原料之環境下進行時，由於以第3製 程所成長的I I I族氮化物半導體結晶之結晶性不佳，故以 -16- 546850 五、發明說明（15) 使第2製程在不含金屬原料之環境下進行較佳。而且，第 2製程時之含氮源的環境可使用含氨或吡啶之環境。 進行該第2製程時環境之壓力以1 〇〇〇〜1 X l〇5Pa較佳。 又，以上述第2製程氮化的I I I族金屬的微粒子爲含有 藉由截面透過電子顯微鏡（TEM )解析的結果、由多結晶及/ 或非晶質所成者、且含有未反應的金屬者。 上述第2製程以在第1製程以上之溫度進行較佳。本發 明人等之實驗結果使第2製程在第1製程以上之溫度下進 行時，可製作結晶性佳的I I I族氮化物半導體結晶。另外， 爲進行金屬粒子之氮化反應時，具體而言第2製程以700 °C以上較佳、更佳者爲90(TC以上之溫度下進行。 第2製程之I I I族金屬微粒子的氮化可藉由使堆積有微 粒子之基板在含有氮源之環境中、700 t以上之溫度下保 持1〜1 Q分鐘予以進行。 第3製程以在第2製程以上之溫度下進行較佳。使第3 製程在第2製程以上之溫度進行時，具有可使成長的！ ί ][ 族氮化物半導體高品質化的優點。具體而言，第3製程以 7〇0°C以上之溫度下較佳、更佳者爲90(TC以上之溫度。 g亥第3製程可使π I族氮化物半導體結晶之形成藉由有 機金屬化學氣相成長法（MOCVD)、分子線外延法（MBE)、氣 相成長法（VPE)等各種氣相成長法進行。尤其是由於具有 薄膜成長的優點，故藉由有機金屬化學氣相成長法形成 U I族氮化物半導體結晶者較佳。上述有機金屬化學氣相 -1 7 - 546850 五、發明說明（16) 成長法係使用含有有機金屬化合物與氮源之氣體作爲環境 氣體，在1 000〜lX105Pa之壓力進行成長之習知有機金 屬化學氣相成長法。 特別是藉由M0CVD法進行第3製程時，一般而言溫度爲 1〇0 0 °C時可得結晶性佳的氮化鎵系化合物半導體係爲已 知。此係氮化鎵系化合物半導體之成長型式在1 000°c附近 之溫度以上與以下時不同，在1 0 0 0 °c以上之溫度下爲橫 方向成長強的型式。此時，以低轉位形成表面形態佳的結 晶膜。 本發明I I I族氮化物半導體結晶之製造方法的第2構成 ，係先於第1製程中、不含氮源之環境中使用至少一種含 有 I η與G a與A1之金屬元素的有機金屬原料的熱分解， 在藍寶石基板上使由1種以上I η與Ga與A丨所成的金屬 1 (金屬 1 以 I nuGavAlw 表示，惟 u + v + w=l、0$ u‘ 1、0€ v S 1、0 S w S 1 )在該金屬1之熔點以上的溫度T1下堆積。 繼後之第2製程係在不含有機金屬原料、含氮源之環境中 、溫度Τ2 ( Τ2 2 Τ 1 )下使金屬1氮化。另外，繼後之第3 製程係在上述堆積有金屬1之藍寶石基板上、溫度Τ3(Τ3 -Τ 2 )下藉由有機金屬化學氣相成長法使I I I族氮化物半 導體（ΙΠ族氮化物半導體以InxGayAlzN表示，惟x + y + z二1 、〇$ X S 1、〇$ y $ 1、0 S z ‘ 1 )結晶外延成長者。 藉由上述方法在藍寶石基板上使結晶性佳的I I I族氮化 物半導體結晶外延成長。而且，該方法與習知使用低溫緩 -18- 546850 五、發明說明（17) 衝層的方法相比，不需嚴密控制製造條件、可容易製造高 品質的III族氮化物半導體結晶。 再者，本發明人等發現藉由上述藍寶石基板具有（000 1) 面、且（ 000 1 )面之垂直軸自&lt;000 1 &gt;方向傾斜於特定方向， 可增強11 I族氮化物半導體結晶之成長形式較佳的分段流 動成長。該分段流動成長，由於最強調垂直軸傾斜的特定 方向爲&lt;1-100〉方向，且自&lt;〇〇〇1&gt;方向之傾斜角度爲0.2。 〜1 5 °時最爲所強調，故可作爲理想的製作高品質π I族 氮化物半導體結晶之條件使用。 又，爲有效地使有機金屬原料熱分解時，溫度T 1爲 20 0°C以上、且T1以金屬1之熔點以上的溫度較佳。更佳 者使溫度T1爲900°C以上，有機金屬原料之分解接近於 1〇〇％、且堆積的金屬1爲熔融狀態。又使I 11族氮化物半 導體結晶外延成長的溫度T3以700 °c以上、理想爲1000 °C以上，可保證氮源之分解充分地進行。 由於上述金屬1以高於熔點的溫度下堆積，藉由本身之 表面張力在藍寶石基板上不會形成層狀、以粒狀形狀，由 原子間力顯微鏡（TEM)之觀察所確認。然後該粒狀之金屬1 ，在上述第2製程使用氮源氮化後亦保持相同的形狀。 I I I族氮化物半導體結晶之外延成長，係以該粒爲核來進 行，故可得結晶性佳的π 1族氮化物半導體結晶。 又，上述第2製程氮化的金屬1，藉由截面透過電子顯 微鏡（ΤΕΜ)解析的結果，由多結晶形成、且該多結晶不在 -19- 546850 五、發明說明（18) 金屬與氮之化學量論比爲1 : 1之區域（該區域之組成以 I n uGavAlwNk 表示，惟確認 了包含 + V + 、0 S u，v，w S 1 、0 &lt; k &lt; 1 )。該點係爲同時供應有機金屬原料與氮源、在 低溫下堆積、其後用以在高溫下結晶化進行熱處理的習知 之低溫緩衝層、與本發明之氮化金屬1方法之成長形式不 同的差異點。 本發明ΠI族氮化物半導體結晶之製造方法的第3構成， 其特徵包含在加熱的基板上供應11 I族金屬原料、將I j j 族金屬原料及/或其分解生成物堆積於該基板上之第1製 程、與其後使該基板在含氮源之環境中熱處理之第2製程 、其後，使用I I I族金屬原料與氮源在該基板上以氣相法 成長111族氮化物半導體的第3製程。 於第1製程中，作爲環境中所含有的11 I族金屬原料， 可使用有機金屬化合物、金屬鹵化物、金屬等，惟其中以 使用有機金屬化合物較佳。作爲I I I族元素之有機金屬化 合物，可使用如三甲基鎵（TMG)或三甲基鋁（TMA)或三甲基 銦（TMI)或雙環戊二烯銦（Cp2In)之化合物。 又，於第1製程中以S 1、M g等I I I族金屬以外之元素 作爲摻雜之目的，在環境中可含有矽烷（s i &amp; )、二砂院 (S i 2H6)、雙環戊二烯鎂（Cp2Mg )等。 又，第1製程以在環境中不含氮源者較佳。在第1製程 中含有氨等之氮源時，成長的氮化鎵系化合物半導體結晶 膜之表面形態不會成爲鏡面。此係如專利第3〇26〇87號公 -20- 546850 五、發明說明（19 ) 報或特開平4 _ 29 7023號公報以習知技術所記載。在此作 爲惰性載運氣體廣爲使用的N2氣體係不作爲氮源。n2之分 解溫度比氨或吡啶等通常的氮源爲高、作爲氮源並不是有 效。因此，此等發明中於第1製裎之環境中包含n2氣體， k寸本發明之效果不會有大的阻礙。 又，第1製程中亦可包含氫氣、氮氣、稀有氣體等於環 境中。 又，依本發明人等之實驗結果可知，以第2製程在第1 製程以上之溫度進行時，可製作結晶性佳的Π I族氮化物 半導體結晶。再於用以進行金屬1之氮化反應，具體而言 第2製程係700°C以上、更佳爲900 °C以上之溫度進行爲 理想。特別是使用1 000°C以上之溫度可獲得良好的結晶性 又，作爲第3製程所使用的I 11族氮化物半導體之成長 方法，以使用有機金屬化學氣相成長（MOCVD )法較佳。並 由採用該方法，使第1製程至第3製程可在同一成長爐中 進行。 使用有機金屬化學氣相成長法來成長I I I族氮化物半導 體時，用來進行第3製程的溫度以1 000°C以上爲最佳。 特別是第3製程以1 1 〇〇°C以上之溫度進行時容易於得鏡面 結晶，故較佳。在含有氫之環境中進行第3製程時，有容 易控制結晶性及表面形態之優點。 再如上述，本發明所使用的基板以藍寶石爲宜，藍寶石 -21 - 546850 五、發明說明（20) 基板具有（0001)面、該（ 000 1 )面之垂直軸自&lt;〇〇〇1&gt;方向傾 斜於特定方向爲理想。再者’藍寶石基板之垂直軸作傾斜 的特定之方向爲&lt;i-i〇〇&gt;方向，且自&lt;00〇1&gt;方向之傾斜角 度以0.2°〜1 5°爲宜亦如上所述。 如上述，藍寶石基板具有（000 1 )面、該（ 000 1 )面之垂直 軸自&lt;000 1 &gt;方向朝&lt;1 - 1〇〇&gt;方向傾斜〇 .2°〜15°之角度時， 在基板上成長的I II族氮化物半導體結晶之表面具有 (0 0 0 1)面、且該表面之垂直軸自&lt;0 0 0 1 &gt;方向傾斜於特定之 方向。在此I 11族氮化物半導體結晶之表面傾斜的特定方 向成爲&lt;11-20&gt;方向。此係III族氮化物半導體結晶，與 基板之面方位比較旋轉30°c來成長者。此時，在基板上 成長的III族氮化物半導體結晶之表面自&lt;000 1 &gt;方向所傾 斜的角度爲 0.2 °〜1 5 °時，因由增強於分段流動成長， 故作爲製造高品質的I I I族氮化物半導體結晶之條件爲理 想。 又，此製造方法亦可包含在第1製程之前稱爲熱退火的 公知之熱處理製程。熱退火係於基板爲藍寶石時廣爲使用 、在成長爐內進行洗淨處理之一種，具體而言，一般在含 有氫或氮之環境中以1000〜1200 °c之溫度下處理基板。 又，此製造方法係可分第1製程爲數次進行。此時，以 第1次與第2次、第2次與第3次等、可改變環境中含有 的I Π族金屬原料之種類或組成、混合比等。又，亦可改 變基板之溫度或進行處理時間等之條件。 -22- 546850 五、發明說明（2〇 將第1製程分成數次實行時，在最先開始的環境中含有 的I I I族金屬原料，以含有A 1之原料較佳。A 1係在I I I 族金屬中熔點高、爲容易附著於基板上之原料◦ 又，此製造方法可在第1製程與第2製程之間及/或第 2製程與第3製程之間，可包含不含金屬原料及氮源之環 境中處理基板之退火製程。並由該退火製程可促進金屬微 粒子之集散、可形成更合適的形狀之π I族金屬微粒子。 此時，進行退火處理之溫度以π I族金屬微粒子之熔點 以上爲佳、更佳爲900°C以上、最佳爲1 000°C以上。又， 進行退火之環境係以含有氫爲宜。 於本發明，可邊改變第2製程之基板溫度來進行。在此 情況進行第2製程之溫度，不用說以氮源之分解溫度以上 爲宜。具體而言使所有第2製程全部爲70(TC以上，更佳 爲900°C以上、最佳爲l〇〇〇°C以上進行爲理想。 又，以結束的溫度高於開始第2製程的溫度爲理想。 又，開始第2製程的溫度與進行第1製程的溫度相同， 並可使結束第2製程之溫度與用以進行第3製程的溫度相 同。 又，邊改變溫度來進行第2製程時，伴隨溫度的變更亦 可有變更載運氣體之種類或流量、又爐內之壓力。 其次，依本發明之氮化鎵系化合物半導體的製造方法依 照圖面詳細說明。 第1圖係於氮化鎵系化合物半導體層形成時各製程（步 -23- 546850 五、，蒼明說明（22) 驟）之成長機構說明圖，第2圖係表示此等發明之氮化鎵 系化合物半導體層形成時的熱圖案之一例圖。 此等發明之氮化鎵系化合物半導體，係槪略以如次步驟 形成在基板上。亦即，如第1圖（a )所示首先於步驟A (第 1製程）中、在基板上附著金屬元素、較佳由I I I族金屬元 素所成的金屬核（金屬粒）S a。在此階段S a之形狀以不連 續地散佈之粒、以液狀覆蓋於表面亦可。接著，於步驟 B(第2製程），退火該金屬核Sa(第1圖（b))。並由該退火 處理，在第1製程完全未變成不連續的粒狀S a ,亦成爲 理想的不連續粒狀之形狀。接著在步驟C (第3製程），氮 化退火後之金屬核S a 1作爲成長核S b (第1圖（c ))。該成 長核Sb乃帶有爲任何形狀時，只要是以適當的密度分布 時即作爲成長核之功能者。然而，成長核Sb之形狀會影 響氮化鎵系化合物半導體層之結晶性，亦藉由申請人等之 實驗判明。特別是與基板1平行的平坦頂面及具有與基板 1成某角度相交的平坦側面之大致梯形狀的I I I族氮化物 半導體結晶爲宜。而該成長核Sb，例如留意進行氮化時之 環境氣體、爐內壓力、基板溫度或基板溫度之熱圖像可形 成較佳的形狀。 而且，於步驟D(第4製程）中，具有其成長核Sb之基 板 1上使氮化鎵系化合物半導體結晶層成長（第1圖（d )) 。該成長主要是邊伴隨轉位朝水平方向進行，並由此，確 保在垂直方向充分的層厚（例如2 // m )、又水平方向獲得平 -24- 546850 五、發明說明（23) 坦的氮化鎵系化合物半導體2 (第1圖（e ))。 上述各步驟A〜D可在MOCVD法之成長裝置內連續的進 行。而具，於實行步驟A之前如第2圖所示，例如先使由 藍寶石所成基板在M0CVD法之成長裝置內、高溫加熱至 1〇O0°C〜120O°C (第2圖爲1 170°C )進行熱淸理，除去表 面之氧化膜等。接著，使成長裝置之溫度例如下降5°C〜 2〇〇°C左右保持於一定溫度（第2圖爲11〇〇 °C)，在其一定 溫度下實行步驟A、步驟B及步驟C。其次，由步驟C之 氮化處理的形成成長核Sb之途中，使成長裝置之溫度昇 溫 5°C〜200 °C程度保持於一定溫度（第2圖爲1 16CTC )， 在該一定溫度下實行步驟D，使成長核S b更成長氮化鎵 系化合物。 尙，上述說明與第1圖所示之製程爲此等發明之一例， 惟此等之本發明並不受此等限制者。例如，熱淸理可因應 於需要來進行。又，有關溫度之圖案亦不受第2圖之圖案 所限制者，因應於成長使用的爐之形狀或有機金屬原料、 氮源、載運氣體之種類、流量等採用適當之條件爲宜。具 體而言，自步驟A至步驟C之各製程的溫度可以不同，步 驟A與步驟B、步驟B與步驟C之溫度分別爲不同亦可。 又，步驟D之溫度亦可較自步驟A至步驟C之溫度爲低， 亦可爲同樣溫度。 如此在本發明之此等實施形態，係先在基板1上附著金 屬核Sa、以其金屬核sa爲基來形成成長核Sb、在其成長 -25- 546850 五、發明說明（24) 核上更予以成長氮化鎵系化合物。附著於基板1上之金屬 核 Sa，係由有機金屬氣體之流量或流通時間、處理溫度 等可控制其成長，故亦可自由地控制金屬核S a存在於基 板 1上的密度。 又，由在該金屬核Sa予退火處理，與基板之濕潤性效 果產生的集使金屬核Sa本身增大垂直方向之尺寸（Sal 在第1圖（b ))，在無金屬核S a之部分產生金屬蒸發而減 少附著物形成S a 1附著部分與其間的基板表面露出之空間 所構成的基板面。並由此，可控制氮化結果所得的成長核 S b的密度爲較佳的狀態。特別是進行退火時之環境氣體、 溫度、壓力、時間等具有控制密度的效果之條件。此等條 件必須由作爲金屬核S a所附著的金屬種類或爐的形狀適 當地選擇。由本申請人等之實驗作爲環境氣體使用氫、作 爲、溫度使用9 00t以上之溫度、辨知爲實施5分鐘以上之 退火較佳。 又其後，由實予氮化處理來氮化金屬核Sa 1 ,變化成爲 氮化物半導體構成的成長核Sb。成長核Sb係如上述，取 具有與基板平行的平坦頂面與平坦側面之大致梯形狀截面 的形狀爲較佳。控制成長核Sb之形狀可以氮化處理時之 條件來控制。特別是進行氮化時之環境氣體、溫度、壓力 等對控制形狀具有效果之條件。此等之條件以作爲金屬核 S a所附著的金屬種類或使用於氮化處理的氮原料、爐之形 狀等需要適當地選擇。在本申請人之實驗，作爲環境氣體 -26- 546850 五、發明說明（25) 係氫、作爲溫度係使用900 t：以上之溫度、辨明了在氮化 製程之間使溫度上昇爲理想。 而且，在該成長核Sb上更予成長另使氮化鎵系化合物 半導體，故氮化鎵系化合物係以如埋相鄰的成長核S b間 予地成長，埋完相鄰的成長核s b間之空間後，在其上成 爲平坦層成長。因而，最後在基板上，可形成具備所希望 的層厚與良好結晶性的氮化鎵系化合物半導體2之層。 曰亥化纟豕系化合物半導體層之表面由氮化鎵系化合物覆 蓋，故與疊層於其上的氮化鎵系化合物半導體可保持極佳 良好的格子整合性，因而，在基板上藉由氮化鎵系化合物 半導體層之可形成具有良好結晶性之氮化鎵系化合物半導 體各層。而且，使用該氮化鎵系化合物半導體製造半導體 發光元件時，亦可確實地提高其發光特性。 又，使用上述方法製作的半導體發光元件，對電子機器 用、車輛搭載用、交通信號用其他電器裝置，可利用爲良 好亮度等發光特性的光源。 上述半導體所使用的基板可使用玻璃、Sic、Si、GaAs 、藍寶石等。特別是上述基板爲藍寶石（A 1 20 3 )時，有獲 得高品質的結晶及廉價得手的優點。 作爲藍寶石基板之面方位係可使用m面、a面、c面等， 但其中以c面（（000 1 )面）較佳。又，本發明所使用的基板 ，以使用於第1製程前進行如有機洗淨或蝕刻之前處理時 可保持基板表面一定的狀態乃理想。 -27- 546850 五、發明說明（26) 又在第1製程中於附著基板上的金屬核之材料可使用A ] 或 Ga、In等之金屬。於此本發明係特別是，金屬核以 I n L1GavAlwr_ u +v + w二 1、〇 $ u $ ι、〇 $ v $ 1、〇 $ w g ι )能表 示之111族金屬爲理想。若金屬核爲I n uG a v A 1 w時有與使 其後成長的氮化鎵系化合物半導體之親和性高的優點。又， 此等111族金屬的金屬核亦可添加作雜質之S 1、Be、Mg 等I I I族以外之金屬。再者，由有機金屬原料之分解使金 屬核附著時，在形成的金屬核中難含有碳或氫、鹵素等雜 質，但此等亦可作爲金屬核使用。 又，金屬核之附著係可由有機金屬原料或金屬鹵化物之 熱分解、或蒸鍍或濺射等依各種方法進行。 在本發明係使控制金屬核之密度或形狀容易，故特別使 用由有機金屬原料之熱分解使上述金屬核附著的方法較佳 。作爲有機金屬原料使用含有三甲基鎵（TMG)或三乙基鎵 (TEG)、三甲基鋁（TMA)、三甲基銦（TMI )、雙環戊二烯銦 (Cp2In)之鎵、鋁或銦的有機金屬原料時可使如inuGavMw 之I Π族金屬之金屬核附著。 又，將第1製程在含氨之氮源的環境下進行時，由於有 時會產生如金屬原子之表面移動之阻礙問題，故將上述第 1 製程在不含氮源之環境下進行較佳。又於此處，作爲惰 1生的載運氣體廣爲使用的n2氣體係不考慮爲氮源。n2之分 解溫度係高於氨或吡啶等通常之氮源、作爲氮源並不是有 效。因此，於第1製程之環境中包含N2氣體，並不阻礙 -28- 546850 五、發明說明C 27) 此等發明之玫果。具體而言，作爲環境氣體可使用氫、稀 有氣體、氮等。 又，將第1製程在金屬核之熔點以上溫度進行爲佳。當 使第1製程以金屬核之熔點以上溫度進行時，在基板上使 金屬原子之移動圓滑地進行、有容易形成金屬核的優點。 再者，所謂以第1製程堆積於基板表面之金屬核，係爲 在基板表面上以連續分散所堆積的金屬之微粒子。金屬之 微粒子亦可部分的相互接合。附著於如此基板表面的金屬 核之狀態可由如AFM (原子間力顯微鏡）之測定方法觀察。 以第1製程形成的主要金屬核，係自基板面至粒子頂的 高度爲5 0人〜1000A程度，自基板與垂直方向看粒子時其 自粒子一端至端之長度爲100 A〜10000A程度，表面密 度爲 lXl06cnT2 〜lXl01(3cnT2 程度。 又，在退火之製程僅流動不含氮源及有機金屬原料之載 運氣體進行金屬核之退火時，可有效率地產生金屬核之凝 集故理想。作爲載運氣體可使用氫、稀有氣體、氮等，尤 其是氫氣具有除去金屬核表面之氧化物的作用，故最理想 。又，金屬核之退火以金屬核之熔點以上溫度，且以7 0 0 °C以上之溫度進行時因金屬之凝集有效地產生故理想。 將該退火之製程在第1製程以上之溫度來進行爲理想。 本發明人等之實驗結果，當退火製程以第1製程以上之溫 度進行時，可製作結晶性佳的氮化鎵系化合物半導體結晶 。其中，使退火製程與第1製程之溫度相同時，係可行形 -29- 546850 五、發明說明（28) 成良好結晶性的氮化鎵系化合物半導體、因藉由裝置的爐 內狀態之控芾ϋ亦容易，故實施性優異。 又，將氮化金屬核之製程在含有金屬原料之環境下進行 時，在下一製程成長的氮化鎵系化合物半導體結晶係結晶 性不良，故氮化金屬核的製程在不含金屬原料之環境中進 行爲理想。又在此等之發明，氮化金屬核之際含氮源之環 境可使用含氨或吡啶的環境。又，進行該製程之際之環境 壓力爲1000〜1 X l〇5Pa爲理想。 在上述氮化製程氮化金屬核形成的成長核，由截面透過 電子顯微鏡（TEM)解析的結果，由多結晶及/或非晶質所成 、且含有未反應的金屬者。 又用以進行金屬核之氮化反應以氮化製程爲700°C以上 、更理想以 900°C以上之溫度進行時，用以製作結晶性良 好的氮化鎵系化合物半導體結晶爲理想。 由金屬核之氮化形成金屬核，係藉可將堆積金屬核之基 板在含氮源之環境中以7 〇 〇 C以上溫度保持1〜1 〇分鐘程 度來進行。 又，使該氮化製程在退火製程以上之溫度進行爲理想。 本發明人等之實驗結果，係氮化製程以退火製程以上之溫 度進行時，可製作了結晶性良好的氮化鎵系化合物半導體 結晶。其中，氮化製程與退火製程之溫度相同的狀況，係 可形成結晶性良好的氮化鎵系化合物半導體、依裝置的爐 內溫度亦容易控制，故實施性優異。 •30- 546850 五、發明說明（29) 再於具有成長核之基板上使氮化鎵系化合物半導體成長 的製程，在70CTC以上之溫度、更理想爲以900 °C以上之 溫度進行時，有可使氮化鎵系化合物半導體高品質化的優 點。 又，氮化鎵系化合物半導體之成長製程，可採用有機金 屬化學氣相成長法（M0CVD)、分子線外延法（MBE)、氣相成 長法（VPE)等各種氣相成長法進行。特別是於此等發明， 係有薄膜成長可能的優點，故以有機金屬化學氣相成長法 形成氮化鎵系化合物半導體結晶爲理想。作爲本發明之有 機金屬化學氣相成長法，可使用含有有機金屬化合物與氮 源之氣體作爲環境氣體，可採用在1 000〜lXl〇5Pa程度 之壓力進行成長的公知之有機金屬化學氣相成長法。 又將氮化鎵系化合物半導體之成長製程在氮化處理以上 之溫度進行爲理想。在本發明人等之實驗結果，使氮化鎵 系化合物半導體之成長製程以氮化處理以上之溫度進行時， 可製作了結晶性良好的氮化鎵系化合物半導體結晶。其中， 使氮化鎵系化合物半導體之成長製程與氮化製程之溫度相 同的情況，係可形成結晶性良好的氮化鎵系化合物半導體 、依裝置的爐內狀態亦容易控制，故實施性優異。 尙，上述說明中，附著金屬核S a於基板上、在該金屬 核S a上施予退火處理，惟亦可重複進行金屬核S a之附著 以代替該退火。並由重複進行該金屬核S a之附著，亦可 適當地控制由步驟C所形成的成長核S b之密度。 -31- 546850 五、發明說明（3〇) 在此情況，由附著最初金屬核的前期製程、與進行第2 次之金屬核附著的後期製程、因應於基板1之附著性來選 擇流通原料的種類，變成容易控制成長核S b之密度或形 狀。在本發明前期製程係流通至少含有一種含鋁之有機金 屬原料、含鎵之有機金屬原料及含銦之有機金屬原料的有 機金屬原料之含蒸氣的氣體之製程，後期製程係流通與前 期製程不同含有機金屬原料蒸氣的氣體之製程爲理想。此 時，例如在前期製程予以流通附著性佳的含鋁之原料於基 板、在基板上以所希望密度形成金屬核S a ,在後期製程 流通附著性不良的G a或I n、可製作具有如在A 1之周圍上 纒住Ga或I η構造的金屬核S a。亦可使該前期製程與後期 製程交替著僅進行1次，惟以交替著進行2次以上爲理想 〇 其後，不予進行退火，由氮化進入成長核之形成，但 在此情況，亦由以適當地控制氮化可形成具有良好形狀的 成長核Sb。此係與使用退火來控制金屬核Sa 1之密度時同 樣。與採用退火時同樣，進行氮化時之環境氣體、溫度、 壓力等即爲具控制形狀效果的條件。此等條件需要由作爲 金屬核S a附著的金屬種類或氮化處理使用的氮原料、爐 形狀等適當地選擇。在申請人之實驗係作爲，環境氣體使 用氫、作爲溫度採用90(TC以上之溫度、在氮化製程之間 明白了亦可上升溫度。 又於此情況將氮化鎵系化合物半導體之成長製程以氮化 -32- 546850 五、發明說明（31) 製程以上之溫度進行較理想。本發明人等之實驗結果，係 將氮化鎵系化合物半導體之成長製程以氮化製程以上之溫 度進行時，可製作了結晶性良好的氮化鎵系化合物半導體 結晶。其中，使氮化鎵系化合物半導體之成長製程與氮化 製程之溫度相同時，係可形成結晶性良好的氮化鎵系化合 物半導體、因依裝置的爐內狀態亦容易控制，故實施性優 異。 依本發明氮化鎵系化合物半導體之製造方法，如上所述 ’在基板上附著金屬核、成長，作爲使用藍寶石基板，在 基板上形成氮化鎵系化合物半導體之成長速度慢的光罩層 、並由選擇成長氮化鎵系化合物半導體，形成結晶性優異 的膜。 製造具有良好結晶性之氮化鎵系化合物半導體結晶膜的 機構依第9圖（a )〜（g )說明。 如第9圖（a )所示，在加熱至規定溫度的藍寶石基板 1 3 1上，以流通含S i之原料氣體3與氨氣體4 ,使2個彼 此化合物間反應在氮化矽膜基板1上形成氮化矽之膜5。 該膜5之形成因從散佈在基板上的活性點開始，故在膜5 之形成初期無法形成均勻地覆蓋全體。因此，適當地控制 成長時間時，在藍寶石基板1上形成由所生成的氮化矽5 覆蓋的區域、與露出藍寶石之區域6 (第9圖（b ))。接著， 由111族元素所成的液滴狀之粒7供應於區域6後（第9 圖（c )),流通氨予以反應、在區域6生成I Π族氮化物8 ( -33 - 546850 五、發明說明（32) 第9圖（d )),以氮化矽5覆蓋的區域上沒有產生氮化鎵系 化合物半導體之成長核，自露出藍寶石面之區域6成長結 晶 9(第9圖（e)),在氮化砂膜5上朝橫方向成長（第9圖 (f ))。結果，結晶9覆蓋於藍寶石基板1全面上（第9圖 (g ))，可控制由藍寶石與氮化鎵系化合物半導體之間格子 定數之不同所產生的貫通轉位之成長方向，大多數的轉位 描繪環閉住、不會朝上下方傳移，降低貫通轉位之密度形 成良質的結晶。 製作光罩層之際，除同時流通S1原料氣體與氨等之氮 氣原料氣體的方法外，預先可在藍寶石面上流通氨部份地 氮化表面，對該處流通S i原料氣體稀疏地製作單層分量 之氮化矽作成光罩層的方法。又，製造氧化矽層作爲光罩 層時，由熱淸理以活性化藍寶石表面之氧原子，對該處流 通S i原料氣體亦可稀疏地製作單層份量之氧化矽。 再者，在藍寶石基板上形成具成長速度差的層之方法， 係流通於同時加熱s i原料氣體與111族原料氣體的藍寶 石基板上，其後流通热的方法爲有效。 第10圖（a )〜（f)中表示使用該’方法時之成長過程模態 圖。首先，在加熱的基板1上流通S i原料氣體3與I I I 族原料氣體3 ’（第1 0圖（a ))。結果，S i原料氣體3與I I I 族原料氣體3 ’分解、在藍寶石基板1上以規定間隔附著矽 原子之集合體1 0與I I I族金屬之液滴狀粒7 (第1 〇圖（b )) 。其次，流通氨4時，各個予以氮化、可在基板1上形成 -34- 546850 五、發明說明（33 ) 由氮化矽所成的成長速度慢的膜5，與由氮化鎵系化合物 半導體所成的成長速度快的膜8構成的光罩層（第1 〇圖 (c))。在該光罩層上成長氮化鎵系化合物半導體9時，與 第9圖之實施例相同地，由氮化鎵系化合物半導體所成膜 8上以選擇性的成長結晶9 ,並由該選擇性成長予實現提 高結晶性。 又，弟9圖與弟1 0圖g兌明的方法，必須於形成光罩層 後之處理或成長在1 000度以上之高溫下進行。原因係在 6 0 0度等之低溫下，成由I I I族元素之金屬所成液滴狀粒 7或形成氮化鎵系化合物半導體8之際，於於發生的過程 不會充分引起遷移，故以氧化矽或氮化矽覆蓋藍寶石基板 1 或緩衝層之區域，亦產生成長發生核，變成損害選擇成 長性。 或者，在光罩層上進行形成氮化鎵系化合物半導體層9 時，在600度等之低溫係於成長初期不會充分引起遷移， 故即使以氧化矽或氮化矽覆蓋藍寶石基板1或緩衝層之區 域，亦產生成長發生核損害選擇成長性。 本發明可利用的含S!之原料氣體，可使用矽烷（SiH4) 或二矽烷（Si 2H6)。 形成上述光罩層之製程，可在繼後之成長氮化鎵系化合 物半導體的成長裝置中進行。 如上述依本發明，係含在加熱的基板上僅流通有機金屬 原料的製程，在基板上成長氮化鎵系化合物半導體，與由 -35 - 54685〇 五、發明說明（34) 修溫緩衝法相比具有更良好的結晶性、具有平坦的鏡面狀 之表面，作爲半導體元件使用可獲得具充分良好的結晶性 之良好半導體結晶膜。結果，可抑制結晶成長缺陷由來在 凹坑部分的電流之漏洩、或貫通轉位等之轉位由來的發光 強度減少等對半導體元件不利的現象，並依此可提高發光 輸出。 其次，以更具體的實施例說明本發明II I族氮化物半導 體結晶及氮化鎵系化合物半導體之製造方法，惟本發明不 受此等所限定。以下之各實施例係使用藍寶石基板作爲基 板，氮化鎵系化合物半導體層之形成係使用M0CVD法進行 〇 y施例1 敘述Iπ族氮化物半導體結晶之製造方法的實施例。 基板係採用具（000 1 )面之藍寶石單結晶基板。該基板由 丙酮進行有機洗淨後，載置於碳化矽（s i C)製感應器上固 定於M0CVD法之成長裝置。MOCVD法之成長裝量係由RF感 應加熱方式控制溫度，又感應器插入有插入熱電對之石英 管，成長裝置之溫度可由該熱電偶測定。 將基板固定於成長裝置後，首先在氫氣環境中昇溫至 1180°C、進行熱處理1〇分鐘以除去基板表面之氧化膜等 。其後，降溫成長裝置之溫度至1 1 00 °C、同樣在不含氮 源之氫氣環境中以1 2 ν m ο 1 / m i η供應作爲有機金屬原料之 三甲基鋁（ΤΜΑ ) 1分鐘。結果，由ΤΜΑ之熱分解在藍寶石 -36- 546850 五、發明說明（35) 基板上堆積金屬之A 1。繼後停止供應TMA、使成長裝置之 溫度昇溫至 1 1 80°C、以0 . 2mo 1 / mi η供應作爲氮源之氨 (ΝΗ 3 ) 3分鐘、進行所氮化堆積的A 1。其後不變化ΝΗ3之供 應量、保持成長裝置之溫度於1 1 80 °c狀態下，以1 40从 mol / nun供應作爲有機金屬原料之三甲基鎵（TMG)、在堆積 有A 1之基板上成長氮化鎵1 . 1 V m外延成長。其後，冷却 成長裝置之溫度至室溫取出基板。 如此製作的外延成長晶圓之表面爲鏡面，外延成長的氮 化鎵層之X線搖蕩曲線之半振幅脈衝寬度爲5 9 5秒。由此 可知，外延成長的氮化鎵層係結晶性優異者。 實施例2 與實施例1相同方法，在具（ 000 1 )面之藍寶石基板上進 行有機洗淨，再固定於成長裝置進行熱處理。其後，在不 含氮源之氫氣環境中保持成長裝置之溫度於1 180 °C狀態下 、分別以1 2 &quot; m ο 1 / m i η供應作爲有機金屬原料之三甲基銘 (ΤΜΑ)與三甲基鎵（TMG)l分鐘。結果在藍寶石基板上堆積 A 1與Ga之合金。停止供應TMA與TMG後，使成長裝置之 溫度保持於1 180°C下，供應0.2mol/min氨（NH3)3分鐘、 進行堆積的A 1與G a合金之氮化。其後供應氨保持成長裝 置之溫度保持於1180°C下，以140//mol/min供應三甲基 鎵（TMG)於成長裝置、在堆積A1與Ga合金之基板上外延 成長氮化鎵1 . 1 // 111。 如此成長的外延晶圓之表面爲鏡面，外延成長的氮化鎵 -37- 546850 五、發明說明（36) 層之X線搖蕩曲線之半振幅脈衝寬度爲720秒。由此可知 外延成長的氮化鎵層爲結晶性優異者。 又，以原子間力顯微鏡（AFM )觀察該氮化鎵層之表面時， 觀察了表示作步驟流動成長的原子步驟之列。該原子步驟 之歹U，較外延晶圓中心部於晶圓周邊部的特定方向，以更 爲等間隔呈現平行的列。此係指晶圓周邊部之（000 1 )面的 垂直軸以自&lt;◦ 0 0 1 &gt;方向傾斜於特定方向的部分，增強步驟 流動成長。而且該方向爲&lt;1-100〉方向。 再於，以透過電子顯微鏡（TEM)觀察該外延成長晶圓之 藍寶石基板與氮化鎵層界面之截面。觀察結果，由有機金 屬之熱分解堆積的金屬作氮化之多結晶，在基板與氮化鎵 之界面觀察。多結晶具六方晶之晶系，其高度爲5〜 1 Ο nm。係// - EDS分析可知，在上述多結晶中A 1組成與G a 組成並不一樣、再於金屬與氮之化學量論比自1 : i偏移 之區域（區域之組成以i nuGa、,AlwNk表示，惟觀察了有 u + v+w=l、〇$ u，v,w$ 1、〇&lt;k&lt; 1)。 又，以調查本實施例2之結晶成長機構爲目的進行以下 之實驗。與實施例1相同方法，在具有（000丨）面之藍寶石 基板進行有機洗淨再固定於成長裝置進行熱處理。其後， 與實施例2相同條件，在不含氮源之氫氣環境中保持成長 裝置之溫度於1 1 80°C .下、供應TMA與TMG於成長裝置， 在藍寶石基板上堆積A1與Ga之合金。停止供應TMA與 TMG後，保持成長裝置之溫度保持於丨i8〇t：下，供應 -38- 546850 五、發明說明（37) 〇 · 2 m 〇丨/ m i η氣（N Η 3) 3分鐘、進行堆積的A 1與G a合金之 氮化。其後，使成長裝置之溫度降下至室溫。 以原子間力顯微鏡（A F Μ )觀察依上述方法製作的晶圓之 表面結果，觀察到氮化高度約5 0 n m、直徑約〇 . 1 A m之粒 狀金屬的多結晶。多結晶並未有覆蓋藍寶石基板表面之全 面，多結晶與多結晶之間爲平坦。本實施例2之氮化鎵層 的外延成長係以該粒狀之多結晶爲核進行。 又，以調查堆積於基板表面之I I I族金屬微粒子狀態爲 目的時進行以下之實驗。 與實施例1相同的方法，在具有（ 0001 )面之藍寶石基板 上進行有機洗淨再固定於成長裝置進行熱處理。其後，與 實施例2相同條件，在不含氮源之氫氣環境中保持成長裝 置之溫度於1 1 80°C下、供應TMA與TMG於成長裝置，在 藍寶石基扳上堆積A1與Ga之合金。其後，降下成長裝置 之溫度至室溫以AFM觀察表面狀態。 結果，在藍寶石基板表面觀察了高度約100A程度、大 小約500人前後之微粒子，表面密度爲1 X 1〇8cm_2。亦觀 察到了微粒子之一部分爲互相聯繫者。 實_施例3 與實施例1相同方法，在具（〇〇〇 1 )面之藍寶石基板上進 行有機洗淨，再固定於成長裝置進行熱處理。其後，在不 含氮源之氫氣環境中降下成長裝置之溫度至丨丨㈧艽下、分 別以 6 // m ο 1 / m 1 η、1 8 // m ο 1 / m 1 η、1 8 // m 〇 1 / m i η 供應作爲 -39- 546850 五、發明說明C 38) 有機金屬原料之三甲基鋁（TMA )與三甲基鎵（TMG )與三甲基 銦（TMI)3分鐘。結果在藍寶石基板上堆積Μ與Ga與In 之合金。停止上述有機金屬原料供應後，昇溫成長裝置之 溫度至1丨8 0 °C ,供應0 · 2 m ο 1 / m i η氨（N Η 3) 3分鐘、進行堆 積的A1與G a與I η合金之氮化。再保持供應具以成長裝 置之溫度爲 1180°C下，以140/imol/min供應三甲基鎵 (TMG)於成長裝置、在堆積A1與Ga與In合金之基板上成 長氮化鎵層1 . 1 // m。 如此成長的外延成長晶圓之表面爲鏡面，外延成長的氮 化鎵層之X線搖蕩曲線之半振幅脈衝寬度爲6 2 0秒。由此 可知外延成長的氮化鎵層，係爲結晶性優異者。 尙於上述實施例1〜3，係作爲I I I氮化物半導體結晶將 氮化鎵層作外延成長，但亦可成長InxGayAlzN所示之III 族氮化物半導體之混晶。 實施例4 於實施例4，係採使用I I I族氮化物半導體結晶之製造 方法，對於使用氮化鎵系化合物半導體的半導體發光元件 之製造方法加以說明。L 546850 5. Description of the invention (13),% of sapphire. In particular, when the substrate is sapphire (Al203), there are advantages in that high-quality crystals can be obtained and they can be obtained at a low price. The surface orientation of the sapphire substrate is using m-plane, a-plane, and c-plane. Among them, the c-plane (000 1 plane) is preferred, and the vertical axis of the substrate surface is used. &lt; 000 1 &gt; The direction is more inclined in a specific direction. In addition, the substrate used in the present invention is preferably processed before the use of the first process, such as organic cleaning or etching, to keep the surface of the substrate in a certain state. As the fine particles of the group ΠI metal deposited on the surface of the substrate in the first process of this manufacturing method, A 1 or G a, I η and the like can be used. Here, the fine particles of the group I I I metal of the present invention are particularly preferably InuGavAlw (u + v + w = 1, OS 1, OS vS 1, 0 S 1). When the I I I group metal is InuGavAlw, it has the advantage that it has a high affinity with the subsequently grown I I I group nitride semiconductor. Furthermore, metals other than Group III, such as Si, Be, and Mg, may be added to the fine particles of these Group III metals. In addition, when a group II I metal is deposited by decomposition of a metal compound, the formed particles of the group I I I metal contain impurities such as carbon, hydrogen, and halogen, but these can also be used as metal particles. The deposition of group I and II metal fine particles in this manufacturing method can be performed by various methods such as thermal decomposition of an organic metal raw material or a metal halide, or vapor deposition or sputtering. In particular, it is preferable to deposit the fine particles of the group I I I metal by thermal decomposition of the organic metal raw material. As the organometallic raw material, a compound of trimethylgallium (TMG), triethylgallium (TEG), trimethylaluminum (TMA), trimethylindium (TMI), or dicyclopentadiene indium (Cp21η) can be used. By the thermal analysis of the organometallic raw materials -1 5-546850 V. Description of the invention (14) When the particles of the above I I I group metals are accumulated, there is an advantage that the metal particles can be deposited by i n s i t U. When the above-mentioned first process is carried out in an environment containing a nitrogen source containing ammonia, since the problem of preventing surface migration will occur, the above-mentioned first process is made! The process is preferably performed in a nitrogen-free environment. Furthermore, N2 gas, which is widely used as an inert carrier gas, is not considered here as a nitrogen source. The decomposition temperature of n2 is higher than that of general nitrogen sources such as ammonia and pyridine, and is not very effective as a nitrogen source. Therefore, these methods do not hinder the effect when N2 gas is contained in the environment in the first process. Specifically, hydrogen, a rare gas, nitrogen, and the like can be used as the ambient gas. In the present invention, the first process is preferably performed at a temperature equal to or higher than the melting point of the above-mentioned Group 11 metal. When the first process is performed at a temperature higher than the melting point of the group I I I metal, there is an advantage that atoms on the substrate can easily migrate and form fine particles. The particles of Group 111 metal deposited on the substrate surface in this first process are particles of Group I I I metal which are discontinuously dispersed and deposited on the substrate surface. Fine particles of a group III metal may be bonded to each other. The state of the fine particles of the Group I 11 metal deposited on the substrate surface can be observed using an AFM (Interatomic Force Microscope) measurement method. The height of the particles of the main I Π metal formed by the first process from the substrate surface to the top of the particles is 50 ~ 1000A, and when the particles are viewed from a direction perpendicular to the substrate, the length from one end to the other end of the particles is 100 ~ 10000A. The surface density is 1 × 106cirT2 to 1 × 101QcnT2. When the second process is carried out in an environment containing metal raw materials, the crystallinity of the group III nitride semiconductor crystal grown in the third process is not good, so -16-546850 V. Description of the invention (15) Make the second process It is better to perform in an environment without metal raw materials. In addition, the environment containing a nitrogen source during the second process may be an environment containing ammonia or pyridine. The pressure of the environment during the second process is preferably 1000 to 1 × 105 Pa. In addition, the microparticles of the group III metal nitrided in the above-mentioned second process are those containing polycrystalline and / or amorphous results of analysis by cross-section transmission electron microscopy (TEM), and those containing unreacted metals. . The second process is preferably performed at a temperature equal to or higher than the first process. As a result of experiments conducted by the present inventors, when the second process is performed at a temperature equal to or higher than the first process, an I I I nitride semiconductor crystal having excellent crystallinity can be produced. In addition, in order to perform the nitriding reaction of metal particles, specifically, the second process is performed at a temperature of 700 ° C or higher, and more preferably 90 ° C or higher. Nitriding of group III metal fine particles in the second process It can be performed by keeping the substrate on which the fine particles are accumulated in an environment containing a nitrogen source at a temperature of 700 t or more for 1 to 1 Q minutes. The third process is preferably performed at a temperature higher than the second process. When the third process is performed at a temperature higher than the second process, it can grow! Ί] [Group nitride semiconductors have the advantage of high quality. Specifically, the third process is preferably at a temperature of 700 ° C or higher. The more preferred temperature is 90 ° C or higher. The third process of ghail enables the formation of π group I nitride semiconductor crystals by organometallic chemical vapor growth (MOCVD), molecular wire epitaxy (MBE), gas, etc. Various vapor phase growth methods such as phase growth method (VPE) are performed. Especially because of the advantages of thin film growth, it is preferred to form UI group nitride semiconductor crystals by organometallic chemical vapor growth. The organometallic chemical vapor phase described above -1 7-546850 V. Invention Ming (16) The growth method is a conventional organometallic chemical vapor growth method that uses a gas containing an organometallic compound and a nitrogen source as an ambient gas to grow at a pressure of 1 000 to 1 × 105 Pa. Especially, the third method is the MOCVD method. During the manufacturing process, it is generally known that gallium nitride-based compound semiconductors with good crystallinity can be obtained at a temperature of 1000 ° C. The growth pattern of this type of gallium nitride-based compound semiconductor is around 1 000 ° c. The temperature is higher than the temperature below, and it is a type with strong growth in the transverse direction at a temperature above 1000 ° C. At this time, a crystal film with a good surface morphology is formed with a low translocation. The group III nitride semiconductor crystal of the present invention The second configuration of the manufacturing method is the thermal decomposition of an organic metal raw material containing at least one metal element of I η and G a and A1 in an environment that does not contain a nitrogen source in the first process, and causes the 1 or more metals 1 formed by I η and Ga and A 丨 (Metal 1 is represented by I nuGavAlw, but u + v + w = 1, 0 $ u '1, 0 € v S 1, 0 S w S 1) Deposited at a temperature T1 above the melting point of the metal 1. The next second The process is to nitride the metal 1 in an environment containing no organic metal raw materials and a nitrogen source at a temperature T2 (T2 2 T1). In addition, the subsequent third process is on the sapphire substrate on which the metal 1 is deposited. Group III nitride semiconductor (IIIII nitride semiconductor is represented by InxGayAlzN at temperature T3 (Τ3 -Τ 2) by organometallic chemical vapor phase growth method, but x + y + z 二 1, 〇 $ XS 1, 〇 $ y $ 1, 0 S z '1) Crystal epitaxial growth. By the above method, a crystal of an I I I group nitride semiconductor having good crystallinity is epitaxially grown on a sapphire substrate. In addition, this method is easier to manufacture high-quality III-nitride semiconductor crystals without the need to strictly control the manufacturing conditions, as compared with the conventional method of using a low temperature retarder. Furthermore, the present inventors have found that the above-mentioned sapphire substrate has a (000 1) plane and a vertical axis of (000 1) plane from &lt; 000 1 &gt; The direction is inclined to a specific direction, which can enhance the segmented flow growth of a better growth form of the 11 I nitride semiconductor crystal. This segmented flow grows because the specific direction that emphasizes the vertical axis tilt most is &lt; 1-100> direction, and since &lt; 00〇1 &gt; The tilt angle in the direction is 0.2. It is most emphasized at ~ 15 °, so it can be used as an ideal condition for producing high-quality π group I nitride semiconductor crystals. In order to effectively thermally decompose the organometallic raw material, the temperature T 1 is preferably 200 ° C. or higher, and T 1 is preferably a temperature higher than the melting point of the metal 1. More preferably, the temperature T1 is 900 ° C or higher, the decomposition of the organic metal raw material is close to 100%, and the deposited metal 1 is in a molten state. In addition, the temperature T3 at which the crystal growth of the group I 11 nitride semiconductor epitaxially grows is 700 ° C or more, and preferably 1000 ° C or more, which can ensure that the decomposition of the nitrogen source proceeds sufficiently. Since the above-mentioned metal 1 is deposited at a temperature higher than the melting point, it does not form a layered, granular shape on the sapphire substrate by its own surface tension, and was confirmed by observation by an atomic force microscope (TEM). Then, the granular metal 1 maintains the same shape after being nitrided with a nitrogen source in the second process. I I Group I nitride semiconductor crystals are epitaxially grown, and this grain is used as the core. Therefore, a group 1 nitride semiconductor crystal with good crystallinity can be obtained. In addition, as a result of the analysis of the cross-section transmission electron microscope (TEM), the nitrided metal 1 in the second process was formed from polycrystals, and the polycrystals were not in the range of -19 to 546850. 5. Description of the invention (18) Stoichiometric region of 1: 1 (the composition of this region is represented by I n uGavAlwNk, but it is confirmed that it contains + V +, 0 S u, v, w S 1, 0 &lt; k &lt; 1). This point is a conventional low-temperature buffer layer that supplies an organometallic raw material and a nitrogen source at the same time, accumulates at a low temperature, and is then used for crystallization at a high temperature for heat treatment, and a growth form different from the method of the metal nitride 1 method of the present invention. Point of difference. The third configuration of the method for manufacturing a group III nitride semiconductor crystal according to the present invention is characterized in that it comprises supplying a group I metal raw material on a heated substrate, and depositing a group I jj metal raw material and / or a decomposition product thereof on the substrate. The first process, followed by the second process in which the substrate is heat-treated in an environment containing a nitrogen source, and thereafter, the third process of growing a group 111 nitride semiconductor by a gas phase method on the substrate using a group III metal raw material and a nitrogen source is performed. Process. In the first process, as a Group 11 metal raw material contained in the environment, an organometallic compound, a metal halide, a metal, or the like can be used, but among them, an organometallic compound is preferably used. As the organometallic compound of the I I I group element, a compound such as trimethylgallium (TMG) or trimethylaluminum (TMA) or trimethylindium (TMI) or dicyclopentadiene indium (Cp2In) can be used. In addition, in the first process, elements other than Group III metals such as S1 and Mg are used as doping purposes, and silane (Si &), Nishain (S i 2H6), and dicyclopentane may be contained in the environment. Magnesium (Cp2Mg) and the like. The first process is preferably one that does not contain a nitrogen source in the environment. When a nitrogen source such as ammonia is contained in the first process, the surface morphology of the grown gallium nitride-based compound semiconductor crystal film does not become a mirror surface. This is described in the conventional technology, such as Patent No. 3,026,087, -20-546850, V. Invention Description (19), or JP-A-4_29 7023. The N2 gas system, which is widely used as an inert carrier gas, is not used as a nitrogen source. The decomposition temperature of n2 is higher than ordinary nitrogen sources such as ammonia and pyridine, and it is not effective as a nitrogen source. Therefore, in these inventions, n2 gas is contained in the environment of the first system, and the effect of the k-inch invention is not greatly hindered. In addition, the first process may also include hydrogen, nitrogen, and rare gases in the environment. In addition, according to the experimental results of the present inventors, it is known that when the second process is performed at a temperature higher than the first process, a group I nitride semiconductor crystal having excellent crystallinity can be produced. The nitriding reaction for metal 1 is specifically performed at a temperature of 700 ° C or more, more preferably 900 ° C or more. Particularly, good crystallinity can be obtained at a temperature of 1 000 ° C or higher. As a method for growing the Group 11 nitride semiconductor used in the third process, an organic metal chemical vapor growth (MOCVD) method is preferred. By using this method, the first process to the third process can be performed in the same growth furnace. When an organometallic chemical vapor growth method is used to grow the I I I group nitride semiconductor, the temperature for performing the third process is preferably 1 000 ° C or higher. In particular, it is preferable that the third process is carried out at a temperature of 1100 ° C or higher because it is easy to obtain mirror crystals. When the third process is performed in an environment containing hydrogen, there is an advantage that crystallinity and surface morphology can be easily controlled. As mentioned above, the substrate used in the present invention is preferably sapphire. Sapphire -21-546850 V. Description of the invention (20) The substrate has a (0001) plane, and the vertical axis of the (000 1) plane is &lt; 00〇1 &gt; The direction is preferably inclined to a specific direction. Furthermore, the specific direction in which the vertical axis of the sapphire substrate is tilted is &lt; i-i〇〇 &gt; direction, and since &lt; 00〇1 &gt; The inclination angle of the direction is preferably 0.2 ° to 15 ° as described above. As described above, the sapphire substrate has a (000 1) plane, and the vertical axis of the (000 1) plane is &lt; 000 1 &gt; &lt; 1-1〇〇 &gt; When the direction is inclined at an angle of 0.2 ° to 15 °, the surface of a group II nitride semiconductor crystal grown on a substrate has a (0 0 0 1) plane, and the surface is perpendicular to the surface. Axis self &lt; 0 0 0 1 &gt; The direction is inclined to a specific direction. In this specific direction in which the surface of the I 11 nitride semiconductor crystal is inclined becomes &lt; 11-20 &gt; direction. This is a group III nitride semiconductor crystal that grows by rotating 30 ° c compared to the surface orientation of the substrate. At this time, the surface of the group III nitride semiconductor crystal grown on the substrate &lt; 000 1 &gt; When the angle of inclination of the direction is 0.2 ° to 15 °, the growth is enhanced by segmental flow, so it is ideal as a condition for manufacturing a high-quality I I I nitride semiconductor crystal. This manufacturing method may include a well-known heat treatment process called thermal annealing before the first process. Thermal annealing is widely used when the substrate is sapphire, and it is cleaned in a growing furnace. Specifically, the substrate is generally processed at a temperature of 1000 to 1200 ° C in an environment containing hydrogen or nitrogen. In addition, this manufacturing method can be performed several times in a first process. At this time, the type, composition, mixing ratio, etc. of the Group I and II metal raw materials contained in the environment can be changed by the first and second times, the second and third times, and the like. In addition, conditions such as the temperature of the substrate and the processing time may be changed. -22- 546850 V. Description of the Invention (20) When the first process is divided into several implementations, the Group III metal raw materials contained in the first environment are preferably the ones containing A1. A1 is in Group III Metal has a high melting point and is a material that easily adheres to substrates. Also, this manufacturing method can be between the first process and the second process and / or between the second process and the third process. An annealing process for processing a substrate in a nitrogen source environment. The annealing process can promote the collection and distribution of metal particles and form a more appropriate shape of the π group I metal particles. At this time, the annealing temperature is set at π group I metal particles The melting point is preferably at least 900 ° C, more preferably at least 1 000 ° C. In addition, the environment for annealing is preferably hydrogen-containing. In the present invention, the substrate temperature in the second process can be changed while In this case, the temperature for performing the second process is needless to say that it is higher than the decomposition temperature of the nitrogen source. Specifically, all the second processes should be 70 ° C or more, more preferably 900 ° C or more, and most preferably Ideally performed above 100 ° C It is preferable that the end temperature is higher than the temperature at which the second process is started. The temperature at which the second process is started is the same as the temperature at which the first process is performed, and the temperature at which the second process is ended and the temperature at which the third process is performed can be made. The temperature is the same. When the second process is performed while changing the temperature, the type or flow rate of the carrier gas and the pressure in the furnace may be changed as the temperature changes. Second, the gallium nitride-based compound semiconductor according to the present invention The manufacturing method is explained in detail according to the drawings. Figure 1 is an explanatory diagram of the growth mechanism of each process (steps 23-546850, Cang Ming (22) step) during the formation of a gallium nitride-based compound semiconductor layer, and Figure 2 This is an example of a thermal pattern when the gallium nitride-based compound semiconductor layers of these inventions are formed. The gallium nitride-based compound semiconductors of these inventions are formed on the substrate in the following steps. That is, as described in As shown in FIG. 1 (a), in step A (first process), a metal core (metal particle) S a formed of a metal element, preferably a group III metal element, is first attached to the substrate. At this stage S a Not connected It is also possible to disperse the ground particles and cover the surface with a liquid. Then, in step B (second process), the metal core Sa is annealed (Fig. 1 (b)). This annealing process is completed in the first process. The non-continuous granular S a also becomes