TWI474510B - 具有孔隙之磊晶結構及其成長方法 - Google Patents
具有孔隙之磊晶結構及其成長方法 Download PDFInfo
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- 238000000034 method Methods 0.000 title claims description 68
- 239000000758 substrate Substances 0.000 claims description 39
- 239000011148 porous material Substances 0.000 claims description 13
- 238000005530 etching Methods 0.000 claims description 11
- 238000001020 plasma etching Methods 0.000 claims description 8
- 238000009616 inductively coupled plasma Methods 0.000 claims description 7
- 229910002601 GaN Inorganic materials 0.000 claims description 6
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 claims description 6
- 150000004767 nitrides Chemical class 0.000 claims description 6
- 230000000737 periodic effect Effects 0.000 claims description 6
- 239000004065 semiconductor Substances 0.000 claims description 6
- 229910010272 inorganic material Inorganic materials 0.000 claims description 4
- 239000011147 inorganic material Substances 0.000 claims description 4
- 238000000059 patterning Methods 0.000 claims description 4
- 229910052594 sapphire Inorganic materials 0.000 claims description 4
- 239000010980 sapphire Substances 0.000 claims description 4
- 238000001039 wet etching Methods 0.000 claims description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 3
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 3
- 238000005229 chemical vapour deposition Methods 0.000 claims description 3
- 229910000449 hafnium oxide Inorganic materials 0.000 claims description 3
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 claims description 3
- 238000002248 hydride vapour-phase epitaxy Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000001451 molecular beam epitaxy Methods 0.000 claims description 3
- MZLGASXMSKOWSE-UHFFFAOYSA-N tantalum nitride Chemical compound [Ta]#N MZLGASXMSKOWSE-UHFFFAOYSA-N 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 229920002120 photoresistant polymer Polymers 0.000 description 3
