TW393786B - Method for manufacturing an epitaxial chip - Google Patents

Method for manufacturing an epitaxial chip Download PDF

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TW393786B
TW393786B TW087104571A TW87104571A TW393786B TW 393786 B TW393786 B TW 393786B TW 087104571 A TW087104571 A TW 087104571A TW 87104571 A TW87104571 A TW 87104571A TW 393786 B TW393786 B TW 393786B
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gas
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TW087104571A
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Min Shr
Shr-Shiung Jan
Jian-Shin Tzeng
Jeng-Da Guo
Wei-Jr Lai
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Min Shr
Jan Shr Shiung
Tzeng Jian Shin
Guo Jeng Da
Lai Wei Jr
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Priority to TW087104571A priority Critical patent/TW393786B/zh
Priority to US09/102,675 priority patent/US6110809A/en
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Publication of TW393786B publication Critical patent/TW393786B/zh

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    • 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
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • C30B29/403—AIII-nitrides
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/10—Inorganic compounds or compositions
    • C30B29/40—AIIIBV compounds wherein A is B, Al, Ga, In or Tl and B is N, P, As, Sb or Bi
    • C30B29/403—AIII-nitrides
    • C30B29/406—Gallium nitride
    • 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
    • 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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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Description

Λ7 Λ7 ^濟部中央標率局貝工消资合作，iL印^; 五、發明説明（1 ) 發明背景 〇本發明係關於-種磊晶片的製造方法，尤其是關於一種 可作馬雷射二極體基板之三族金屬氮化物磊晶片的製造方 法。 过一五狹氮化物的研究在近年來受到相當大的矚目，尤其 ::日本日亞化學公司在1993年宣稱高亮度藍光發光二極 二將進入量產後，才目關研究多集中在發光二極體的研究而 田射一極體雖有突破，但是没有晶，格匹配的基板來降低其 缺陷治、度，一直是個研究瓶頸。.二般成長在氧化鋁基板上 的氮化鎵，因晶格匹配的差異高達14%，因此氣化嫁羞晶 層内的缺1¾法度約1〇7-丨。咖-2，無法用來當作雷射二極體咖代 layer ’即使近來氮化鎵雷射二極體巳被研製出來，但其生 叩週期過短，仍有待改善，因此尋找一晶格匹釔的基板一 直是一個研究的重要課題，除了單晶氧化鋁❻叩沖丨代： 基板外，碳化矽⑸C)基板亦是另一被考慮採用的基板‘，但 其價格昂貴’不適合大量使用，且其與氮化鎵的晶格匹配 差異爲3.5%，並不能達到完全匹配。因此如何得到與三族 金屬氮化物晶格匹配且容易取得而又價格便宜的基板，是 在研究雷射二極體時，所必須克服的問題。 爲了取彳于和氮化鎵晶格匹配的基板，與其尋找異質蟲晶 的基板，何不直接製作氮化鎵基板呢？其原因是因爲氮（N) 在氮化嫁的飽和蒸氣壓很南的緣故。若要以一般拉單晶的 方式’拉出氮化鎵單晶並不容易，成長溫度需高達攝氏 1800度以上，且成長壓力也需多達兩萬個大氣壓以上，才 L: \ £/：τ\ Ε. 1 \ e. 10'^6. Γ>〇Ί·\ MFΥ — 4 — 本紙悵尺度適用中國國家標準（CNS ) Λ4規格（2丨0X297公f ) (請先閱讀背面之注意事項再填寫本頁)
•1T vm 經漪部中央標準局員工消费合忭，社印裝 Λ7