the ideal discontinuous granular shape. Then in step C (third process), the metal core S a 1 after nitriding annealing is used as the growing core S b (Figure 1) (C)). When the growth core Sb has any shape, it can function as a growth core as long as it has an appropriate density distribution. However, the shape of the growth core Sb will affect the gallium nitride compound semiconductor The crystallinity is also determined by experiments by the applicant and the like. In particular, it is preferable that the flat top surface parallel to the substrate 1 and the roughly III-shaped nitride semiconductor crystal having a flat side surface that intersects the substrate 1 at an angle are suitable. The growing nuclei Sb can be formed into a better shape by paying attention to the thermal image of the ambient gas, the pressure in the furnace, the substrate temperature, or the substrate temperature during the nitridation. Then, in step D (fourth process), a gallium nitride-based compound semiconductor crystal layer is grown on the substrate 1 having the growth core Sb (Fig. 1 (d)). The growth is mainly carried out in the horizontal direction along with the indexing, and thus, to ensure a sufficient layer thickness in the vertical direction (for example, 2 // m), and to obtain a flat horizontal direction in the horizontal direction -24- 546850 V. Description of the Invention (23) Tan GaN-based compound semiconductor 2 (Fig. 1 (e)). Each of the above steps A to D can be performed continuously in a growing apparatus of the MOCVD method. Before performing step A, as shown in FIG. 2, for example, the substrate made of sapphire is first heated in a growth device of the MOCVD method at a high temperature of 100 ° C. to 120 ° C. (1 170 in the second figure). ° C) for thermal treatment to remove the oxide film on the surface. Next, the temperature of the growing device is lowered, for example, by about 5 ° C to 200 ° C and maintained at a constant temperature (Figure 1 is 1100 ° C), and steps A, B, and C are performed at the constant temperatures. Next, in the process of forming the growing nuclei Sb by the nitriding treatment in step C, the temperature of the growing device is increased by 5 ° C to 200 ° C and maintained at a constant temperature (Figure 16 is 16CTC), and the temperature is controlled at the constant temperature. In step D, the growth nuclei S b are further grown into gallium nitride-based compounds. Alas, the process described above and the process shown in FIG. 1 is an example of these inventions, but these inventions are not limited by these. For example, thermal management can be performed as needed. In addition, if the temperature pattern is not limited by the pattern in Figure 2, it is appropriate to adopt appropriate conditions according to the shape of the furnace used for growth, the type of organic metal raw materials, the nitrogen source, the type of carrier gas, and the flow rate. Specifically, the temperatures of the processes from step A to step C may be different, and the temperatures of steps A and B, and steps B and C may be different. In addition, the temperature of step D may be lower than the temperature from step A to step C, and may be the same temperature. Thus, in these embodiments of the present invention, a metal core Sa is first attached to the substrate 1, and a growth core Sb is formed based on the metal core Sa. On the growth -25- 546850, the core of the invention (24) Furthermore, a gallium nitride-based compound is grown. The growth of the metal core Sa attached to the substrate 1 can be controlled by the flow rate, flow time, and processing temperature of the organometallic gas, so the density of the metal core Sa existing on the substrate 1 can be freely controlled. In addition, the annealed treatment of the metal core Sa and the wettability effect of the substrate increase the size of the metal core Sa itself in the vertical direction (Sal in FIG. 1 (b)). A part of the metal surface is evaporated to reduce the formation of attachments. The substrate surface formed by the space between the attachment part and the surface of the substrate exposed between S a 1 is reduced. In this way, the density of the growing nuclei S b obtained as a result of the nitriding can be controlled to a preferable state. In particular, conditions such as ambient gas, temperature, pressure, and time during annealing have the effect of controlling density. These conditions must be appropriately selected by the type of metal to which the metal core Sa is attached or the shape of the furnace. In experiments by the applicant and the like, it is preferable to use hydrogen as an ambient gas, and to use a temperature of 9,000 t or more, and it is determined that annealing is performed for 5 minutes or more. Thereafter, the metal core Sa 1 is nitrided by performing a nitriding treatment, and changes into a growth core Sb composed of a nitride semiconductor. The growth nucleus Sb is as described above, and preferably has a substantially trapezoidal cross-section having a flat top surface and a flat side surface parallel to the substrate. The shape of the growing nuclei Sb can be controlled by the conditions during the nitriding treatment. In particular, conditions such as ambient gas, temperature, and pressure during nitriding are effective for controlling the shape. These conditions need to be appropriately selected depending on the type of metal to which the metal core Sa is attached, the nitrogen raw material used for the nitriding treatment, the shape of the furnace, and the like. In the applicant's experiments, as an ambient gas -26- 546850 V. Description of the invention (25) Hydrogen system, 900 t as temperature system: The temperature above, it is clear that it is ideal to increase the temperature between nitriding processes. Furthermore, the growth core Sb is further grown and a gallium nitride-based compound semiconductor is grown. Therefore, the gallium nitride-based compound is grown indirectly by burying adjacent growth cores Sb, and the adjacent growth cores sb are completely buried. After the interspace, a flat layer grows on top of it. Therefore, finally, a layer of a gallium nitride-based compound semiconductor 2 having a desired layer thickness and good crystallinity can be formed on the substrate. The surface of the hafnium-based compound semiconductor layer is covered with a gallium nitride-based compound, so it can maintain excellent grid integration with the gallium nitride-based compound semiconductor laminated on it. Therefore, Each layer of a gallium nitride-based compound semiconductor layer having good crystallinity can be formed. Furthermore, when a semiconductor light-emitting element is manufactured using this gallium nitride-based compound semiconductor, its light-emitting characteristics can be reliably improved. In addition, the semiconductor light-emitting element produced by the above method can be used as a light source with good light-emitting characteristics such as brightness for electronic appliances, vehicles, and other electrical devices for traffic signals. The substrate used for the semiconductor can be glass, Sic, Si, GaAs, sapphire, or the like. In particular, when the substrate is sapphire (A 1 20 3), it has the advantages of obtaining high-quality crystals and being inexpensive. As the plane orientation of the sapphire substrate, m-plane, a-plane, and c-plane can be used, but among them, the c-plane ((000 1) plane) is preferred. In addition, it is desirable that the substrate used in the present invention can maintain a constant state of the substrate surface when used before the first process, such as organic cleaning or pre-etching. -27- 546850 V. Description of the invention (26) In the first process, a metal core such as A] or Ga, In, etc. can be used as the material of the metal core on the substrate. Herein, the present invention is in particular that the metal core is preferably a group 111 metal represented by I n L1GavAlwr_ u + v + w (1, 0 $ u $ ι, 0 $ v $ 1, 0 $ w g). When the metal core is I n uG a v A 1 w, there is an advantage that it has a high affinity with a gallium nitride-based compound semiconductor that allows subsequent growth. In addition, metal cores of these Group 111 metals may be added as metals other than Groups I I and I such as S 1, Be, and Mg as impurities. In addition, when the metal core is attached by decomposition of the organometallic raw material, it is difficult to contain impurities such as carbon, hydrogen, and halogen in the formed metal core, but these can also be used as the metal core. The adhesion of the metal core can be performed by various methods such as thermal decomposition of an organic metal raw material or a metal halide, vapor deposition, or sputtering. In the present invention, since it is easy to control the density or shape of the metal core, it is particularly preferable to use a method of attaching the metal core by thermal decomposition of an organic metal raw material. As organic metal raw materials, gallium and aluminum containing trimethylgallium (TMG) or triethylgallium (TEG), trimethylaluminum (TMA), trimethylindium (TMI), and dicyclopentadiene indium (Cp2In) are used. Or indium organometallic raw materials can attach metal cores such as inuGavMw Group I Π metals. In addition, when the first process is performed in an environment containing a nitrogen source containing ammonia, problems such as obstacles to the surface movement of metal atoms may occur. Therefore, it is preferable to perform the first process in an environment that does not include a nitrogen source. . Here again, the n2 gas system, which is widely used as a carrier gas for inert gas generation, is not considered as a nitrogen source. The decomposition temperature of n2 is higher than ordinary nitrogen sources such as ammonia or pyridine, and it is not effective as a nitrogen source. Therefore, the inclusion of N2 gas in the environment of the first process does not hinder -28- 546850 V. Invention Description C 27) The fruits of these inventions. Specifically, hydrogen, a rare gas, nitrogen, and the like can be used as the ambient gas. The first process is preferably performed at a temperature above the melting point of the metal core. When the first process is performed at a temperature higher than the melting point of the metal core, the movement of metal atoms on the substrate is smoothly performed, and there is an advantage that the metal core is easily formed. The metal nuclei deposited on the surface of the substrate in the first process are fine particles of continuously dispersed metal deposited on the surface of the substrate. The fine particles of metal may be partially bonded to each other. The state of the metal core adhered to the surface of such a substrate can be observed by a measurement method such as AFM (Interatomic Force Microscope). The main metal core formed in the first process is from 50 to 1000A in height from the substrate surface to the top of the particles. When the particles are viewed from the substrate and the vertical direction, the length from one end to the end of the particles is 100 A to 10000A. The surface density is about lXl06cnT2 to lXl01 (3cnT2. In addition, in the annealing process, only the carrier gas containing no nitrogen source and organic metal raw materials is flowed to anneal the metal cores, which can efficiently generate agglomeration of the metal cores. Ideal as a carrier The gas can be hydrogen, noble gas, nitrogen, etc. Especially, hydrogen has the effect of removing oxides on the surface of the metal core, so it is the most ideal. In addition, the annealing of the metal core is at a temperature above the melting point of the metal core, and at a temperature of 70 ° C When the above temperature is performed, it is ideal because metal aggregation is effectively generated. The annealing process is preferably performed at a temperature higher than the first process. According to the experimental results of the inventors, when the annealing process is at a temperature higher than the first process During the process, a gallium nitride-based compound semiconductor crystal with good crystallinity can be produced. Among them, when the temperature of the annealing process is the same as that of the first process, it is feasible. 546850 V. Description of the invention (28) A gallium nitride compound semiconductor that has good crystallinity is easy to control the state of the furnace of the device, so it has excellent implementability. In addition, the manufacturing process of the nitrided metal core is When performed in an environment containing metal raw materials, the crystallinity of the gallium nitride-based compound semiconductor crystal grown in the next process is poor, so it is desirable to perform the process of manufacturing a metal nitride core in an environment containing no metal raw materials. According to the invention, an environment containing nitrogen or pyridine can be used as the environment of the nitrogen-containing source when the metal core is nitrided. In addition, the environment pressure during the process is preferably 1000 to 1 X 105 Pa. Nitriding is performed in the nitriding process. Growth nuclei formed by metal nuclei are analyzed by cross-section transmission electron microscopy (TEM), and are formed of polycrystalline and / or amorphous materials and contain unreacted metals. They are also used to perform the nitriding reaction of metal nuclei to When the nitriding process is performed at a temperature of 700 ° C or more, and more preferably at a temperature of 900 ° C or more, a gallium nitride-based compound semiconductor crystal with good crystallinity is ideal. The metal core is formed by nitriding the metal core. This can be performed by holding the substrate with the stacked metal cores in an environment containing a nitrogen source at a temperature of 700 ° C. or higher for about 1 to 10 minutes. The nitriding process is preferably performed at a temperature higher than the annealing process. As a result of experiments by the inventors, when the nitriding process is performed at a temperature higher than the annealing process, a gallium nitride compound semiconductor crystal with good crystallinity can be produced. Among them, the nitriding process has the same temperature as the annealing process. It can form a gallium nitride-based compound semiconductor with good crystallinity, and it is easy to control the temperature in the furnace of the device, so it is excellent in implementation. • 30-546850 V. Description of the invention (29) Nitrogen is added on a substrate with a growing core When the process of growing a gallium-based compound semiconductor is performed at a temperature of 70CTC or more, and more preferably 900 ° C or more, there is an advantage that the quality of the gallium nitride-based compound semiconductor can be improved. The growth process of gallium nitride-based compound semiconductors can be performed by various vapor growth methods such as organic metal chemical vapor growth (MOCVD), molecular wire epitaxy (MBE), and vapor phase growth (VPE). In particular, since these inventions have the advantage that a thin film can be grown, it is desirable to form a gallium nitride-based compound semiconductor crystal by an organic metal chemical vapor growth method. As the organometallic chemical vapor phase growth method of the present invention, a gas containing an organometallic compound and a nitrogen source can be used as an ambient gas, and a known organometallic chemical vapor phase growth method that can be grown at a pressure of about 1,000 to 1 × 105 Pa can be used. law. It is also preferable that the growth process of the gallium nitride-based compound semiconductor is performed at a temperature higher than the nitriding treatment. As a result of experiments by the present inventors, when the growth process of the gallium nitride-based compound semiconductor is performed at a temperature equal to or higher than the nitriding treatment, a gallium nitride-based compound semiconductor crystal having good crystallinity can be produced. Among them, when the growth process of the gallium nitride-based compound semiconductor is the same as the temperature of the nitridation process, a gallium nitride-based compound semiconductor with good crystallinity can be formed, and it is easy to control depending on the state of the furnace of the device, so the implementation is excellent . Alas, in the above description, the metal core Sa is attached to the substrate and an annealing treatment is performed on the metal core Sa, but the metal core Sa may be repeatedly attached instead of the annealing. By repeating the attachment of the metal core S a, the density of the growth core S b formed in step C can be appropriately controlled. -31- 546850 V. Description of the invention (30) In this case, the material to be circulated is selected according to the pre-production process of attaching the first metal core, the post-production process of performing the second metal core attachment, and the adhesion to the substrate 1. The type becomes easy to control the density or shape of the growth nuclei S b. In the early stage of the present invention, a process of circulating a vapor-containing gas containing at least one organometallic material containing aluminum, an organometallic material containing gallium, and an organometallic material containing indium is carried out. The post-process system is different from the prestage process. The process of gas containing organic metal raw material vapor is ideal. At this time, for example, an aluminum-containing raw material with good adhesion and adhesion can be distributed on the substrate in the early stage, and a metal core S a can be formed on the substrate at a desired density. In the later stage, a poor adhesion G a or I n can be distributed. For example, the metal core S a of Ga or I η structure is pinched around A 1. It is also possible to alternate the pre-process and post-process only once, but it is ideal to perform the alternating process more than twice. After that, annealing is not performed and the formation of growing nuclei from nitridation is performed. However, in this case, the By appropriately controlling the nitridation, a growing core Sb having a good shape can be formed. This is the same as when annealing is used to control the density of the metal core Sa 1. As in the case of annealing, the ambient gas, temperature, pressure, etc. during nitriding are conditions that have the effect of controlling the shape. These conditions need to be appropriately selected depending on the type of metal to be attached to the metal core Sa, the nitrogen raw material used in the nitriding treatment, the shape of the furnace, and the like. In the applicant's experimental system, hydrogen was used as the ambient gas, and a temperature of 90 ° C or higher was used as the temperature. The temperature can also be raised between nitriding processes. In this case, the growth process of the gallium nitride-based compound semiconductor Nitriding-32-546850 V. Invention description (31) process temperature is ideal. The experimental results of the inventors and others are when the growth process of gallium nitride compound semiconductor is performed at a temperature higher than the nitriding process. A gallium nitride-based compound semiconductor crystal with good crystallinity can be produced. When the growth process of the gallium nitride-based compound semiconductor is the same as the temperature of the nitriding process, a gallium nitride-based compound semiconductor with good crystallinity can be formed. According to the method of the present invention, the state of the furnace is also easy to control, so the implementation is excellent. According to the method for manufacturing a gallium nitride-based compound semiconductor of the present invention, as described above, a metal core is adhered to a substrate and grown as a sapphire substrate. A slow growth mask layer is formed on the gallium nitride compound semiconductor, and the semiconductor layer is selectively grown by selective growth. A film with excellent crystallinity is formed. The mechanism for manufacturing a gallium nitride-based compound semiconductor crystal film with good crystallinity is described with reference to Figs. 9 (a) to (g). As shown in Fig. 9 (a), it is heated to A silicon nitride film 5 is formed on the silicon nitride film substrate 1 by circulating a Si-containing raw material gas 3 and an ammonia gas 4 on a sapphire substrate 1 3 1 at a predetermined temperature. This film 5 Since the formation starts from the active points scattered on the substrate, it is not possible to cover the entire body uniformly in the initial stage of the formation of the film 5. Therefore, when the growth time is appropriately controlled, the silicon nitride 5 formed on the sapphire substrate 1 is formed. The covered area and the area 6 where the sapphire is exposed (Figure 9 (b)). Then, the droplet-like particles 7 made of a group 111 element are supplied to the area 6 (Figure 9 (c)), and ammonia is circulated. It was reacted to generate Group I nitride 8 (-33-546850 in area 6) 5. Description of the invention (32) Figure 9 (d)), no gallium nitride-based compound semiconductor was generated in the area covered by silicon nitride 5. The growth nucleus grows from the area 6 where the sapphire surface is exposed to grow crystal 9 (Figure 9 (e)). The sand film 5 grows in the horizontal direction (Fig. 9 (f)). As a result, the crystal 9 covers the entire surface of the sapphire substrate 1 (Fig. 9 (g)). The growth direction of through-transposition caused by the difference in the number of lattices, most of the inversion depiction rings are closed, and they will not be transferred upward and downward, reducing the density of through-transposition to form good crystals. In addition, in addition to the method of simultaneously circulating the S1 source gas and the nitrogen source gas such as ammonia, ammonia can be partially nitrided on the sapphire surface in advance, and a single layer of nitrogen can be produced sparsely through the S i source gas. A method for forming a photomask layer from silicon. In addition, when a silicon oxide layer is used as a photomask layer, the oxygen atoms on the surface of the sapphire are activated by thermal treatment, and a single-layer amount can be made sparsely through the Si source gas flowing there. Of silicon oxide. In addition, the method of forming a layer with a difference in growth rate on the sapphire substrate is a method of circulating a sapphire substrate which simultaneously heats the si raw material gas and the group 111 raw material gas, and then a method of circulating heat is effective. Figs. 10 (a) to (f) show modal diagrams of the growth process when this method is used. First, the Si source gas 3 and the I I I group source gas 3 'are flowed on the heated substrate 1 (Fig. 10 (a)). As a result, the Si source gas 3 and the group III source gas 3 ′ were decomposed, and the aggregate 10 of silicon atoms and the droplet-like particles 7 of the group III metal were adhered to the sapphire substrate 1 at predetermined intervals (Fig. 10 (b). ). Next, when ammonia 4 is circulated, each is nitrided to form -34- 546850 on the substrate 1. V. Description of the invention (33) Slow growth film 5 made of silicon nitride and gallium nitride-based compound A photomask layer made of a film 8 made of a semiconductor and having a high growth rate (Fig. 10 (c)). When a gallium nitride-based compound semiconductor 9 is grown on the photomask layer, the crystal 9 is selectively grown on the film 8 made of the gallium nitride-based compound semiconductor in the same manner as in the embodiment shown in FIG. 9. Sexual growth is expected to improve crystallinity. In addition, the method shown in Figure 9 and Figure 10g must be performed after the photomask layer is formed or grown at a high temperature of more than 1,000 degrees. The reason is that at a low temperature such as 600 ° C, when droplet-like particles 7 or gallium nitride-based compound semiconductors 8 formed from a metal of a group III element are formed, migration will not be sufficiently caused during the process. Covering the area of the sapphire substrate 1 or the buffer layer with silicon oxide or silicon nitride also generates growth nuclei, which damages the selective growth. Alternatively, when the gallium nitride-based compound semiconductor layer 9 is formed on the photomask layer, migration at the initial stage of growth at a low temperature of 600 ° C or the like does not sufficiently cause migration, so even if the sapphire substrate 1 or the buffer is covered with silicon oxide or silicon nitride The layer of the region also produces growth and nuclear damage. As the source gas containing S! Which can be used in the present invention, silane (SiH4) or disilane (Si 2H6) can be used. The process for forming the photomask layer can be performed in a subsequent growth device for growing a gallium nitride-based compound semiconductor. As described above, according to the present invention, the process includes the process of circulating only organic metal raw materials on a heated substrate, and the growth of a gallium nitride-based compound semiconductor on the substrate, which is in accordance with -35-546850.5. Compared with a surface having a better crystallinity and a flat mirror-like surface, a semiconductor crystal film having a sufficiently good crystallinity can be obtained by using it as a semiconductor element. As a result, it is possible to suppress a phenomenon that is detrimental to the semiconductor element, such as a leakage of current due to a crystal growth defect in the pit portion, or a decrease in luminous intensity due to a translocation such as penetrating inversion, and the luminous output can be improved accordingly. Next, the manufacturing method of the Group II I nitride semiconductor crystal and the gallium nitride-based compound semiconductor of the present invention will be described with more specific examples, but the present invention is not limited thereto. Each of the following examples uses a sapphire substrate as a substrate, and the formation of a gallium nitride-based compound semiconductor layer is performed by a MOCVD method. Example 1 Describes an example of a method for manufacturing a group Iπ nitride semiconductor crystal. The substrate is a sapphire single crystal substrate with a (000 1) surface. The substrate was organically cleaned with acetone, and then placed on a silicon carbide (siC) sensor and fixed to a growth device of the MOCVD method. The growth volume of the MOCVD method is controlled by the RF induction heating method, and the sensor is inserted with a quartz tube inserted with a thermoelectric pair. The temperature of the growth device can be measured by the thermocouple. After the substrate is fixed to the growth device, it is first heated to 1180 ° C in a hydrogen atmosphere, and heat-treated for 10 minutes to remove the oxide film on the surface of the substrate. Thereafter, the temperature of the growing device was reduced to 1 100 ° C, and trimethylaluminum (TMA) was also supplied as an organometallic raw material at 1 2 ν m ο 1 / mi η in a hydrogen environment without a nitrogen source for 1 minute. . As a result, the thermal decomposition of TMA deposited sapphire-36-546850 on the substrate of the invention (35). A1 of the metal was deposited on the substrate. Subsequently, the supply of TMA was stopped, the temperature of the growing device was raised to 1 80 ° C, and ammonia (NΗ 3) as a nitrogen source was supplied at 0.2 mo 1 / mi η for 3 minutes to perform nitriding deposition of A 1. Thereafter, the supply amount of ΝΗ3 was not changed, and the temperature of the growing device was maintained at 1 1 80 ° C. Trimethylgallium (TMG), which is an organometallic raw material, was supplied at 1 40 from mol / nun. 1.1 V m epitaxial growth of GaN on the substrate. Thereafter, the substrate was cooled down to room temperature to take out the substrate. The surface of the epitaxially grown wafer thus produced was a mirror surface, and the half-amplitude pulse width of the X-ray oscillation curve of the epitaxially grown gallium nitride layer was 595 seconds. This shows that the epitaxially grown gallium nitride layer is excellent in crystallinity. Example 2 In the same manner as in Example 1, organic cleaning was performed on a sapphire substrate having a (000 1) surface, and then it was fixed to a growth apparatus for heat treatment. Thereafter, the temperature of the growth device was maintained at 1 180 ° C in a hydrogen environment without a nitrogen source, and trimethylamine (TMA) was supplied as an organic metal raw material at 1 2 &quot; m ο 1 / mi η, respectively. With trimethylgallium (TMG) for 1 minute. As a result, an alloy of Al and Ga was deposited on the sapphire substrate. After the supply of TMA and TMG was stopped, the temperature of the growing device was maintained at 1 180 ° C, and 0.2 mol / min ammonia (NH3) was supplied for 3 minutes to perform nitriding of the stacked Al and Ga alloys. Thereafter, the temperature of the ammonia-maintaining growth device was maintained at 1180 ° C, and trimethylgallium (TMG) was supplied at 140 // mol / min to the growth device to epitaxially grow gallium nitride on a substrate on which A1 and Ga alloys were deposited. . 1 // 111. The surface of the epitaxial wafer thus grown is a mirror surface, and the epitaxially grown gallium nitride -37- 546850 V. Description of the invention The half-amplitude pulse width of the X-ray oscillation curve of the (36) layer is 720 seconds. This shows that the epitaxially grown gallium nitride layer is excellent in crystallinity. In addition, when the surface of the gallium nitride layer was observed with an atomic force microscope (AFM), a list of atomic steps indicating flow growth was observed.歹 U of this atomic step presents parallel rows at evenly spaced intervals from the specific direction of the epitaxial wafer center portion to the wafer peripheral portion. This refers to the vertical axis of the (000 1) plane of the wafer &lt; ◦ 0 0 1 &gt; The part whose direction is inclined to a specific direction enhances the flow growth of the step. And the direction is &lt; 1-100> direction. Then, the cross section of the interface between the sapphire substrate and the gallium nitride layer of the epitaxially grown wafer was observed with a transmission electron microscope (TEM). As a result of observation, the metal deposited by the thermal decomposition of organic metal was used as a nitrided polycrystal and observed at the interface between the substrate and gallium nitride. The polycrystal has a hexagonal crystal system, and its height is 5 to 10 nm. System // EDS analysis shows that in the above polycrystal, the composition of A 1 and G a are different, and the stoichiometric ratio of metal and nitrogen is shifted from 1: i (the composition of the region is i nuGa, , AlwNk said, but observed that u + v + w = 1, 〇 $ u, v, w $ 1, 〇 &lt; k &lt; 1). The following experiments were conducted for the purpose of investigating the crystal growth mechanism of the second embodiment. In the same manner as in Example 1, organic cleaning was performed on a sapphire substrate having a (000 丨) surface, and the substrate was fixed to a growth apparatus for heat treatment. Thereafter, under the same conditions as in Example 2, the temperature of the growing device was maintained at 1 1 80 ° C in a hydrogen environment without a nitrogen source, and TMA and TMG were supplied to the growing device, and A1 and Ga were deposited on a sapphire substrate. alloy. After stopping the supply of TMA and TMG, keep the temperature of the growing device at 丨 i0〇t: below, supply -38-546850 V. Description of the invention (37) 〇 · 2 m 〇 丨 / mi η gas (N Η 3) 3 minutes 3. Nitriding of the stacked A 1 and G a alloys. Thereafter, the temperature of the growing device was lowered to room temperature. As a result of observing the surface of the wafer prepared by the above method with an atomic force microscope (AFM), polycrystalline crystals of granular metal having a height of about 50 nm and a diameter of about 0.1 Am were observed. The polycrystal does not cover the entire surface of the sapphire substrate, and the polycrystal and polycrystal are flat. The epitaxial growth of the gallium nitride layer in this Example 2 is performed using the granular polycrystals as a core. In order to investigate the state of the group I I I metal fine particles deposited on the substrate surface, the following experiments were performed. In the same manner as in Example 1, organic cleaning was performed on a sapphire substrate having a (0001) plane, and then it was fixed to a growth apparatus and heat-treated. Thereafter, under the same conditions as in Example 2, the temperature of the growth device was maintained at 1 180 ° C in a hydrogen environment without a nitrogen source, and TMA and TMG were supplied to the growth device. A1 and Ga were deposited on a sapphire substrate. alloy. Thereafter, the temperature of the growing device was lowered to room temperature, and the surface condition was observed by AFM. As a result, fine particles of about 100A in height and about 500 persons in size were observed on the surface of the sapphire substrate, and the surface density was 1 × 108 cm_2. It was also observed that part of the particles were interconnected. Example 3 The same method as in Example 1 was used to organically clean a sapphire substrate having a surface of (0001), and then fixed it to a growth apparatus to perform heat treatment. After that, the temperature of the growing device was lowered to 丨 丨 ㈧ 艽 in a hydrogen environment without a nitrogen source, respectively, 6 // m ο 1 / m 1 η, 1 8 // m ο 1 / m 1 η, 1 8 // m 〇1 / mi η supplied as -39- 546850 V. Description of the invention C 38) Trimethylaluminum (TMA) and trimethylgallium (TMG) and trimethylindium (TMI) 3 as organometallic raw materials minute. As a result, an alloy of M, Ga, and In was deposited on the sapphire substrate. After stopping the supply of the above-mentioned organometallic raw materials, the temperature of the growing device was raised to 1 丨 80 ° C, and 0 · 2 m ο 1 / mi η ammonia (N Η 3) was supplied for 3 minutes, and A1 and G a and I η were stacked. Nitriding of alloys. At the same time, the temperature of the growing device was maintained at 1180 ° C, and trimethylgallium (TMG) was supplied at 140 / imol / min to the growing device, and a gallium nitride layer was grown on the substrate on which the A1 and Ga and In alloys were deposited. . 1 // m. The surface of the epitaxially grown wafer thus grown is a mirror surface, and the half-amplitude pulse width of the X-ray oscillation curve of the epitaxially grown gallium nitride layer is 620 seconds. This shows that the epitaxially grown gallium nitride layer is one having excellent crystallinity. In the foregoing Examples 1 to 3, the gallium nitride layer was epitaxially grown as a crystal of I I I nitride semiconductor, but a mixed crystal of a group III nitride semiconductor shown by InxGayAlzN can also be grown. Embodiment 4 In Embodiment 4, a manufacturing method using a crystal of a group III nitride semiconductor is adopted, and a method of manufacturing a semiconductor light-emitting element using a gallium nitride-based compound semiconductor will be described.