- 238000000605 extraction Methods 0.000 description 2
- 238000010849 ion bombardment Methods 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000407 epitaxy Methods 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
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Description
本發明是有關於一種磊晶結構以及一種磊晶成長方法,且特別是有關於一種具有孔隙之磊晶層以及此磊晶層的磊晶成長方法。
近年來,發光二極體(Light Emitting diode)的技術快速發展。為了提高發光二極體的光取出率,圖案化藍寶石基板(Patterned sapphire substrate)技術已廣泛被使用於現有氮化鎵發光二極體產品中。然而為求進一步提升光取出效率,更有先進技術開發出於氮化鎵磊晶材料中製造具有孔隙結構之發光二極體。在製造具有孔隙結構之發光二極體的習知技術中,很難精確地控制孔隙的體積大小及形狀,因此造成孔隙型發光二極體的品質不穩定。有鑑於此,目前亟需一種新的製造方法,其能改善上述問題。
因此,本發明之一目的係提供一種磊晶成長方法,俾能在磊晶層中形成孔隙結構,且能夠精準地控制孔隙的型態。此磊晶成長方法,包含下述步驟。首先,提供一基材。隨後,形成一犧牲層於基材上。接著,圖案化犧牲層,以在基材上形成複數間隔排列之凸起物,並且使凸起物之間的基材表面裸露出。隨後,在裸露部分之基材上磊晶成長一第一磊晶層,使第一磊晶層覆蓋每一凸起物的一部分,
並露出每一凸出物的頂面。在磊晶成長第一磊晶層之後,蝕刻移除凸起物,以形成複數露出基材表面之孔隙。然後,在第一磊晶層上磊晶成長一第二磊晶層,使孔隙被第一磊晶層及第二磊晶層包覆。
在一實施方式中,基材為一藍寶石基板或矽基板。
在一實施方式中,第一磊晶層包含週期表IIIA族的氮化物半導體材料(group IIIA nitride semiconductor)。
在一實施方式中,第二磊晶層包含週期表IIIA族的氮化物之半導體材料。
在一實施方式中,第一、第二磊晶層是氮化鎵所構成。
在一實施方式中,第一及第二磊晶層是以氫化物氣相磊晶製程(hydride vapor phase epitaxy process)、有機金屬化學氣相沉積製程(metal organic chemical vapor deposition process)或分子束磊晶製程(molecular beam epitaxy process)形成。
在一實施方式中,第二磊晶層成長時,其水平方向的成長速率大於鉛垂方向的成長速率。
在一實施方式中,犧牲層為一無機材料層。
在一實施方式中,犧牲層包含氧化矽或氮化矽。
在一實施方式中,每一凸出物之一最大高度為約0.5μm至約3μm,每一凸出物之一底部寬度為約0.5μm至約5μm。
在一實施方式中,每一凸起物之一錐形角(taper angle)為小於或等於約90度
在一實施方式中,圖案化犧牲層之步驟包含以感應耦
合電漿反應離子蝕刻(Inductively Coupled Plasma Reactive Ion Etching,ICP RIE)犧牲層。
在一實施方式中,凸出物是以濕式蝕刻法移除。
在一實施方式中,溼式蝕刻法所用的蝕刻劑包含氟化銨(NH4
F)以及氟化氫(HF)。
在一實施方式中,每一孔隙之開口面積為每一孔隙底部面積的約5%至約50%。
在一實施方式中,基材表面更包括一緩衝層。
本發明之另一態樣係揭露一種磊晶結構。此磊晶結構包含一基材、一第一磊晶層、一第二磊晶層以及一封閉氣室。第一磊晶層配置在基材上方。第二磊晶層配置在第一磊晶層上。封閉氣室埋設在第一磊晶層和第二磊晶層中,封閉氣室具有一底部以及一頂部,封閉氣室的底部和頂部分別形成在第一磊晶層和第二磊晶層中,且封閉氣室的頂部的寬度小於底部的寬度。
在一實施方式中,封閉氣室的頂部包含一圓弧面,且封閉氣室的底部實質上為一平面。
在一實施方式中,封閉氣室的一縱剖面為梯形。
在一實施方式中,封閉氣室包含一階梯狀側壁,且頂部及底部實質上為相對的兩平面。
在一實施方式中,上述之磊晶結構更包含一緩衝層,緩衝層位在基材與第一磊晶層之間,且封閉氣室的底部接觸緩衝層。
在一實施方式中,上述之磊晶結構更包含一圖案化犧牲層配置在基材上,且圖案化犧牲層的上表面形成封閉氣
室的底部。
