TWI466287B - Substrate for epitaxy and its manufacturing method - Google Patents
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- 239000000758 substrate Substances 0.000 title claims description 99
- 238000000407 epitaxy Methods 0.000 title claims description 25
- 238000004519 manufacturing process Methods 0.000 title description 12
- 239000013078 crystal Substances 0.000 claims description 63
- 238000005530 etching Methods 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 10
- 230000006911 nucleation Effects 0.000 claims description 8
- 238000010899 nucleation Methods 0.000 claims description 8
- 238000001039 wet etching Methods 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 4
- 230000007547 defect Effects 0.000 description 12
- 238000009826 distribution Methods 0.000 description 6
- 239000007787 solid Substances 0.000 description 5
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- 229910002601 GaN Inorganic materials 0.000 description 3
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 229910052594 sapphire Inorganic materials 0.000 description 2
- 239000010980 sapphire Substances 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 238000004581 coalescence Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- QPJSUIGXIBEQAC-UHFFFAOYSA-N n-(2,4-dichloro-5-propan-2-yloxyphenyl)acetamide Chemical compound CC(C)OC1=CC(NC(C)=O)=C(Cl)C=C1Cl QPJSUIGXIBEQAC-UHFFFAOYSA-N 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 238000000059 patterning Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 238000000206 photolithography Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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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
- H01L33/02—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 characterised by the semiconductor bodies
- H01L33/20—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 characterised by the semiconductor bodies with a particular shape, e.g. curved or truncated substrate
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