本實施例4所製作的半得體發光元件用外延成長層構·造 ，如第6圖所示在具有c面之藍寶石基板Π上’依格子 不整合結晶之外延成長方法、自基板側依序疊層帶1 x 1〇17cirr3電子濃度之2 // m低Si摻雜GaN層12、帶1 X 1〇19cm·3電子濃度之1 μ m高Si摻雜GaN層13、帶1 X -40- 546850 五、發明說明（39) l〇】7cr3電子濃度之i〇〇AIn() ]Ga〇 9n覆蓋層14、自GaN障 壁層開始結束於GaN障壁層，由6層70A之GaN障壁層 15與5層20A之摻雜In。2Ga() SN阱層16所成多重量子阱 構造、30A之無摻雜的In〇 2Ga() 8n擴散防止層 π、 8χ 1 0i7cr]正孔濃度之〇 . 15 μ m Mg摻雜GaN層1 8、帶5 X 1018cr3正孔濃度i〇0AMg摻雜19之構造。 又，本實施例4製作的半導體發光元件之電極構造的平視 圖表示於第7圖。 上述具有半導體發光元件構造之外延層之晶片的製作使 用M0CVD法以下述程序進行。 首先，將藍寶石基板導入感應加熱式加熱器之RF線圈 中所設置石英製反應爐中。藍寶石基板在取代氮氣的小型 收容室中載置於加熱用碳製感應器上。導入試料後，流通 氮氣純化反應爐內。 偏及流通氮氣1 0分鐘後，作動感應加熱式加熱器、花 1〇分鐘昇溫基板溫度至1 1 7 0 °C、同時使爐內之壓力爲 50hPa。並仍保持基板溫度於1170°C、邊流通氫氣與氮氣 放置9分鐘、進行基板表面之熱淸理。 進行熱淸理間，流通氫氣載運氣體於連接在反應爐作爲 原料，放入有三甲基鎵（TMGa)之容器（起泡器）及放入有三 甲基鋁（TMA 1 )之容器（起泡器）之容器的配管，開始起泡。 各起泡器之溫度係使用用以調整溫度之恆溫槽調整爲一定 。由起泡產生的TMGa及TMA1之蒸氣自成長製程開始至、 -41 - 546850 五、名务明說明（40) 與載運氣體一起流通於除害裝置之配管，通過除害裝置放 出於系統外。 於熱淸理結束後，關閉氮氣載運氣體之閥、對反應爐內 之氣體供應僅以氫氣者。 切換載運氣體後，降溫基板之溫度降低至1 1 oot、調 整爐內之壓力至lOOhPa。確認在110(TC溫度穩定後，同 時切換TMG與TMA配管之閥，將含有TMGa與TMA1蒸氣之 氣體供應於反應爐內，開始在藍寶石基板上進行附著金屬 核之處理。所供應的TMGa與TMA1之混合比，以配置於起 泡配管的流量調整器調整爲莫耳比例成2 : 1。 經1分30秒間之處理後，同時切換TMGa與TMA1配管 之閥，停止將含有TMGa與TMA1之蒸氣的氣體供應於反應 爐內，經1 0秒後，內切換氨氣體配管之閥，開始供應氨 氣體於爐內。 經1Q秒後繼續流通氨，昇溫感應器之溫度爲1160t。 在感應器溫度之昇溫中，調整TMG a配管的流量調整器之 流量。又，開始SiH4之流通。至低S!摻雜之GaN層成長 開始之間，S〗H4與載運氣體一起流通於除害裝置之配管， 通過除害裝置放出於系統外。 確認感應器之溫度成爲1 1 60 °C後，等待溫度之穩定、 其後切換TMGa與S!H4之閥開始對爐內供應TMGa與 開始低S i摻雜之G aN成長，約經過1小時1 5分鐘進行上 述GaN層之成長。流通S i H4之量係事前已檢討，將低S i -42- 546850 五、發明說明（41 ) 摻雜GaN層之電子濃度調整爲1 X l〇17cm_3。 如此形成膜厚2 // m之低S i摻雜GaN層。 再者，在該低Si摻雜GaN層上成長高Si摻雜之η型 G a Ν層。於成長高S i摻雜之G a Ν層後，經過1分鐘停止 供應TMG與S i H4對爐內。其間變更S i H4之流通量。而流 通的量係於事前已檢討，調整成爲高Si摻雜GaN層之電 子濃度爲1 X 1019cm·3。氨仍以該流量繼續供應於爐內。 停止1分鐘後，再開始供應TMG a與S i H4、經由4 5分鐘 進行了成長並藉由該操作形成膜厚1 // m之高Si摻雜GaN 層。 成長高S〗摻雜GaN層後，切換TMGa與SiH4之閥，予 停止此等原料供應給於爐內。邊使氨依原樣流通、切換閥 使載運氣體由氫切換爲氮。其後，將基板之溫度自1 1 60 °C降下至800t：，同時將爐內之壓力由lOOhPa變更爲 2 0 〇 hPa。 在等待變更爐內溫度之間，改變S i H4之供應量。所流通 之量係於事前已檢討，調整s 1摻雜I nG aN覆蓋層之電子 濃度成爲1 X 10 17cm·3。氨仍以原來流量繼續供應於爐內。 又，預先開始將載運氣體流通於三甲基銦（TM I )與三乙 基i豕（TEGa)之起泡器。SiH4氣體、及由起泡產生的TMIn 及 TEGa之蒸氣’係直到覆蓋層之成長製程開始，與載運 氣體一起流通於配管、通過除害裝置放出於系統外。 其後，等待爐內裝置之穩定，同時切換TMIn與TEGa與 -43 - &gt;、發明說明C 42) S i H4之閥，開始此等之原料供應於爐內。經由約1 0分鐘 _續供應，形成成爲膜厚100Α之Si摻雜In() {a。yN覆 寥層。 其後，切換TMI、TEG及SiH4之閥，停止了供應此等之 赓料。 接著，製作由GaN所成障壁層與由ln() 2Ga() 8N所成阱層 所構成的多重量子阱構造。於製作多重量子阱構造時，在 Si摻雜覆蓋層上，首先形成GaN障壁層、在 笋GaN障壁層上形成lnQ 2GaQ 8n阱層。重複疊層該構造5 次後，在第5層之ln() 2GaQ.(sN阱層上形成第6層之GaN障 莖層，使兩側自GaN障壁層所構成的構造。 亦即，結束Si摻雜InnGa^J覆蓋層之成長後，經過 3 〇秒停止後，進行基板溫度或爐內之壓力、載運氣體之 流量或種類原樣作切換TEGa之閥進行供應TEGa於爐內。 經過7分鐘進行供應TEGa後，再次切換閥停止供應TEG a 結束GaN障壁層之成長。並由此，形成膜厚70A之GaN障 壁層。 進行GaN障壁層成長之間，流通於除外設備之配管的 Τ Μ I之流量’與覆蓋層成長時相比，以莫耳流量調整爲2 倍 ° 於GaN障壁層成長結束後，經過30秒鐘停止供應III 族原料後，基板溫度或爐內之壓力、載運氣體之流量或種 類仍以原樣，切換TEGa與TMIn之閥、進行對爐內供應 -44- 546850 五、發明說明（43) TEG與TMI。經過2分鐘進行供應TEGa與TMIn後，再度 切換閥停止供應TEGa與TMIn結束In().2GaQ.8N阱層之成長 。形成膜厚20A之In。2Ga。SN覆蓋層。 結束In() 2GaQ.8N阱層成長後，經過30秒鍾停止供應 工I I族原料後，基板溫度或爐內之壓力、載運氣體之流量 或種類仍以原樣，開始供應TEGa於爐內，再以進行GaN 障壁層之成長。 重複如此步驟5次，製作5層之GaN障壁層與5層之 In0 阱層。再者，在最後之ln() 2Ga().8N阱層上形成 G a N障壁層。 在該GaN障壁層作結束的多重量子阱構造上，製作無摻 之8N擴散防止層。 停止供應TEGa、GaN障壁層之成長結束後，經過1分鐘 使基板之溫度與載運氣體之種類、流量在相同狀態下，使 爐內之壓力變更爲lOOhPa。 又作成預先開始流通載運氣體於三甲基鋁（TMA )之起泡 器。由起泡產生的TMA之蒸氣，係於開始擴散防止層之成 長製程至，係與載運氣體一起流通於配管、通過除害裝置 放出於系統外。The epitaxial growth layer structure and construction of the semi-detailed light-emitting element manufactured in this Example 4 are shown in FIG. 6 on the sapphire substrate Π having the c-plane. Laminated with 1 x 1〇17 cirr3 electron concentration 2 // m low Si-doped GaN layer 12, with 1 X 1010 cm · 3 electron concentration 1 μm high Si-doped GaN layer 13, with 1 X -40 -546850 V. Description of the invention (39) l〇] 7cr3 electron concentration iOOAIn ()] Ga〇9n cover layer 14, starting from the GaN barrier layer and ending with the GaN barrier layer, 6 layers of 70A GaN barrier layer 15 And 5 layers of 20A doped with In. 2Ga () SN well layer 16 multiple quantum well structure, 30A undoped In〇2Ga () 8n diffusion prevention layer π, 8χ 1 0i7cr] positive hole concentration of 0.15 μm Mg doped GaN layer 1 8. Structure with 5 X 1018cr3 positive hole concentration iOOAMg doped with 19. A plan view of the electrode structure of the semiconductor light-emitting element produced in the fourth embodiment is shown in FIG. The wafer having the epitaxial layer of the semiconductor light-emitting device structure was fabricated using the MOCVD method in the following procedure. First, a sapphire substrate was introduced into a quartz-made reaction furnace provided in an RF coil of an induction heating heater. The sapphire substrate was placed on a heating carbon sensor in a small storage chamber instead of nitrogen. After introducing the sample, purify the inside of the reaction furnace by flowing nitrogen. After 10 minutes of partial nitrogen flow, the induction heating heater was operated, and the substrate temperature was raised to 110 ° C for 10 minutes while the pressure in the furnace was set to 50 hPa. The temperature of the substrate was maintained at 1170 ° C, and the mixture was allowed to stand for 9 minutes while flowing hydrogen and nitrogen. The substrate was then thermally treated. During the thermal process, a hydrogen carrier gas is circulated to the reaction furnace as a raw material, and the container (bubble) containing trimethylgallium (TMGa) and the container (bubble) containing trimethylaluminum (TMA 1) are placed. The piping of the container) started to foam. The temperature of each bubbler is adjusted to be constant by using a constant temperature bath to adjust the temperature. The vapors of TMGa and TMA1 generated by the foaming process start from the growth process to -41-546850 V. Mingwuming (40) circulates with the carrier gas in the piping of the detoxification device and is discharged out of the system through the detoxification device. After the thermal digestion is completed, the valve carrying the nitrogen gas is closed, and only the hydrogen is supplied to the gas in the reaction furnace. After the carrier gas is switched, the temperature of the cooling substrate is reduced to 11 oot, and the pressure in the furnace is adjusted to 100 hPa. After confirming that the temperature of 110 ° C is stable, the valves of the TMG and TMA pipes are switched at the same time, and the gas containing TGa and TMA1 vapor is supplied into the reaction furnace, and the metal core attachment process is started on the sapphire substrate. The mixing ratio is adjusted to a molar ratio of 2: 1 by the flow regulator arranged in the bubble pipe. After processing for 1 minute and 30 seconds, the valves of the TMGa and TMA1 pipes are switched at the same time, and the steam containing TMGa and TMA1 is stopped. The gas was supplied to the reaction furnace. After 10 seconds, the valve of the ammonia gas piping was switched internally to start supplying ammonia gas to the furnace. After 1Q seconds, ammonia was continued to flow and the temperature of the temperature sensor was 1160t. At the temperature of the sensor During the temperature rise, adjust the flow rate of the flow regulator of the TMG a piping. Also, start the flow of SiH4. Between the beginning of the growth of the low S! Doped GaN layer, S〗 H4 and the carrier gas flow through the piping of the detoxification device. It is released from the system through the detoxification device. After confirming that the temperature of the sensor has reached 1 1 60 ° C, wait for the temperature to stabilize, and then switch the valve of TMGa and S! H4 to start supplying TMGa to the furnace and start low S i doping. Miscellaneous G aN Growth, the growth of the above-mentioned GaN layer takes about 1 hour and 15 minutes. The amount of circulating Si H4 has been reviewed beforehand, and the low Si -42-546850 will be lowered. 5. Description of the invention (41) Electron concentration adjustment of the doped GaN layer It is 1 X 1017 cm_3. In this way, a low Si-doped GaN layer with a film thickness of 2 // m is formed. Furthermore, a high Si-doped n-type Ga n layer is grown on the low Si-doped GaN layer. After growing a high Si-doped GaN layer, the supply of TMG and SiH4 to the furnace was stopped after 1 minute. During this period, the circulation of SiH4 was changed. The circulation was reviewed beforehand and adjusted to high Si The electron concentration of the doped GaN layer was 1 X 1019 cm · 3. Ammonia was still supplied in the furnace at this flow rate. After stopping for 1 minute, the supply of TMG a and Si H 4 was resumed, and the growth was carried out in 45 minutes. This operation forms a high Si-doped GaN layer with a film thickness of 1 // m. After growing a high S-doped GaN layer, the valves of TMGa and SiH4 are switched, and the supply of these materials to the furnace is stopped. While the ammonia is as it is The flow and switching valve switches the carrier gas from hydrogen to nitrogen. After that, the temperature of the substrate is lowered from 1 1 60 ° C to 800t :, while the pressure in the furnace is reduced from l OOhPa was changed to 200 Hour Pa. While waiting to change the temperature in the furnace, the supply of Si H4 was changed. The amount of circulation was reviewed beforehand, and the electron concentration of the s 1 doped I nG aN coating was adjusted to 1 X 10 17cm · 3. Ammonia continues to be supplied into the furnace at the original flow rate. In addition, the carrier gas was previously circulated through the bubblers of trimethylindium (TM I) and triethyl i 豕 (TEGa). The SiH4 gas and the vapors of TMIn and TEGa generated by the bubbling are used until the growth process of the cover layer is started. It is circulated with the carrier gas in the piping, and is discharged out of the system through a detoxification device. After that, wait for the stability of the equipment in the furnace, and simultaneously switch the valves of TMIn, TEGa and -43-&gt;, Invention Description C 42) S i H4, and start to supply these raw materials in the furnace. After about 10 minutes of continuous supply, a Si-doped In () {a with a film thickness of 100 A was formed. yN covers few layers. Thereafter, the valves of TMI, TEG and SiH4 were switched, and the supply of these materials was stopped. Next, a multiple quantum well structure composed of a barrier layer made of GaN and a well layer made of ln () 2Ga () 8N was fabricated. When manufacturing a multiple quantum well structure, a GaN barrier layer is first formed on the Si-doped cladding layer, and an lnQ 2GaQ 8n well layer is formed on the GaN barrier layer. After repeatedly stacking the structure five times, a GaN barrier layer of the sixth layer was formed on the ln () 2GaQ. (SN well layer) of the fifth layer, and the structure consisting of the GaN barrier layers on both sides was completed. After the growth of the Si-doped InnGa ^ J cladding layer, after 30 seconds of stopping, the temperature of the substrate or the pressure in the furnace, the flow rate or the type of the carrier gas is switched as a TEGa valve to supply TEGa in the furnace. After 7 minutes After the supply of TEGa, the switching valve was stopped again to stop the supply of TEG a to terminate the growth of the GaN barrier layer. As a result, a GaN barrier layer with a thickness of 70A was formed. The GaN barrier layer was grown and passed through the TM of the piping of the excluded equipment. The flow rate is adjusted to 2 times the Mohr flow rate when compared with the cover layer growth. After the GaN barrier layer growth is completed, the supply of Group III materials is stopped after 30 seconds. The substrate temperature or the pressure in the furnace and the The flow or type is still the same, switch the valve of TEGa and TMIn, and supply to the furnace -44- 546850 V. Description of the invention (43) TEG and TMI. After 2 minutes of supplying TEGa and TMIn, switch the valve again to stop supplying TEGa End with TMIn In (). 2GaQ.8N well The layer grows. An In.2Ga.SN cover layer with a thickness of 20A is formed. After the growth of the In () 2GaQ.8N well layer is stopped, the supply of Group II raw materials is stopped after 30 seconds, the substrate temperature or the pressure in the furnace, and the transport The flow rate or type of gas is still the same, and TEGa is started to be supplied in the furnace to grow the GaN barrier layer. Repeat this step 5 times to make 5 layers of GaN barrier layers and 5 layers of In0 well layers. Furthermore, in Finally, a G a N barrier layer is formed on the ln () 2Ga (). 8N well layer. On the multiple quantum well structure where the GaN barrier layer is finished, an 8N diffusion-free layer is made without doping. The supply of TEGa and GaN barrier layers is stopped. After the growth is completed, the temperature of the substrate and the type and flow rate of the carrier gas are changed under the same state for 1 minute, and the pressure in the furnace is changed to 100 hPa. It is also made to start the circulation of the carrier gas to trimethyl aluminum (TMA) in advance. Bubbler. The vapor of TMA generated by foaming is from the beginning of the growth process of the diffusion prevention layer, and is circulated with the carrier gas in the piping, and is discharged out of the system through the harm removal device.

等待爐內之壓力穩定，切換TEG a與TM A 1之閥，開始將 止匕等之原料供應於爐內。其後，經過約3分鐘進行成長後， 停止供應TEGa與TMA1、停止無摻雜之Al() 2Ga() iSN擴散防 止層之成長。並由此形成膜厚爲30A之無摻雜Al() 2Ga() 8N -45 - 546850 五、發明說明（44 ) 擴散防止層。 在該無摻雜之A 1 () 2Ga() 8N擴散防止層上製作Mg摻雜之 G a N 層。 停止供應TEG與TMA，結束無摻雜之A1() 2Ga() sN擴散防 止層之成長後，經過2分鐘使基板之溫度上昇至1 〇 6 〇, 變更爐內之壓力爲2 0 0 h P a。再者，將載運氣體變更更氫 〇 又，預先開始流通載運氣體於雙環戊二烯鎂（cp2Mg)之 起泡器。由起泡產生的C p 2 M g之蒸氣係自開始μ g摻雜G a N 層之成長製程，與載運氣體一起流通於除害裝置之配管、 通過除害裝置放出於系統外。 變更溫度與壓力等待爐內之穩定，切換TMGa與Cp2Mg 之閥，開始將此等之原料供應於爐內。流通C p 2 M g之量係 於事前已檢討，將Mg摻雜GaN覆蓋層之正孔濃度調整爲 8 X 1017cm_3。其後，約經過6分鐘進行成長後，停止供應 丁 M G a與C p 2 M g、停止M g摻雜G a N層之成長。並由此形成 膜厚0.15// m之Mg摻雜GaN層。 在該Mg摻雜之GaN層上製作Mg摻進之InGaN層。 停止供應TMGa與Cp2Mg，使Mg摻雜之GaN層之成長結 束後，經過2分鐘使基板之溫度下降至8 0 0 °C ,同時變更 載運氣體爲氫。爐內之壓力仍依2〇〇 hPa。 變更Cp2Mg之流量，使Mg摻雜in() 2Ga()川層之Mg摻雜 與M g塗料G a N層相同。並由事前之檢討，在該摻雜量， -46- ^46850Wait for the pressure in the furnace to stabilize, switch the valves of TEG a and TM A 1, and start to supply raw materials such as daggers into the furnace. Thereafter, after about 3 minutes of growth, the supply of TEGa and TMA1 was stopped, and the growth of the undoped Al () 2Ga () iSN diffusion prevention layer was stopped. Thus, a non-doped Al () 2Ga () 8N -45-546850 film thickness of 30A is formed. 5. Description of the Invention (44) A diffusion prevention layer. A Mg-doped G a N layer was formed on the undoped A 1 () 2Ga () 8N diffusion prevention layer. After stopping the supply of TEG and TMA and ending the growth of the non-doped A1 () 2Ga () sN diffusion prevention layer, the temperature of the substrate was raised to 1.06 in 2 minutes, and the pressure in the furnace was changed to 200 h P a. In addition, the carrier gas was changed to a hydrogen gas, and the carrier gas was previously circulated in a bubbler of dicyclopentadiene magnesium (cp2Mg). The vapor of C p 2 M g generated by foaming is a growth process of μ g doped G a N layer from the beginning. It flows with the carrier gas in the piping of the detoxification device and is discharged out of the system through the detoxification device. Change the temperature and pressure to wait for the stability in the furnace, switch the valves of TMGa and Cp2Mg, and start to supply these raw materials in the furnace. The amount of circulating C p 2 M g was reviewed beforehand, and the positive hole concentration of the Mg-doped GaN cap layer was adjusted to 8 X 1017 cm_3. Thereafter, after about 6 minutes of growth, supply of Mg a and C p 2 M g was stopped, and growth of the M g-doped G a N layer was stopped. Thus, an Mg-doped GaN layer having a film thickness of 0.15 // m was formed. A Mg-doped InGaN layer is formed on the Mg-doped GaN layer. After stopping the supply of TMGa and Cp2Mg, after the growth of the Mg-doped GaN layer was completed, the temperature of the substrate was lowered to 800 ° C after 2 minutes, and the carrier gas was changed to hydrogen. The pressure in the furnace is still 200 hPa. The flow rate of Cp2Mg was changed so that the Mg doping of the Mg-doped in () 2Ga () layer was the same as that of the M a coating G a N layer. And by prior review, at this doping amount, -46- ^ 46850

l、發明說明（45) 5知私/ M g ί爹雑I η () ! G a u y N層之止孔濃度爲5 χ 1〇1 &lt;s c m」 〇 等待基板溫度穩定，切換TMIn與TEGa與Cp2Mg之閥， _始將此等之原料供應於爐內◦其後，約經過分鐘進 行成長後，停止供應TEGa與TMIn與CpiMg、以停1丨：心摻 雜I η 〇 , G a Q 9 N層之成長。並由形成膜厚爲丄〇 〇 a之μ g摻雜 &amp; In()丨Ga() 9N 層。l. Description of the invention (45) 5 Intellectual Property / M g ί 雑 I η ()! G auy N layer stop hole concentration is 5 χ 1〇1 &lt; scm '' 〇 Wait for the substrate temperature to stabilize, switch TMIn and TEGa and The valve of Cp2Mg _ began to supply these raw materials in the furnace. After that, after about one minute of growth, the supply of TEGa and TMIn and CpiMg was stopped to stop. 1: Heart doped I η 〇, G a Q 9 N-tier growth. And a μg doped &amp; In () 丨 Ga () 9N layer with a film thickness of OO a is formed.