\M 昏明説明（2 ) 能將氮留在氮化鎵單晶内，所以並不是一個適當的晶體成 長方式，在1990年曰本名古屋大學以傳統氫化物氣相磊晶 (HVPE)的方式在氧化鋁基板上成長氮化鎵單晶，其所形成 之氮化鎵的表面並不是很平坦，且氮化鎵的特性也不是很 好：到1992年’爲了改進氮化鎵單晶的表面，採用和氮化 鎵有機金屬化學氣相沈積（MOCVD)磊晶成長在氧化鋁基板 的類似方法，先在氧化鋁基板上濺鍍氧化鋅當缓衝層，再 以HVPE的方式成長氮化鎵單晶，但是其改進的效果仍不理 / 想。 以氫化物氣相磊晶（HVPE)成長氮化鎵（GaN)，一般是用氣 化氫（HC1)氣體通過800°C以上高溫的鎵（Ga)金屬表面，形成 氣化鎵（GaCl)蒸.氣’再和氨氣（NH3)在1〇〇〇〜120CTC高溫反應 形成氮化鎵沈積在基板表面以形成氮化鎵磊為層，其反 應式如下： 2HC1 + 2Ga -> 2GaCl + H2 2GaCl + 2NH3 + H2 2GaN + 2NH4C1 此種習用之磊晶片製造方式，有如下的問題： 1-除，了氣化鎵和氨所反應生成之白色氣化按Wh4ci)粉末 外’過量或未反應之氣化氫和氨氣更會形成大量額外的 氣化銨粉末’不僅嚴重影響氮化鎵磊晶層表面平整度， 且造成系統的粉塵量大增，對抽氣系統的壽命影響很 大。 2.此外’氣化虱是一具有南腐蚀性的有毒氣體，人體只要 暴露在濃度5 ppm的氯化氫氣氛下，便會對人體造成傷 L:'E>:nc liKlrOMFY - 5 - 太紙张尺尼逆用中國园家標率（CNS ) Λ4規格（2丨OX 297公發 {請先閱讀背面之注意事項#填寫本頁) .裝·
，1T A7 B7 本紙張 五、發明説明（ 菩’且對系統也有很強烈的腐蚀作用。 综上可知，現有的習用方式不僅無法提供理想的H 屬氮化物蟲晶片，且會形成粉塵、有毒氣體等環保問= 故而-種創新的製造方法，其可克服習用技術之問題並处 有效提供理想的三族金屬氮化物系晶片，乃爲業界所企= 發明综述 本發明首揭利用三族金屬之三氣化物直接與含氣元素之 氣體反應生成三族金屬氮化物的'叙造方法。由於本發明免 除了使用有毒的氣化氫氣體，不僅克服了氯化氫本身所造 成的環保問題，更可避免氯化銨粉末在三族金屬氮化物合 成前產生，而違到理想的磊晶品質在本發明之方法中， 基板與二族金屬氮化物蟲晶層的晶格匹配與否盖不重要， 故可選用各種易於取得之基板，如三氧化二鋁（义203)、碳 化矽（SiC)、矽（Si)、砷化鎵（GaAs)、磷化鎵（GaP)、氮化鎵 (GaN)或氮化鋁鎵（AIGaN)等其中之一。 此外，在本發明之方法中，於開始沈積磊晶層之前，亦 可先於基板上形成一緩衝層。再者，由於本發明之三族金 屬氮化物磊晶層可以很容易地沈積至相當大的厚度，故於 慕晶層形成後，可將基板及/或缓衝層剝去，而形成一完 全爲三族金屬氮化物之基板。 本發明之方法所形成之磊晶層並不限於某單一三族金屬 與氮之二元化合物’而可以是各種三族金屬與氮之二元化 合物’如氮化鎵、氮化鋁及氮化銦；此外，更可以是上述
r-tX^CVMFV 、〇»S用中國國家標率（CNS > Λ4· ( 21()χ 297公及） 广裂-- ; * • t {請先閲讀背^-之注意事項再填湾本頁) 、-· 經"部中央標準局員工消费合作社印裝 Λ7 __—_ ____B7 五、發明説明（4 ) ~~~~ 一疋化合物間各種比例組合之三元或四元化合物。 圖式之簡單説明 圖1爲本發明實施例所應用之系統簡圖。 圖2爲本發明實施例之X射線繞射頻譜圖。 圖3爲本發明實施例之掃描式電子顯微鏡的照片。 較佳實施例説明 本發明之詳細技術内容可藉應用本發明之方法以生成氮 化鎵磊晶片爲例説明如下： 圖1所7F爲本發明實施例所應 '角之系統簡圖，在本實施 例中係直接以三氯化鎵當鎵源而與氨氣反應生成氮化鎵， 其反應式如下：
GaCl3 + 4NH3 GaN +t3NH4C1 由於直接以三氣化鎵來成長氮化鎵，故可避兔氯化銨粉 末在氣化鎵合成前產生，以確保磊晶的品質。 二氣化鎵在室溫下爲白色固體，只須加溫至攝氏90度左 右，即可取其蒸氣壓來成長；相較於先前技術須於攝氏 800度以上的高溫來形成氣化鎵蒸氣，可知本發明在系統 設計上可較先前技術更爲簡便且更容易施行。 如圖I所示之系統簡圖，由於三氣化鎵和氨氣反應相當 地劇烈，所以三氣化鎵源和氨氣是分開送入反應腔，在靠 近南溫反應區之前才將兩種反應物混和，如此可減少氣化 按粉末的形成。於本實施例中，該高溫反應區之溫度可爲 攝氏300至〗400度之間，較佳爲攝氏500至1400度之間。此 外’在本實施例中’於三氣化鎵和氨氣進行反應之前，可 L-: \ E/.T1* S1 , S 1. DO〇\ MFY _ ] _ .張;Uiit用中ϋ標準（CNS )八4規^7^297公势) (請先閱讀背而之注意事項再填寫本頁) .裝_
、1T 393786 A7 B7 五、發明説明（5 先於基板上通入三氣化鎵蒸 > 、 又或風氣二者之一並於攝氏 500至丨400度之間的溫度下進行 铒八 订表面熱處理。 本實施例之成長流量條件如下 卜·氮氣200 seem，氨氣2〇〇 _，氫氣5〇sccm，三氣化鎵1〇〇_—。 圖2爲本實施例之X射線繞射頻譜圖，由χ射線繞射頻雄 來看，58度位置的X射線訊號所代表的爲氮化鎵陶]平面 族：有訊號存在’ #由圖3的掃描式電子顯微鏡的表面照 片觀察得知’有六角形的圖案在氮〆匕鎵薄膜的表面上，由 橫截面的掃描式電子顯微鏡的厚复量測得知，其成長速率 約爲每小時2.4微米。 以上所揭示者爲本發明之一實施例，其係用於説明本發 明之技術内容，而非用於限定本發《月之範園；任何熟於本 項技藝之士基於本發明之揭示或敎示所做之各蠢不脱離本 發明技術理念的修改均屬於本發明之範圍。 (請先閲讀背私之注意事項再填寫本頁) 裝- -丁 _ -3 經濟部中夬標準局貝工消费合作社印製