在一實施方式中,該封閉氣室的高度為約0.5μm至約3μm,該封閉氣室的底部的寬度為約0.5μm至約5μm。
為了使本揭示內容的敘述更加詳盡與完備,下文針對了本發明的實施態樣與具體實施例提出了說明性的描述;但這並非實施或運用本發明具體實施例的唯一形式。以下所揭露的各實施例,在有益的情形下可相互組合或取代,也可在一實施例中附加其他的實施例,而無須進一步的記載或說明。
在以下描述中,將詳細敘述許多特定細節以使讀者能夠充分理解以下的實施例。然而,可在無此等特定細節之情況下實踐本發明之實施例。在其他情況下,為簡化圖式,熟知的結構與裝置僅示意性地繪示於圖中。
第1圖繪示本發明一實施方式之磊晶成長方法100的流程圖,磊晶成長方法100至少包含步驟110至步驟160。第2A-2F圖繪示方法100中各製程階段的剖面示意圖。在此揭露之磊晶成長方法可應用於製造發光二極體或製造平面顯示器。
在步驟110中,提供基材210,如第2A圖所示。基材210可例如為藍寶石基板、矽基板或其他適合於磊晶成長的基板。
在步驟120中,在基材210上形成犧牲層220,如第
2B圖所示。在一實施方式中,犧牲層220為無機材料層。犧牲層220可例如為氧化矽或氮化矽等無機材料所製成。
在步驟130中,對犧牲層220進行圖案化,以形成複數凸起物222。這些凸起物222彼此間隔地排列在基材210上,兩個凸起物222之間的間隙讓基材210的表面裸露出。
在一實施方式中,可先在犧牲層220上形成具有一定圖案的光阻層,光阻層覆蓋欲形成凸起物222的區域,並暴露出其他部分的犧牲層220。然後,再藉由蝕刻製程來移除暴露出的犧牲層220,而形成凸起物222。具體而言,是藉由光阻層的圖案來決定凸起物222的上視輪廓。關於凸起物222的剖面形狀,可經由適當的蝕刻技術來控制凸起物222的剖面形狀。在一具體實例中,利用感應耦合電漿反應離子蝕刻(Inductively Coupled Plasma Reactive Ion Etching,ICP RIE)的製程技術來蝕刻暴露出的犧牲層220。感應耦合電漿反應離子蝕刻技術能夠同時提供具方向性的離子轟擊蝕刻以及不具方向性的反應性離子蝕刻,所以能夠形成半球形狀的凸起物222。藉由調整ICP RIE中的製程參數,能夠分別控制離子轟擊的蝕刻速率和反應性離子的蝕刻速率,而形成不同剖面形狀的凸起物222,例如可形成梯形剖面的凸起物222或矩形剖面的凸起物,下文將更詳細敘述。
在一較佳實施例中,每一凸起物222的錐形角(taper angle)α是小於或等於約90度,每一凸出物之一最大高度H為約0.5μm至約3μm,每一凸出物之一底部寬度為W約0.5μm至約5μm。凸起物222的外觀形狀決定後
續步驟中的孔隙形狀,下文將更詳細敘述。
在步驟140中,在裸露出之基材210上磊晶成長第一磊晶層231,使第一磊晶層231覆蓋凸起物222之一部分,但凸出物222的頂面222t是曝露在第一磊晶層231之外,如第2D圖所示。詳言之,在磊晶成長第一磊晶層231時,第一磊晶層231會沿著凸起物222的表面磊晶成長。若不終止磊晶成長製程,第一磊晶層231將會完全覆蓋凸起物222。因此,本發明之一特徵在於,在第一磊晶層231完全覆蓋凸起物222之前,終止第一磊晶層231的磊晶成長,使凸出物的頂面222t曝露出來,避免第一磊晶層231完全包覆凸起物222。
在一實施方式中,第一磊晶層231包含週期表IIIA族的氮化物半導體材料(group IIIA nitride semiconductor),例如氮化鎵。第一磊晶層231可藉由氫化物氣相磊晶製程(hydride vapor phase epitaxy process)、有機金屬化學氣相沉積製程(metal organic chemical vapor deposition process)或分子束磊晶製程(molecular beam epitaxy process)來形成。
在步驟150中,蝕刻移除凸起物222,而形成複數孔隙224,並使基材210之一部分表面露出,如第2E圖所示。因為凸出物的頂面222t是曝露在第一磊晶層231之外,所以可利用濕式蝕刻製程來移除這些凸出物222,而形成孔隙224。蝕刻劑可例如為包含氟化銨(NH4
F)以及氟化氫(HF)的混合溶液。詳言之,孔隙224的位置、體積及外觀形狀大致上是取決於凸起物222的位置、體積及形狀以及第一磊晶層231覆蓋凸起物222的程度。因此,根據本發明的
實施方式,能夠藉由步驟130中圖案化犧牲層220的步驟,控制凸起物222的形狀、體積以及排列方式,而得以事先精準地控制步驟140所形成的孔隙224的型態。