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- H01L21/20—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy
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- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
- C30B25/02—Epitaxial-layer growth
- C30B25/18—Epitaxial-layer growth characterised by the substrate
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- C—CHEMISTRY; METALLURGY
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- 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
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- C30B25/00—Single-crystal growth by chemical reaction of reactive gases, e.g. chemical vapour-deposition growth
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Description
本發明是有關於一種基板及其製作方法,特別是指一種磊晶用基板及其製作方法。
一般用於磊晶(epitaxy)的磊晶用基板是將單晶棒經切片、拋光、化學清洗後得到,而以這樣過程製得的磊晶用基板,其表面必然會有應力殘留、或是缺陷存在,也因此,以這樣的磊晶用基板磊晶成長出磊晶層體時,會延續此等缺陷而使得磊晶出的磊晶層體的晶體品質較差,進而影響所製得之元件的工作效能。
參閱圖1,為解決上述的問題,圖案化磊晶用基板1使其切割、拋光而得的頂面11還包含有多數自該頂面11向下延伸的凹孔12是常用的作法,形成的凹孔12彼此相間隔且週期地排列,而使得磊晶成長元件的磊晶層體時,成核(nuclearation)成長(grain growth)並聚集(coalescence)發生的頂面11面積因凹孔12的存在而減少,進而減少缺陷延續發生的機會,以得到磊晶品質較佳的磊晶層體。
但是上述的磊晶用基板1仍是自切片、拋光而成的頂面11上成核、成長並聚集,所以磊晶出的磊晶層體依舊會延續缺陷而無法進一步地提升磊晶層體的晶體品質,所以上述的磊晶用基板1仍需要加以改進。
因此,本發明之一目的,即在提供一種適於磊晶成長並減少因基板而形成缺陷的磊晶用基板。
此外,本發明之另一目的,即在提供一種製作適於磊晶成長並減少因基板而形成缺陷之磊晶用基板的製作方法。
於是,本發明磊晶用基板包含一頂面,及複數自該頂面向下延伸的晶面。
每n個晶面構成一角錐形的凹孔,n是不小於3的正整數,每一凹孔的其中一晶面與頂面的連接線至另一最相鄰凹孔的最相鄰晶面與頂面之連接線的間距不大於50nm,而使得用該磊晶用基板磊晶時自該等晶面成核後成長並聚集。
再者,本發明磊晶用基板的製作方法包含以下四個步驟。
首先於一單晶結構的基板頂面上以蝕刻選擇比較該基板高的材料形成一層具有多數個整齊排列之穿孔的遮覆層。
接著經該遮覆層自該基板頂面向下濕蝕刻,而在該基板對應於每一穿孔的位置處形成一個至少由三第一次蝕刻面構成的凹穴。
再接著移除該遮覆層,使該基板頂面裸露。
最後自該基板頂面與該等第一次蝕刻面進行濕蝕刻而沿該基板的結晶構造移除該基板的預定結構,使得該每一凹穴成為一由n個自該基板頂面斜向下延伸的晶面構成的角錐形凹孔,其中,n是不小於3的正整數,製得該磊晶用基板。
本發明之功效在於:當使用本發明磊晶用基板進行磊晶時,是自該等晶面成核後成長並聚集,而可得到缺陷較少、晶體品質較佳的磊晶層體,進而提升以此磊晶用基板製作出的元件的工作效能。
有關本發明之前述及其他技術內容、特點與功效,在以下配合參考圖式之一個較佳實施例的詳細說明中,將可清楚的呈現。
參閱圖2、3,本發明磊晶用基板9的一較佳實施例,是六方晶體結構的藍寶石基板,包含一頂面91,及複數自該頂面91向下延伸的晶面92,其中,每三晶面92構成一呈正三角錐形且開口為正六角形的孔洞93,每一晶面92與該頂面91具有二實質等長且夾成120°的連接邊922。