Mg摻雜I n() ,Ga。層之成長結束後，停止對感應加熱 式加熱器通電，將基板之溫度經過20分鐘降溫至室溫。 降溫中反應爐內之環境僅由氮氣構成。其後，確認基板溫 度降至室溫，取出晶圓於大氣中。 由以上的步驟’製作具有半導體發光元件用外延成長層 構造之晶圓。在此Mg摻雜GaN覆蓋層與Mg摻雜 I n() jGa() 9N層，沒有進行係用以使p型載運活性化不進行 退火處理亦呈p型。 接著，使用在上述藍寶石基板上疊層有外延成長層構造 之晶圓製作一種半導體發光元件之發光二極體。 對於製作的晶圓係由公知之微影術在 Mg 摻雜 I n。，Ga() 9N層之表面18a上，自表面側依序順序具疊層鈦 、鋁、金之構造的p電極結合襯墊1 2與僅由接合其的Au 所成的透光性P電極2 1，製作p側電極。 再於其後對晶圓進行乾式蝕刻，使形成高Si摻雜GaN 層之η側電極的部分2 3露出、在露出的部分製作由N i、 -47- 546850 五、發明說明（46 ) A 1所成的η電極2 2。並由此等作業，在晶圓上製作帶如 第7圖所示形狀的電極。 依如此形成ρ側及η側電極之晶圓，光製、硏磨藍寶石 基板之內面作成鏡狀面。其後，切斷該晶圓爲350 // m角 之正方形晶片'並使電極在上載置於α線框架上、以金線 結線於引導線框架作發光元件。 如上述所製作的發光二極體之ρ側及η側之電極間以順 方向流通電流時，於電流20πιΑ之順方向電壓爲3 . 0V ◦又， 通過ρ側之透光性電極觀察發光時，發光波長爲470nm, 發光輸出顯示爲6cd。如此矽發光二極體之特性，係由製 作的晶圓大致全面所製作的發光二極體，以無不均勻地獲 得。 實施例5 ， 說明氮化鎵系化合物半導體結晶之製造方法實施例。 在本實施例如第1圖所示，以步驟A—步驟B—步驟C — 步驟D之順序、在藍寶石基板上形成氮化鎵系化合物半導 體層。首先作爲步驟A，係流通包含三甲基鋁（TMA )之蒸氣 與三甲基鎵（TMG )之蒸氣以莫耳比1 : 2混合氣體之氣體、 在基板上施予附著金屬核的處理，步驟B係在氫氣中進行 退火，步驟C係流通氫與氨之混合氣體，進行退火後金屬 核之氮化處理以形成成長核，其後，步驟D係流通TMGa 與氨、使成長核再形成氮化鎵、製作在藍寶石基板上具備 氮化鎵結晶膜之氮化鎵系化合物半導體層。 -48- 546850 五、發明說明（47) 其具體的步驟如下述。亦即，先將藍寶石基板導人設置 在感應加熱式加熱器之RF線圈中的石英製反應爐Ψ。藍 寶石基板在取代氮氣的小型收容室中、載置於加熱川碳製 感應器卜.。導入試料後，流通氮氣使純化反應爐內。 流通氮氣1 0分鐘後，作動感應加熱式加熱器，經過1〇 分鐘溫昇基板溫度至1 170t。保持基板溫度1 1 70 t下， 邊流通使氫氣與氮氣放置9分鐘，進行基板表面之熱淸理 〇 進行熱淸理之間，裝入流通氫載運氣體於原料之」甲基 鎵（TMGa)之容器（起泡器）及裝入三甲基鋁（TMA)之容器（起 泡器）的各配管，開始起泡。尙，各起泡器之溫度係使用 用以調整溫度之恆溫槽調整爲一定。又，各起泡器之配管 係連結於反應路。由起泡產生的TMGa與TMA1之蒸氣，係 直到氮化鎵系化合物半導體層之成長製程開始至、與載運 氣體一起流通於除害裝置之配管、通過除害裝置放出於系 統外。 結束淸理後，關閉氮氣載運氣體之閥、僅以氫氣供應於 反應爐內。 切換載運氣體後，降溫基板溫度至110(rc。確認溫度 在1100C穩疋後，问日寸切換TMGa與TMA1配管之閥，將 含TMG a與了 M A 1之蒸氣的氣體供應於反應爐內，在藍寶石 基板t開始附著金屬核的處理。供的TMGa與TMA 1之混 合比，係以設置在起泡的配管的流毚調整器調整爲莫耳比 -49 - 546850 五、發明說明（48) 2 :卜 處理1分 30秒鐘後，同時切換TMGa與TMA1之配管的 閥，停止供應含TMGa與TMA 1蒸氣之氣體於反應爐内。仍 依原樣，保持3分鐘、使形成的金屬核在氫氣載運氣體中 退火。 退火3分鐘後，切換氨氣配管的閥、對爐內開始供應氨 氣、進行退火後之金屬核氮化處理、形成成長核。 流通1 0分鐘後，昇溫感應器之溫度昇溫至Η 60 °C °感 應器溫度之昇溫中、調整TMGa配管的流量調整器之流量 。確認感應器之溫度成爲H 60°C後，等待溫度之穩定、 其後切換TM Ga之閥、開始供應TMG a於爐內、其成長核更 成長了氮化鎵。 經過1 /J、時進行上述氮化鎵結晶膜之成長後，切換 TMGa配管之閥，完成原料之供應於反應爐停止成長。氮 化鎵結晶膜之成長結束後，停止對感應加熱式加熱器之通 電，經過2 ◦分鐘使基板之溫度降溫至室溫。降溫中使反 應爐內之環境與成長中相同地由氨與氮與氫構成，惟確認 基板之溫度成300°C後，停止供應氨與氫。其後，邊流通 氮氣使基板溫度降溫至室溫、取出試料於大氣中。 由上述之製程’製作藍寶石基板上形成有不摻雜之膜厚 2 # m的氮化鎵結晶膜之試料。取出的基板爲無色透明、成 長面爲鏡面。 其次，以上述方法對成長的不摻雜氮化鎵結晶膜進行 -50- 546850 五、發明說明（49) XRC測定。測定係採用Cu /3線X線發生源作爲光源、在對 稱面之（0 0 0 2 )面與非對稱面之（1 〇 - 1 2 )面進行。—般而言， 半化鎵系化合物半導體時，（0002 )面之XRC光譜半振幅脈 衝寬度爲結晶之平坦性的指標，（1 0 - 1 2 )面之XRC光譜半 値振幅脈衝寬度成轉位密度之指標。 本該測定結果依本發明方法製作的不摻雜氮化鎵結晶膜， 在（ 0002 )面之測定係半振幅脈衝寬度爲2 30秒、在（10 - 12) 面係半振幅脈衝寬度呈3 5 0秒，皆爲良好。 又，上述氮化鎵結晶膜之最表面使用一般原子間力顯微 鏡（AFM)觀察。結果，在表面見不到成長凹坑、觀察了良 好形態之表面。 又，用以測定上述氮化鎵結晶膜之蝕刻凹坑密度時，將 試料在硫酸與磷酸之混合溶液中以2 8 0 °C處理1 0分鐘。該 試料之表面由以AFM觀察測定鈾刻凹坑密度時，約爲5 X 1〇7cm_2左右。 又，在上述過程與至中途完全爲同製程，在氮化鎵結晶 膜成長之前停過程，製作自成長爐中取出的試料，將使其 表面形態由原子間力顯微鏡（AFM)觀察時，藍寶石表面散 佈有作爲成長核之具梯形狀之剖面的氮化鋁結晶塊。 實施例6 在本實施例如第3圖所示，交替重複3次步驟A與步驟 B後，以步驟C—步驟D之順序在藍寶石基板上形成氮化 鎵系化合物半導體層。首先以步驟A係流通含有三甲基鋁 -5 1 - 546850 五、發明說明（5〇) (TM A 1 )蒸氣的氣體處理施予在基板上附著金屬核，步驟B 係在氫氣中進行退火，重複3次該步驟A與步驟b後，以 步驟C流通氣與氣之混合氣體，退火後進行金屬核之氮化^ 處理形成成長核，其後，以步驟D流通TMGa與氨在成冑 核更成長氮化鎵、製作在藍寶石基板上具備有氮化鎵結晶 膜之氮化鎵系化合物半導體層。 其具體的步驟如下所述。首先與上述第1實施例時同樣 在基板表面進行熱淸理、同時在進行其熱淸理之間，在:裝 入原料之三甲基鎵（TMGa )之容器（起泡器）及裝入三甲基銘 (TM A)之容器（起泡器）的各配管流通氫氣載運氣體，開始 起泡。尙且，各起泡器之溫度係用以調整溫度之恆溫槽言周 整爲一定。又，各起泡器之配管係連結於反應路。由起泡 產生的TMGa與TMA1之蒸氣，係直到氮化鎵系化合物半導 體層之成長製程開始至、與載運氣體一起流通於除害裝置 之配管、通過除害裝置放出於系統外。 結束熱淸理後，關閉氮氣載連氣體之閥、僅在反應爐內 供應氫氣。 切換載負氣體後，使基板溫度降溫至1丨60它。確認溫 度穩定於1 1 60°C後，切換TMA之配管的閥、供應於含有 Τ Μ A之蒸氣的氣體反應爐，經3分鐘處理後，停止供應含 有TMA1蒸氣之氣體於反應爐◦其後，依原樣保持3分鐘 、使形成的金屬核在氫氣載運氣體中退火。3 〇秒鐘之退火 後，再切換TMA之配管的閥、供應含TM A1蒸氣的氣體於 -52- 546850 五、發明說明（51) 反應爐內、將金屬核予以附著。與第1次相同地處理3分 鐘後，停止供應含TMA 1蒸氣的氣體予反應爐內。依原樣 保持30秒鐘將形成的金屬核在氫氣載運氣體中退火。其 後，再進行一次此等製程，合#重複3次金屬核之形成與 退火（步驟A—步驟B)。於第3次退火後，切換氨氣體之 酉己管的閥，供應氨氣使於爐內、進行退火後之金屬核氮化 處理、形成成長核。 經10秒鐘流通後，切換TMGa之閥。開始對爐內供應 TMGa、再於成長核成長氮化鎵。 經過1小時進行上述氮化鎵結晶膜之成長後，切換 TMGa之配管的閥，結束原料之供應於反應爐停止成長。 於氮化鎵結晶膜之成長結束後，停止對感應加熱式加熱器 之通電，經過2 0分鐘使基板之溫度降溫至室温。降溫中 係使反應爐內之環境與成長中相同地由氨與氮與氫構成， 惟確認基板之溫度成300 °C後，停止供應氨與氫。其後， 邊使氮氣流通降溫基板溫度至室溫、取出試料於大氣中。 由上述製程製作在藍寶石基板上形成不摻雜之膜厚2 “ m 的氮化鎵結晶膜之試料。取出的基板爲無色透明、成長面 爲鏡面。 其次，以上述方法進行所成長的不摻雜氮化鎵結晶膜之 X R C測定。湏[J定係使用C u /3線X線發生源作光源、在對稱 面之（ 0002 )面與非對稱面之（1〇_ 12)面進行。 該測定結果，本發明方法所製作的不摻雜氮化鎵結晶膜， -53- 546850 五、發明說明（52) 係在（ 0002 )面測定的半振幅脈衝寬度爲300秒、（10-12) 面之半振幅脈衝寬度爲3 20秒，皆佳。 又，t述氮化鎵結晶膜之最表面採用…般的原子問力顯 微鏡（AFM )觀察。結果，在表面未見到成長凹坑、觀察有 良好形態之表面。 又，爲測定上述氮化鎵結晶膜之蝕刻凹坑密度時，使試 料在硫酸與隣酸之混合溶液中、280 °C處理1 〇分鐘。將該 試料之表面由AFM觀察測定触刻凹坑密度時，約爲7 X 1〇7cm_2程度。 又，在上述製程與途中至爲完成相同製程，於氮化鎵結 晶膜成長前停止製程自成長爐取出試料製作，將其表面形 態由原子間力顯微鏡（AFM )觀察時，藍寶石表面散佈有作 成長核之具梯形狀截剖的氮化鋁結晶塊。 如此在本貫施例’由於重複金屬核之形成及退火，故^可^ 增加金屬核在基板上的密度、或控制退火後金屬核^： _狀 的機會，因而更精度良好地可進行其控制，亦使依丨廉^ # 屬核爲形成的氮化鎵系化合物半導體層，可作成更&amp;明2 形狀、品質者。 尙，本實施例6，重複金屬核之形成與退火爲3 &amp; ^ 其重複次數亦可爲2次或4次以上，因應其必要適當纟也$ 定即可。 WM例】 A與步 本實施例7係如第4圖所示，交替重複2次步驟 -54- 546850 五、發明說明（53) 驟B與步驟c後，進行步驟D，在藍寶石基板上形成氮化 鎵系化合物半導體層。首先作爲步驟A，係以三甲基鋁 (TMA1 )之蒸氣與三甲基鎵（TMGa)之蒸氣與三甲基銦（TMIn) 之蒸氣爲莫耳比混合i : 2 : 4的氣體流通、施於在基板上 附著金屬核的處理，步驟B係爲在氫氣中進行退火處理， 步驟C係爲流通氫與氨之混合氣體，退火後進行金屬核之 氮化處理形成成長核。重複2次該步驟A與步驟B與步驟 C後，步驟D係爲流通TMGa氨、再於成長氮化鎵成長核 '製作了在藍寶石基板上具備有氮化鎵結晶膜之氮化鎵系 化合物半導體層。 其具體的步驟如下所述。首先與上述第1實施例時相同， 在基板表面進行熱淸理、同時在進行淸理之間，在裝入原 料之三甲基鎵（TMGa)之容器（起泡器）、裝導入有三甲基鋁 (TMA1)之容器（起泡器）、及裝入有三甲基銦（TMIn)容器（ 起泡器）的各配管流通氫氣載運氣體，開始起泡。尙，各 起泡器之溫度係使用用以調整溫度之恆溫槽調整爲一定。 又，各起泡器之配管係連結於反應路。由起泡產生的 TMGa、TMA1與TMIn之蒸氣，係直到氮化鎵系化合物半導 體層之成長製程開始至、與載運氣體一起流通於除害裝置 之配管、通過除害裝置放出於系統外。 熱淸理結束後，關閉氮氣載運氣體之閥、使供應於反應 爐內之氣體僅爲氫氣。 切換載運氣體後，降溫基板溫度至900°C。確認溫度穩 -55- 546850 五、發明說明（54 ) 定於900°C後，同時切換TMGa、TMA1及TMIn之配管的閥 、使含有TMGa ' ΤΜΑ1及TMIn蒸氣的氣體供應於反應爐內， 開始進行使金屬核附著藍寶石基板上的處理。供應的TMGa 、TMA1及了Min之混合比，係以設置於起泡配管的流量調 整器調整成爲莫耳比2: 1:4。 於處理3分鐘後，同時切換TMG a、TM A 1及TM I η配管之 閥、停止供應含TMGa、ΤΜΑ1及ΤΜΙ η之蒸氣的氣體於反應 爐內。依原樣保持3 0秒鐘，使形成的金屬核在氫氣載運 氣體中退火。 於30秒鐘之退火後，切換氨配管之閥，開始在爐內供 應氨、進行經氮化處理退火後之金屬核、形成成長核。 經過1分鐘流通氨後，切換氨配管之閥，停止對爐內供 應氨氣體，將其原樣狀態保持3 0秒鐘後，同時再切換 TMGa、ΤΜΑ1及TMIn配管之閥，供應含TMGa、ΤΜΑ1及 TMIn蒸汽的氣體於反應爐內，再度在藍寶石基板上附著金 屬核。經處理3分鐘後，同時切換TMGa、TMA1及TMIn配 管之閥，停止反應爐內供應含TMGa、TMA1及TMIn蒸汽之 氣體。依原樣保持30秒鐘，在氫載運氣體中退火所形成 的金屬核。退火3 0秒鐘之後，切換氨氣體配管之閥，開 始供應氨氣體至爐內，進行氮化處理經退火後之金屬核， 形成成長核。如此，進行2次形成金屬核與退火及形成成 長核（步驟A—步驟B—步驟C)。 經1 0秒鐘流通後，使感應器之溫度昇溫至1 1 6 0 °C。感 -56- 546850 五、發明說明（55) 應器溫度之昇溫中調整TMG a配管的流量調整器之流量。 確認感應器之溫度爲1 1 60 °C後，保持溫度之穩定、其後 切換TMGa之閥開始爐內之TMGa供應再成長氮化鎵於成長 核。 經過1 /_]、時進行上述氮化鎵結晶膜之成長後，切換 TMGa配管之閥，結束原料之供應於反應爐停i_h成長。於 氮化鎵結晶膜成長結束後，停止對感應加熱式加熱器之通 電，經過2〇分鐘降溫基板之溫度至室溫◦降溫中使反應 爐內之環境與成長中相同地由氨與氮與氫構成，惟確認基 板之溫度成 300°C後，停止供應氨與氫◦其後，邊使氮氣 流通降溫基板溫度至室溫、將試料取出於大氣中。 由以上之製程，製作在藍寶石基板上形成未摻雜之膜厚 2 ν m的氮化鎵結晶膜之試料。取出的基板爲無色透明、成 長面爲鏡面。 其次，依上述方法進行成長的不摻雜氮化鎵結晶膜之 X RC測定。測J定係使用Cu A線X線發生源作爲光源、在對 稱面之（ 0002 )面與非對稱面之（10 - 1 2)面進行。 該測定結果，本發明方法所製作的不摻雜氮化鎵結晶膜， 在（ 0002 )面之測定係半振幅脈衝寬度爲250秒、（10 - 12) 面之半振幅脈衝寬度呈爲300秒，皆佳。 又，上述氮化鎵結晶膜之最表面使用一般的原子間力顯 微鏡（AFM )觀察◦結果，在表面未見到成長凹坑、觀察有 良好形態之表面。 -57- 546850 五、發明說明（56 ) 又，用以測定上述氮化鎵結晶膜之鈾刻凹坑密度時，使 試料在硫酸與磷酸之混合溶液中以2 80°C下處理1 0分鐘。 將該試料之表面由A F Μ觀察測定蝕刻門坑密度，約爲3 X 1〇7 c it 2程度。 又，在上述過程與至途中完全爲同樣製程，於氮化鎵結 晶膜成長之前停止過程製作、自成長爐取出的試料，其表 面形態以原子間力顯微鏡（A F Μ )觀察時，在藍寶石表面散 佈有作爲成長核之具有梯形狀剖面的氮化鋁結晶塊。 如此該實施例7 ’係使由於金屬核之形成與退火及形成 成長核重複，故可增加金屬核之基板h的密度、或退火後 金屬核之形狀、或成長核之形狀的控制機會，因而，將其 控制可更精度良好地進行，亦可更使依據該金屬核及成長 核形成的氮化鎵系化合物半導體層更作成爲所希望的形狀 、品質者。 尙，本實施例7，重複金屬核之形成與退火與成長核之 形成爲2次，惟其反覆次數亦可爲3次以上，因應必要適 當地設定即可。 實施例8 本實施例係如第5圖所示，以步驟A1與步驟A 2之2階 段（前期製程與後期製程），其從依步驟步驟C —步驟 D之順序在藍寶石基板上形成氮化鎵系化合物半導體層。 首先，作爲步驟A 1，係流通含有三甲基鋁（TMA丨）蒸氣之 氧體、於下一步驟A2，流通含有三甲基鎵（TMGa )蒸氣之氣 -58- 546850 五、發明說明（57) 體、在基板上施予附著金屬核的處理。其後，步驟B係在 氫氣中進行退火，步驟c係流通氫與氨之混合氣體，進行 退火後之金屬核氮化以形成成長核，其後，步驟D係流通 TMGa與氨更成長氮化鎵於成長核、製作在藍寶石基板上具 備氮化鎵結晶膜之氮化鎵系化合物半導體層。 其具體的步驟如下所述。首先與h述實施例丨時同樣， 進行基板表面之熱淸理、同時於進行其熱淸理之間，在裝 入原料的三甲基鎵（TMGa )之容器（起泡器）及裝入三甲基銘 (TMA )之容器（起泡器）之各配管流通氫氣載運氣體，開始 起泡。尙，各起泡器之溫度係使用用以調整溫度之恆溫槽 調整爲一定。又，各起泡器之配管連接於反應路。由起泡 產生的T M G a與T M A 1之蒸氣，係直到氮化鎵系化合物半導 體層之成長製程開始至、與載運氣體一起流通於除害裝置 之配管、通過除害裝置放出系統外。 結束熱淸理後，關閉氮氣載運氣體之閥、使對反應爐內 之氣體供應僅爲氫氣。 切換載運氣體後，降溫基板溫度至1 1 0(TC。確認溫度 穩定於1 100 T：後，切換TMA1配管之閥、供應含有TMA1 蒸氣之氣體於反應爐內，在藍寶石基板上開始金屬核（A n 之附著處理。經過1分鐘進行該處理後，切換TMA 1配管 之閥，停止供應含有TMA 1蒸氣之氣體於反應爐內（步驟 A1 )。其後，切換TMGa配管之閥、供應含TMGa蒸氣之氣 體於給反應爐內，開始在藍寶石基板上處理金屬（G a )核之 -59- 546850 ------------___ 五、發明說明（58) 附著。將使該處理經過進行2分鐘後，切換TMG a配管之 的閥、停止供應含TMGa蒸氣之氣體於反應爐內（步驟A2 ) 。如此將金屬核之形成分爲2階段（步驟A1—步驟A2)進 行。 其後保持5分鐘、將形成的金屬核在氫氣載運氣體中退 火經過。5分鐘之退火後，切換氨配管之閥 '開始供應氨 氣體於爐內、進行退火後之金屬核之氮化處理、形成成長 核。 1〇秒鐘之流通後，昇溫感應器之溫度至Η 60 °C。於感 應器溫度之昇溫中，調整TMGa配管之流量調整器之流量 。確認感應器之溫度成爲1 1 60 °C後，等待溫度之穩定、 其後切換TMGa之閥、開始供應TMGa於爐內、在成長核更 成長氮化鎵。 經過1小時進行上述氮化鎵結晶膜之成長後，切換 T M G a配管之閥，結束原料之供應於反應爐停止成長。，結 束氮化鎵結晶膜成長後，停止對感應加熱式加熱器之通電 經過20分鐘降溫基板之溫度至室溫。在降濫中以反應爐 內之環境與成長中相同地由氨與氮與氫構成，惟確認基板 之溫度成爲300°C後，停止供應氨與氫。其後，一邊流動 氮氣一邊降溫至室溫基板溫度、取出試料於大氣中。 依以上之製程’製作了在監寶石基板上形成不摻雜之膜 厚2 // m的氮化鎵結晶膜之試料。取出的基板爲無色透明 、成長面爲鏡面。 -60- 546850 五、發明說明（59) 其次，以上述方法進行成長的不摻雜氮化鎵結晶膜之 X R C測定。測定使用C u /3線X線發生源作爲光源、在對稱 面之（0 0 0 2 )面與非對稱面之（1 0 - 1 2 )面進行。 該測定結果，以本發明之方法製作的不摻雜氮化鎵結晶 膜，係（0002 )面之測定爲半振幅脈衝寬度爲180秒、（ΙΟ-ΐ 2)面之振幅脈衝 寬度呈 290 秒。 又，上述氮化鎵結晶膜之最表面使用一般的原子間力顯 微鏡（AFM )觀察◦結果，表面上見不到成長凹坑、觀察有 良好的形態之表面。 又，用以測定上述氮化鎵結晶膜之蝕刻凹坑密度，將試 料在硫酸與磷酸之混合溶液中以280 °C處理10分鐘。該試 料之表面以 AFM觀察測定蝕刻凹坑密度時，約爲1 X 1〇7cnT2程度。 又，在上述過程與至途中完全爲同樣製程，於氮化鎵結 晶膜成長之前停止過程製作、自成長爐中取出的試料，將 其表面形態以原子間力顯微鏡（AFM )觀察時，在藍寶石表 面上散佈有作爲成長核具梯形狀剖面的氮化鋁結晶塊。 如此，本實施例8係將金屬核之形成分爲前期製程與後 期製成2階段來進行，故作成金屬核之金屬種類可爲多樣 化，又可更精度良好地控制金屬核在基板上之密度，因而 ，依據此金屬核形成的氮化鎵系化合物半導體層作成更爲 所希望之形狀、品質者。 尙本實施例8，係將金屬核之形成分爲前期製程與後期 6 546850 五、發明說明（6〇 ) 製程之2階段進行、分別各進行1次，惟該前期製程與後 期製程亦可構成重複2次以上進行◦又，不只是2階 ， 亦可分爲以3階以t進行。如此增加重複次數、增加階 數， 更高精度來進行金屬核之形成。 乂 本實施例8，係金屬核之肜成 成 階 進行後 使金屬核在氫氣載運氣體中退火 但 省略該退火製程 。惟此時必須適當地確地選擇用 形成金屬核之原料種類 或進行氮化金屬核時 環境氣體溫度、壓力等 條件。 實施例9 本實施 例 9，係 與 述實: 施例4(第 5 圖）時同樣 使 步 驟 A爲步 驟 A 與步驟A 階 其 :後 步驟B — 步 驟 C — &gt;步驟 D 順序 在藍寶石 基板 形 成 氮化鎵系化 口 物 半 導 體層。 首 先步驟 A 流通含有三甲基鋁（TMA )蒸 氣 氣 體 、於下 ——一 步驟A ，流通含 有三甲基 鎵 (TMGa )與三 甲 基 銦 (TMIn) : 混合比混 合蒸氣 氣 體、實施附 著 屬 核 於基板 處理。 此時 與實施例 4 時 同 使 實 施 步 驟 A 溫度與實施步驟A 溫度設 定 爲互相的溫 度 同 〇 其後 步 驟B 在氫氣 進行退火 步驟C 流 通 氫 與 氨混合氣體氨退火後進行屬核氮化處理形成成長核氨 其後氨步驟D 流通TMGa與氨更成長忍化録於成長核 、製作在藍寶石基板具備有氮化嫁結晶膜氮化嫁系化 合物半導體層。 其具體步驟如下所述。首先與述實施例時同樣氨在 -62- 546850 五、發明說明（6〇 基板表面進行熱淸理、同時在進行熱淸理之間，在裝入原 料的三甲基鎵（TMGa)之容器（起泡器）、裝入三甲基隹呂 (T M A 1 )之容器（起泡器）及裝入有二屮基銦（Τ Μ I η )之容器（ 起泡器）的各配管流通氫氣載運氣體，開始起泡◦尙，各 起泡器之溫度，係使用用以調整溫度之恆溫槽調整爲一定 。又，各起泡器之配管連接於反應路。由起泡產生的 TMGa與ΤΜΑ1與TMIn之蒸氣，係直到氮化鎵系化合物半導 體層之成長製程開始至、與載運氣體·一起流通於除害裝置 之配管、通過除害裝置放出於系統外。 結束熱淸理後，關閉氮氣載運氣體之氣閥、對反應爐內 之供應氣體僅爲氫氣。 切換載運氣體後，降溫基板溫度至1 1 60 °C。確認溫度 穩定於H60°C後，切換TMA1配管之閥、供應含有TMA1 蒸氣之氣體於反應爐內，開始在藍寶石基板上附著（A 1 )金 屬核處理。該處理進行經過1分鐘後，切換TMA1配管之 閥，停止供應含有TMA 1蒸氣之氣體至反應爐內（步驟A 1 ) 。其後，控制通電於RF線圈之電流，變更感應器之溫度 爲9 50 °C。10秒鐘等待溫度穩定後，同時切換TMGa與 TMIn配管之閥、供應含TMGa與TMIn蒸氣的氣體於反應爐 丨內，開始在藍寶石基板上附著（G a、I η )金屬核之處理。供 應的TMG a與TM I η之混合比係以設置起泡配管中的流量調 整器調整爲莫耳比例成爲1 : 2。進行該處理經過2分鐘後， Μ時切換TMGa與TMIn配管之閥 '停止供應含TMGa與 -63- 546850 五、發明說明（62) Τ Μ I η蒸氣的氣體於反應爐（步驟A 2 )。如此分金屬核之形 成2階段（步驟A1—步驟A2)進行，同時各步驟之成長溫 度設定位不同的溫度。 其後，保持5分鐘、將形成的金屬核在氫氣載運氣體中 退火。5分鐘之退火後，再切換氨氣體配管之閥、對爐內 開始供應氨氣體、進行退火後之金屬核氮化處理、形成成 長：核。 流通1 0秒鐘後，昇溫感應器之溫度至1 1 60°C °於感應 器之溫度昇溫中，調整TMG a配管的流量調整器之流量。 確認感應器之溫度成爲1 1 6 0 °C後，等待溫度之穩定、其 後切換TMG a之閥、開始對爐內供應TMG a、使成長核上更 成長氮化鎵。 經過1小時進行上述氮化鎵結晶膜之成長後，切換 TMGa配管之閥，結束原料供應於反應爐停止成長。於結 束氮化鎵結晶膜成長後，停止對感應加熱式加熱器之通電， 經過20分鐘降溫基板之溫度至室溫。在降溫中與反應爐 內之環境成長相同’由氨與氮與氫構成，惟確認基板之溫 度成爲3 0 0 °C後，停止供應氨與氫。其後，邊流通氮氣降 溫基板溫度至室溫、取出試料於大氣中。 由以上之製程，製作在藍寶石基板上形成不摻雜之膜厚 2 // m的氮化鎵結晶膜之試料。取出的基板爲無色透明，成 長面爲鏡面。 其次，以上述方法進行成長的不摻雜氮化鎵結晶膜之 -64- 546850 五、發明說明（63) XRC測定。測定係使用Cu /3線X線發生源作爲光源、以對 稱面之（ 0002 )面與非對稱面之（丨2 )面進行。 該測定結果’依本發明方法製作的不摻雜氮化鎵結晶膜， (〇0 0 2 )面之測疋爲半振幅脈衝寬度爲丨9 0秒、（1 〇 - 1 2 )面 之半振幅脈衝寬度呈2 6 0秒。 又，上述氮化鎵結晶膜之最表面使用一般的原子間力顯 微鏡（AFM)觀察。結果，在表面未見到成長凹坑、觀察到 良好形態之表面。 又，用以測定_h述氮化鎵結晶膜之蝕刻凹坑密度，將試 料在硫酸與磷酸之混合溶液中以280t處理1 0分鐘。以 A F Μ觀察該試料之表面測定蝕刻凹坑密度時，約爲1 X 1〇7 c r2程度。 又，上述製程與至途中完全爲同樣製程，製作於氮化鎵 結晶膜成長之前停止過程自成長爐中取出的試料，將其表 面形態以原子間力顯微鏡（AFM)觀察時，藍寶石表面散佈 有作爲成長核具有梯形狀剖面的氮化鋁結晶塊。 如此在本實施例9，係金屬核之形成分成2階段進行、 同時各階段之成長溫度設定位爲不同溫度，故可使成爲金 屬核之金屬種類多樣化，同時可適合於其金屬的溫度確實 地附著，並可以更精度良好地控制在金屬核之基板上的密 度，因此，可使依據此金屬核形成的氮化鎵系化合物半導 體層作成更爲所希望的形狀、品質者。 尙，於本實施例9，以分2階段進行金屬核之形成後， -65- 546850 五、發明說明（64 ) 將金屬核在氫氣載運氣體中退火，但亦可省掉該退火製程 。又此時，於交替進行金屬核之形成製程與氮化製程2次 以上後，亦可使氮化鎵系化合物半導體層成長。 b匕較例1 製作用以與上述實施例1〜3及5〜9所製作的各試料比 較時之試料。在比較例與[習知技術]欄中說明的特開平4_ 2 9 7023號公報之實施例所報告同樣採用形成低溫緩衝層之 製程，在基板上形成不摻雜之膜厚2 // m的氮化鎵結晶膜 。取出的基板爲無色透明、成長面爲鏡面。 其次，進行由上述先前方法所得的不摻雜氮化鎵結晶膜 之XRC測定時，（〇〇〇2)面之測定係半振幅脈衝寬度爲400 秒、（1 0 - 1 2 )面之半振幅脈衝寬度呈5 0 0秒。 又，上述氮化鎵結晶膜之最表面使用AFM觀察。結果， 袠面上以稀疏看到成長凹坑、觀察到表示大多轉位存在的 弧之短階台所成的形態表面。 又，用以測定上述氮化鎵結晶膜之蝕刻凹坑密度，將試 料與實施例5作相同的處理、以AFM觀察表面測定蝕刻凹 坑密度。並依此，蝕刻凹坑密度爲2 X l〇9cm·2。 實施例1 0 本實施例1 〇 ,係依實施例8記載的方法在基板上形成 氮化鎵系化合物半導體層，在其基板上之氮化鎵系化合物 半導體層再疊層別的一氮化鎵系化合物半導體層，構成半 導體發光元件。 - 66- 546850 五、發明說明（65) 胃6 _係實施例1 〇所製作的半導體發光元件之剖面構 造以模式的表示圖。在本實施例10係採用MOCVD法、於 力口熱爲闻溫的藍寶石基板1 1上，先流通含三甲基鋁（TMA 1 ) 蒸氣 ' 氣體、接著流通含三甲基鎵（TMGa )蒸氣之的氣體流 形丨丧金屬核於基板上後，在氫氣中退火金屬核、其後予 以流通氨氣來氮化金屬核、其上形成具1 X l〇17cm·3之電子 濃度2// m之低Sl摻雜GaN層12、在此低Si摻雜GaN層 上二依序疊層具i X 10Mcm-3電子濃度之1 &quot; m高Sl摻雜GaN 層13'具lXl〇17cm_3電子濃度之10〇Aln()1Ga()9N覆蓋層 1 4、自GaN障壁層15開始結束於GaN障壁層15，6層之 7 ◦入GaN障壁層15與5層之20人不摻雜的InQ 2Ga() 8N阱層 1 6所成多重量子阱構造、3〇人之不摻雜的ai() 2Ga() 8N擴散 防止層Π、具8χ 1017cm·3正孔濃度之0 . 5 // m Mg摻雜GaN 層 18、具 5 χ 1〇ucnr3之正孔濃度i〇0AMg摻雜塗料 In。iGa()yN層19疊層，製作具有半導體發光元件用之多 層構造晶圓。其次，使用具有在藍寶石基板上疊層的多層 構造之晶圓製作發光二極體。 製作上述多層構造之晶圓係使用MOCVD法依以下步驟進 行。 胃先，將藍寶石基板1 1導入於設置在感應加熱式加熱 器之RF線圈中的石英製之反應爐中。藍寶石基板1 1在氮 ^取代的小型收容室中載置於加熱用碳製感應器上。導入 @祠·後，流通氮氣使反應爐內純化。 -67- 546850 五、發明說明（66 ) 經過1 〇 鐘氮氣流通後，作動感應加熱式加熱器、經 過1 〇分鐘後昇溫基板溫度至1 1 7 0 °C、同時使爐內之壓力 爲5 0hPa。將基板溫度仍保持於丨1 70°c、邊使氫氣與氮氣 流通邊放置9分鐘、進行基板表面之熱淸理處理。 在進行熱淸理之間，將氫氣載運氣體流通於連接反應爐 之裝入原料的三甲基鎵（TMG a )之容器（起泡器）及裝入三甲 基鋁（TMA1 )之容器（起泡器）之配管，開始起泡。各起泡器 之溫度係使用用以調整溫度之恆溫槽調整爲-定。由起泡 產生的TMG a與TM A 1之蒸氣係至成長製程開始止、與載運 氣體一起流通於除害裝置之配管，通過除害裝置放出於系 統外。 於熱淸理結束後，關閉氮氣載運氣體之閥、使供應於反 應爐內之氣體僅爲氫氣。 如換載運氣體後，降溫基板之溫度至1100 °c、同時調 整爐內之壓力爲lOOhPa。確認溫度穩定於1100°C後，切 換TMA1配管之閥，將含有TMA1蒸氣之氣體供應於反應爐 內，開始在藍寶石基板上附著金屬（A 1 )核之處理。以該處 理進行經過1分鐘後，切換TM A1配管之閥、停止供應含 TMA蒸氣之氣體於反應爐內。其後，切換TMGa配管之閥 、將含有TMGa蒸氣之氣體供應於反應爐內、在藍寶石基 板1 1上開始使金屬（Ga )核附著之處理。該處理經過進行2 分鐘後，切換TMGa配管之閥，停止供應含TMG。蒸氣之氣 體反應爐內。如此分成2階段進行金屬核之形成。 -68- 546850 五、發明說明（67) 其後保持5分鐘，將形成的金屬核在氫氣載運氣體中退 火。退火5分鐘後，切換氨氣體配管之閥，開始於爐內供 應氨氣體，進行退火後之金屬核之氮化處理，形成成長核 。半:此處係如實施例4所述。 於10秒之後邊繼續流通氨，邊昇溫感應器之溫度至 1 1 60°C。在感應器之溫度昇溫中調整TMGa配管之流量調 整器之流量。又，開始流通S 1 H4。直到開始低S i摻雜之 G a N層成長至之間，S 1 H4與載運氣體一起流通於除害裝置 之配管，通過除害裝置放出於系統外。 確認感應器之溫度成爲1 1 60 °C後，等待溫度之穩定、 其後切換TMGa與SiH4之閥、開始對爐內供應TMGa與 S 1 H4,開始低摻雜之GaN成長，經過約1小時1 5分鐘進 行上述GaN層之成長。流通SiH4之量係於事前已檢討， 並調整成爲低Si摻雜GaN層之電子濃度爲1 X 10 17cnT 3。 如此形成膜厚2 &quot; m之低S i摻雜GaN層1 2 ◦ 再者，在該低Si摻雜GaN層12上成長Si摻雜之η型 GaN層。亦即，成長低Si摻雜之GaN層12後，經過1分 鐘停止了對爐內供應TMGa與SiH4。其間變更Si H4之流通 量。所流通的量係於事前已檢討，並調整成爲S 1摻雜 GaN層之電子濃度爲1 X 1019cm_3。氨仍以原流量繼續供應 於爐內。停止1分鐘後，再開始供應TMGa與S i H4、經過 4 5分鐘進行成長並由此操作形成膜厚1 // m之高S i摻雜 G a N 層 1 3。 - 69- 546850 五、發明說明（68) 成長高Si摻雜GaN層後，切換TMGa與SiH4之閥，停 止此等原料之供應於爐內。氨仍依原樣流通、切換閥使載 運氣體自氫切換爲氮。其後，使基板之溫度自丨丨60 I降 F至800C，同時使爐內之壓力自lOOhPa變更200hPa。 在等待變更爐內溫度之間，變更了 SlH4之供應量。流通 之量在事前已檢討，調整Si摻雜InGaN覆蓋層之電子濃 度爲1 X 1017 cm·3。氨仍依原流量繼續供應於爐內。又，預 先開始將流通載運氣體於三甲基銦（TM I η )與二乙基鎵 (TEGa)之起泡器。SiH4氣體、及由起泡產生的TMIn及 TEGa之蒸氣係於開始覆蓋層之成長製程至，與載運氣體 一起流通於配管、通過除害裝置放出於系統外。 其後，等待爐內之狀態至穩定，同時切換TM I η與TEG a 與SiH42_,開始將此等之原料供應於爐內。經過約1〇 分鐘後繼續供應，形成膜厚1 00A之S 1摻雜I n() jGaQ 9N 覆蓋層1 4。 其後，切換TMI、TEG及SiH4之閥，停止供應此等之原 料° 其次，製作由G a N所成障壁層1 5與由I n () 2 G a () 8 N所成 阱層1 6構成的多重量子阱構造。當製作多重量子阱構造 時，在Si摻雜InQ iGa。9n覆蓋層14上首先形成GaN障壁 層15、在其GaN障壁層1 5上形成I n() 2Ga() 8N阱層1 6。將 此構造疊層5層後，在第5層之In() 2Ga() SN阱層16 _匕形 成第6層之GaN障壁層1 5 ,作成兩側以GaN障壁層1 5夾 -70- 546850 五、發明說明（69) 住。 用以形成第1之GaN層時，於S i摻雜In。/a。yN覆蓋 層14成長結束後，經過30秒停止後，基板溫度或爐內之 壓力、載運氣體之流量或種類仍依原樣，切換TEG(;之閥、 進行TEGa供應於爐內。經過7分鐘進行供應TEGa後，再 度切換閥停[h供應TEGa結束了 GaN障壁層1 5之成長。並 由此，形成膜厚70A之GaN障壁層1 5。 進行成長GaN障壁層15之間，流通於除害設備之配管 的TMIn之流量與覆蓋層1 4成長時比較，以莫耳流量調整 爲2倍。 於GaN障壁層1 5成長結束後，經過30秒鐘停止供應 I I I族原料後，基板溫度或爐內之壓力、載連氣體之流量 或種類仍依原樣，切換TEGa與TMIn之閥、對爐內供應 TEGa與TMIn。經過2分鐘進行供應TEGa與TMIn後，再 度切換閥停止供應TEGa與TMIn結束了 In() 2GaQ 8N阱層 16之成長◦並由此，形成膜厚20人之In() 2Ga() 8N阱層16 ο 結束I n () 2 G a。8 Ν阱層1 6之成長後，經過3 0秒鍾停止供 應I II族原料後，基板溫度或爐內之壓力、載運氣體之流 量或種類仍依原樣，開始供應TEG a於爐內，再度進行 GaN障壁層15之成長。 如次之步驟重複5次，製作5層之GaN障壁層1 5與5 層之In() 2Ga() 8N阱層16。再於最後之In。2Ga。SN阱層16 -71 - 546850 五、發明說明（7〇) 上形成GaN障壁層15。 在該G a N障壁層1 5結束的多重量子阱構造上，以下述 步騾製作無f参雜之A 1 ◦ 2 G a。8 N擴散防山層1 7。亦即，停 止供應TEG a、G a N障壁層1 5之成長結束後，於1分鐘內 使基板溫度與載連氣體之種類、流量仍與γ述相同下，變 更爐內之壓力爲1 OOhPa。 預先開始流通載運氣體流通於三甲基鋁（TMA丨）之起泡器 。由起泡產生的TMA 1之蒸氣係直到開始擴散防止層之成 長製程至，與載運氣體一起流通於除害裝置之配管、通過 除害裝置放出於系統外。 等待至爐內之壓力穩定，切換TEGa與TMA1之閥，開始 供應此等之原料於爐內。其後，經過約3分鐘進行成長後， 停止供應TEGa與TMA1、停止無摻雜之A 1() 2Ga() 8N擴散防 止層17之成長。並由此，形成膜厚 3〇A之無摻雜 A 1 () 2 G a () 8 N擴散防止層1 7。 該無摻雜之A 1 () 2GaQ 8N擴散防止層1 7上，以下述製程 製作Mg摻雜之GaN層18。亦即，停止供應TEGa與TMA1， 在無摻雜之Al()2Ga()8N擴散防止層17之成長結束後，經 2 分鐘上昇基板之溫度至1 060 °C 、變更爐內之壓力爲 2 OOhPa。再於變更載運氣體爲氫。又，預先予以開始將載 運氣體流通於雙環戊二烯鎂（Cp2Mg )之起泡器。由起泡產 生的Cp2Mg之蒸氣係直到開始Mg摻雜GaN層之成長製程 至，與載運氣體一起流通於除害裝置之配管、通過除害裝 -72- 546850 五、發明說明（71) 置放出於系統外。 變更溫度與壓力等待爐內之壓力穩定，切換TMGa與Mg is doped with I n (), Ga. After the growth of the layer is completed, the induction heating heater is stopped, and the temperature of the substrate is reduced to room temperature after 20 minutes. The environment in the reaction furnace during cooling is composed of nitrogen only. Thereafter, it was confirmed that the temperature of the substrate was lowered to room temperature, and the wafer was taken out to the atmosphere. A wafer having an epitaxial growth layer structure for a semiconductor light-emitting element is manufactured by the above steps'. Here, the Mg-doped GaN cap layer and the Mg-doped I n () jGa () 9N layer are not performed to activate the p-type carrier and do not perform an annealing treatment, but are also p-type. Next, a light-emitting diode of a semiconductor light-emitting element is fabricated using a wafer in which an epitaxial growth layer structure is laminated on the sapphire substrate. For the fabrication of the wafers, I n was doped in Mg by well-known lithography. On the surface 18a of the Ga () 9N layer, a p-electrode bonding pad 12 having a structure of laminated titanium, aluminum, and gold is sequentially formed from the surface side, and a light-transmitting P electrode made of only Au bonded to it. 2 1. Make p-side electrode. After that, the wafer is dry-etched to expose the portion 2 3 where the n-side electrode of the high Si-doped GaN layer is formed, and the exposed portion is made of Ni, -47- 546850. 5. Description of the invention (46) A Ηelectrode 2 2 formed by 1. With these operations, an electrode having a shape as shown in FIG. 7 was formed on the wafer. According to the wafer in which the ρ-side and η-side electrodes are formed in this manner, the inner surface of the light-made and honing sapphire substrate is made into a mirror-like surface. After that, the wafer was cut into a square wafer with an angle of 350 // m ′, and the electrodes were placed on an α-ray frame, and gold wires were bonded to the lead frame as a light-emitting element. When a current flows in the forward direction between the ρ-side and η-side electrodes of the light-emitting diode produced as described above, the forward voltage at a current of 20πιA is 3.  0V ◦ When the light emission is observed through a translucent electrode on the ρ side, the light emission wavelength is 470nm, and the light emission output is 6cd. Such characteristics of silicon light-emitting diodes are light-emitting diodes made of wafers that are made in a comprehensive manner, and are obtained without unevenness. Embodiment 5 describes an embodiment of a method for manufacturing a crystal of a gallium nitride-based compound semiconductor. As shown in FIG. 1 of this embodiment, a gallium nitride-based compound semiconductor layer is formed on a sapphire substrate in the order of steps A-B-C-D. First, as step A, a vapor containing a mixture of trimethylaluminum (TMA) and trimethylgallium (TMG) in a molar ratio of 1: 2 is applied to a substrate, and a metal core is attached to the substrate. Step B is annealing in hydrogen, step C is flowing a mixed gas of hydrogen and ammonia, and the nitriding treatment of the metal core is performed after annealing to form growing nuclei. Thereafter, step D is flowing TMGa and ammonia to re-form the growing nuclei. GaN, and a GaN-based compound semiconductor layer including a GaN crystal film on a sapphire substrate. -48- 546850 V. Description of the invention (47) The specific steps are as follows. That is, a sapphire substrate is first introduced into a quartz reaction furnace, which is set in an RF coil of an induction heating heater. The sapphire substrate is placed in a small chamber containing nitrogen instead of a sensor made of heated carbon. . After introducing the sample, nitrogen was passed into the purification reaction furnace. After 10 minutes of nitrogen flow, the induction heating heater was operated, and the substrate temperature was raised to 1 170 t after 10 minutes. Maintain the substrate temperature at 1 1 70 t, and let the hydrogen gas and nitrogen gas flow for 9 minutes while carrying out the thermal treatment on the surface of the substrate. Between the thermal treatments, a hydrogen carrier gas flowing into the raw material is methyl gallium (TMGa). The piping of the container (foamer) and the container (foamer) filled with trimethylaluminum (TMA) started to foam. Alas, the temperature of each bubbler is adjusted by using a constant temperature bath to adjust the temperature. The piping of each bubbler is connected to the reaction path. The vapors of TMGa and TMA1 generated by the bubbling are performed until the growth process of the gallium nitride-based compound semiconductor layer is started, and circulates with the carrier gas in the piping of the detoxification device, and is discharged out of the system through the detoxification device. After finishing the process, the valve carrying the nitrogen gas was closed, and only the hydrogen was supplied to the reactor. After the carrier gas was switched, the substrate temperature was reduced to 110 ° C. After confirming that the temperature was stable at 1100C, the valve of the TMGa and TMA1 piping was switched to supply the gas containing the vapor of TMG a and MA 1 to the reaction furnace. The process of attaching a metal core to the sapphire substrate t is started. The mixing ratio of the supplied TMGa and TMA 1 is adjusted by the flow regulator installed in the bubbly pipe to Morse ratio -49-546850 5. Explanation of the invention (48) 2: After processing for 1 minute and 30 seconds, simultaneously switch the valve of the piping of TMGa and TMA1 to stop supplying the gas containing TMGa and TMA 1 vapor in the reaction furnace. Still as it is, keep it for 3 minutes so that the formed metal cores are in Annealing in a hydrogen carrier gas. After 3 minutes of annealing, the valve of the ammonia gas piping is switched, ammonia gas is supplied to the furnace, and the annealed metal nuclei are nitrided to form growing nuclei. After 10 minutes of circulation, the temperature of the sensor is increased. When the temperature rises to Η 60 ° C °, the flow rate of the flow regulator of the TMGa piping is adjusted. After confirming that the temperature of the sensor has reached H 60 ° C, wait for the temperature to stabilize, then switch the valve of TM Ga, Started supply of TMG a In the furnace, the growth nuclei have grown gallium nitride. After the growth of the above-mentioned gallium nitride crystal film at 1 / J, the valve of the TMGa piping is switched to complete the supply of raw materials and stop the growth in the reactor. Nitriding After the growth of the gallium crystal film is completed, the power to the induction heating heater is stopped, and the temperature of the substrate is cooled to room temperature in 2 ◦ minutes. During the cooling, the environment in the reactor is changed from ammonia, nitrogen, and hydrogen in the same way as during growth Structure, but after confirming that the temperature of the substrate is 300 ° C, stop supplying ammonia and hydrogen. After that, the temperature of the substrate is lowered to room temperature while nitrogen is flowing, and the sample is taken out to the atmosphere. A sample of an undoped gallium nitride crystal film with a thickness of 2 # m. The substrate taken out was colorless and transparent, and the growth surface was a mirror surface. Next, the grown undoped gallium nitride crystal film was subjected to -50- 546850 V. Description of the invention (49) XRC measurement. The measurement is performed by using Cu / 3 line X-ray generation source as the light source on the (0 0 0 2) plane of the symmetrical plane and the (1 0-1 2) plane of the asymmetric plane. .—Generally speaking, gallium halide For compound semiconductors, the half-amplitude pulse width of the XRC spectrum on the (0002) plane is an index of the flatness of the crystal, and the half-amplitude amplitude pulse width of the XRC spectrum on the (1 0-1 2) plane is an index of the index density. This measurement result The non-doped gallium nitride crystal film produced according to the method of the present invention has a half-amplitude pulse width on the (0002) plane of 2 30 seconds, and a half-amplitude pulse width on the (10-12) plane of 350 seconds. All were good. The outermost surface of the gallium nitride crystal film was observed using a general interatomic force microscope (AFM). As a result, no growth pits were seen on the surface, and a well-formed surface was observed. When measuring the etch pit density of the gallium nitride crystal film, the sample was treated at 280 ° C for 10 minutes in a mixed solution of sulfuric acid and phosphoric acid. When the surface of the sample was measured by AFM observation to determine the density of uranium pits, it was about 5 × 107 cm 2. In addition, when the above process is completely the same process as the middle process, the process is stopped before the growth of the gallium nitride crystal film, and the sample taken out of the growth furnace is produced, and the surface morphology of the sample is observed by an atomic force microscope (AFM). On the surface, there is a ladder-shaped cross section of aluminum nitride crystals as growth nuclei. Embodiment 6 As shown in FIG. 3 of this embodiment, step A and step B are repeated three times alternately, and a gallium nitride-based compound semiconductor layer is formed on the sapphire substrate in the order of steps C to D. Firstly, a gas treatment containing trimethylaluminum-5 1-546850 is circulated in step A. V. Description of the invention (50) (TM A 1) vapor is applied to attach a metal core to the substrate. Step B is annealed in hydrogen. After repeating this step A and step 3 three times, the gas and gas mixed gas is passed in step C, and the metal core is nitrided after annealing to form a growing nuclei, and then TMGa and ammonia are passed through in step D to form a hafnium. The core grows gallium nitride, and a gallium nitride-based compound semiconductor layer provided with a gallium nitride crystal film on a sapphire substrate is produced. The specific steps are as follows. First, as in the first embodiment described above, the substrate is thermally cured, and at the same time, the thermal curing is performed in a container (bubble) containing trimethylgallium (TMGa) as a raw material, and The piping of the container (foamer) of trimethylammonium (TM A) circulates hydrogen carrier gas and starts foaming. In addition, the temperature of each bubbler is constant in the constant temperature bath used to adjust the temperature. The piping of each bubbler is connected to the reaction path. The vapor of TMGa and TMA1 generated by the bubbling is from the beginning of the growth process of the semiconductor layer of the gallium nitride-based compound to the piping that flows with the carrier gas in the detoxification device and is discharged out of the system through the detoxification device. After the thermal process is completed, the nitrogen-containing gas valve is closed, and hydrogen is supplied only in the reaction furnace. After the load gas is switched, the substrate temperature is reduced to 1 丨 60 ° C. After confirming that the temperature is stable at 1 1 60 ° C, switch the valve of the TMA piping and supply it to the gas reactor containing TIMA vapor. After 3 minutes of treatment, stop supplying the gas containing TMA1 vapor to the reactor. The metal nuclei formed were annealed in a hydrogen carrier gas for 3 minutes as they were. After annealing for 30 seconds, the valve of the TMA piping is switched and the gas containing TM A1 vapor is supplied at -52- 546850. 5. Description of the invention (51) The metal core is attached to the reactor. After 3 minutes of treatment in the same manner as the first time, the supply of gas containing TMA 1 vapor to the reactor was stopped. The formed metal core was annealed in a hydrogen carrier gas by keeping it as it was for 30 seconds. Thereafter, these processes are performed again, and the formation and annealing of metal nuclei are repeated 3 times (step A to step B). After the third annealing, the valve of the ammonia tube was switched, and ammonia gas was supplied in the furnace, and the annealed metal nuclei were subjected to nitriding treatment to form growing nuclei. After 10 seconds of circulation, the valve of TMGa was switched. Started supplying TMGa to the furnace and growing gallium nitride in the growing nuclei. After the growth of the above-mentioned gallium nitride crystal film was performed in 1 hour, the valve of the piping of TMGa was switched, and the supply of the raw materials was stopped in the reaction furnace. After the growth of the gallium nitride crystal film is completed, the power to the induction heating heater is stopped, and the temperature of the substrate is cooled to room temperature after 20 minutes. During cooling, the environment in the reactor is made up of ammonia, nitrogen, and hydrogen in the same way as during growth. However, after confirming that the temperature of the substrate is 300 ° C, the supply of ammonia and hydrogen is stopped. Thereafter, the temperature of the substrate was lowered to room temperature while flowing nitrogen gas, and the sample was taken out to the atmosphere. A sample for forming an undoped gallium nitride crystal film with a thickness of 2 "m on a sapphire substrate was prepared by the above process. The substrate was taken out as colorless and transparent, and the growth surface was a mirror surface. Next, the grown undoped was carried out by the above method. XRC measurement of hetero-gallium nitride crystal film. 定 [J is determined by using Cu / 3 line X-ray source as light source, on the (0002) plane of the symmetry plane and the (10-12) plane of the asymmetric plane. As a result of this measurement, the undoped gallium nitride crystal film produced by the method of the present invention has a half-amplitude pulse width of 300 seconds measured at (0002) and (10-12) measured at (0002) on the (0002) plane. The half-amplitude pulse width of the surface is 3 to 20 seconds, which is all good. Moreover, the outermost surface of the gallium nitride crystal film is observed with an atomic force microscope (AFM). As a result, no growth pits are seen on the surface. 1. Observe the surface with good morphology. In order to measure the etch pit density of the gallium nitride crystal film, the sample is treated in a mixed solution of sulfuric acid and orthoacid at 280 ° C for 10 minutes. The surface of the sample When measured by AFM observation, the density of the touch pits is about 7 X 107. m_2. In addition, before the above process and the middle to complete the same process, stop the process before the growth of the gallium nitride crystal film, take out the sample from the growth furnace, and observe the surface morphology of the sapphire surface with an atomic force microscope (AFM). Scattered aluminum nitride crystal blocks with ladder-shaped cross-sections are used as growth nuclei. In this example, 'the repeated formation and annealing of metal nuclei can increase the density of the metal nuclei on the substrate or control the annealing. After the metal core ^: _ shaped opportunity, so its control can be carried out with better accuracy, and the gallium nitride-based compound semiconductor layer formed according to the metal core can be made more &amp; Ming 2 shape, quality尙, in this Example 6, the formation and annealing of the repeated metal cores are 3 &amp; ^ The number of repetitions may also be 2 or 4 or more, as necessary, it may be determined as appropriate. WM Example] A and Step 7 of this embodiment is shown in FIG. 4, and steps 2 to 54-546850 are repeated alternately. 