Claims (1)

  1. A8 B8 C8 D8 393786 π、申請專利範圍 1. 一種磊晶片的製造方法，用以於一基板上形成具有三族 金屬氮化物之磊晶層，該方法包括： 提供一基板； 提供一第一氣體源，其中該第—氣體分子中包含氮元 素： 提供一第二氣體源，其中該第二氣體中含有該三族金屬 之三氣化物； 使该第一氣體與該第二氣體於二加熱區中進行反應，並 使該反應生成之三族金屬氮化‘沈積於該基板上。 2·如申請專利範圍第1項之方法，其中該基板之材料可爲 二氧化二鋁、碳化矽、矽、砷化鎵、磷化鎵、氮化鎵或 氮化鋁鎵其中之一。 、 3-如申請專利範圍第1項之方法，其中更包括；於進行反 應前’先於該基板上通入該第一氣體作表面熱處理。 4·如申請專利範園第丨項之方法，其中更包括：於進行反 應前’先於該基板上通入該第二氣體作表面熱處理。 5.如申請專利範圍第！項之方法，其中該第—氣體爲氨 氣·。 6‘如申請專利範圍第1項之方法，其中該三族金屬之氮化 物可爲氮化鎵、氮化鋁、氮化銦或其各種比例組合之三 元或四元化合物。 7.如申請專利範圍第1項之方法，其中該加熱區之溫度可 爲攝氏300至1400度之間。 8·如申請專利範圍第7項之方法，其中該加熱區之溫度係 L： ^ E.'.TV S 1 \ ^ ] η >6. HFV ~ ^ 本紙張尺度適用巾關轉準（CNS ) ( 210X297公羡)~~~ '~~' --—- (請先閲讀背面之注意事項再填寫本頁) .裝. 、1T. 輕_ 部中夬棣準局員工消f合作社印製 ABCD 393786 六、申請專利範圍 爲攝氏500至1400度之間。 9.如申請專利範圍第3或4項之方法’其中該熱處理之溫 度係爲攝氏500至1400度之間。 1(1.如申請專利範圍第I項之方法，其中更包括：於進行反 應前，先於該基板上形成一緩衝層。 11. 如申請專利範圍第1或1〇項之方法，，其中更包栝：於該. 磊晶層形成後，將該基板剝去的步驟。 12. 如申請專利範園第1〇項之方法，其中更包括：於#蟲晶 層形成後，將該基板及緩衝層'剝去的步驟。 (請先閲讀背面之注意Ϋ項再填寫本頁) -裝· 經濟部t央標率局員工消費合作社印製 —1〇 — ____^ Μ氏張尺度適用中國國家標準（CNS } Α4規格（210Χ297公釐）
TW087104571A 1998-03-26 1998-03-26 Method for manufacturing an epitaxial chip TW393786B (en)

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TW087104571A TW393786B (en) 1998-03-26 1998-03-26 Method for manufacturing an epitaxial chip
US09/102,675 US6110809A (en) 1998-03-26 1998-06-23 Method for manufacturing an epitaxial wafer with a group III metal nitride epitaxial layer

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TW087104571A TW393786B (en) 1998-03-26 1998-03-26 Method for manufacturing an epitaxial chip

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TW393786B true TW393786B (en) 2000-06-11

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