詳細地說,該等晶面92自該頂面91向下延伸,該頂面91是(0001)面,且該等晶面92是{}面族群,其中之一,其中,k為不小於2且不大於5的正整數,任一晶面92與該頂面91的巨觀夾角是119°~156°,每三個晶面92構成該呈正三角錐形的凹孔93,該等凹孔93成週期排列,每一晶面92與該頂面91具有二實質等長且夾成120°的連接邊922,且任一連接邊922的長度是1μm~5μm,並且,每一凹孔93的深度是0.3μm~3μm,每一凹孔93的其中一晶面92與頂面91的連接邊922,至另一最相鄰凹孔93的最相鄰晶面92與頂面91之連接邊922的間距不大於500nm。如此,當用該磊晶用基板9磊晶時,該頂面91可供成核的面積實質為零,成核後成長並聚集均是自該等凹孔93的三晶面92進行,進而減少缺陷延續發生的機會,得到磊晶品質較佳的磊晶層體,進而提升以該磊晶用基板9製作出的元件之工作效能。
參閱圖4,上述的磊晶用基板9是依序進行以下四個步驟後製作出來的。
參閱圖4、5,首先進行步驟21,於單晶棒經切片、拋光、化學清洗後得到的單晶結構的基板31上,以蝕刻選擇比較該基板31高的材料形成一層具有多數個整齊排列之穿孔71的遮覆層7。
詳細地說,此步驟21是在完成標準清洗流程(standard cleaning procedure)後移除表面污染層的基板31上,形成一層二氧化矽(SiO2
)構成的薄層後,以黃光微影(photolithography)製程形成具有多數個規則地整齊交錯排列的穿孔71而成該遮覆層7,其中,該等穿孔71的截面形狀是正多邊形,較佳地,該等穿孔71是直徑為1μm~5μm的圓柱形,任二相鄰之穿孔71的間距是1μm~5μm。
參閱圖4、圖6,並配合參閱圖7,在形成該遮覆層7之後接著進行步驟22,以該遮覆層7當作遮罩(mask)自該基板31向下濕蝕刻而在該基板31對應於每一穿孔71的位置處形成一個由一連接面941與三第一次蝕刻面942構成的凹穴94。
詳細地說,本步驟22是將混合100毫升的98vol%的硫酸與50毫升的85vol%的磷酸的蝕刻劑,保持260℃經該遮覆層7蝕刻該基板31,蝕刻時間是10~20分鐘;此蝕刻開始時是自每一裸露出穿孔71的頂面區域向下形成不規則延伸的連接面941,繼之,自連接面941朝遠離穿孔71中心軸方向蝕刻擴大連接面941的範圍,同時朝向底面方向蝕刻形成自連接面941斜向下沿晶體結構之晶面方向延伸的區域而成三平行於晶體結構之晶面方向的第一次蝕刻面942,而形成如圖7所繪示之概似三角錐形且深度為0.3μm~3μm的凹穴94。
參閱圖4、圖8,於該磊晶用基板9頂面91形成該等凹穴94後實施步驟23,以氫氟酸(HF)移除該遮覆層7而使該基板31頂面32裸露。
參閱圖4、圖9,最後實施步驟24,自該基板31之頂面32與該等第一次蝕刻面942進行濕蝕刻而沿該基板31的結晶構造移除該基板31預定結構,使得該每一凹穴94成為由三個自該磊晶用基板9之頂面91斜向下延伸的晶面92構成的正三角錐形之凹孔93,製得該磊晶用基板9。
詳細地說,是將混合100毫升的98vol%的硫酸與50毫升的85vol%的磷酸而製作出的蝕刻劑,並保持蝕刻劑溫度在260℃,蝕刻劑自該磊晶用基板9的頂面91、每一凹穴94的連接面941與三第一次蝕刻面942朝向底面方向再次濕蝕刻10~20分鐘,蝕刻劑沿連接面941與三第一次蝕刻面942的晶體結構斷面處蝕刻,而使連接面941被蝕刻成沿晶體結構之晶面方向延伸,之後平行晶體結構之晶面方向蝕刻使連接面941與三第一次蝕刻面942成連續平面,進而成三完全平行該三第一次蝕刻面942方向延伸的晶面92,且該三晶面92構成型態精確的正三角錐形且開口為正三角形的凹孔93,如圖9所示,之後,再繼續蝕刻以控制該孔洞93之開口擴大成為正六角形,即製得如圖2所示的磊晶用基板9。
參閱圖10,以相同的磊晶條件,於圖2所示之現有的磊晶用基板1和本發明磊晶用基板9磊晶成長氮化鎵磊晶層體後,以X光繞射檢視(XRD)可知,以本發明磊晶用基板9所磊晶出的磊晶層體不對稱面半高寬為274 arcsec,遠小於用現有的磊晶用基板1所磊晶出的磊晶層體不對稱面半高寬為436 arcsec,證明用本發明磊晶用基板9磊晶成長之氮化鎵磊晶層體的缺陷較少、晶體品質較佳。
參閱圖11、12,由Trace-Pro模擬於上述用現有的磊晶用基板1和本發明磊晶用基板9磊晶成長氮化鎵磊晶層體製得的固態發光元件的燭光分佈結果可知,以本發明磊晶用基板9製得的固態發光元件的最大燭光是每立體角4.75毫瓦(即4.75mW/sr),明顯大於以現有的磊晶用基板1製得的固態發光元件的最大燭光每立體角3.75毫瓦,表示以本發明磊晶用基板9所製作出的固態發光元件之工作效能確實優於以現有的磊晶用基板1所製作出的固態發光元件。
另外要說明的是,本發明並非只能應用於磊晶製作固態發光元件,實際上,只要是製作應用磊晶製程且必須獲得高品質之磊晶層體的元件結構,例如製作太陽能電池、高速電晶體(HEMTs)等都可以應用本發明,對於熟悉此領域人士而言,可輕易地組合實施,故不在此一一舉例詳述;此外,上述本發明雖以六方晶體結構的藍寶石基板作為實現說明,但是對於其他晶體結構的磊晶用基板,類似地可藉由計算、控制遮覆層7的多數穿孔71的排列位置與態樣,以及進行第一、二次濕蝕刻的過程,而可以使得以切片、拋光而成的基板的頂面面積實質減少至無法成核成長並聚集,進而減少缺陷延續發生的機會,進而獲得最佳磊晶品質的磊晶層體,由於晶體結構種類眾多,且對於熟悉本技術領域人士而言,可自本發明而輕易轉用實現,故不在此一一舉例詳述。