5. Description of the invention (53) After step B and step c, step D is performed to form a gallium nitride compound on the sapphire substrate. Semiconductor layer. First as a step A, based on the mixture of the vapor of trimethylaluminum (TMA1) and the vapor of trimethylgallium (TMGa) and the vapor of trimethylindium (TMIn) as a molar ratio i: 2: 4 The process of attaching a metal core to the substrate, step B is an annealing treatment in hydrogen, and step C is a flow of a mixed gas of hydrogen and ammonia. After annealing, the metal core is nitrided to form a growing core. Repeat step A twice. After step B and step C, in step D, a gallium nitride-based compound semiconductor layer provided with a gallium nitride crystal film on a sapphire substrate is prepared by flowing TMGa ammonia and growing gallium nitride to grow nuclei. The specific steps are as follows. First, in the same manner as in the first embodiment described above, the substrate surface is thermally treated, and at the same time, the container (bubble) containing trimethylgallium (TMGa) as a raw material is loaded, and the top three are introduced. The container (foamer) of base aluminum (TMA1) and each pipe containing the trimethylindium (TMIn) container (bubble generator) flowed with a hydrogen carrier gas to start foaming. Alas, the temperature of each bubbler is adjusted to a constant value using a constant temperature bath for temperature adjustment. The piping of each bubbler is connected to the reaction path. The vapors of TMGa, TMA1, and TMIn generated by the bubbling are performed until the growth process of the semiconductor layer of the gallium nitride-based compound is started, circulated with the carrier gas in the piping of the detoxification device, and discharged out of the system through the detoxification device. After the thermal digestion is completed, the nitrogen-carrying gas valve is closed so that the gas supplied to the reaction furnace is only hydrogen. After the carrier gas is switched, the substrate temperature is reduced to 900 ° C. Confirm that the temperature is stable -55- 546850 V. Description of the invention (54) After setting at 900 ° C, switch the valves of the pipes of TMGa, TMA1 and TMIn at the same time, so that the gas containing TMGa 'TIMA1 and TMIn vapor is supplied to the reaction furnace, start A process of attaching a metal core to a sapphire substrate is performed. The mixing ratio of the supplied TMGa, TMA1 and Min is adjusted by the flow regulator set on the bubble pipe to a Morr ratio 2: 1: 4. After 3 minutes of processing, the valves of the TMG a, TM A 1 and TM I η pipes were switched at the same time, and the supply of gas containing vapors of TMGa, TMA1 and TMI η was stopped in the reactor. It was left as it was for 30 seconds, and the formed metal core was annealed in a hydrogen carrier gas. After the annealing for 30 seconds, the valve of the ammonia piping was switched, ammonia was supplied in the furnace, and the metal cores annealed by nitriding treatment were formed to form growth nuclei. After 1 minute of ammonia circulation, the valve of the ammonia piping was switched to stop supplying ammonia gas to the furnace, leaving it in its original state for 30 seconds, and then the valve of the TMGa, TIMA1 and TMIn piping was also switched to supply TMGa, TIMA1 and The gas of TMIn steam is in the reaction furnace, and the metal core is attached to the sapphire substrate again. After 3 minutes of treatment, the valves of the TMGa, TMA1 and TMIn pipes were switched at the same time, and the supply of gas containing TMGa, TMA1 and TMIn steam in the reactor was stopped. The metal nuclei formed were annealed in a hydrogen carrier gas as they were for 30 seconds. After 30 seconds of annealing, the valve of the ammonia gas piping was switched to start supplying ammonia gas into the furnace, and the nitrided metal cores were subjected to nitriding treatment to form growth nuclei. In this way, the formation of metal nuclei and annealing and the formation of nuclei were performed twice (step A-step B-step C). After 10 seconds of circulation, the temperature of the sensor was raised to 116 ° C. Sense -56- 546850 V. Description of the invention (55) Adjust the flow rate of the flow regulator of the TMG a piping during the temperature rise of the reactor. After confirming that the temperature of the sensor is 1 1 60 ° C, keep the temperature stable, and then switch the TMGa valve to start the supply of TMGa in the furnace and grow gallium nitride in the growing core. After 1 / _], the growth of the above-mentioned gallium nitride crystal film is performed, the valve of the TMGa piping is switched, and the supply of raw materials is stopped in the reaction furnace to stop the growth of i_h. After the growth of the gallium nitride crystal film is completed, the power to the induction heating heater is stopped, and the temperature of the substrate is cooled to room temperature after 20 minutes. During the cooling, the environment in the reaction furnace is changed from ammonia and nitrogen to the growth. The composition of hydrogen, but after confirming that the temperature of the substrate was 300 ° C, the supply of ammonia and hydrogen was stopped. Then, the temperature of the substrate was reduced to room temperature while nitrogen gas was circulated, and the sample was taken out to the atmosphere. According to the above process, a sample for forming an undoped gallium nitride crystal film with a thickness of 2 ν m on the sapphire substrate was prepared. The substrate taken out is colorless and transparent, and the growth surface is a mirror surface. Next, the X RC measurement of the grown undoped gallium nitride crystal film was performed according to the method described above. The J-determination system uses Cu A line X-ray source as the light source, and is performed on the (0002) plane of the symmetrical plane and the (10-12) plane of the asymmetric plane. As a result of the measurement, the half-amplitude pulse width of the non-doped gallium nitride crystal film produced by the method of the present invention on the (0002) plane was 250 seconds, and the half-amplitude pulse width of the (10-12) plane was 300 seconds. All good. In addition, the outermost surface of the gallium nitride crystal film was observed using a general interatomic force microscope (AFM). As a result, no growth pits were observed on the surface, and a surface with a good shape was observed. -57- 546850 5. Description of the invention (56) When measuring the uranium pit density of the above gallium nitride crystal film, the sample is treated in a mixed solution of sulfuric acid and phosphoric acid at 2 80 ° C for 10 minutes. . The surface of this sample was observed by AFM to measure the density of the etched gate pits, which was about 3 × 107 c it 2. In addition, in the above process, the process is exactly the same as before. The sample produced from the growth furnace was stopped before the gallium nitride crystal film was grown. When the surface morphology was observed with an atomic force microscope (AF Μ), it was on the surface of sapphire. Agglomerates of aluminum nitride crystals having a ladder-shaped cross section are interspersed as growing nuclei. In this way, the embodiment 7 ′ is because the formation and annealing of the metal core and the formation of the growth core are repeated, so the density of the substrate h of the metal core, the shape of the metal core after annealing, or the shape of the growth core can be controlled. The control can be performed more accurately, and the gallium nitride-based compound semiconductor layer formed based on the metal core and the growth core can be made to have a desired shape and quality. Alas, in this Example 7, the formation of the repetitive metal nucleus and the formation of the annealing nucleus and the growth nucleus are repeated twice, but the number of iterations may also be three or more, which may be appropriately set as necessary. Embodiment 8 As shown in FIG. 5, this embodiment is performed in steps A1 and A 2 of the two stages (pre-production process and post-production process), and the nitride is formed on the sapphire substrate in the order of step C to step D. A gallium-based compound semiconductor layer. First, as step A1, an oxygen gas containing trimethylaluminum (TMA 丨) vapor is circulated, and in the next step A2, a gas containing trimethylgallium (TMGa) vapor is circulated. -58- 546850 5. Description of the invention ( 57) A metal core is attached to the substrate. Thereafter, step B is annealing in hydrogen, step c is flowing a mixed gas of hydrogen and ammonia, and the annealed metal nuclei are nitrided to form growing nuclei. Thereafter, step D is flowing TMGa and ammonia to further grow and nitride. Gallium is grown on a nucleus, and a gallium nitride-based compound semiconductor layer including a gallium nitride crystal film on a sapphire substrate is produced. The specific steps are as follows. First, in the same manner as in the embodiment described above, the substrate surface is thermally treated, and at the same time the thermal treatment is performed, the container (bubble) containing the raw material trimethylgallium (TMGa) and the Each pipe of the container (foamer) of trimethylamine (TMA) circulates hydrogen carrier gas and starts to foam. Alas, the temperature of each bubbler is adjusted to a constant value using a constant temperature bath for temperature adjustment. The piping of each bubbler is connected to the reaction path. The vapors of T M G a and T M A 1 generated by the blistering are from the time when the growth process of the gallium nitride-based compound semiconductor layer starts, to the piping of the detoxification device together with the carrier gas, and the system is discharged through the detoxification device. After the thermal process is completed, the valve carrying the nitrogen gas is closed so that the gas supply to the reaction furnace is only hydrogen. After switching the carrier gas, lower the temperature of the substrate to 110 (TC. Confirm that the temperature is stable at 1 100 T: After that, switch the valve of the TMA1 piping, supply the gas containing TMA1 vapor into the reactor, and start the metal core on the sapphire substrate ( A n attachment process. After performing this process for 1 minute, the valve of the TMA 1 piping is switched, and the supply of gas containing TMA 1 vapor is stopped in the reaction furnace (step A1). Thereafter, the valve of the TMGa piping is switched, and TMGa is supplied. The gas of steam is in the reaction furnace and begins to process the metal (G a) core on the sapphire substrate -59- 546850 ------------___ 5. Description of the invention (58) will be attached. Will make After this process has been carried out for 2 minutes, the valve of the TMG a piping is switched, and the supply of the gas containing TMGa vapor into the reaction furnace is stopped (step A2). In this way, the formation of the metal core is divided into two stages (step A1-step A2). After that, it was held for 5 minutes, and the formed metal core was annealed in a hydrogen carrier gas. After 5 minutes of annealing, the valve of the ammonia piping was switched to start supplying ammonia gas in the furnace, and the nitriding treatment of the metal core after annealing was performed. 2. Form a growth nucleus. After the flow of seconds, increase the temperature of the sensor to Η 60 ° C. While the temperature of the sensor is increasing, adjust the flow rate of the flow regulator of the TMGa piping. After confirming that the temperature of the sensor is 1 1 60 ° C, wait for the temperature After that, the valve of TMGa was switched, the supply of TMGa in the furnace was started, and gallium nitride was grown in the growing nuclei. After the growth of the above-mentioned gallium nitride crystal film in 1 hour, the valve of the TMG a pipe was switched to end the raw material. Supply to the reaction furnace to stop growing. After ending the growth of the gallium nitride crystal film, stop energizing the induction heating heater to cool the temperature of the substrate to room temperature after 20 minutes. The environment and growth in the reaction furnace are in the process of falling down. It is composed of ammonia, nitrogen, and hydrogen in the same way, but after confirming that the temperature of the substrate has reached 300 ° C, the supply of ammonia and hydrogen is stopped. After that, the temperature of the substrate is reduced to room temperature while flowing nitrogen, and the sample is taken out into the atmosphere. In the manufacturing process, a sample was formed on the super-precious stone substrate to form an undoped gallium nitride crystal film with a thickness of 2 // m. The removed substrate was colorless and transparent, and the growth surface was a mirror surface. -60- 546850 V. Description of the Invention (59) Next, the XRC measurement of the grown undoped gallium nitride crystal film was performed by the above method. The measurement uses a Cu / 3 line X-ray generation source as a light source on the (0 0 0 2) plane of the symmetry plane. The measurement is performed on the (10-12) plane of the asymmetric plane. As a result of the measurement, the undoped gallium nitride crystal film produced by the method of the present invention is measured as the half-amplitude pulse width of the (0002) plane for 180 seconds. The amplitude pulse width of the (ΙΟ-ΐ 2) plane was 290 seconds. The outermost surface of the above-mentioned gallium nitride crystal film was observed using a general interatomic force microscope (AFM). As a result, no growth pits, Observe the surface with good morphology. In addition, to measure the etch pit density of the gallium nitride crystal film, the sample was treated at 280 ° C for 10 minutes in a mixed solution of sulfuric acid and phosphoric acid. When the surface of this sample was measured by AFM observation to measure the density of the etch pits, it was about 1 × 107cnT2. In addition, in the above process, the process is exactly the same as the process until the gallium nitride crystal film is grown. The sample produced from the growth furnace is stopped and the surface morphology is observed with an atomic force microscope (AFM). Aluminium nitride crystal ingots are scattered on the surface as a ladder-shaped cross section of the growth core. In this way, the embodiment 8 divides the formation of the metal core into two stages, that is, a pre-production process and a post-production process. Therefore, the type of metal used to form the metal core can be diversified, and the metal core on the substrate can be controlled more accurately. Therefore, the gallium nitride-based compound semiconductor layer formed based on the metal core is formed to have a more desirable shape and quality.尙 In this embodiment 8, the formation of the metal core is divided into a pre-stage process and a post-stage 6 546850. V. Description of the invention (60) The two stages of the process are carried out one at a time, but the pre-stage process and the post-stage process can also constitute It is repeated two or more times. It is not limited to two steps, and it may be divided into three steps and t. In this way, the number of repetitions and the order are increased, and the formation of metal cores is performed with higher accuracy.乂 In the eighth embodiment, after the formation of the metal core is performed, the metal core is annealed in a hydrogen carrier gas, but the annealing process is omitted. However, at this time, the conditions such as the temperature and pressure of the ambient gas when the metal core is to be used or the metal core is nitrided must be properly selected. Example 9 This example 9 is the same as described in the example: in the case of Example 4 (figure 5), Step A is the same as Step A and Step A. The following steps: Step B — Step C — &D; Step D is on the sapphire substrate. A gallium nitride based semiconductor layer is formed. First step A circulates vapor gas containing trimethylaluminum (TMA), and next-a step A, circulates vapor gas containing trimethylgallium (TMGa) and trimethylindium (TMIn): mixing ratio mixed vapor gas, implement attachment Focus on substrate processing. At this time, the temperature of Step A and the temperature of Step A were set to be the same as those of Example 4. Then, Step B was annealed in hydrogen. Step C was mixed with hydrogen and ammonia, and then subjected to nuclear nitriding. Formation of growth nuclei and subsequent ammonia step D. The flow of TMGa and ammonia is recorded in the growth nuclei, and the nitrided compound semiconductor layer is formed on the sapphire substrate with a nitrided crystal film. The specific steps are as follows. First, the ammonia is at -62-546850 in the same way as in the examples. V. Description of the invention (60. The substrate surface is thermally treated, and at the same time, the material is filled with trimethylgallium (TMGa). (Bubble generator), a container (bubble generator) filled with trimethylpyrrolium (TMA 1), and a container (bubble generator) filled with difluorinated indium (TMI η), and hydrogen gas was flowed through each pipe The carrier gas starts to foam. 尙, the temperature of each bubbler is adjusted to be constant by using a constant temperature tank to adjust the temperature. In addition, the piping of each bubbler is connected to the reaction path. TMGa and TMA1 produced by the bubble The vapor with TMIn is from the time when the growth process of the gallium nitride-based compound semiconductor layer is started, and it is circulated with the carrier gas in the piping of the detoxification device, and is discharged out of the system through the detoxification device. After the thermal treatment is completed, the nitrogen is turned off. The gas valve of the carrier gas and the supply gas to the reactor are only hydrogen. After the carrier gas is switched, the substrate temperature is reduced to 1 1 60 ° C. After confirming that the temperature is stable at H60 ° C, the valve of the TMA1 piping is switched and the supply contains TMA1 Vapor gas in a reaction furnace (A 1) metal core treatment on the sapphire substrate was started. After the process was performed for 1 minute, the valve of the TMA1 piping was switched to stop supplying the gas containing TMA 1 vapor to the reaction furnace (step A 1). Thereafter, Control the current applied to the RF coil, change the temperature of the sensor to 9 50 ° C. After 10 seconds wait for the temperature to stabilize, switch the valves of the TMGa and TMIn pipes and supply the gas containing TMGa and TMIn vapor in the reactor. Started the process of attaching (G a, I η) metal cores to the sapphire substrate. The mixing ratio of the supplied TMG a and TM I η was adjusted by setting the flow regulator in the foaming pipe so that the mole ratio became 1: 2. After 2 minutes of this treatment, the valve of the TMGa and TMIn piping was switched at 'M' to stop supplying TMGa and -63-546850. V. Description of the invention (62) T M I η vapor in the reactor (step A 2). In this way, the formation of metal nuclei is performed in two stages (step A1 to step A2), and the growth temperature of each step is set at a different temperature. Thereafter, the metal nuclei formed are annealed in a hydrogen carrier gas for 5 minutes. 5 minutes Retreat After that, the valve of the ammonia gas piping is switched, the ammonia gas is supplied to the furnace, the annealed metal nucleation process is performed, and the growth is formed: the nucleus. After 10 seconds of circulation, the temperature of the temperature sensor rises to 1 60 ° C ° As the temperature of the sensor rises, adjust the flow rate of the flow regulator of the TMG a piping. After confirming that the temperature of the sensor has reached 1 160 ° C, wait for the temperature to stabilize, then switch the valve of TMG a and start TMG a is supplied in the furnace to grow gallium nitride on the growing nuclei. After the growth of the above-mentioned gallium nitride crystal film is performed for 1 hour, the valve of the TMGa pipe is switched, and the supply of raw materials is stopped in the reaction furnace. After the growth of the gallium nitride crystal film, the power to the induction heating heater was stopped, and the temperature of the substrate was lowered to room temperature after 20 minutes. During the temperature decrease, the environment grows in the same way as in the reactor. It consists of ammonia, nitrogen, and hydrogen. However, after confirming that the temperature of the substrate has reached 300 ° C, the supply of ammonia and hydrogen is stopped. Thereafter, the temperature of the substrate was lowered to room temperature while flowing nitrogen gas, and the sample was taken out into the atmosphere. According to the above process, a sample for forming an undoped gallium nitride crystal film with a thickness of 2 // m on a sapphire substrate was prepared. The taken-out substrate is colorless and transparent, and the grown surface is a mirror surface. Secondly, the above-mentioned method was performed for the growth of a non-doped gallium nitride crystal film. -64- 546850 V. Description of the invention (63) XRC measurement. The measurement was performed using a Cu / 3 ray X-ray source as the light source, and the (0002) plane of the symmetrical plane and the (丨 2) plane of the asymmetric plane. The result of the measurement is that the undoped gallium nitride crystal film produced according to the method of the present invention has a half amplitude pulse width of 990 seconds and a half of the (100- 1 2) plane. The amplitude pulse width is 260 seconds. The outermost surface of the gallium nitride crystal film was observed using a general interatomic force microscope (AFM). As a result, no growth pits were observed on the surface, and a well-formed surface was observed. In addition, to measure the etch pit density of the gallium nitride crystal film, the sample was treated in a mixed solution of sulfuric acid and phosphoric acid at 280 t for 10 minutes. When the surface of the sample was observed with AFM and the etch pit density was measured, it was about 1 × 107 cr2. In addition, the above-mentioned process is exactly the same process as before. Samples taken out of the growth furnace were stopped before the gallium nitride crystal film was grown. When the surface morphology was observed with an atomic force microscope (AFM), the sapphire surface was scattered An aluminum nitride crystal block having a ladder-shaped cross section as a growing core. In this way, in the ninth embodiment, the formation of the metal core is performed in two stages, and the growth temperature of each stage is set to different temperatures, so that the type of metal that becomes the metal core can be diversified, and the temperature of the metal can be adapted to the actual temperature. It can adhere to the ground and control the density on the substrate of the metal core with higher accuracy. Therefore, the gallium nitride-based compound semiconductor layer formed based on the metal core can be made into a more desirable shape and quality. Alas, in this Example 9, after forming the metal core in two stages, -65- 546850 V. Description of the invention (64) The metal core is annealed in a hydrogen carrier gas, but the annealing process can also be omitted. At this time, the gallium nitride-based compound semiconductor layer can also be grown after the metal core formation process and the nitridation process are alternately performed more than two times. b. Comparative Example 1 Samples were prepared for comparison with the samples prepared in Examples 1 to 3 and 5 to 9 described above. The method described in the comparative example and the example of Japanese Unexamined Patent Publication No. 4_ 2 9 7023 described in the column of [Known Technology] also adopts a process for forming a low-temperature buffer layer, and an undoped film thickness of 2 // m is formed on the substrate. Crystal film of gallium nitride. The substrate taken out was colorless and transparent, and the growth surface was a mirror surface. Next, when the XRC measurement of the undoped gallium nitride crystal film obtained by the above-mentioned method is performed, the measurement of the (002) plane has a half-amplitude pulse width of 400 seconds and half of the (10-12) plane. The amplitude pulse width is 500 seconds. The outermost surface of the gallium nitride crystal film was observed using AFM. As a result, the morphological surface formed by the short steps of the arc indicating the existence of most of the transitions was observed sparsely on the concrete surface, and the growth pits were seen sparsely. To measure the etch pit density of the gallium nitride crystal film, the sample was treated in the same manner as in Example 5, and the etch pit density was measured with an AFM observation surface. In accordance with this, the etch pit density is 2 × 109 cm · 2. Embodiment 10 This embodiment 10 is a method of forming a gallium nitride-based compound semiconductor layer on a substrate according to the method described in embodiment 8, and another gallium nitride layer is laminated on the gallium nitride-based compound semiconductor layer on the substrate. A gallium-based compound semiconductor layer constitutes a semiconductor light emitting element. -66- 546850 V. Description of the invention (65) Stomach 6 _ is a schematic representation of the cross-sectional structure of the semiconductor light-emitting element manufactured in Example 10. On the sapphire substrate 11 of the tenth embodiment, which adopts the MOCVD method and heats the temperature of the mouth, a vapor containing trimethylaluminum (TMA 1) vapor is first circulated, followed by a vapor containing trimethylgallium (TMGa) After the metal nuclei are deposited on the substrate, the metal nuclei are annealed in hydrogen, and then ammonia gas is circulated to nitride the metal nuclei. An electron concentration of 1 X 1017 cm · 3 is formed thereon 2 // m low-Sl doped GaN layer 12, on this low Si-doped GaN layer, two sequentially stacked with i X 10Mcm-3 electron concentration 1 &quot; m high-Sl doped GaN layer 13 'with lX1017cm_3 electrons Concentration: 10Aln () 1Ga () 9N cover layer 1 4. Starting from GaN barrier layer 15 and ending with GaN barrier layer 15, 7 of 6 layers ◦ 20 people doped with InQ in GaN barrier layers 15 and 5 The 2Ga () 8N well layer 16 has a multiple quantum well structure, a 30-person non-doped ai () 2Ga () 8N diffusion prevention layer Π, and a 0 × 1017cm3 positive hole concentration of 0.  5 // m Mg-doped GaN layer 18. A positive hole concentration i00AMg doped with In of 5 x 10 ucnr3. The iGa () yN layer 19 is laminated to produce a multi-layer structure wafer for semiconductor light emitting elements. Next, a light-emitting diode is fabricated using a wafer having a multilayer structure laminated on a sapphire substrate. The fabrication of the above-mentioned multi-layered wafer is performed by the MOCVD method according to the following steps. Stomach first, a sapphire substrate 11 was introduced into a quartz furnace in an RF coil of an induction heating heater. The sapphire substrate 11 is placed on a heating carbon sensor in a small storage chamber replaced with nitrogen. After introducing @ 寺 ·, purify the inside of the reactor by flowing nitrogen. -67- 546850 V. Description of the invention (66) After the nitrogen gas flow for 10 minutes, the induction heating heater is operated. After 10 minutes, the temperature of the substrate is raised to 1 170 ° C, and the pressure in the furnace is 5 0hPa. The substrate temperature was still maintained at 1 70 ° C, and the substrate surface was thermally treated by allowing it to stand for 9 minutes while circulating hydrogen gas and nitrogen gas. Between the thermal processes, a hydrogen carrier gas is circulated in a container (bubble) containing trimethylgallium (TMG a) charged with raw materials connected to the reaction furnace and a container (trimethylaluminum (TMA1)) Bubbler) piping to start foaming. The temperature of each bubbler is adjusted to minus using the constant temperature bath used to adjust the temperature. The vapors of TMG a and TM A 1 generated by the foaming system are circulated in the piping of the detoxification device together with the carrier gas until the growth process is started, and are discharged out of the system through the detoxification device. After the thermal process is completed, the valve carrying the nitrogen gas is closed so that the gas supplied to the reactor is only hydrogen. For example, after changing the carrier gas, lower the temperature of the substrate to 1100 ° C and adjust the pressure in the furnace to 100hPa. After confirming that the temperature was stable at 1100 ° C, the valve of the TMA1 piping was switched, a gas containing TMA1 vapor was supplied to the reaction furnace, and a process of attaching a metal (A 1) core to the sapphire substrate was started. After one minute of this process, the valve of the TM A1 piping was switched to stop supplying the gas containing TMA vapor to the reaction furnace. Thereafter, the valve of the TMGa piping was switched, a gas containing TMGa vapor was supplied into the reaction furnace, and a process of attaching a metal (Ga) core to the sapphire substrate 11 was started. After 2 minutes of this process, the valve of the TMGa piping was switched to stop the supply of TMG. Vapor gas in a gas reactor. The formation of metal nuclei was performed in two steps as described above. -68- 546850 V. Description of the invention (67) After that, the formed metal core is annealed in a hydrogen carrier gas for 5 minutes. After 5 minutes of annealing, the valve of the ammonia gas piping was switched to start supplying ammonia gas in the furnace, and the nitriding treatment of the metal core after annealing was performed to form a growing core. Half: This is as described in Example 4. After 10 seconds, continue to circulate ammonia and increase the temperature of the sensor to 1 1 60 ° C. Adjust the flow rate of the flow regulator of TMGa piping as the temperature of the sensor rises. In addition, S 1 H4 was distributed. Until the low Si-doped G a N layer grows to between, S 1 H4 circulates with the carrier gas in the piping of the detoxification device, and is discharged out of the system through the detoxification device. After confirming that the temperature of the sensor has reached 1 1 60 ° C, wait for the temperature to stabilize, then switch the valves of TMGa and SiH4, start supplying TMGa and S 1 H4 to the furnace, and start the growth of low-doped GaN. After about 1 hour The growth of the GaN layer was performed in 15 minutes. The amount of SiH4 in circulation was reviewed beforehand, and the electron concentration adjusted to a low Si-doped GaN layer was 1 X 10 17cnT 3. In this way, a low Si-doped GaN layer 12 with a film thickness of 2 m is formed. Further, a Si-doped n-type GaN layer is grown on the low Si-doped GaN layer 12. That is, after the low Si-doped GaN layer 12 was grown, the supply of TMGa and SiH4 to the furnace was stopped after 1 minute. During this period, the flow rate of Si H4 was changed. The amount of circulation was reviewed beforehand, and the electron concentration of the S 1 doped GaN layer was adjusted to 1 X 1019 cm_3. Ammonia continues to be supplied to the furnace at the original flow. After stopping for 1 minute, the supply of TMGa and Si H4 was resumed, and growth was performed after 45 minutes, and a Si-doped G a N layer 1 3 with a film thickness of 1 // m was formed by this operation. -69- 546850 5. Description of the invention (68) After growing a high Si-doped GaN layer, switch the valves of TMGa and SiH4 to stop the supply of these raw materials in the furnace. Ammonia still flows as it is, and the switching valve switches the carrier gas from hydrogen to nitrogen. Thereafter, the temperature of the substrate was reduced from 60 I to 800 C, and the pressure in the furnace was changed from 100 hPa to 200 hPa. While waiting to change the temperature in the furnace, the supply of SlH4 was changed. The amount of circulation has been reviewed beforehand, and the electron concentration of the Si-doped InGaN cladding layer is adjusted to 1 X 1017 cm · 3. Ammonia continues to be supplied to the furnace at the original flow rate. In addition, a bubbler in which a carrier gas was circulated in trimethylindium (TM I η) and diethylgallium (TEGa) was previously started. The SiH4 gas and the vapors of TMIn and TEGa generated by the bubbling are started from the growth process of the coating layer, and circulate with the carrier gas in the piping, and are discharged out of the system through the harm removal device. After that, wait for the state in the furnace to stabilize, and switch TMI η and TEG a and SiH42_ at the same time, and start to supply these raw materials in the furnace. After about 10 minutes, the supply was continued to form a S 1 doped I n () jGaQ 9N cover layer 14 with a film thickness of 100 A. After that, the valves of TMI, TEG, and SiH4 were switched, and the supply of these materials was stopped. Second, a barrier layer 15 made of G a N and a well layer 1 made of I n () 2 G a () 8 N were produced. 6 structure of multiple quantum wells. When a multiple quantum well structure is fabricated, InQ iGa is doped in Si. First, a GaN barrier layer 15 is formed on the 9n cladding layer 14 and an In () 2Ga () 8N well layer 16 is formed on the GaN barrier layer 15. After stacking this structure with 5 layers, a 6th layer of GaN barrier layer 15 is formed on the In () 2Ga () SN well layer 16 of the fifth layer, and a GaN barrier layer 15 is sandwiched on both sides -70- 546850 V. Description of Invention (69) Live. When forming the first GaN layer, In is doped with Si. / a. After the yN cover layer 14 has grown, after 30 seconds of stopping, the temperature of the substrate or the pressure in the furnace, the flow rate or type of the carrier gas is still the same, the TEG (; valve is switched, and TEGa is supplied to the furnace. After 7 minutes After the supply of TEGa, the switching valve was stopped again. The supply of TEGa ended the growth of the GaN barrier layer 15. As a result, a GaN barrier layer 15 with a film thickness of 70A was formed. The growth of the GaN barrier layer 15 was passed through and eliminated. The TMIn flow rate of the piping of the equipment is compared with the Mohr flow rate when the cover layer 14 grows. It is adjusted to 2 times the Mohr flow rate. After the growth of the GaN barrier layer 15 is completed, the supply of group III materials is stopped after 30 seconds. The internal pressure, the flow rate or type of the carrier gas are still the same, the TEGa and TMIn valves are switched, and TEGa and TMIn are supplied to the furnace. After 2 minutes of TEGa and TMIn supply, the switching valve stops supplying TEGa and TMIn again The growth of the In () 2GaQ 8N well layer 16 is formed. Thus, an In () 2Ga () 8N well layer 16 with a thickness of 20 is formed. Ο After the growth of the I n () 2 G a. 8 Ν well layer 16 is completed. After 30 seconds, the supply of Group I and II materials is stopped. The pressure, the flow rate or the type of the carrier gas is still the same, and TEG a is started to be supplied in the furnace to grow the GaN barrier layer 15 again. If the next step is repeated 5 times, 5 layers of GaN barrier layers 15 and 5 are produced. In () 2Ga () 8N well layer 16. Then the last In. 2Ga. SN well layer 16 -71-546850 5. Invention description (70) A GaN barrier layer 15 is formed on the G a N barrier layer On the structure of the multiple quantum well completed at 15, the following steps are followed to produce A 1 without f-figure: 2 G a. 8 N diffusion hill-proof layer 1 7. That is, the supply of TEG a, G a N barrier layer 1 is stopped. After the growth of 5 is completed, the substrate temperature and the type and flow rate of the carrier gas are still the same as those described in γ within 1 minute, and the pressure in the furnace is changed to 100 HPa. The carrier gas is started to flow through the trimethyl aluminum (TMA) in advance.丨) bubbler. The vapor of TMA 1 generated by the bubble generation process until the diffusion prevention layer starts, flows with the carrier gas in the piping of the detoxification device, and is discharged out of the system through the detoxification device. Wait until The pressure in the furnace is stable. The valves of TEGa and TMA1 are switched and the supply of these raw materials in the furnace is started. Thereafter, after about 3 minutes of growth, the supply of TEGa and TMA1, and the non-doped A 1 () 2Ga () 8N diffusion prevention layer 17 were stopped growing. Thus, a non-doped film with a thickness of 30 A was formed. Hetero A 1 () 2 G a () 8 N diffusion preventing layer 17 7. On the undoped A 1 () 2 GaQ 8N diffusion preventing layer 17, a Mg-doped GaN layer 18 is produced by the following process. That is, the supply of TEGa and TMA1 was stopped, and after the growth of the undoped Al () 2Ga () 8N diffusion prevention layer 17 was completed, the substrate temperature was raised to 1 060 ° C in 2 minutes, and the pressure in the furnace was changed to 2 OOhPa. Then change the carrier gas to hydrogen. In addition, a bubbler for circulating a carrier gas through dicyclopentadiene magnesium (Cp2Mg) was started in advance. The vapor of Cp2Mg generated by the foaming process until the beginning of the growth process of the Mg-doped GaN layer is passed through the piping of the detoxification device together with the carrier gas, through the detoxification device -72- 546850 V. Description of the invention (71) Release Outside the system. Change the temperature and pressure to wait for the pressure in the furnace to stabilize, switch between TMGa and

Cp2Mg之閥，開始將此等之原料供應於爐內。流通Cp2Mg 之量係於事前已檢討，調整Mg摻雜GaN覆蓋層之正孔濃 度成爲8X1〇 17cm」。其後，約經過6分鐘進行成長後，停 止供應TMGa與Cp2Mg、停止Mg摻雜之GaN層之成長。並 由此形成膜厚〇.1 5 // m之Mg摻雜G aN層1 8。 該Mg摻雜之GaN層1 8上製作Mg摻雜InGaN層1 9。亦 即，停止供應TMGa與Cp2Mg，Mg摻雜之GaN層1 8之成長 結束後，經過2分鐘下降基板之溫度至800 °C ,同時變更 載運氣體爲氫。爐內之壓力仍依原樣爲200hPa。 變更Cp2Mg之流量，使Mg摻雜I n。2Ga() 8N層1 9之Mg ^雜量與M g摻雜G a N層相同。並由事前之檢討，在該摻 雜量知曉了 Mg摻雜In。/ a() 9N層之正孔濃度成爲5 X !〇丨8Cm·、 等待基板溫度成穩定，切換TMIn與TEGa與Cp2Mg之閥， 陶始供應此等之原料於爐內。其後，約經過1 0分鐘進行 成長後，停止供應TEGa與TMIn與Cp2Mg、停止了 Mg摻雜 1 lGa() 層μ之成長。並由此形成膜厚100A之Mg摻 雑1〜如(）9N層19。 結束Mg摻雜In() ,GaQ 9N層19之成長後，停止對感應加 熱式加熱器之通電，經由20分鐘降溫基板之溫度至室溫。 在降溫中使反應爐內之環境僅由氮氣構成。其後，確認基 546850 五、發明說明（72) 板溫度降溫至室溫，取出試料於大氣中。取出的晶圓帶有 黃味的透明，成長面爲鏡面。 由以上之製程’製作具有半導體發光元件用之多層構造 晶圓。在此處M g摻雜G a N覆蓋層18與μ g摻雜 I n () {a。yN層1 9，即使未進行退火處理使p型載體用以活 性化亦呈P型。 接著，使用上述在藍寶石基板1 1上疊層外延成長層構 造之晶圓以製作一種半導體發光元件之發光二極體。 有關取出於大氣中的晶圓，係藉由習知之光刻法 (Photol i t ho gr aphy )如第 7 圖所示在 l〇〇AMg 摻雜 I n〇 βa。9N層1 8之表面1 8a上，形成具有自表面側依序 疊層鈦、鋁、金構造的結合襯墊20，與形成僅由金所成透 明性電極，製作了 P側電極2 1。 再於其後，進行晶圓之乾蝕刻，使形成高Si摻雜GaN 層Π之η側由電極的部分1 3露出，在露出的部分1 3 1製 作由N ; A1所成η側電極22。並由此等作業，在晶圓上製 作具第7圖所示形狀的電極。 如此，有關形成Ρ側及η側電極之晶圓，係硏磨光製藍 寶石基板之背面爲鏡狀面。其後，將該晶圓切斷爲 3 5 0 // m角之正方形晶片，並使電極於上方載置在引線框 架、結線金線於引導線框架作成發光元件。 如上述所製作的發光二極體之P側及η側之電極間流通 順時間方向電流時，於電流20mA之順方向電壓爲3 . 0V。 -74- 546850 五、發明說明（73) 又，通過p側透光性電極觀察發光時，發光輸出呈4 7 0 n m , 發光出力爲6cd。 於本實施例，係說明父替重複2次由TMA 1之流通（步驟 A 1 )與流通ΤΓ M G a (步驟A 2 )形成金屬核，，其後並未沒有進 行退火（步驟B )下進行金屬核之氮化（步驟C )，其上使用 成長氮化鎵系化合物半導體（步驟D )的製程，成長氮化鎵 系化合物半導體製造半導體發光元件之例。所製作元件之 構造與第6圖所示構造相同。 上述元件構造試料之製作，係使用M0CVD法由以下之製 程進行。首先，將藍寶石基板11導入設置於感應加熱式 力D熱器之RF線圈中的石英製之反應爐中。藍寶石基板係 在氮氣取代的小型收容室中載置於加熱用之碳製感應器上 °導入試料後，流通氮氣使反應爐內純化。 於進行附著金屬核製程之前，與實施例6同樣進行熱退 火。又，其間同樣與實施例6使用的原料開始起泡，使產 生的蒸氣通過除害裝置以放出於爐外。 熱淸理結束後，關閉氮氣載運氣體之氣閥、作成反應爐 內僅供應氫氣。 切換載運氣體後，降溫基板溫度至1100 °C、調整爐內 之壓力爲10〇hPa。確認溫度於U〇〇°C穩定後，切換TMA1 酉己管之閥、將含有TMA 1之蒸氣之氣體供應至反應爐內， 在藍寶石基板上開始附著鋁金屬核之處理。經2分鐘後， -75- 546850 五、發明說明（74 ) 切換ΤΜΑ 1配管之閥，停止供應ΤΜΑ 1於反應爐。，於1秒 鐘後切換TMGa配管之閥、將含有TMGa蒸氣之氣體供應至 反應爐內，對附著於藍寶石基板上的鋁金屬核h開如附著 嫁之處理。於4分鐘後切換T M G a配管之閥、停[h T M G a之 供應於爐內。重複2次該ΤΜΑ 1與TMGa供應於反應爐內之 操作。 與停止第 2次含TMGa蒸氣之氣體供應於反應爐內之同 時，切換氨氣體配管之閥、開始供應氨氣體至爐內，開始 了金屬核之氮化。 再者，於1 〇秒鐘後持續流通氨，昇溫感應器之溫度至 1 1 60t，接著進入製作低Si摻雜之GaN層。然而由與實 施例10相同步驟依序成長低S 1摻雜GaN層1 2、高S 1摻 雜GaN層1 3、In() jGa。9N覆蓋層14、6層之GaN障壁層與 5 層I n () 2 G a () 8 N附層1 6相互豐層的多重量子阴1構造、 A 1 〇 2Ga() 8N擴散防止層1 7、Mg摻雜GaN層1 8、Mg摻雜 I n〇 2Ga() 8N 層 19。 晶圓之最表面層的Mg摻雜ln() jGa() 9N層之成長結束後， 停止對感應加熱式加熱器之通電，使基板之溫度經過2 〇 分fe降溫至室溫。降溫中反應爐內之環境僅以氮氣構成。 其後，確認基板溫度降溫至室溫，取出試料於大氣中。所 取出的晶圓係帶有黃味透明，成長面爲鏡面。 由以上之步驟製作具半導體發光元件用之多層構造晶圓 。在本晶圓上由與實施例6相同的製程形成電極予以晶片 -76- 546850 五、發明說明（75) 化，裝於引線框架來結線，作成發光元件。 如上述所製作的發光二極體之p側及η側電極間流通順 時間方向電流時，於電流20mA之順方向電壓爲3 . 2V。又， 通過P側透光性電極觀察發光時，發光波長爲470nm ,發 光輸出呈5 c d ◦ 實施例1 2 本實施例係依本發明的方法在基板上形成氮化鎵系化合 物半導體層，在其基板上之氮化鎵系化合物半導體層再疊 層別的氮化鎵系化合物半導體層來構成半導體發光元件。 第8圖係實施例1 2所製作的半導體發光元件之剖面構 造以模式的表示圖。本實施例係使用MOCVD法、在加熱爲 高溫的藍寶石基板Η上首先流通含三甲基鋁（TMA)蒸氣之 氣體、接著流通含三甲基鎵（TMGa)蒸氣之氣體，在基板上 形成金屬核後。於氫氣中退火金屬核、其後以流通氨來氮 化金屬核、在其上形成具lXl〇i7cm·3電子濃度之2/am低 S 1摻雜GaN層12、在此低Si摻雜GaN層上依序疊層具1 X 1019cm·3電子濃度之1 K m高si摻雜GaN層13、自GaN 障壁層15開始結束於GaN障壁層15，由6層之7〇AGaN _壁層15與5層之20A無摻雜之ln() 2Ga。8N阱層16所成 多重量子畊構造、30A之無摻雜之Al〇 2Ga().8N擴散防止層 1 7、具8χ 1〇 &quot;cm」正孔濃度之〇.丨5 β mMg摻雜GaN層18 疊層，製作了具有半導體發光元件用之多層構造晶圓。接 著，使用疊層於此藍寶石基板上具多層構造之晶圓製作發 -77- 546850 五、發明說明（76) 光二極體。 製作上述多層構造之晶圓係使用M0CVD法由以下步驟進 行。 首先，將藍寶石基板11導入設置在感應加熱式加熱器 之RF線_屮的彳ί英製反應爐屮。藍寶石基板1 1在氮氣取 代的小型收容室箱中載置於加熱用之碳製感應器上。導入 g式料後，流通氮氣使反應爐內純化。 經過氮氣流通1 0分鐘後，作動感應加熱式加熱器、經 過丨0分鐘升溫基板溫度至1 1 7 0 °C、同時使爐內之壓力爲 5 0 h P a。將基板溫度仍保持於1 1 7 0 °C、邊流通氫器與氮氣 放置9分鐘、進行基板表面之熱淸理。 在進行熱淸理間，以流通載運氣體於連接反應爐依爲原 料裝有三甲基鎵（TMGa)之容器（起泡器）及裝入有三甲基鋁 (T M A 1 )之容器（起泡器）之配管內，開始起泡◦各起泡器之 溫度使用用以調整溫度之恆溫槽調整爲一定。由起泡所產 生的TMGa與TMA1之蒸氣自成長製程開始至、與載運氣體 一起流通至除害裝置之配管，通過除害裝置放出至系統外 〇 於熱淸理結束後，關閉氮氣載運氣體之閥、供應於反應 爐內之氣體僅以氫氣者。 切換載運氣體後，降溫基板之溫度至1 1 60°C、同時調 整爐內之壓力爲1 0 0 h P a。確認溫度於1 1 6 0 T：穩定後，切 換TMA1配管之閥，將含有TMA1蒸氣之氣體供應至反應爐 -78 - 546850 五、發明說明（77) 內，開始在藍寶石基板上進行附著金屬（A1)核之處理。此 處理經過3分鐘進行後，切換TMA 1配管之閥、停止供應 含TMA1蒸氣之氣體至反應爐內。其後，切換TMGa配管之 閥、供應含有TMG a蒸氣之氣體至反應爐內、在藍寶石基 板1 1上開始進行金屬（Ga )核之附著處理。將該處理經過3 分鐘進行後，切換TMGa配管之閥，停止供應含TMGa蒸氣 之氣體至反應爐內。如此分成2個階段進行形成金屬核。 其後保持5分鐘，將所形成的金屬核在氫氣載運氣體中 退火。經5分鐘之退火後，切換氨氣體配管之閥，開始供 應氨氣體至爐內，進行退火後之金屬核氮化，形成成長核 〇 持續流通氨，調整TMGa配管之流量調整器之流量。又， 開始流通S 1 H4。至開始低S 1摻雜之GaN層成長之間， S i H4與載運氣體…起流通於除害裝置之配管，通過除害裝 置以放出至系統外。 等待TMGa與SiH4之流量穩定、其後切換TMGa與SiH4 之閥開始對爐內供應TMGa與SiH4 ,開始低摻雜之GaN成 長，經過約1小時1 5分鐘進行上述G a N層之成長。流通 s 1 H4之量於事前已檢討，乃調整S 1摻雜GaN層之電子濃 度成爲1 X 1017cm·3。如此形成膜厚2// m之低Si摻雜GaN 層1 2。 再者，在該低S i摻雜GaN層12上成長S i摻雜之η型 G a Ν層成長。亦即，成長低S 1摻雜之G a N層1 2後，經過 -79- 五、發明說明（78) 1分鐘停il:對爐內之供應TMG a與s丨I。其間變更s i h之 流通量◦所流通之量係在事前已檢討，調整S1摻雜GaN 層之電子濃度調整成爲i X丨〇 i9c3。氨乃依原流量繼續供 應至爐內。經1分鐘之停止後，再開始供應TMG a與s i η 4 、經過45分鐘進行成長並由該操作形成膜厚之高Si 摻雜GaN層1 3。 成長局S 1摻雜GaN層1 3後，切換TMGa與S 1 H4之閥 停止此寺原料供應至爐內。氨仍依原樣流通、切換閥將載 蓮氣體自氫切換爲氮。其後，自1 1 6 0 °c降下基板之溫度 至8 0 0 °C，同時變更爐內之壓力1 〇 〇 h p a至2 〇 〇 h P a。 等待爐內溫度改變變更之間，氨係依原流量繼續供應氨 至爐內。又，預先開始流通載運氣體於三甲基銦（TM〗n )與 三乙基鎵（TEGa)之起泡器。由起泡產生的TMIn及TEGa之 蒸氣係直到活性層之成長製程至，係與載運氣體--起流通 於除害裝置之配管、通過除害裝置放出於系統外。 其次，製作由GaN所成障壁層1 5與由In() 2Ga() SN所成 阱層1 6構成的多重量子阱構造。於製作多重量子阱構造， 係在Si摻雜GaN接觸層13上，首先形成GaN _壁層15、 其GaN障壁層15上形成In() 2Ga() 8N阱層16。將此構造疊 層5層後，在第5層之In().2Ga() 8N阱層16上形成第6層 之GaN障壁層1 5 ,作成以G aN障壁層1 5夾住兩側的構造 〇 用以形成第1之GaN層，依於原來的基板溫度或爐内之 -80- 546850 五、發明說明（79) 壓力、載負氣體之流量或種類下，切換TEG a之閥繼續供 應TEGa至爐內。經過7分鐘進行供應TEGa後，再度切換 閥停止供應TEGa結束了 GaN障壁層1 5之成長◦並由此形 成膜厚7 0 A之g a N障壁層1 5。 結束GaN障壁層15之成長後，經過30秒鐘停止供應 III族原料後，仍依原基板溫度或爐內之壓力、載運氣體 之流量或種類，切換TEG a與TMI η之閥進行供應TEG a與 TM I η至爐內。經過2分鐘進行供應TEG a與TM I η後，再 度切換閥停止供應TEGa與TMIn結束In() 2Ga() SN阱層16 之成長。並由此形成膜厚2〇A之In。2Ga。8N阱層16。 結束Ιϋ() 2Ga() 8n阱層16之成長後，經過30秒鐘停止供 應、III族原料後，仍依原基板溫度或爐內之壓力、載運氣 體之流量或種類開始供應TEGa至爐內，再度進行GaN障 壁層15之成長。 重複如此歩驟5次，製作了 5層之GaN障壁層1 5與5 層之In() 2Ga() 8N阱層16。再於在最後之In。2Ga() 8N阱層 16上形成GaN障壁層15。 在該GaN障壁層15結束的多重量子阱構造上，以下述 步驟，製作無摻雜之A 1 () 2Ga() 8N擴散防止層1 7。亦即， 停止TEG a之供應、結束G aN障壁層1 5之成長後，經1分 鐘在基板溫度與載運氣體之種類、流量爲相同下，變更爐 內之壓力爲1 OOhPa。 預先開始流通載運氣體於二甲基鋁（TM A 1 )之起泡器。由 -81 - 546850 五、發明說明（so) 起泡產生的 ΤΜΑ 1之蒸氣係直到開始擴散防止層之成長製 程至，與載運氣體一起流通於除害裝裝之配管、通過除齊 裝置放出於系統外。 等待爐內之壓力穩定，切換TEGa與TMA1之閥，開始此 等原料之供應至爐內。其後，經過約3分鐘進行成長後， 停止供應TEGa與TMA1、停止無摻雜之Al() 2Ga() 8N擴散防 止層17之成長。並由此形成膜厚30Α之無摻雜 Α 1 g 2Ga() tSN擴散防止層17。 在該無摻雜之A 1 () Wa() 8N擴散防止層1 7 h，依以下製 程製作M g慘雜之G a N層1 8。亦即，停止供應TEG a與 TMA1,使無摻雜之Aiq 2Ga(} 8N擴散防止層17的成長結束 後，經2分鐘上昇基板之溫度至丨〇 6 〇 〇c、變更爐內之壓 力爲200hPa。再將載運氣體變更爲氫。又，預先開始流 通載運氣體於雙環戊二烯鎂（Cp2Mg )之起泡器。由起泡產 生的Cp^g之蒸氣係直到開始心摻雜GaN層之成長製程 至，與載運氣體-起流通於除害裝置之配管、通過除害裝 置放出於系統外。 變更溫度與壓力以等待爐內之壓力穩定，切換TMGa與 C p^g之氣閥，開始此等原料之供應至爐內。流通Cp2Mg 之里係於事_已檢g寸，§周整M g摻雜G a N覆蓋層之正孔濃 度成爲8 X 10 17cm·3。其後，約經過6分鐘進行成長後，停 止供應TMGa與Cp2Mg、停止Mg摻雜GaN層之成長。並由 此形成膜厚〇.1 5 // m之M g摻雜g a N層1 8。 -82- 546850 五、發明說明（81) 在該Mg摻雜之GaN層18上，依以驟製作Mg摻雜 之InGaN層19。亦即，停止供應了嶋與以心，Mg摻雜 之GaN層1 8之成長結束後，變更載運氣體爲氫、降低氨 之流通W电仝部流量之1 %。爐内之壓力仍依原來之 2〇〇h P a。 其後，止對感應加熱式加熱器通電，經2 〇分鐘使基 板之溫度降至军溫◦降溫中使反應爐內之環境由氮氣中含 有丨％热之混合氣體構成。其後，確認基板溫度降至室溫， 將試料取出至大氣中。取出的晶圓帶有黃味的透明，成長 面爲鏡面。 由以上之步驟製作具有半導體發光元件用多層構造之晶 圓。此處Mg摻雜GaN層18，係不予進行用以使p型載體 活性化之退火處理亦呈p型。 接著，使用上述監寶石基板Η上疊層外延成長層構造 之晶圓製作半導體發光元件之—種的發光二極體。 有關取出於大氣中的晶圓，係依習知微影術如第7圖所 示，在Mg摻雜之GaN層18之表面18a上，自表面側依序 具與鈦、鋁、金疊層構造的結合襯墊20、與形成由金與氧 化鎳之2層構造所成的透明性電極，製作了 p側電極21 〇 再於其後，對晶圓進行乾式蝕刻、使形成高S i摻雜 G a N層1 3之η側電極部分1 3 1露出，在露出的部分1 3 1 製作由Νι、Α1所成的η側電極22。並由此等作業，在晶 -83 - 546850 五、發明說明（82) 圓上製作具如第7圖所示形狀之電極。 如此有關形成p側及η側電極之晶圓，係硏磨、光製藍 寶石基板之內面成鏡狀面。其後，切斷該晶圓成3 5 0 // m 角之正方形晶片，使電極在上述載置於引起線樞架上、以 金線結線於引線框架作爲發光元件。 如上述所製作發光二極體之p側及η側電極間流通順方 向電流時，電流20mA之順方向電壓爲3 . 0V。又，通過ρ 側之透光性電極觀察發光時，發光波長爲47 2nm,發光輸 出爲5.9cd 。 比較例2 比較例2係使用習知形成低溫緩衝層之製程，在基板上 形成不摻雜之膜厚2 // ηι的氮化鎵結晶膜，在該低溫緩衝 層上製作具有與實施例1 0相同疊層構造之晶圓。取出的 晶圓帶有黃味透明、成長面爲鏡面。 將此晶圓，與實施例1 0同樣地形成ρ側及η側之電極， 硏磨、光製藍寶石基板之內面作成鏡狀面。 其後，切斷該晶圓爲3 5 0 // m角之正方形晶片，使電極 於上方載置在引線框架上、以金線結線於引線框架作成發 光元件。 如上述所製作的發光二極體之P側及η側電極間流通順 方向電流時，電流20mA之順方向電壓爲4 . 0V係高者。又， 通過P側透光性電極觀察發光時，發光波長爲4 7 0 n m ,發 光輸出爲3cd係呈低之値。 -84- 546850 五、發明說明（83) 此係因依本發明方法在基板上良好地形成氮化鎵系化合 物半導體層，故提高了發光層之結晶性、乃由提高發光之 量子效率所致。 實施例1 3 其次，說明在基板上形成氮化鎵系化合物半導體之成長 速度慢的光罩層、使氮化鎵系化合物半導體結晶成長之實 施例。 本實施例係依照第9圖所示之製程在基板上成長結晶。 使用M0CVD法、在加熱高溫的藍寶石基板上流通氨與二矽 院（Sl2H6)後，流通TMG與TMA之混合氣體、其後予以流 通氨，形成具有以氮化矽覆蓋的區域與在藍寶石基板上附 著氮化鋁與氮化鎵區域的層作爲光罩層，其上疊層未摻雜 之GaN層製作試料。 製作上述含GaN層之試料，係使用M0CVD法由以下步驟 進行。 首先，將藍寶石基板導入感應加熱式加熱器之RF線圈 中所設置的石英製反應爐中。藍寶石基板載置於加熱用之 碳製感應器上。導入試料後使反應爐抽真空排出空氣，流 通氮氣使反應爐內純化。 流通1 0分鐘氮氣後，作動感應加熱式加熱器、經1 〇分 鐘昇溫基板溫度至1170°C。保持基板溫度於117(TC、邊 流通氫氣與氮氣放置9分鐘、進行基板表面之熱淸理。 進行熱淸理間，將氫氣載運氣體流通於連接於反應爐之 -85- 546850 五、發明說明（84 ) 裝入爲原料的三甲基鎵（TMG )之容器（起泡器）的配管，使 氫氣載負氣體流通，開始起泡。各起泡器之溫度係使用用 以調整溫度之恆溫槽調整爲…定。由起泡所產生的TMG之 蒸氣自成長製程開始至、與載運氣體一起流通於除害裝置 之配管，通過除害裝置放出至系統外。 於熱淸埋處理結束後，切換氨之配管與：：矽烷之配管閥 、在藍寶石基板上流通氨與二矽烷1分鐘。其後，切換氨 之配管與二矽烷之配管閥、停止供應氨與二矽烷。接著， 切換由氮氣所成的載運氣體之閥，開始供應氮氣於反應爐 內。其1分鐘後，切換TMG與TMA之配管的閥、將含TMG 與 TMA蒸氣的載運氣體供應至反應爐內1分鐘後，切換 TMG與TMA配管之閥停止供應TMG與TMA至反應爐。同時， 切換由氮氣所成載運氣體之閥，開始將氮氣供應至反應爐 內。其1分鐘後，切換氨配管之閥開始氨供應至反應爐， 流通氨10分鐘後，切換閥停止供應，供應作載運氣體之 氮氣。並由該製程，在藍寶石基板上形成由氮化矽所成區 或5與由氮化鎵鋁所成區域8構成的光罩層。 形成光罩層後，降溫基板1之溫度至116CTC。確認溫 度在1 1 60 °C穩定後，切換氨氣體配管之閥，開始將供應 氨4至爐內。約流通1分鐘後，切換TMG配管之閥、供應 含TMG蒸氣之氣體至反應爐內，在光罩層上進行GaN層9 之成長。 約經過2小時進行上述G a N層之成長後，切換TMG配管 -86- 546850 五、發明說明（85) 之閥結束原料供應至反應爐而停止成長。 結束G a N層之成長後，停止通電於感應加熱式加熱器， 與實施例1同樣的步驟取出試料於大氣中。 由上述製程，製作在藍寶石基板1上形成光罩層，於其 -h形成不摻雜之膜厚2 β m的G aN層之試料。取出的基板 爲無色透明、成長面爲鏡面。 其次，依以上述方法進行成長的不摻雜GaN層之XRC測 疋。測定係採用C u /3線X線發生源爲光源、在對稱面之 (0 002 )面與非對稱面之（10_12)面進行。-般而言，爲氮 化鎵系化合物半導體時，（0002 )面之XRC光譜半振幅脈衝 寬度成爲結晶之平坦性的指標，（10-12)面之XRC光譜半 振幅脈衝寬度成爲轉位密度之指標。該測定結果依本發明 方法製作的不摻雜GaN層，在（ 0002 )面之測定係半振幅脈 衝寬度爲280秒、（10 - 12 )面之半振幅脈衝寬度呈300秒 〇 又，上述GaN層之最表面係使用AFM觀察。結果，在表 面並未見到沒有成長凹坑、觀察到良好形態之表面。 又，用以測定上述GaN層之蝕刻凹坑密度，將試料在 2 8 0度之硫酸與磷酸之混合溶液中處理1 0分鐘，以AFM觀 察表面測定蝕刻凹坑密度。由此該蝕刻凹坑密度約爲9 X 1〇6cnT2左右。 實施例14 本實施例係依照第1 〇圖所示之製程在基板上成長結晶 -87- 546850 五、發明說明（86) 。使用M0CVD法、在高溫下流通氨於經氮化的藍寶石基板 上，流通矽院與TMG之混合氣體，其後由流通氨，形成由 氮化矽覆蓋的區域與藍寶石基板面上附著氮化鎵之區域所 成層爲光罩層，於其上疊層未摻雜之GaN層製作試料。 製作上述含G aN層之試料係採用與實施例1 3所用相同 的裝置、以MOCVD法由以下進行步驟。 首先，與實施例1 3同樣，將藍寶石基板導人反應爐中， 與實施例1 3相同步驟進行熱淸理。進行熱淸理間與實施 例1同樣開始容器（起泡器）之起泡。 於熱淸理處理結束後，切換氨配管之閥、在藍寶石基板 上使氨流通20分鐘。其後，切換氨配管之閥停止供應氨 。接著，切換由氮氣所成的載運氣體之閥，開始將氮氣供 應至反應爐內。其後，切換矽烷配管與TMG配管之閥、在 藍寶石基板上流通矽烷與TMG30秒鐘◦其後，切換TMG配 管與矽烷配管之閥、停止供應TMG與矽烷。繼後，切換由 氮氣所成的載運氣體之閥，開始將氮氣供應至反應爐內。 其1分鐘後，切換氨配管之閥、開始供應氨至反應爐，流 通氨1 0分鐘後，切換閥停止供應，供應載運氣體之氮氣 。並由該製程，在藍寶石基板上形成由氮化矽所成區域5 及氮化鎵所成區域8構成的光罩層。 形成光罩層後，降溫低基板1之溫度至1 1 80°C。確認溫 度在1 1 8 0 °C穩定後，切換氨之配管之閥，開如供應氨至 反應爐◦約流通1分鐘後，切換TMG配管之閥、供應含 -88- 546850 五、發明說明（87) TMG蒸氣之氣體至反應爐內，在光罩層上進行GaN層之成 長。 約經過2小時進行上述GaN層9之成長後，切換TMG配 管之閥結束供應至原料反應爐停止成長。 結束G aN層成長後，停止通電於感應加熱式加熱器，與 實施例1「司樣步驟取出試料於大氣中。 由以」：之製程製作/在藍寶石基板1上形成光罩層5,8 、於其上形成不摻雜之膜厚2 V⑴的GaN層9之試料。取 出的基板爲無色透明、成長面爲鏡面。 其次，以上述方法進行成長的不摻雜GaN層之XRC測定 。測定結果，本實施例製作的不摻雜GaN層，（0002 )面之 測疋係半振幅脈衝寬度爲2 9 0秒、（1 0 - 1 2 )面之半振幅脈 衝寬度呈4 2〇秒。 又，上述GaN層之最表面採用AFM觀察。結果，表面並 無見到成長凹坑、觀察到良好形態之表面。 又，用以測定上述G a N層之蝕刻凹坑密度時，與實施例 3同樣處理試料，由AFM觀察表面測定蝕刻凹坑密度。依 此’該蝕刻凹坑密度約爲6x 107cm_2左右。 實施例1 5 本實施例說明含有由實施例丨3記載的方法製造氮化鎵 系化合物半導體之製程、使用氮化鎵系化合物半導體之半 導體發光元件的製造方法。半導體發光元件之疊層構造係 與實施例1 2記載相同，作成第8圖所示構造。採用 -89- 546850 五、發明說明（％) MOCVD法、在加熱高溫的藍寶石基板上流通後氨與二矽烷 (S 1爪），流通TMG與ΤΜΑ之混合氣體、其後流通氨，形 成由氮化砂覆蓋的區域與由GaAIN覆蓋的區域所成光罩層 上开》成具1 x 1 〇17cm·3電子濃度之2 β m低Si摻雜GaN層1 2 、Λ ^低S 1摻雜g a N層k序依g疊層具1 X 1 〇 19 c m」電子 度之1 V m高s 1摻雜GaN層1 3、自GaN障壁層1 5開始 結束於GaN障壁層15，6層之7〇AGaN障壁層15與5層 2〇A之慘雜之In。2Ga。8N阱層16所成多重量子阱構造、 3 〇A之摻雜之In() 2Ga() 8N擴散防止層17、具8&gt;&lt;l〇17cm_3正 孔濃度之0 · 1 5 // mMg摻雜GaN層1 8疊層，製作具有半導 體發光元件用多層構造之晶圓。接著，使用具有疊層在藍 寶石基板上的多層構造之晶圓以製作發光二極體。 首先，使用M0CVD法依照與實施例1 3相同的步驟，在 藍寶石基板上形成具平坦表面之丨X 1〇]7cm·3電子濃度的 2 // m之低S !摻雜GaN層1 2。其後，依照與實施例丨2所 示相同地步驟，在低S i摻雜GaN層上依序疊層高S 1摻雜 GaN層13、多重量子阱構造、Al() 2Ga() 8N擴散層17、心 摻雜GaN層1 8。 有關取出於大氣中晶圓，係由習知之微影術形成自P型 I nGaN層表面側具依與鈦、鋁、金疊層之構造的結合襯墊 、具依金與鎳氧化物之序疊層構造的透光性電棰，製作P 俱α電極。 再於其後對晶圓進行乾式蝕刻，使形成η側謹極部分之 -90- 546850 五、發明說明（89) η型G a N層露出、在露出的部分製作由A 1所成的^側電極 〇 如此對肜成Ρ側及η側電極之晶圓，硏磨光製藍寶石基 板之內面作成鏡狀之面。其後，切斷該晶_爲3 5 0 μ m角 之正方形晶片，並使電極在上方載置於引線框架、以金線 結線於引線樞架作成發光元件。 如上述製作的發光二極體之P側及η側之電極間流通順 方向電流時，於電流20mA之順方向電壓爲3 . 0V。又，經 由P側透光性電極觀察發光時，發光波長爲4 6 5 n m ,發光 輸出爲3 c d。 [產業上之利用價値] 採用本發明之I I I族氮化物半導體結晶之製造方法時， 與習知使用低溫緩衝層之方法相比，不必要嚴密地控制製 造條件、可容易地在基板上製造高品質之I I I族氮化物半 導體結晶之薄膜。 結果，使用本發明之ί Π族氮化物半導體結晶之製造方 法，採用氮化鎵系化合物半導體來製造半導體發光元件時， 可製作高亮度在晶圓面內具大致約均一特性之發光二極體 管。 又，本發明之I I I族氮化物半導體結晶之製造方法及氮 化鎵系化合物半導體，係在基板上先附著金屬核、依其金 屬核爲基礎形成成長核、對其成長核再予成長氮化鎵系化 合物半導體層。附著於基板上的金屬核，由有機金屬氣體 -91 - 546850 五、發明說明（9〇 ) 之流量或流通時間、處理溫度等可控制其成長，故可自由 地控制金屬核存在於基板上的密度。 又，由於其金屬核施予退火及氮化處埋、金屬核變成可 自由成長於垂直力向、水平方向，故可控制所得成長核於 所希望的肜狀（例如略梯形狀）◦时[L ,再於該成長核h成 長氮化鎵系化合物半導體層，故氮化鎵系化合物半導體層 ’係如埋沒相鄰的成長核間邊、轉位邊成長，埋層相鄰的 成長核間後在其上成長爲平坦的層。因而，最後在基板上 ’可形成具備所希望的層厚及良好結晶性之氮化鎵系化合 物半導體層。 形成於該基板上的氮化鎵系化合物半導體層，可與疊層 於其上的氮化鎵系化合物半導體保持極爲良好的格子整合 性，因而，可在基板上形成具良好的結晶性之氮化鎵系化 合物半導體各層。而，使用該氮化鎵系化合物肀導體製造 半導體發光元件時，亦可確實地提高其發光特性。 又，採用本發明方法製作的半導體發光元件，可利用爲 電子機器用、車輛搭載用、交通信號用其他電器裝置作爲 高亮度之光源。使用本發明方法製作的半導體發光元件， 與使用習知方法製作的半導體發光元件相比，由於有結晶 性良好的特徵、故採用其製作的光源裝置，發光之效率佳 、惡化之速度慢可持久耐用特徵。並由此，可省電力化、 低成本化、低交換頻率化。 -92- 546850 五、發明說明 (91 ) 主要元件對照表 S a 金屬核 S b 成長核 Sal 退火處理後之金屬核 1 基板 2 氮化鎵系化合物半導體 3 含Si之原料氣體 3， I I I族原料氣體 4 /ΞΞ： Miffi 熱米、證 5 氮化砂之膜 6 露出藍寶石的範圍 7 液滴狀粒 8 I I I族氮化物 9 成長結晶 1〇 矽原子之集合體 11 藍寶石基板 12 低摻雜GaN層 13 高摻雜GaN層 14 I n () , G a () 9 N 覆蓋層 15 G aN障壁層 16 I n n 2 G a。8 N P井層 17 A 1 () 2 G a () 8 N擴散防止層 18 M g摻雜GaN層 -93- 546850 五、發明說明 (92 ) 18a Mg摻雜In() jGa() yN層之表面 19 M g 摻雜 I η () , G a μ N 層 20 結合襯墊 2 1 透明性P電極 2 2 η側電極 13 1 形成η側電極部分 -94-Cp2Mg valve started to supply these raw materials in the furnace. The amount of circulating Cp2Mg has been reviewed beforehand, and the positive hole concentration of the Mg-doped GaN cap layer has been adjusted to 8 × 10 17 cm ”. Thereafter, after about 6 minutes of growth, the supply of TMGa and Cp2Mg was stopped, and the growth of the Mg-doped GaN layer was stopped. Thus, a Mg-doped G aN layer 18 having a film thickness of 0.1 5 // m is formed. A Mg-doped InGaN layer 19 is formed on the Mg-doped GaN layer 18. That is, after the supply of TMGa and Cp2Mg is stopped, the growth of the Mg-doped GaN layer 18 is completed, and the temperature of the substrate is lowered to 800 ° C after 2 minutes, and the carrier gas is changed to hydrogen. The pressure in the furnace was still 200 hPa as it was. The flow rate of Cp2Mg was changed so that Mg was doped with I n. The Mg content of the 2Ga () 8N layer 19 is the same as that of the M g-doped G a N layer. Based on prior review, it was known that Mg was doped with In at the doped amount. / a () The positive hole concentration of the 9N layer becomes 5 X! 〇 丨 8Cm ·, wait for the substrate temperature to stabilize, switch the valves of TMIn, TEGa and Cp2Mg, Tao Shi supplies these raw materials in the furnace. Thereafter, after about 10 minutes of growth, the supply of TEGa, TMIn, and Cp2Mg was stopped, and the growth of the Mg-doped 1 Ga () layer µ was stopped. Thus, a Mg erbium-doped 1 ~ such as () 9N layer 19 having a film thickness of 100A is formed. After the growth of the Mg-doped In () and GaQ 9N layer 19 is finished, the energization of the induction heating heater is stopped, and the temperature of the substrate is reduced to room temperature through 20 minutes. During the temperature reduction, the environment in the reaction furnace was composed of only nitrogen. After that, it was confirmed that the base was 546850. V. Description of the invention (72) The temperature of the plate was reduced to room temperature, and the sample was taken out into the atmosphere. The removed wafer is yellow-colored and transparent, and the growth surface is a mirror surface. A multi-layered wafer having a semiconductor light-emitting element is manufactured by the above process'. Here, M g doped G a N cap layer 18 and μ g doped I n () {a. The yN layer 19 is P-type even if the p-type support is not activated by annealing. Next, a wafer having an epitaxial growth layer laminated on the sapphire substrate 11 is used to produce a light emitting diode of a semiconductor light emitting element. The wafer taken out from the atmosphere was doped with I n〇 βa at 100 AMg as shown in Fig. 7 by a conventional photolithography method (Photolite). On the surface 18a of the 9N layer 18, a bonding pad 20 having a structure in which titanium, aluminum, and gold are sequentially laminated from the surface side is formed, and a transparent electrode made of only gold is formed to produce a P-side electrode 21. After that, dry etching of the wafer is performed, so that the n-side of the high Si-doped GaN layer Π is exposed from the electrode portion 13 and the exposed portion 1 3 1 is made of the n-side electrode 22 made of N; A1 . In this way, an electrode having a shape shown in FIG. 7 is fabricated on the wafer. In this way, the wafer on which the P-side and η-side electrodes are formed is a mirror-shaped surface of the sapphire substrate made of honing. After that, the wafer was cut into a square wafer with an angle of 3 50 // m, and the electrodes were placed on the lead frame and the gold wires were bonded to the lead frame to form a light emitting element. When the current in the forward direction flows between the P-side and η-side electrodes of the light-emitting diode manufactured as described above, the forward-direction voltage at a current of 20 mA is 3.0 V. -74- 546850 V. Description of the invention (73) In addition, when the light emission is observed through the p-side light-transmitting electrode, the light emission output is 470 nm, and the light output is 6cd. In this embodiment, it is explained that the parent replaces the metal core from the circulation of TMA 1 (step A 1) and the circulation TΓ MG a (step A 2) twice, and then it is performed without annealing (step B). Nitriding of a metal core (step C) is an example of manufacturing a semiconductor light-emitting element by growing a gallium nitride-based compound semiconductor using a process of growing a gallium nitride-based compound semiconductor (step D). The structure of the produced element is the same as that shown in FIG. The above-mentioned device structure samples were produced by the following process using MOCVD method. First, the sapphire substrate 11 is introduced into a quartz furnace in an RF coil of an induction heating force D heater. The sapphire substrate is placed on a carbon-based sensor for heating in a small storage room replaced by nitrogen. After introducing the sample, nitrogen is passed through the reactor to purify it. Prior to the process of attaching a metal core, heat annealing was performed in the same manner as in Example 6. In the meantime, similarly to the raw material used in Example 6, foaming was started, and the generated steam was passed through a detoxification device to be discharged out of the furnace. After the heat treatment is completed, the gas valve of the nitrogen-carrying gas is closed, and only hydrogen is supplied in the reaction furnace. After the carrier gas was switched, the substrate temperature was reduced to 1100 ° C, and the pressure in the furnace was adjusted to 100 hPa. After confirming that the temperature was stable at U ° C, the valve of the TMA1 tube was switched, a gas containing the vapor of TMA1 was supplied to the reaction furnace, and the treatment of attaching an aluminum metal core on the sapphire substrate was started. After 2 minutes, -75- 546850 Fifth, the description of the invention (74) The valve of TIMA 1 piping was switched to stop supplying TIMA 1 to the reaction furnace. After 1 second, the valve of the TMGa piping was switched, and a gas containing TMGa vapor was supplied into the reaction furnace, and the aluminum metal core h attached to the sapphire substrate was treated as if it were attached. After 4 minutes, the valve of the T M G a piping was switched and the supply of [h T M G a in the furnace was stopped. The operation of supplying the TMA 1 and TMGa in the reactor was repeated twice. At the same time that the second supply of TMGa vapor-containing gas to the reactor was stopped, the valve of the ammonia gas piping was switched to start supplying ammonia gas to the furnace, and the nitriding of the metal nuclei began. Furthermore, ammonia was continuously circulated after 10 seconds, and the temperature of the sensor was raised to 11060t, and then the production of a low Si-doped GaN layer was performed. However, a low S 1 doped GaN layer 1 2, a high S 1 doped GaN layer 1 3, and an In () jGa were sequentially grown by the same steps as those in Example 10. 9N cladding layer 14 and 6 layers of GaN barrier layer and 5 layers of I n () 2 G a () 8 N attached layer 1 6 multiple quantum cathode structures that are mutually enriched, A 1 〇2Ga () 8N diffusion prevention layer 1 7. Mg-doped GaN layer 1 8. Mg-doped I nO2Ga () 8N layer 19. After the growth of the Mg-doped ln () jGa () 9N layer on the topmost surface of the wafer is completed, the power to the induction heating heater is stopped, and the temperature of the substrate is cooled to room temperature after 20 minutes. The environment in the reaction furnace during cooling is made of nitrogen only. Thereafter, it was confirmed that the temperature of the substrate was lowered to room temperature, and the sample was taken out into the atmosphere. The removed wafer is yellow and transparent, and the growth surface is mirror surface. A multilayer structure wafer for a semiconductor light-emitting element is manufactured by the above steps. Electrodes are formed on this wafer by the same process as in Example 6. -76- 546850 Fifth, the invention is described in (75), and is mounted on a lead frame to form a light-emitting element. When the current in the forward direction flows between the p-side and n-side electrodes of the light-emitting diode manufactured as described above, the forward-direction voltage at a current of 20 mA is 3.2 V. In addition, when the light emission was observed through the P-side transparent electrode, the light emission wavelength was 470 nm and the light emission output was 5 cd. Example 1 2 This example is a method of forming a gallium nitride compound semiconductor layer on a substrate according to the method of the present invention. The gallium nitride-based compound semiconductor layer on the substrate is further laminated with another gallium nitride-based compound semiconductor layer to constitute a semiconductor light emitting element. Fig. 8 is a schematic diagram showing a cross-sectional structure of the semiconductor light-emitting element manufactured in Example 12; In this embodiment, a gas containing trimethylaluminum (TMA) vapor is first circulated on a sapphire substrate Η heated to a high temperature by using the MOCVD method, and then a gas containing trimethylgallium (TMGa) vapor is circulated to form a metal on the substrate. After nuclear. Anneal the metal nuclei in hydrogen, then nitride the metal nuclei by circulating ammonia, form a 2 / am low S 1 doped GaN layer 12 with an electron concentration of 1 × 10 7 cm · 3, and low Si doped GaN here 1 Km high Si-doped GaN layer 13 with an electron concentration of 1 X 1019 cm · 3 is sequentially stacked on the layers, starting from the GaN barrier layer 15 and ending with the GaN barrier layer 15, and consisting of 6 layers of 70AGaN_wall layer 15 With 5 layers of 20A undoped ln () 2Ga. Multiple quantum farming structure formed by 8N well layer 16 and 30A non-doped AlO2Ga (). 8N diffusion prevention layer 1 7. With 8χ 10 &quot; cm '' positive hole concentration of 0.5 β mMg doping The GaN layer 18 was laminated to produce a multilayer structure wafer having a semiconductor light emitting element. Next, a wafer with a multilayer structure laminated on this sapphire substrate was used to make the hair-77-546850. V. Description of the invention (76) Photodiode. The multi-layered wafer is fabricated by the following steps using MOCVD. First, the sapphire substrate 11 is introduced into an English-made reaction furnace 设置 installed in an RF line of an induction heating heater. The sapphire substrate 11 is placed on a carbon sensor for heating in a small storage chamber box replaced by nitrogen. After introducing the g-type material, the reaction furnace was purified by flowing nitrogen gas. After 10 minutes of nitrogen flow, the induction heating heater was activated, and the substrate temperature was raised to 110 ° C over 0 minutes, while the pressure in the furnace was set to 50 h Pa. The substrate temperature was maintained at 1 170 ° C, and a hydrogen generator and nitrogen gas were allowed to stand for 9 minutes to perform thermal treatment on the substrate surface. In the thermal process, a container (bubble) filled with trimethylgallium (TMGa) and a container (bubble filled with trimethylaluminum (TMA 1)) are filled with a carrier gas and connected to a reaction furnace. ) In the piping, foaming starts. ◦ The temperature of each bubbler is adjusted to a constant value by using a constant temperature bath to adjust the temperature. The vapors of TMGa and TMA1 generated by the foaming process start from the growth process to the piping that circulates with the carrier gas to the detoxification device and is discharged to the outside of the system through the detoxification device. After the thermal process is completed, the nitrogen carrier gas is closed. The valve and the gas supplied to the reactor are only hydrogen. After the carrier gas is switched, the temperature of the substrate is reduced to 110 ° C, and the pressure in the furnace is adjusted to 100 h Pa. Confirm that the temperature is 1 1 6 0 T: After stabilization, switch the valve of the TMA1 piping to supply the gas containing TMA1 vapor to the reactor -78-546850 5. In the description of the invention (77), metal attachment on the sapphire substrate ( A1) Nuclear processing. After three minutes of this treatment, the valve of the TMA 1 piping was switched and the supply of gas containing TMA1 vapor to the reaction furnace was stopped. Thereafter, the valve of the TMGa piping was switched, a gas containing TMG a vapor was supplied into the reaction furnace, and a metal (Ga) core attachment process was started on the sapphire substrate 11. After this process has been performed for 3 minutes, the valve of the TMGa piping is switched to stop supplying the gas containing TMGa vapor to the reaction furnace. The metal core is formed in two steps as described above. After that, for 5 minutes, the formed metal core was annealed in a hydrogen carrier gas. After 5 minutes of annealing, the valve of the ammonia gas piping was switched to start supplying ammonia gas into the furnace, and the annealed metal nuclei were nitrided to form growth nuclei. Continue to circulate ammonia and adjust the flow rate of the flow regulator of the TMGa piping. In addition, S 1 H4 was distributed. Until the growth of the low S 1 doped GaN layer begins, Si H4 and the carrier gas… circulate through the piping of the detoxification device and are discharged to the system through the detoxification device. Wait for the flow of TMGa and SiH4 to stabilize, and then switch the valves of TMGa and SiH4 to start supplying TMGa and SiH4 to the furnace, and begin to grow the low-doped GaN. After about 1 hour and 15 minutes, the above-mentioned G a N layer grows. The amount of circulating s 1 H4 has been reviewed beforehand, and the electron concentration of the S 1 doped GaN layer is adjusted to 1 X 1017 cm · 3. Thus, a low Si-doped GaN layer 12 with a film thickness of 2 // m was formed. Furthermore, a Si-doped n-type G a N layer is grown on the low Si-doped GaN layer 12. That is, after growing a low S 1 doped G a N layer 1 2, -79- V. Invention description (78) Stop for 1 minute il: Supply TMG a and s 丨 I to the furnace. In the meantime, the flow rate of s i h was changed. The flow rate was reviewed beforehand. The electron concentration of the S1 doped GaN layer was adjusted to i X 丨 〇 i9c3. Ammonia continues to be supplied to the furnace at the original flow rate. After stopping for 1 minute, the supply of TMG a and s i η 4 was resumed, growth was performed after 45 minutes, and a high Si-doped GaN layer 13 with a film thickness was formed by this operation. After growing the S 1 doped GaN layer 1 3, the valves of TMGa and S 1 H4 are switched to stop the supply of the raw materials to the furnace. Ammonia is still flowing as it is, and the switching valve switches the carrier gas from hydrogen to nitrogen. After that, the temperature of the substrate was lowered from 1 160 ° C to 800 ° C, and the pressure in the furnace was changed from 100 h p a to 2000 h p a at the same time. After waiting for the temperature in the furnace to change, the ammonia system continues to supply ammonia to the furnace at the original flow rate. In addition, a bubbler for carrying a carrier gas between trimethylindium (TM) n and triethylgallium (TEGa) was started in advance. The vapors of TMIn and TEGa generated by the foaming process until the growth of the active layer reach the carrier gas, circulate through the piping of the detoxification device, and are discharged out of the system through the detoxification device. Next, a multiple quantum well structure composed of a barrier layer 15 made of GaN and a well layer 16 made of In () 2Ga () SN was fabricated. To make a multiple quantum well structure, a GaN_wall layer 15 is first formed on the Si-doped GaN contact layer 13, and an In () 2Ga () 8N well layer 16 is formed on the GaN barrier layer 15. After stacking this structure with five layers, a sixth layer of GaN barrier layer 15 was formed on the fifth layer of In (). 