綜上所述,本發明磊晶用基板9與現有的磊晶用基板1相比,該頂面91實質可供成核的面積為零,當以本發明磊晶用基板9進行磊晶時,是在該等晶面92上成核成長,所以磊晶出的磊晶層體不會延續該頂面91之缺陷而使磊晶層體的缺陷較少、晶體品質提升,並且經由燭光分佈圖驗證,以本發明磊晶用基板9所製作出的固態發光元件的工作效能確實較佳;另外,藉由二段式濕蝕刻製程,先以該遮覆層7的多數穿孔71精確地控制第一次濕蝕刻出的凹穴94形成位置,並控制進行第二次濕蝕刻的時間將凹穴94精確蝕刻成由晶面92構成的凹孔93,進而成型出本發明磊晶用基板9,故確實能達成本發明之目的。
惟以上所述者,僅為本發明之較佳實施例而已,當不能以此限定本發明實施之範圍,即大凡依本發明申請專利範圍及發明說明內容所作之簡單的等效變化與修飾,皆仍屬本發明專利涵蓋之範圍內。
1...磊晶用基板
11...頂面
12...凹孔
21...步驟
22...步驟
23...步驟
24...步驟
31...基板
32...頂面
7...遮覆層
71...穿孔
9...磊晶用基板
91...頂面
92...晶面
922...連接邊
93...凹孔
94...凹穴
941...連接面
942...第一次蝕刻面
圖1是一立體剖視示意圖,說明現有的磊晶用基板;
圖2是一立體剖視示意圖,說明本發明磊晶用基板的一較佳實施例;
圖3是一掃描電子顯微鏡(SEM)圖,說明本發明磊晶用基板的該較佳實施例的態樣;
圖4是一流程圖,說明本發明磊晶用基板的較佳實施例的製作方法;
圖5是一立體剖視示意圖,輔助說明圖4的製作方法;
圖6是一立體剖視示意圖,輔助說明圖4的製作方法;
圖7是一立體放大圖,輔助說明圖4的製作方法中,經第一次濕蝕刻成的凹穴;
圖8是一立體剖視示意圖,輔助說明圖4的製作方法;
圖9是一立體放大圖,輔助說明圖4的製作方法中,第一次濕蝕刻所成的凹穴經第二次濕蝕刻後所成的凹孔;
圖10是一X光繞射圖,說明本發明磊晶用基板的該較佳實施例其磊晶薄膜以X光繞射技術進行品質檢測的數據;
圖11是一燭光分佈圖,說明以現有的磊晶用基板所製作出固態發光元件的燭光分佈;及
圖12是一燭光分佈圖,說明以本發明磊晶用基板的該較佳實施例所製作出固態發光元件的燭光分佈。
9...磊晶用基板
91...頂面
92...晶面
922...連接邊
93...凹孔
Claims (8)
- 一種磊晶用基板,包含:一頂面;及複數自該頂面向下延伸的晶面,其中,每n個晶面構成一角錐形的凹孔,n是不小於3的正整數,每一凹孔的其中一晶面與頂面的連接線至另一最相鄰凹孔的最相鄰晶面與頂面之連接線的間距不大於500nm,而使得用該磊晶用基板磊晶時自該等晶面成核後成長並聚集。
- 根據申請專利範圍第1項所述的磊晶用基板,其中,該磊晶用基板是六方晶體結構,且每三個晶面構成一個正三角錐形的凹孔,每一凹孔的深度是0.3μm~3μm,且任一晶面與頂面的連接線的長度是1μm~5μm。
- 根據申請專利範圍第2項所述的磊晶用基板,其中,該頂面是(0001)面,該等晶面是{}面族群其中之一,任一晶面與該頂面的巨觀夾角是119°~156°。
- 根據申請專利範圍第1項所述的磊晶用基板,其中,該磊晶用基板是六方晶體結構,每一凹孔是由三個晶面構成的,且每一晶面與該頂面具有二實質等長且夾成120°的連接邊,每一凹孔的深度是0.3μm~3μm,且任一連接邊的長度是1μm~5μm。
- 根據申請專利範圍第4項所述的磊晶用基板,其中,該頂面是(0001)面,該等晶面是{}面族群其中之一,任一晶面與頂面的巨觀夾角是119°~156°。
- 一種磊晶用基板的製作方法,包含:(a) 於一單晶結構的基板頂面上以蝕刻選擇比較該基板高的材料形成一層具有多數個整齊排列之穿孔的遮覆層;(b) 經該遮覆層自該基材頂面向下濕蝕刻,而在該基板對應於每一穿孔的位置處形成一個至少由三第一次蝕刻面構成的凹穴;(c) 移除該遮覆層,使該基板頂面裸露;及(d) 自該基板頂面與該等第一次蝕刻面進行濕蝕刻而沿該基板的結晶構造移除該基板的預定結構,使得該每一凹穴成為一由n個自該基材頂面斜向下延伸的晶面構成的角錐形凹孔,其中,n是不小於3的正整數,製得該磊晶用基板。
- 根據申請專利範圍第6項所述的磊晶用基板的製作方法,其中,該步驟(d)是進行濕蝕刻至所形成的每一凹孔的任一晶面與該頂面的連接處是直線,且兩最相鄰凹孔彼此最相鄰的晶面與該頂面連接處的間距不大於500nm為止。
- 根據申請專利範圍第7項所述的磊晶用基板的製作方法,其中,該基板是六方晶體結構且頂面是(0001)面,同時,該步驟(a)形成的遮覆層的穿孔是正多邊形,開口是1μm~5μm,且任二相鄰之穿孔的間距是1μm~5μm。
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