2Ga () 8N well layer 16 to make the G aN barrier layer 15 sandwich the two sides. Structure 0 is used to form the first GaN layer. Depending on the original substrate temperature or -80- 546850 in the furnace. 5. Description of the invention (79) The pressure and the flow rate or type of the load gas are switched to continue the supply of the TEG a valve. TEGa into the furnace. After 7 minutes of TEGa supply, the valve was switched again to stop the supply of TEGa, and the growth of the GaN barrier layer 15 was completed. As a result, a g a N barrier layer 15 with a film thickness of 70 A was formed. After the growth of the GaN barrier layer 15 is stopped, after stopping the supply of Group III raw materials for 30 seconds, the TEG a and TMI η valves are switched to supply TEG a according to the original substrate temperature or the pressure in the furnace, the flow rate or type of the carrier gas. With TM I η into the furnace. After 2 minutes of supplying TEG a and TM I η, the switching valve stopped supplying TEGa and TMIn again to end the growth of the In () 2Ga () SN well layer 16. Thus, In was formed to a thickness of 20 A. 2Ga. 8N 井 层 16。 8N well layer 16. After the growth of the Iϋ () 2Ga () 8n well layer 16 is stopped, after 30 seconds, the supply is stopped, and after the III group of raw materials, TEGa is still supplied to the furnace according to the original substrate temperature or the pressure in the furnace, the flow rate or type of the carrier gas. The growth of the GaN barrier layer 15 is performed again. This step was repeated 5 times, and 5 layers of GaN barrier layers 15 and 5 layers of In () 2Ga () 8N well layer 16 were produced. Then at the last In. A GaN barrier layer 15 is formed on the 2Ga () 8N well layer 16. On the multiple quantum well structure in which the GaN barrier layer 15 is completed, an undoped A 1 () 2Ga () 8N diffusion prevention layer 17 is produced in the following steps. That is, after stopping the supply of TEG a and ending the growth of the G aN barrier layer 15, the substrate temperature and the type and flow rate of the carrier gas were the same in 1 minute, and the pressure in the furnace was changed to 100 hPa. A bubbler carrying a carrier gas in dimethyl aluminum (TM A 1) was started in advance. -81-546850 V. Invention description (SO) The vapor of TIMA 1 produced by the foaming process until the start of the diffusion prevention layer growth process until it circulates with the carrier gas in the piping of the harm removal equipment, and is discharged through the removal device. Outside the system. Wait for the pressure in the furnace to stabilize, switch the valves of TEGa and TMA1, and start the supply of these materials into the furnace. Thereafter, after about 3 minutes of growth, the supply of TEGa and TMA1 was stopped, and the growth of the undoped Al () 2Ga () 8N diffusion preventing layer 17 was stopped. Thus, an undoped A 1 g 2Ga () tSN diffusion preventing layer 17 having a film thickness of 30A is formed. On the undoped A 1 () Wa () 8N diffusion prevention layer for 17 h, a M g miscellaneous Ga N layer 18 was produced by the following process. That is, after the supply of TEG a and TMA1 is stopped, and the growth of the undoped Aiq 2Ga (} 8N diffusion prevention layer 17 is completed, the temperature of the substrate is increased to 〇〇〇〇〇2 in 2 minutes, and the pressure in the furnace is changed to 200hPa. The carrier gas was changed to hydrogen. In addition, the carrier gas was previously circulated in a bubbler of dicyclopentadiene magnesium (Cp2Mg). The vapor system of Cp ^ g generated by the foaming until the beginning of the doped GaN layer Grow the process to the piping that flows with the carrier gas through the detoxification device and release it out of the system through the detoxification device. Change the temperature and pressure to wait for the pressure in the furnace to stabilize, switch the gas valves of TMGa and C p ^ g, and start The supply of these raw materials is supplied to the furnace. The inside of circulating Cp2Mg is a matter of inspection. The pore concentration of the Mg-doped G a N coating on the whole surface becomes 8 X 10 17cm · 3. After that, about After 6 minutes of growth, the supply of TMGa and Cp2Mg was stopped, and the growth of the Mg-doped GaN layer was stopped. From this, a M g-doped ga N layer with a film thickness of 0.1 5 // m was formed. -82- 546850 V. Description of the invention (81) On the Mg-doped GaN layer 18, a Mg-doped InGaN layer 19 is fabricated in a step. That is, After the supply of dysprosium and silicon was stopped, after the growth of the Mg-doped GaN layer 18 was completed, the carrier gas was changed to hydrogen and the flow of ammonia was reduced by 1%. The pressure in the furnace was still the same as the original. 〇h P a. Thereafter, the induction heating heater was stopped, and the temperature of the substrate was lowered to the military temperature within 20 minutes. During the cooling, the environment in the reaction furnace was composed of a mixed gas containing 丨% heat in nitrogen. Thereafter, it was confirmed that the temperature of the substrate was lowered to room temperature, and the sample was taken out to the atmosphere. The taken-out wafer was yellow-colored and transparent, and the growth surface was a mirror surface. A wafer having a multilayer structure for a semiconductor light-emitting device was produced by the above steps. Here, the Mg-doped GaN layer 18 is p-type without the annealing treatment for activating the p-type carrier. Next, a semiconductor light-emitting device is fabricated by using the wafer with the epitaxial growth layer structure laminated on the above-mentioned gem substrate. Element—a kind of light-emitting diode. The wafer taken out from the atmosphere is based on conventional lithography, as shown in FIG. 7, on the surface 18a of the Mg-doped GaN layer 18, depending on the surface side. Sequence lining with titanium, aluminum and gold laminated structure 20. With the formation of a transparent electrode made of a two-layer structure of gold and nickel oxide, a p-side electrode 21 was produced. Then, the wafer was dry-etched to form a high Si-doped G a N layer. The η-side electrode part 1 3 1 of 1 3 is exposed, and the η-side electrode 22 made of Ni and A1 is made on the exposed part 1 3 1. With this operation, the crystal-83-546850 V. Description of the invention (82 ) An electrode with a shape as shown in Fig. 7 is fabricated on a circle. Thus, the wafers on which the p-side and η-side electrodes are formed are mirror-shaped on the inner surface of the honing and light sapphire substrate. Thereafter, the wafer was cut into a square wafer with an angle of 3 50 // m, and the electrodes were placed on the lead frame, and gold wires were connected to the lead frame as the light-emitting element. When a forward current flows between the p-side and n-side electrodes of the light-emitting diode manufactured as described above, the forward voltage of 20 mA is 3.0 V. When light emission was observed through a translucent electrode on the ρ side, the light emission wavelength was 472 2 nm, and the light emission output was 5.9 cd. Comparative Example 2 Comparative Example 2 uses a conventional process for forming a low-temperature buffer layer, and an undoped gallium nitride crystal film with a thickness of 2 // η is formed on a substrate. 0 Wafers of the same stack structure. The removed wafer has a yellow smell and is transparent, and the growing surface is a mirror surface. On this wafer, electrodes on the ρ side and η side were formed in the same manner as in Example 10, and the inner surface of the sapphire substrate made of honing and light was made into a mirror-like surface. Thereafter, the wafer was cut into a square wafer with an angle of 3 50 // m, and the electrodes were placed on the lead frame above, and a gold wire was connected to the lead frame to form a light emitting element. When the forward current flows between the P-side and η-side electrodes of the light-emitting diode manufactured as described above, the forward voltage of 20 mA is 4.0 V, which is the higher. In addition, when light emission was observed through the P-side translucent electrode, the light emission wavelength was 470 nm, and the light output was 3cd, which was low. -84- 546850 V. Explanation of the invention (83) This is because the gallium nitride compound semiconductor layer is formed on the substrate according to the method of the present invention, so the crystallinity of the light-emitting layer is improved, which is caused by the quantum efficiency of light emission. . Example 1 3 Next, an example of forming a gallium nitride-based compound semiconductor with a slow growth photomask layer on a substrate and growing a gallium nitride-based compound semiconductor crystal will be described. In this embodiment, crystals are grown on the substrate according to the process shown in FIG. 9. The MCVD method was used to circulate ammonia and silicon dioxide (Sl2H6) on a heated high-temperature sapphire substrate. Then, a mixed gas of TMG and TMA was circulated, and ammonia was then circulated to form a region covered with silicon nitride and on a sapphire substrate. The layer with the aluminum nitride and gallium nitride regions attached was used as a photomask layer, and an undoped GaN layer was laminated thereon to prepare a sample. The above-mentioned GaN-containing layer was prepared by the following steps using MOCVD. First, a sapphire substrate was introduced into a quartz reaction furnace provided in an RF coil of an induction heating heater. The sapphire substrate is placed on a carbon sensor for heating. After introducing the sample, the reaction furnace was evacuated to exhaust air, and nitrogen was passed through the reactor to purify the inside of the reaction furnace. After flowing nitrogen for 10 minutes, the induction heating heater was operated, and the substrate temperature was raised to 1170 ° C over 10 minutes. Keep the temperature of the substrate at 117 ° C, and place it for 9 minutes while flowing hydrogen and nitrogen, and perform thermal treatment on the surface of the substrate. During the thermal treatment, the hydrogen carrier gas is circulated to the reactor connected to the reactor -85- 546850 5. Description of the invention (84) The piping of the container (bubble) filled with trimethylgallium (TMG) as a raw material allows hydrogen-bearing gas to circulate and start foaming. The temperature of each bubbler is a constant temperature used to adjust the temperature The tank is adjusted to ... definitely. The vapor of TMG generated by the foaming process starts from the growth process to the pipe that circulates with the carrier gas in the detoxification device, and is discharged to the outside of the system through the detoxification device. Ammonia piping and :: Silane piping valve, ammonia and disilane flow through the sapphire substrate for 1 minute. After that, the ammonia piping and disilane piping valve were switched, and the supply of ammonia and disilane was stopped. Then, the nitrogen was switched The formed carrier gas valve starts to supply nitrogen into the reaction furnace. After 1 minute, the valve of the piping of TMG and TMA is switched, and the carrier gas containing TMG and TMA vapor is supplied to the reaction furnace for 1 minute. The valve that switches the TMG and TMA piping stops supplying TMG and TMA to the reactor. At the same time, the valve that switches the carrier gas made of nitrogen starts supplying nitrogen into the reactor. After 1 minute, the valve that switches the ammonia piping starts ammonia supply. To the reactor, after circulating ammonia for 10 minutes, the switching valve was stopped to supply nitrogen as a carrier gas. By this process, a region made of silicon nitride or a region made of 5 and gallium aluminum nitride was formed on a sapphire substrate. Mask layer composed of 8. After the mask layer is formed, the temperature of substrate 1 is cooled to 116CTC. After confirming that the temperature is stable at 1 1 60 ° C, the valve of the ammonia gas piping is switched to start supplying ammonia 4 to the furnace. About circulation After 1 minute, the valve of the TMG piping was switched, a gas containing TMG vapor was supplied into the reaction furnace, and the GaN layer 9 was grown on the mask layer. After the above-mentioned G a N layer growth was performed in about 2 hours, the TMG piping was switched. -86- 546850 V. Description of the invention (85) The valve stops supplying raw materials to the reactor and stops growing. After the growth of the G a N layer is stopped, the power to the induction heating heater is stopped, and the sample is taken out in the same procedure as in Example 1. In the atmosphere Based on the above process, a sample for forming a photomask layer on the sapphire substrate 1 and forming an undoped G aN layer with a film thickness of 2 β m was formed at -h. The removed substrate was colorless and transparent, and the growth surface was a mirror surface. The XRC measurement of the grown undoped GaN layer was carried out according to the method described above. The measurement was made by using a Cu / 3 line X-ray source as the light source, on the (0 002) plane of the symmetrical plane and (10_12) on the asymmetric plane. In general, when it is a gallium nitride-based compound semiconductor, the half-amplitude pulse width of the XRC spectrum of the (0002) plane becomes an index of the flatness of the crystal, and the half-amplitude pulse width of the XRC spectrum of the (10-12) plane becomes Index of indexing density. As a result of the measurement, the half-amplitude pulse width of the non-doped GaN layer produced by the method of the present invention on the (0002) plane is 280 seconds, and the half-amplitude pulse width of the (10-12) plane is 300 seconds. The outermost surface of the layer was observed using AFM. As a result, no surface with no growth pits and good morphology was observed on the surface. In addition, to measure the etch pit density of the GaN layer, the sample was treated in a mixed solution of sulfuric acid and phosphoric acid at 280 ° C for 10 minutes, and the etch pit density was measured by observing the surface with AFM. Therefore, the density of the etching pits is about 9 × 106cnT2. Embodiment 14 This embodiment grows crystals on a substrate according to the process shown in FIG. 10 -87- 546850 5. Description of the invention (86). Using the MCVD method, ammonia was circulated on a nitrided sapphire substrate at high temperature, and a mixed gas of silicon courtyard and TMG was circulated. Then ammonia was circulated to form a region covered by silicon nitride and gallium nitride was attached to the surface of the sapphire substrate. The layer formed in the area is a photomask layer, and an undoped GaN layer is laminated thereon to make a sample. The preparation of the above-mentioned G aN-containing layer was carried out by the following procedure using the same apparatus as in Example 13 and using the MOCVD method. First, the sapphire substrate was introduced into a reaction furnace in the same manner as in Example 13 and the same procedures as in Example 13 were performed for thermal treatment. The foaming of the container (foamer) was started in the same manner as in Example 1 during the heat treatment. After the thermal treatment was completed, the valve of the ammonia pipe was switched, and ammonia was allowed to flow on the sapphire substrate for 20 minutes. After that, the valve of the ammonia pipe was switched to stop supplying ammonia. Next, the valve of the carrier gas made of nitrogen was switched to start supplying nitrogen into the reaction furnace. Thereafter, the valve of the silane pipe and the TMG pipe was switched, and the silane and TMG were allowed to flow through the sapphire substrate for 30 seconds. Thereafter, the valve of the TMG pipe and the silane pipe was switched, and the supply of TMG and silane was stopped. Then, the valve of the carrier gas made of nitrogen was switched, and the supply of nitrogen to the reaction furnace was started. After 1 minute, the valve of the ammonia piping was switched to start supplying ammonia to the reaction furnace. After 10 minutes of ammonia flow, the switching valve was stopped to supply nitrogen for the carrier gas. In this process, a mask layer composed of a region 5 made of silicon nitride and a region 8 made of gallium nitride is formed on a sapphire substrate. After the mask layer is formed, the temperature of the substrate 1 is lowered to 1 1 80 ° C. After confirming that the temperature is stable at 1 180 ° C, switch the valve of the ammonia piping to open the supply of ammonia to the reactor. After about 1 minute of circulation, switch the valve of the TMG piping to supply -88- 546850. 5. Description of the invention ( 87) The gas of TMG vapor enters the reaction furnace, and the GaN layer is grown on the mask layer. After the growth of the GaN layer 9 is performed in about two hours, the valve for switching the TMG pipe is terminated and the supply to the raw material reaction furnace is stopped. After the G aN layer growth is completed, stop energizing the induction heating heater, and take the sample in the same manner as in Example 1 to take out the sample into the atmosphere. Manufactured by: Production process / Photomask layer 5, 8 formed on the sapphire substrate 1 A sample on which a non-doped GaN layer 9 having a film thickness of 2 V⑴ is formed. The substrate taken out was colorless and transparent, and the growth surface was a mirror surface. Next, the XRC measurement of the grown undoped GaN layer was performed by the above method. As a result of the measurement, the half-amplitude pulse width of the (0002) plane of the undoped GaN layer produced in this example was 290 seconds, and the half-amplitude pulse width of the (1 0-1 2) plane was 4 20 seconds. . The outermost surface of the GaN layer was observed by AFM. As a result, no growth pits were observed on the surface, and a well-formed surface was observed. When measuring the etch pit density of the G a N layer, the sample was treated in the same manner as in Example 3, and the etch pit density was measured from the surface observed by AFM. Accordingly, the density of the etch pits is about 6x 107 cm_2. Example 1 5 This example describes a method for manufacturing a gallium nitride based compound semiconductor using the method described in Example 3 and a method for manufacturing a semiconductor light emitting device using a gallium nitride based compound semiconductor. The laminated structure of the semiconductor light-emitting element was the same as that described in Example 12 and the structure shown in Fig. 8 was produced. Adopt -89- 546850 V. Description of the invention (%) MOCVD method, ammonia and disilane (S 1 claws) are circulated on a sapphire substrate heated at high temperature, a mixed gas of TMG and TMA is circulated, and ammonia is then circulated to form nitrogen. The area covered by the sand and the mask layer formed by the area covered by GaAIN are opened on a 2 β m low Si-doped GaN layer with 1 x 1 〇17cm · 3 electron concentration, and Λ ^ low S 1 doped. The ga N layer k-order and g-layer stack with 1 X 1 〇19 cm "electron degree 1 V m high s 1 doped GaN layer 1 3, starting from GaN barrier layer 15 and ending with GaN barrier layer 15, 6 70AGaN barrier layer 15 and 5 layers of 20A miscellaneous In. 2Ga. Multi-quantum well structure formed by 8N well layer 16, doped In () 2Ga () 8N diffusion prevention layer 17, with 8 &lt; 1017cm_3 positive hole concentration of 0 · 1 5 // mMg doped The hetero GaN layer 18 is stacked to produce a wafer having a multilayer structure for a semiconductor light emitting element. Next, a wafer having a multilayer structure laminated on a sapphire substrate is used to fabricate a light emitting diode. First, a MOCVD method was used to follow the same steps as in Example 13 to form a low S! Doped GaN layer 12 with a flat surface with an electron concentration of X 10 7 cm · 3 2 // m on a sapphire substrate 12. Thereafter, in accordance with the same steps as those shown in Example 2, a high S 1 doped GaN layer 13, a multiple quantum well structure, and Al () 2Ga () 8N diffusion were sequentially stacked on the low S i doped GaN layer. Layer 17, core-doped GaN layer 18. The wafer taken out from the atmosphere is formed by the conventional lithography from the surface side of the P-type I nGaN layer with a bonding pad structured with titanium, aluminum, and gold, and with the order of gold and nickel oxide. A light-transmissive electrode with a laminated structure was fabricated into a P-alpha electrode. After that, the wafer is dry-etched to form -90- 546850 of the η side electrode. V. Description of the invention (89) The η-type G a N layer is exposed, and the exposed portion is made of A 1 ^ The side electrode 〇 In this way, the inner surface of the sapphire substrate made of the sapphire substrate was polished into a mirror-like surface for a wafer having P-side and n-side electrodes. Thereafter, the square wafer having a crystal angle of 350 μm was cut, and the electrode was placed on the lead frame above, and a gold wire was connected to the lead pivot to form a light-emitting element. When the forward current flows between the P-side and η-side electrodes of the light-emitting diode manufactured as described above, the forward voltage at a current of 20 mA is 3.0 V. When the light emission was observed through the P-side translucent electrode, the light emission wavelength was 4 6 5 n m and the light emission output was 3 c d. [Industrial use price] When the manufacturing method of the group III nitride semiconductor crystal of the present invention is used, compared with the conventional method using a low-temperature buffer layer, it is not necessary to strictly control the manufacturing conditions, and it is easy to manufacture high High quality III-nitride semiconductor crystal. As a result, when using the manufacturing method of the Group III nitride semiconductor crystal of the present invention and a semiconductor light-emitting element using a gallium nitride-based compound semiconductor, a light-emitting diode with high uniformity and approximately uniform characteristics in the wafer surface can be produced. tube. In addition, the method for manufacturing a group III nitride semiconductor crystal and the gallium nitride-based compound semiconductor of the present invention include attaching a metal core to a substrate, forming a growth core based on the metal core, and then growing the core. A gallium-based compound semiconductor layer. The metal core attached to the substrate is controlled by the organometallic gas-91-546850. 5. The flow rate, circulation time, and processing temperature of the invention description (90) can control its growth, so it is possible to freely control the presence of the metal core on the substrate. density. In addition, since the metal nuclei are annealed and buried, and the metal nuclei can grow freely in the vertical and horizontal directions, the obtained growth nuclei can be controlled in a desired shape (for example, a slightly ladder shape). L, and then grow the gallium nitride-based compound semiconductor layer at the growth core h, so the gallium nitride-based compound semiconductor layer is grown by burying adjacent growth core edges and transposition edges, and burying the adjacent growth core layers After that it grows into a flat layer. Therefore, finally, a gallium nitride-based compound semiconductor layer having a desired layer thickness and good crystallinity can be formed on the substrate. The gallium nitride-based compound semiconductor layer formed on the substrate can maintain extremely good lattice integration with the gallium nitride-based compound semiconductor stacked thereon, and therefore, it can form nitrogen with good crystallinity on the substrate. Each layer of a gallium-based compound semiconductor. Moreover, when a semiconductor light-emitting device is manufactured using this gallium nitride-based compound rhenium conductor, its light-emitting characteristics can be reliably improved. In addition, the semiconductor light-emitting device manufactured by the method of the present invention can be used as a high-brightness light source for other electric devices for electronic equipment, vehicles, and traffic signals. Compared with semiconductor light-emitting devices made by conventional methods, the semiconductor light-emitting devices produced by the method of the present invention have good crystallinity. Therefore, the light-emitting device produced by the method has good light-emitting efficiency, slow deterioration and long-lasting. Durable features. As a result, it is possible to save power, reduce costs, and reduce the frequency of switching. -92- 546850 V. Description of the invention (91) Comparison table of main components Sa metal core S b growth core Sal metal core after annealing 1 substrate 2 gallium nitride-based compound semiconductor 3 Si-containing raw material gas 3, group III raw material Gas 4 / ΞΞ: Miffi hot rice, certificate 5 Nitrided sand film 6 Exposed sapphire 7 Droplet-like particles 8 Group III nitride 9 Growth crystal 10 Aggregation of silicon atoms 11 Sapphire substrate 12 Low-doped GaN layer 13 Highly doped GaN layer 14 I n (), G a () 9 N cover layer 15 G aN barrier layer 16 I nn 2 G a. 8 NP well layer 17 A 1 () 2 G a () 8 N diffusion prevention layer 18 M g doped GaN layer -93- 546850 V. Description of the invention (92) 18a Mg doped In () jGa () yN layer Surface 19 M g doped with I η (), G a μ N layer 20 bonding pad 2 1 transparent P electrode 2 2 η side electrode 13 1 forming η side electrode portion -94-

Claims (1)

546850 日條正/史止/補先 六、申請專利範圍 第 901 1976 6號「ΠΙ族氮化物半導體結晶之製造方法，氮 化嫁系化合物半導體之製造方法，氮化鎵系化合物半導體 、氮化鎵系化合物半導體發光元件及用其半導體發光元件 的光源」專利案 (92年2月21日修正） 六申請專利範圍： 1 · 一種I I I族氮化物半導體結晶之製造方法，其特徵爲 具備有：第1製程在基板表面堆積III族金屬之微粒 子；第2製程，其後在含有氮源之環境中使該微粒子 氮化，以及第3製程，其後在堆積有該微粒子之基板 表面上由氣相成長法形成11 I族氮化物半導體（Π][族 氮化物半導體以InxGayAlzN表示，惟x + y + z=i、x S 卜 0 ‘ y S 1、0 S z S 1 )結晶。 2 ·如申請專利範圍第1項之i π族氮化物半導體結晶之 製造方法，其中基板爲藍寶石（Α12〇3)。 3 ·如申請專利範圍第1項之I Π族氮化物半導體結晶之 製造方法，其中III族金屬爲InuGavAlw(惟u + v + w= l 、0^u$ 1、OSv^l、OSw^l)。 4 ·如申請專利範圍第1項之I π族氮化物半導體結晶之 製造方法，其中藉由有機金屬原料之熱分解堆積該 111族金屬的微粒子。 5 .如申請專利範圍第1項之I π族氮化物半導體結晶之 製造方法，其中第1製程以不含氮源之環境中進行。 546850 六、申請專利範圍 6 .如申請專利範圍第1或5項之I I I族氮化物半導體結 晶之製造方法，其中第1製程在上述111族金屬之熔 點以上之溫度進行。 7 ·如申請專利範圍第1項之I II族氮化物半導體結晶之 製造方法，其中第2製程在不含金屬原料之環境中 進行。 8 ·如申請專利範圍第！項之I I I族氮化物半導體結晶之 製造方法，其中第2製程以第1製程之溫度以上的 溫度進行。 9 ·如申請專利範圍第i項之I I I族氮化物半導體結晶之 製造方法，其中第3製程在第2製程之溫度以上的溫 度進行。 1 0 .如申請專利範圍第1項之III族氮化物半導體結晶 之製造方法，其中該氣相成長法爲有機金屬化學氣相 成長法。 1 1 ·如申請專利範圍第1項之111族氮化物半導體結晶 之製造方法，其中於第2製程氮化111族金屬之微粒 子者由I 11族氮化物之多結晶及/或非晶質所成、且 含未反應之金屬。 1 2 .如申請專利範圍第1項之ΙΠ族氮化物半導體結晶之 製造方法，其中該藍寶石基板上，更含有形成氮化鎵 系化合物半導體之成長速度慢的光罩層之製程，以選 擇性成長氮化鎵系化合物半導體。 546850 ^、、申请專利範圍 1 3 ·如申請專利範圍第1 2項之m族氮化物半導體結晶之 製造方法，其中形成於基板上的光罩層，係由氮化鎵 系化合物年導體之成長速度慢的材料構成的部分，與 由氮化鎵系化合物半導體之成長速度快的材料構成的 部分所成。 1 4 .如申請專利範圍第1 2項之m族氮化物半導體結晶之 製造方法，其中該光罩層之形成製程，係與氮化鎵系 化合物半導體相同的成長裝置內進行。 1 5 ·如申請專利範圍第1 2項之]π族氮化物半導體結晶之 製造方法，其中該光罩層之形成，係經加熱的藍寶石 在基板上含有Si氣體原料之氣體流通來進行。 1 6 .如申請專利範圍第！ 2項之m族氮化物半導體結晶之 製造方法，其中該光罩層之形成，係在加熱的藍寶石 基板_h同時進行流通含S i氣體原料之氣體與氨。 1 '/·如申請專利範圍第12項之瓜族氮化物半導體結晶之 製造方法，其中包含所形成的光罩層、構成光罩層之 材料爲覆蓋藍寶石面之部分與露出藍寶石面之部分。 ig,如申請專利範圍第12項之m族氮化物半導體結晶之 裟造方法，其中該光罩層之形成，係在加熱的基板上 進行同時流通含111元素的氣體原料之氣體與含S i 氣體原料之氣體。 .· 一種I I I族氮化物半導體結晶之製造方法，其特徵 爲包括第1製程，在不含氮源之環境中，使用至少含 546850 六、申請專利範圍 有一種In與Ga與A1之金屬兀素的有機金屬原料之 熱分解，在藍寶石基板上使至少由一種In與Ga與 A1所成的金屬1(金屬1係以InuGavAlw表示，惟 u + v + w=l、〇$u€l、OSvSl、〇SwSl)，在該金屬 1 之熔點以上的溫度T1下堆積；第2製程，第1製程 後在不含有機金屬原料含氮源之環境中、以溫度Τ2 ( 惟Τ2 - Τ 1 )氮化金屬1 ;以及第3製程，在第2製程 之後在堆積有金屬1之藍寶石基板上、以溫度Τ3 (惟 Τ3 2 Τ2)由有機金屬化學氣相成長法使III族氮化物 半導體（III族氮化物半導體以InxGayAlzN表示，惟 x + y + z=l、OSxSl、OgySl、OSzSl)結晶以外延 成長。 20 .如申請專利範圍第i 9項之111族氮化物半導體結晶 之製造方法，其中藍寶石基板具有（ 0001)面、該 ( 000 1 )面之垂直軸自&lt;〇〇〇1 &gt;方向傾斜於特定方向。 2 1 .如申請專利範圍第20項之111族氮化物半導體結晶 之製造方法，其中該特定方向爲&lt;1-1〇〇&gt;方向、且自 &lt;000 1 &gt;方向傾斜的角度爲〇 · 2°〜15。。 22 ·如申請專利範圍第1 9項之111族氮化物半導體結晶 之製造方法，其中溫度T1爲900°C以上、溫度T3爲 1 000°C 以上。 2 3 .如申請專利範圍第1 9項之ΠI族氮化物半導體結晶 之製造方法，其中於第i製程，有機金屬原料之熱分 546850 六、申請專利範圍 解在氫氣環境中進行。 24 .如申請專利範圍第1 9項之I Π族氮化物半導體結晶 之製造方法，其中堆積於藍寶石基板上之金屬1成粒 狀。 2 5 .如申請專利範圍第24項之11 I族氮化物半導體結晶 之製造方法，其中自粒狀金屬1之基板表面至粒子之 頂點的高度爲50A以上1 000A以下。 2 6 .如申請專利範圍第1 9項之11 I族氮化物半導體結晶 之製造方法，其中包含於第2製程氮化金屬1者由多 結晶所成、且該多結晶含有氮與金屬之化學量論比非 爲 1: 1 之區域範圍（InuGavAlwNk、惟 u + v + w=l、0Su 、v、w$l、0&lt;k&lt;l)。 27. 如申請專利範圍第19項之III族氮化物半導體結晶 之製造方法，其中更在該藍寶石基板上含有，形成氮 化鎵系化合物半導體之成長速度慢的光罩層之製程， 用來選擇性成長氮化鎵系化合物半導體。 28. 如申請專利範圍第27項之m族氮化物半導體結晶之 製造方法，其中形成在基板上的光罩層，係由氮化鎵 系化合物半導體之成長速度慢的材料構成的部分與由 氮化鎵系化合物半導體之成長速度快的材料構成的部 分所成。 29 ·如申請專利範圍第27項之ΠΙ族氮化物半導體結晶之 製造方法，其中該光罩層之形成製程，係與成長氮化 546850 六、申請專利範圍 鎵系化合物半導體相同的裝置內進行。 3 0 ·如申請專利範圍第27項之m族氮化物半導體,結晶之 製造方法，其中該光罩層之形成，係在加熱的藍寶5 基板上進行流通含S i氣體原料之氣體。 3 1 ·如申請專利範圍第27項之m族氮化物半導體結晶之 製造方法，其中該光罩層之形成，係在加熱的藍寶石 基板上進行同時流通含S i氣體原料之氣體與氨。 3 2 ·如申請專利範圍第27項之ΙΠ族氮化物半導體結晶之 製造方法，其中含有所形成的光罩層、構成光罩層之 材料爲‘覆蓋藍寶石面之部分與露出藍寶石面之部分。 3 3·如申請專利範圍第27項之m族氮化物半導體結晶之 製造方法，其中該光罩層之形成，係在加熱的基板上 问時流通含有III族兀素氣體原料之热體與含S i氣 體原料之氣體。 3 4 . —種I I I族氮化物半導體結晶之製造方法，其特徵 爲包含第1製程，供應I I I族金屬原料於加熱的基板 、在該基板上堆積III族金屬原料及/或其分解生成 物；第2製程，其後使該基板在含有氮氣源之環境中 熱處理；以及第3製程，其後使用I Π族金屬原料 與氮源使11 I族氮化物半導體（I I I族氮化物半導體以 InxGayAlzN 表示，惟 x + y + z = l、0Sx€l、0Sy$l、0 $ z S 1 )在該基板上以氣相法成長。 3 5 .如申請專利範圍第3 4項之Π I族氮化物半導體結晶 546850 六、申請專利範圍 之製造方法，其中在基板上成長的I 11族氮化物半導 體結晶之表面具有成（0001)面之面方位、且該表面之 垂直軸自&lt;000 1 &gt;方向傾斜於特定的方向。 3 6 ·如申請專利範圍第3 5項之11 I族氮化物半導體結晶 之製造方法，其中特定之方向爲&lt;11-20&gt;方向、且自 &lt;〇〇〇1&gt;方向的傾斜角度爲0.2°〜15° 。 3 7 ·如申請專利範圍第34項之m族氮化物半導體結晶之 製造方法，其中在該藍寶石基板上更含有，形成氮化 鎵系化合物半導體之成長速度慢的光罩層之製程，以 選擇性成長氮化鎵系化合物半導體。 3 8 ·如申請專利範圍第37項之]π族氮化物半導體結晶之 製造方法，其中在基板上形成的光罩層，係由氮化鎵 系化合物半導體之成長速度慢的材料構成的部分與由 S化鎵系化合物半導體之成長速度快的材料構成的部 分所成。 ° ·妃申請專利範圍第37項之ΠΙ族氮化物半導體結晶之 製造方法，其中該光罩層之形成製程，係與氮化鎵系 化合物半導體成長相同的裝置內進行。 • j，如申請專利範圍第37項之m族氮化物半導體結晶之 k is方法，其中該光罩層之形成，係在加熱的藍寶石 :基板上流通含S i氣體原料之氣體F進行。 :如申請專利範圍第37項之]Π族氮化物半導體結晶之 _造方法，其中該光罩層之形成，係在加熱的藍寶石 546850 六、申請專利範圍 基板上同時流通含s i氣體原料之氣體與氨來進行。 4 2 ·如申請專利範圍第3 7項之瓜族氮化物半導體結晶之 製造方法，其中含所有形成的光罩層、構成光罩層之 材料覆蓋於藍寶石面之部分與露出藍寶石面之部分。 4 3 ·如申請專利範圍第37項之瓜族氮化物半導體結晶之 製造方法，其中該光罩層之形成係在加熱的基板上同 Si氣體 其在基板 時流通含有11 I族元素氣料之氣體與含 原料之氣體。 _ 4 4 · 一種氮化鎵系化合物半導造方法， 上成長氮化鎵系化合物半導體·•結晶層所成，其特徵爲 包含： 第1製程，在基板上附著金屬核； 第2製程：退火該金屬核； 第3製程：使退火後之金屬核氮化以形成成長核； 以及 第4 _程迁具有成長核的基板上成長氮化鎵系化合 物作成氮化鎵系化合物半導體結晶層。 45·如申請專利範圍第44項之氮化鎵系化合物半導體結 晶之製造方法：其中該基板爲藍寶石基板。 …如申請專利範圍第44項之氮化鎵系化合物半導體結 晶之製造方法5其中第1製程，係在加熱的基板上流 含有機金屬原料之蒸氣且不含氮源的氣體來附著金 雾r。 546850 六 申請專利範圍 47 .如申請專利範圍第44項之氮化鎵系化合物半導體結 晶之製造方法，其中該有機金屬原料之蒸氣，係至少 一種含鎵之有機金屬原料、含鋁之有機金屬原料、及 含銦之有機金屬原料中之有機金屬原料之蒸氣。 4 8 .如申請專利範圍第44項之氮化鎵系化合物半導體結 晶之製造方法，其中該第2製程，係在不含氮源及有 機金屬原料之蒸氣、僅流通載運氣體進行退火金屬核 〇 49 .如申請專利範圍第44項之氮化鎵系化合物半導體結 晶之製造方法，其中該第3製程，係流通含有氮源、 且不含有機金屬原料之蒸氣的氣體來進行以使金屬核 之氮化。 5 0 .如申請專利範圍第44項之氮化鎵系化合物半導體結 晶之製造方法，其中該第4製程係流通含有氮源與有 機金屬原料兩者之氣體、由有機金屬氣相成長法成長 氮化鎵系化合物半導體。 51.如申請專利範圍第44或48項之氮化鎵系化合物半 導體結晶之製造方法，其中該第2製程在第1製程之 溫度以上的溫度進行。 5 2.如申請專利範圍第44或49項之氮化鎵系化合物半 導體結晶之製造方法，其中該第3製程在第2製程之 溫度以上的溫度進行。 5 3 .如申請專利範圍第44或50項之氮化鎵系化合物半546850 Nichijo / Shi Zhi / Supplementary Sixth, Patent Application No. 901 1976 6 "Manufacturing method of Group III nitride semiconductor crystal, manufacturing method of nitrided compound semiconductor, gallium nitride compound semiconductor, nitride "Gallium-based compound semiconductor light-emitting element and light source using the semiconductor light-emitting element" patent case (amended on February 21, 1992) Six applications for patent scope: 1 · A method for manufacturing a group III nitride semiconductor crystal, which is characterized by: In the first process, fine particles of a group III metal are deposited on the surface of the substrate; in the second process, the fine particles are nitrided in an environment containing a nitrogen source; The phase growth method forms a group 11 nitride semiconductor (Π) [group nitride semiconductor is represented by InxGayAlzN, but x + y + z = i, x S = 0 'y S 1, 0 S z S 1) crystal. 2. The manufacturing method of the i π group nitride semiconductor crystal according to item 1 of the scope of the patent application, wherein the substrate is sapphire (A1203). 3. The manufacturing method of the Group I / N nitride semiconductor crystal as described in item 1 of the scope of patent application, wherein the Group III metal is InuGavAlw (but u + v + w = l, 0 ^ u $ 1, OSv ^ l, OSw ^ l ). 4. The manufacturing method of the I π group nitride semiconductor crystal according to item 1 of the scope of patent application, wherein fine particles of the group 111 metal are deposited by thermal decomposition of an organic metal raw material. 5. The manufacturing method of I π group nitride semiconductor crystal according to item 1 of the scope of patent application, wherein the first process is performed in an environment containing no nitrogen source. 546850 6. Scope of patent application 6. For the manufacturing method of I I Group I nitride semiconductor crystals under the scope of patent application No. 1 or 5, wherein the first process is performed at a temperature above the melting point of the aforementioned Group 111 metal. 7. The manufacturing method of the Group I and II nitride semiconductor crystals according to item 1 of the scope of patent application, wherein the second process is performed in an environment containing no metal raw materials. 8 · If the scope of patent application is the first! In the method of manufacturing an I I group nitride semiconductor crystal according to the item, the second process is performed at a temperature equal to or higher than the temperature of the first process. 9. The manufacturing method of the I I group I nitride semiconductor crystal according to item i of the patent application range, wherein the third process is performed at a temperature higher than the temperature of the second process. 10. The method for producing a group III nitride semiconductor crystal according to item 1 of the scope of patent application, wherein the vapor phase growth method is an organic metal chemical vapor phase growth method. 1 1 · The method for manufacturing a group 111 nitride semiconductor crystal according to item 1 of the scope of patent application, in which the particles of the group 111 metal are nitrided in the second process by the polycrystalline and / or amorphous group of the group 11 nitride. And contains unreacted metals. 1 2. The method for manufacturing a group III nitride semiconductor crystal according to item 1 of the scope of patent application, wherein the sapphire substrate further includes a process for forming a photoresist layer with a slow growth rate of a gallium nitride compound semiconductor to selectively Growing a gallium nitride-based compound semiconductor. 546850 ^, patent application range 1 · As in the method for manufacturing m-type nitride semiconductor crystals in the patent application item No. 12, wherein the photomask layer formed on the substrate is made of a gallium nitride-based compound, the annual conductor grows. A portion made of a slow material is made of a material made of a gallium nitride-based compound semiconductor with a high growth rate. 14. The method for manufacturing an m-type nitride semiconductor crystal according to item 12 of the scope of the patent application, wherein the formation process of the photomask layer is performed in the same growth device as the gallium nitride-based compound semiconductor. 15 · The method for manufacturing a π-nitride semiconductor crystal according to item 12 of the patent application range, wherein the formation of the photomask layer is performed by heating a sapphire through a gas containing a Si gas source on the substrate. 1 6. If the scope of patent application is the first! The method for manufacturing a group m nitride semiconductor crystal according to item 2, wherein the mask layer is formed by simultaneously flowing a gas containing Si gas and ammonia on the heated sapphire substrate_h. 1 '/ · A method for manufacturing a cucurbit nitride semiconductor crystal according to item 12 of the patent application scope, which includes the formed photomask layer, and the material constituting the photomask layer is a portion covering the sapphire surface and a portion exposing the sapphire surface. ig, for example, a method for fabricating a m-type nitride semiconductor crystal according to item 12 of the application, wherein the formation of the photomask layer is performed on a heated substrate while simultaneously flowing a gas containing 111 element gas and S i Gas The gas of the raw material. . · A method for manufacturing a group III nitride semiconductor crystal, which is characterized in that it includes the first process, in a nitrogen-free environment, at least 546850 is used. 6. There is a metal element of In, Ga, and A1 in the scope of patent application. Thermal decomposition of organic metal raw materials, at least one metal 1 made of In, Ga, and A1 on a sapphire substrate (metal 1 is represented by InuGavAlw, but u + v + w = l, 〇 $ u € l, OSvSl 〇SwSl), deposited at a temperature T1 above the melting point of the metal 1; the second process, after the first process, in a nitrogen-free environment containing no organic metal raw materials, at a temperature of T2 (but T2-T1) nitrogen And a third process, after the second process, a Group III nitride semiconductor (Group III) is formed on a sapphire substrate on which Metal 1 is deposited at a temperature T3 (but T3 2 T2) by an organometallic chemical vapor growth method. The nitride semiconductor is represented by InxGayAlzN, but x + y + z = 1, OSxSl, OgySl, and OSzSl) are epitaxially grown. 20. The method for manufacturing a group 111 nitride semiconductor crystal according to item i 9 of the scope of patent application, wherein the sapphire substrate has a (0001) plane, and the vertical axis of the (000 1) plane is inclined from the &lt; 〇00〇1 &gt; direction In a specific direction. 2 1. The method for manufacturing a group 111 nitride semiconductor crystal according to item 20 of the scope of the patent application, wherein the specific direction is a &lt; 1-1〇〇 &gt; direction, and an angle inclined from the &lt; 000 1 &gt; direction is 〇 2 ° ~ 15. . 22 · If the method for manufacturing a 111-nitride semiconductor crystal according to item 19 of the patent application scope, wherein the temperature T1 is 900 ° C or higher and the temperature T3 is 1 000 ° C or higher. 2 3. For the manufacturing method of Group I nitride semiconductor crystals according to item 19 of the scope of patent application, in the i-th process, the thermal analysis of the organometallic raw material 546850 6. The scope of the patent application is carried out in a hydrogen environment. 24. The method for manufacturing a group I / N nitride semiconductor crystal according to item 19 of the scope of patent application, wherein the metal 1 deposited on the sapphire substrate is granulated. 25. The method for manufacturing a Group I nitride semiconductor crystal according to item 24 of the patent application, wherein the height from the surface of the substrate of the granular metal 1 to the vertex of the particle is 50A or more and 1,000A or less. 26. The method for manufacturing a Group I nitride semiconductor crystal according to item 19 of the patent application, wherein the nitrided metal 1 contained in the second process is made of polycrystals, and the polycrystal contains a chemical of nitrogen and metal. Quantitative ratios other than 1: 1 (InuGavAlwNk, u + v + w = l, 0Su, v, w $ l, 0 &lt; k &lt; l). 27. For example, a method for manufacturing a group III nitride semiconductor crystal according to item 19 of the scope of application for a patent, wherein the sapphire substrate further includes a process for forming a photomask layer with a slow growth rate of a gallium nitride compound semiconductor, and is used for selection. Growth of GaN-based compound semiconductor. 28. For example, a method for manufacturing a group m nitride semiconductor crystal according to item 27 of the patent application, wherein the photomask layer formed on the substrate is composed of a slow-growth material of a gallium nitride-based compound semiconductor and nitrogen. A gallium-based compound semiconductor is made of a material made of a fast-growing material. 29. For example, the manufacturing method of group III nitride semiconductor crystals under the scope of patent application No. 27, in which the formation process of the photomask layer is performed in the same device as the growth nitride nitride 546850 6. The scope of patent application of gallium-based compound semiconductor. 30. The manufacturing method of m-type nitride semiconductors and crystals according to item 27 of the scope of patent application, wherein the formation of the photomask layer is performed by circulating a gas containing Si gas on the heated Sapphire 5 substrate. 3 1 · The method for manufacturing a group m nitride semiconductor crystal according to item 27 of the patent application, wherein the formation of the photomask layer is performed on a heated sapphire substrate by simultaneously flowing a gas containing Si gas and ammonia. 3 2 · The method for manufacturing a group III nitride semiconductor crystal according to item 27 of the patent application scope, which contains the formed photomask layer and the material constituting the photomask layer is ‘the part covering the sapphire surface and the part exposing the sapphire surface. 3 3. The method for manufacturing a group m nitride semiconductor crystal according to item 27 of the scope of the patent application, wherein the photomask layer is formed by circulating a hot body containing a group III element gas raw material and The gas of the Si gas source. 3 4. A method for manufacturing a group III nitride semiconductor crystal, comprising a first process, supplying a group III metal raw material to a heated substrate, and depositing a group III metal raw material and / or a decomposition product thereof on the substrate; In the second process, the substrate is heat-treated in an environment containing a nitrogen source; and in the third process, 11 I-nitride semiconductors (I-nitride semiconductors are represented by InxGayAlzN using a group I metal raw material and a nitrogen source). , Except that x + y + z = l, 0xxl, 0Sy $ l, 0 $ zS1) are grown on the substrate in a vapor phase method. 35. For example, the Group III nitride semiconductor crystal of the scope of application for patent No. 34, 546850 6. The manufacturing method for the scope of patent application, wherein the surface of the group I11 nitride semiconductor crystal grown on the substrate has a (0001) plane And the vertical axis of the surface is inclined from the &lt; 000 1 &gt; direction to a specific direction. 3 6 · If the method for manufacturing a Group I nitride semiconductor crystal according to item 35 of the patent application scope, the specific direction is the &lt; 11-20 &gt; direction, and the inclination angle from the &lt; 〇〇〇1 &gt; direction is 0.2 ° ~ 15 °. 3 7 · If the method for manufacturing a group m nitride semiconductor crystal according to item 34 of the application for a patent, wherein the sapphire substrate further contains a process for forming a photomask layer with a slow growth rate of the gallium nitride-based compound semiconductor, select Growth of GaN-based compound semiconductor. 3 8 · The method for manufacturing a π-group nitride semiconductor crystal according to item 37 of the scope of the patent application, wherein the photomask layer formed on the substrate is a part composed of a gallium nitride-based compound semiconductor with a slow growth rate and It is made of a gallium-based compound semiconductor that has a fast-growing material. ° · The manufacturing method of Group III nitride semiconductor crystals under the scope of patent application No. 37, wherein the formation process of the photomask layer is performed in the same device as the growth of the gallium nitride-based compound semiconductor. • j, as in the k is method for crystallizing a group m nitride semiconductor in item 37 of the patent application, wherein the formation of the photomask layer is performed by flowing a gas F containing Si gas raw material on a heated sapphire: substrate. : For example, in the scope of patent application No. 37] The manufacturing method of group III nitride semiconductor crystals, wherein the formation of the photomask layer is based on heated sapphire 546850. 6. The gas in the scope of patent application simultaneously circulates the gas containing si gas raw materials. With ammonia. 4 2 · The manufacturing method of the cucurbit nitride semiconductor crystal according to item 37 of the patent application scope, which includes all the formed photomask layers, the parts constituting the photomask layer covering the sapphire surface and the part exposing the sapphire surface. 4 3 · The manufacturing method of melons nitride semiconductor crystals according to item 37 of the application, wherein the photomask layer is formed on a heated substrate with Si gas, which flows through the substrate containing 11 I element gas. Gases and gases containing raw materials. _ 4 4 · A gallium nitride-based compound semiconducting manufacturing method, which is formed by growing a gallium nitride-based compound semiconductor and a crystal layer, which includes: a first process, attaching a metal core to a substrate; a second process: Annealing the metal core; the third process: nitriding the annealed metal core to form a growing core; and the fourth step is to grow a gallium nitride-based compound on the substrate having the growing core to form a gallium nitride-based compound semiconductor crystal layer. 45. The method for manufacturing a gallium nitride-based compound semiconductor crystal according to item 44 of the scope of application: wherein the substrate is a sapphire substrate. … For the manufacturing method 5 of gallium nitride-based compound semiconductor crystals in the 44th area of the patent application, the first process involves flowing a gas containing organic metal raw material vapor and containing no nitrogen source to attach gold mist r on a heated substrate. 546850 Six applications for patent scope 47. The manufacturing method of gallium nitride-based compound semiconductor crystals according to item 44 of the patent application scope, wherein the vapor of the organic metal raw material is at least one organic metal raw material containing gallium and organic metal raw material containing aluminum , And vapors of organometallic materials in indium-containing organometallic materials. 48. The method for manufacturing a gallium nitride-based compound semiconductor crystal according to item 44 of the scope of the patent application, wherein the second process is to anneal the metal core in a vapor containing no nitrogen source and organic metal raw materials, and only carrying a carrier gas. 49. The method for manufacturing a gallium nitride-based compound semiconductor crystal according to item 44 of the scope of patent application, wherein the third process is performed by flowing a gas containing a nitrogen source and containing no organic metal raw material vapor to make the metal core Nitriding. 50. The method for manufacturing a gallium nitride-based compound semiconductor crystal according to item 44 of the scope of patent application, wherein the fourth process is to circulate a gas containing both a nitrogen source and an organic metal raw material, and grow nitrogen by an organic metal vapor phase growth method. Gallium-based compound semiconductor. 51. The method for manufacturing a gallium nitride-based compound semiconductor crystal according to claim 44 or 48, wherein the second process is performed at a temperature higher than the temperature of the first process. 5 2. The method for producing a crystal of a gallium nitride-based compound semiconductor according to item 44 or 49 of the scope of patent application, wherein the third process is performed at a temperature higher than the temperature of the second process. 5 3. If the gallium nitride-based compound in the 44th or 50th of the scope of patent application 546850 、申請專利範圍 導體結晶之製造方法，其中該第4製程在第3製程之 溫度以上的溫度進行。 5 4 .如申請專利範圍第44項之氮化鎵系化合物半導體結 晶之製造方法，其中該第1製程與第2製程交互進行 2次以上後、進行第3製程。 5 5 .如申請專利範圍第44項之氮化鎵系化合物半導體結 晶之製造方法，其中該第1製程與第2製程與第3製 程重複進行2次以上後、進行第4製程。 5 6 .如申請專利範圍第44項之氮化鎵系化合物半導體結 晶之製造方法，其中該第1製程，係由流通通含有至 少一種含鋁之有機金屬原料、含鎵之有機金屬原料及 含銦之有機金屬原料中之有機金屬原料之蒸氣的氣體 之前期製程、及流通含有與該前期製程不同的有機金 屬原料之蒸氣的氣體之後期製程兩製程所成。 5 7 .如申請專利範圍第5 5項之氮化鎵系化合物半導體結 晶之製造方法，其中該第1製程，係相互進行前期製 程與後期製程，2次以上之製程、其後再進行第2製 程。 5 8 .如申請專利範圍第44項之氮化鎵系化合物半導體結 晶之製造方法，其中該成長核，係爲具與基板平行， 平坦的頂面與平坦的側面之大致梯形狀的氮化物半導 體結晶。 5 9 .如申請專利範圍第44項之氮化鎵系化合物半導體結 -10- 546850 六、申請專利範圍 晶之製造方法，其中在該第4製程形成的氮化鎵系化 合物半導體結晶層上依序成長別的氮化鎵系化合物半 導體結晶層。 6 0 ·如申g靑專利範圍第4 4項之氮化鎵系化合物半導體結 晶之製造方法，其中在該藍寶石基板上更含有，形成 氮化鎵系化合物半導體之成長速度慢的光罩層之製程， 以選擇性成長氮化鎵系化合物半導體。 6 1 ·如申請專利範圍第60項之氮化鎵系化合物半導體結 晶之製造方法，其中形成在基板上的光罩層，係由氮 化鎵系化合物半導體之成長速度慢的材料構成的部分 與由氮化鎵系化合物半導體之成長速度快的材料構成 的部分所成。 6 2 ·如申請專利範圍第60項之氮化鎵系化合物半導體結 晶之製造方法，其中該光罩層之形成製程，係與成長 氮化鎵系化合物半導體相同的裝置內進行。 6 3 ·如申請專利範圍第60項之氮化鎵系化合物半導體結 晶之製造方法，其中形成該光罩層製程，係在加熱的 藍寶石基板上進行流通含Sl氣體原料之氣體來進行 〇 64.如申請專利範圍第60項之氮化鎵系化合物半導體結 晶之製造方法，其中形成該光罩層，係在加熱的藍寶 石基板上同時流通含Si氣體原料之氣體與氨來進行 0 -11 - 546850 六、申請專利範圍 6 5 ·如申請專利範圍第6〇項之氮化鎵系化合物半導體結 曰曰曰之製造方法，其中包含所形成的光罩層、構成光罩 層之材料覆蓋於藍寶石面之部分與露出藍寶石面之部 分。 66 ·如申請專利範圍第6〇項之氮化鎵系化合物半導體結 晶之製造方法，其中該光罩層之形成，在加熱的基板 上同時流通含有I丨丨族元體原料之氣體與含S i 氣體原料之氣體。 67 · —種氮化鎵系化合物半導製造方法，其係於基板 上成長氮化鎵系化合物半導^結晶層，其特徵爲包含 第1製程’由至少含一種含鋁之有機金屬原料、含 鎵之有機金屬原料及含銦之有機金屬原料的有機金屬 原料之蒸氣的氣體流通基板上的前製程、第1製程含 有與該前期製程不同的有機金屬原料之蒸氣的氣體流 通於基板上的後期製程等兩個製程所成、將金屬核附 著於基板上； 第2製程，氮化該金屬核來形成成長核，以及 桌3製程’在具有成長核之基板上成長氮化鎵系化 合物作成氮化鎵系化合物半導體結晶層。 6 8 ·如申請專利範圍第6 7項之氮化鎵系化合物半導體結 日日之製方法，其中基板爲監寶石基板。 6 9 ·如申請專利範圍第6 7項之氮化鎵系化合物半導體結 -12- 546850 t、申請專利範圍 晶之製造方法，其中該第1製程，係使前期製程與後 期製程相互進行2次以上之製程、其後進行第2製程 〇 7〇.如申請專利範圍第67項之氮化鎵系化合物半導體結 晶之製造方法，其中進行該第1製程與第2製程相互 2次以上後、進行第3製程。 7 1 .如申請專利範圍第67項之氮化鎵系化合物半導體結 晶之製造方法，其中該第1製程，係在加熱的基板上 流通含有有機金屬原料之蒸氣且不含氮源之氣體來進 行附著金屬核。 7 2 .如申請專利範圍第67項之氮化鎵系化合物半導體結 晶之製造方法，其中該第2製程，係流通含有氮源且 不含有機金屬原料之蒸氣的氣體來進行氮化金屬核。 7 3 .如申請專利範圍第67項·之氮化鎵系化合物半導體結 晶之製造方法，其中該第3製程，係流通含有氮源與 有機金屬原料兩者的氣體、藉由金屬氣相成長法成長 氮化鎵系化合物半導體。 7 4 .如申請專利範圍第67或72項之氮化鎵系化合物半 導f:1結晶之製造方法，其中將該第2製程在第1製程 之溫度以上的溫度下進行。 如申請專利範圍第67或73項之氮化鎵系化合物半 導體結晶之製造方法，其中將該第3製程以第2製程 2滔度以上的溫度進行。 546850 、申請專利範圍 7 6 .如申請專利範圍第67項之氮化鎵系化合物半導體結 晶2製造方法，其中該成長核，係具與基板平行、平 坦的頂面與平坦的側面之大致梯形狀的I丨]；族氮化物 半導體結晶。 7 7 ·如申請專利範圍第67項之氮化鎵系化合物半導體結 晶之製造方法，其中包含第4製程在第3製程形成的 氮化鎵系化合物半導體結晶層上依序成長其他的氮化 鎵系化合物半導體結晶層。 7 8 ·如申請專利範圍第67項之氮化鎵系化合物半導體結 晶之製造方法，其中更在該藍寶石基板上含有，形成 氮化鎵系化合物半導體之成長速度慢的光罩層之第5 製程，以選擇性成長氮化鎵系化合物半導體。 7 9 ·如申請專利範圍第7 8項之氮化鎵系化合物半導體結 晶之製造方法，其中形成在基板上的光罩層，係由氮 化鎵系化合物半導體之成長速度慢的材料構成的部分 與由氮化鎵系化合物半導體之成長速度快的材料構成 的部分所成。 8 0 .如申請專利範圍第7 8項之氮化鎵系化合物半導體結 晶之製造方法，其中形成該光罩層之製程，係與成長 氮化鎵系化合物半導體相同的裝置內進行。 8 1 ·如申請專利範圍第7 8項之氮化鎵系化合物半導體結 晶之製造：方法，其中該光罩層之形成，係在經加熱的 藍寶石基板上流通含Si氣體原料之氣體進行。 -14- 546850 六、申請專利範圍 8 2 ·如申請專利範圍第78項之氮化鎵系化合物半導體結 晶之製造方法，其中該光罩層之形成，係在經加熱的 藍寶石基板上同時流通含Si氣體原料之氣體與氨來 進行。 8 3 .如申請專利範圍第78項之氮化鎵系化合物半導體結 晶之製造方法，其中形成的光罩層、含有構成光罩層 之材料覆蓋藍寶石面之部分與露出藍寶石面之部分。 84 ·如申請專利範圍第78項之氮化鎵系化合物半導體結 晶之製造方法，其中該光罩層之形成，係在加熱的基 板上同時流通含有I 11族元素氣體原料之氣體與含S i 氣'料之氣體。 8 5 ·如利範圍第44或67項之氮化鎵系化合物半 導製造方法’其中該氮化鎵系化合物半導體結晶 層乍半導體發光元件的光源。 -15-546850, Patent application scope A method for manufacturing a conductor crystal, wherein the fourth process is performed at a temperature higher than the temperature of the third process. 54. The method for manufacturing a gallium nitride-based compound semiconductor crystal according to item 44 of the scope of the patent application, wherein the first process and the second process are performed twice or more and then the third process is performed. 5 5. The method for manufacturing a gallium nitride-based compound semiconductor crystal according to item 44 of the scope of patent application, wherein the first process, the second process, and the third process are repeated twice or more, and then the fourth process is performed. 56. The method for manufacturing a gallium nitride-based compound semiconductor crystal according to item 44 of the scope of the patent application, wherein the first process is performed by circulation through containing at least one aluminum-containing organic metal raw material, gallium-containing organic metal raw material, and The indium organic metal raw material is composed of two processes, namely, a gaseous process of a vapor of an organometallic material and a gaseous process containing a vapor of an organometallic material different from the previous process. 57. The method for manufacturing a gallium nitride-based compound semiconductor crystal according to item 55 of the scope of patent application, wherein the first process is a pre-process and a post-process each other, a process of two or more times, and then a second process Process. 58. The method for manufacturing a gallium nitride-based compound semiconductor crystal according to item 44 of the scope of patent application, wherein the growth core is a nitride semiconductor having a substantially ladder shape parallel to the substrate, a flat top surface and a flat side surface. crystallization. 5 9. For example, the gallium nitride-based compound semiconductor junction No. 44 of the scope of patent application -10- 546850 6. The manufacturing method of the scope of patent application, wherein the gallium nitride-based compound semiconductor crystal layer formed in the fourth process is formed on the basis of Another GaN-based compound semiconductor crystal layer is sequentially grown. 60. The method for manufacturing a gallium nitride-based compound semiconductor crystal according to item 44 of the patent scope, which is further contained on the sapphire substrate to form a photomask layer with a slow growth rate of the gallium nitride-based compound semiconductor. A process for selectively growing a gallium nitride-based compound semiconductor. 6 1 · The manufacturing method of a gallium nitride-based compound semiconductor crystal according to item 60 of the patent application, wherein the photomask layer formed on the substrate is a part composed of a material with a slow growth rate of the gallium nitride-based compound semiconductor and It is made of gallium nitride-based compound semiconductor. 6 2 · The method for manufacturing a gallium nitride-based compound semiconductor crystal according to item 60 of the application, wherein the formation process of the photomask layer is performed in the same device as the growth of the gallium nitride-based compound semiconductor. 6 3 If the method for manufacturing a gallium nitride-based compound semiconductor crystal according to item 60 of the application for a patent, wherein the process of forming the photomask layer is performed by flowing a gas containing an Sl gas source material on a heated sapphire substrate. 64. For example, a method for manufacturing a gallium nitride-based compound semiconductor crystal with the scope of application for patent No. 60, wherein the photomask layer is formed, and the Si-containing raw material gas and ammonia are simultaneously flowed on the heated sapphire substrate to carry out 0 -11-546850 6. Scope of Patent Application 6 5 · The manufacturing method of gallium nitride-based compound semiconductor junction according to item 60 of the patent application scope, which includes the formed photomask layer and the material constituting the photomask layer covering the sapphire surface. And the part where the sapphire surface is exposed. 66. The method for manufacturing a gallium nitride-based compound semiconductor crystal according to item 60 of the patent application scope, wherein the photomask layer is formed by simultaneously flowing a gas containing an I 丨 丨 group element raw material and an S-containing material on a heated substrate. i Gas of raw materials. 67. A method for manufacturing a gallium nitride-based compound semiconductor, which comprises growing a gallium nitride-based compound semiconducting ^ crystal layer on a substrate, and is characterized in that it comprises a first process' from at least one organic metal raw material containing aluminum, The first and first processes of the gas flow of the vapor of the organometallic material containing gallium and the organometallic material of the indium-containing organometallic material flow through the substrate. Post-process and other two processes, the metal core is attached to the substrate; the second process, the metal core is nitrided to form a growth core, and the table 3 process' gallium nitride-based compounds are grown on a substrate with a growth core A gallium nitride-based compound semiconductor crystal layer. 6 8 · The manufacturing method of gallium nitride-based compound semiconductors according to item 67 of the patent application, wherein the substrate is a gemstone substrate. 6 9 · For the gallium nitride-based compound semiconductor junction in the scope of patent application No. 67, -12- 546850 t, the manufacturing method of the scope of patent application, in which the first process is to make the pre-process and the post-process twice each other. The above process, and then the second process 〇 07. The manufacturing method of the gallium nitride-based compound semiconductor crystal of the 67th scope of the application for a patent, wherein the first process and the second process are performed two or more times, and then The third process. 7 1. The method for manufacturing a gallium nitride-based compound semiconductor crystal according to item 67 of the patent application scope, wherein the first process is performed by flowing a vapor containing an organic metal raw material and a nitrogen source-free gas on a heated substrate Attach a metal core. 72. The method for manufacturing a gallium nitride-based compound semiconductor crystal according to item 67 of the patent application scope, wherein the second process is performed by flowing a gas containing a nitrogen source and containing no vapor of an organic metal raw material to perform metal nitride. 7 3. The method for manufacturing a gallium nitride-based compound semiconductor crystal according to item 67 of the scope of the patent application, wherein the third process is to circulate a gas containing both a nitrogen source and an organic metal raw material by a metal vapor phase growth method. Growing a gallium nitride-based compound semiconductor. 74. The method for manufacturing a f: 1 crystal of a gallium nitride-based compound semiconductor according to claim 67 or 72, wherein the second process is performed at a temperature equal to or higher than the temperature of the first process. For example, a method for manufacturing a gallium nitride-based compound semiconductor crystal with a scope of patent application No. 67 or 73, wherein the third process is performed at a temperature of 2 degrees or more in the second process. 546850, patent application scope 7 6. The manufacturing method of gallium nitride-based compound semiconductor crystal 2 according to item 67 of the patent application scope, wherein the growth core has a substantially trapezoidal shape parallel to the substrate, a flat top surface and a flat side surface. I 丨]; Group nitride semiconductor crystals. 7 7 · The method for manufacturing a gallium nitride-based compound semiconductor crystal according to item 67 of the patent application scope, which includes the fourth process to sequentially grow other gallium nitride on the gallium nitride-based compound semiconductor crystal layer formed in the third process. A compound semiconductor crystal layer. 7 8 · The fifth method of manufacturing a gallium nitride-based compound semiconductor crystal manufacturing method according to item 67 of the patent application, which is further included on the sapphire substrate to form a photomask layer with a slow growth rate. To selectively grow gallium nitride-based compound semiconductors. 7 9 · The method for manufacturing a gallium nitride-based compound semiconductor crystal according to item 7 of the scope of patent application, wherein the photomask layer formed on the substrate is a part composed of a material having a slow growth rate of the gallium nitride-based compound semiconductor. It is formed by a part made of a gallium nitride-based compound semiconductor with a high growth rate. 80. The method for manufacturing a gallium nitride-based compound semiconductor crystal according to item 78 of the patent application scope, wherein the process of forming the photomask layer is performed in the same device as the growth of the gallium nitride-based compound semiconductor. 8 1 · Manufacturing of a gallium nitride-based compound semiconductor crystal according to item 7 of the scope of patent application: Method, wherein the formation of the photomask layer is performed by flowing a gas containing Si gas raw material on a heated sapphire substrate. -14- 546850 VI. Application for patent scope 8 2 · If the method for manufacturing gallium nitride-based compound semiconductor crystals under the scope of patent application No. 78, wherein the photomask layer is formed on a heated sapphire substrate, The Si gas source gas and ammonia were used. 8 3. The method for manufacturing a gallium nitride-based compound semiconductor crystal according to item 78 of the scope of the patent application, wherein the formed photomask layer, the portion containing the material constituting the photomask layer covers the sapphire surface, and the portion exposing the sapphire surface. 84. The method for manufacturing a gallium nitride-based compound semiconductor crystal according to item 78 of the application, wherein the photomask layer is formed by simultaneously flowing a gas containing a group I 11 element-containing gas source material and a Si on a heated substrate. Gas 8 5 · A method for manufacturing a gallium nitride-based compound semiconductor according to item 44 or 67 of the invention, wherein the gallium nitride-based compound semiconductor crystal layer is a light source for a semiconductor light-emitting element. -15-
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