第2G圖繪示本發明一實施方式之步驟150中所形成的孔隙224的上視示意圖。在本實施方式中,在移除凸起物222之後,孔隙開口224a的面積為孔隙底部224b的面積的約5%至約50%,更明確地為約15%至約40%。若孔隙開口224a的面積小於孔隙底部224b的面積的約5%,則很難在步驟150中迅速地移除凸起物222。反之,若孔隙開口224a的面積大於孔隙底部224b的面積的約50%,則第一磊晶層231覆蓋凸起物222的程度不足,而不利於後續的步驟160。因此,根據本發明之諸多實施例,孔隙開口224a的面積較佳為孔隙底部224b的面積的約5%至約50%,更佳為約15%至約40%。
在步驟160中,於第一磊晶層231上磊晶成長第二磊晶層232,使孔隙224被第一磊晶層231及第二磊晶層232包覆,如第2F圖所示。換言之,在步驟160中,藉由磊晶成長第二磊晶層232,使孔隙224變成埋設在第一磊晶層231與第二磊晶層232中的封閉氣室(closed air cell)。第二磊晶層232的形成方法可與前文第一磊晶層231中所述的方法相同。在一實施方式中,第二磊晶層232包含週期表IIIA族的氮化物之半導體材料(group III nitride semiconductor)。在一實例中,第二磊晶層232的材料與第一磊晶層231的材料相同,例如同樣為氮化鎵。在其他實施方式中,為了特別考量整體的光學路徑,第二磊晶層232
的折射率不同於第一磊晶層231的折射率。
在另一實施方式中,第二磊晶層232成長時的水平方向成長速率大於第一磊晶層231的水平方向成長速率。水平方向的成長速率可藉由磊晶製程時的溫度及壓力來控制。在一實例中,第二磊晶層232成長時的溫度大於第一磊晶層231的成長溫度,而且第二磊晶層232成長時的壓力小於第一磊晶層231的成長壓力。為了使第一磊晶層231的膜層結構具有較佳的立體結構,故此時的成長環境為低溫高壓。此外,第二磊晶層232相對於第一磊晶層231而言,則是需要較佳的平坦化能力以及較易水平生長的結構,以覆蓋孔隙224。第二層的成長環境相較於第一磊晶層231是較高溫且低壓的。
如前文步驟130及步驟140中所述,可藉由形成不同剖面形狀的凸起物222,而得到不同形狀的孔隙224。第3A-3D圖繪示本發明另一實施方式之磊晶成長方法中製程階段的剖面示意圖。第3A-3D圖繪示的實施方式中,可形成具有梯形剖面的凸起物222,如第3A圖所示。然後,再磊晶成長第一磊晶層231;第一磊晶層231僅覆蓋凸起物222的一部分,如第3B圖所示。接著,移除凸起物222而形成孔隙224,如第3C圖所示。隨後,再磊晶成長第二磊晶層232將梯形剖面形狀的孔隙224包覆其中,如第3D圖所示。相似地,第3E-3H圖繪示的實施方式中,能夠形成階梯狀剖面形狀的孔隙224。
第4A-4F圖繪示本發明又一實施方式之磊晶成長方法中製程階段的剖面示意圖。在第4A圖中,提供基材210。
在第4B圖中,形成緩衝層212於基材210的表面上。在第4C圖中,在緩衝層212上形成複數個凸起物222。然後,如第4D圖所示,在緩衝層212上磊晶成長第一磊晶層231。接著,如第4E圖所示,移除凸起物222而形成孔隙224。隨後,如第4F圖所示,磊晶成長第二磊晶層232而將孔隙224包覆。
第5A-5B圖繪示本發明再一實施方式之磊晶成長方法中製程階段的剖面示意圖。在本實施方式中,步驟110至步驟140可與前文關於第2A-2D圖的敘述相同。然後,如第5A圖所示,在步驟150中僅蝕刻移除凸起物222的一部分,而不移除全部的凸起物222。詳言之,在蝕刻移除凸起物222的過程中,在完全移除凸起物222之前,終止蝕刻程序,使凸起物222的一部分222a殘留在基材上。隨後,再進行步驟160的磊晶成長第二磊晶層232,使孔隙224被第一磊晶層231及第二磊晶層232包覆。換言之,根據本實施方式,能夠在第一磊晶層231及第二磊晶層232中形成封閉氣室以及埋設其中的凸起物殘留部分222a。在一實施例中,凸起物的殘留部分222a的折射率與第一磊晶層231及/或第二磊晶層232的折射率不同,因此能夠作為另一個光學介質,改變第2F圖繪示之結構中的光學路徑及光學特性。
雖然本發明已以實施方式揭露如上,然其並非用以限定本發明,任何熟習此技藝者,在不脫離本發明之精神和範圍內,當可作各種之更動與潤飾,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。
100‧‧‧方法
110、120、130‧‧‧步驟
140、150、160‧‧‧步驟
210‧‧‧基材
212‧‧‧緩衝層
220‧‧‧犧牲層
222‧‧‧凸起物
222a‧‧‧殘留部分凸起物
222t‧‧‧頂面
224‧‧‧孔隙
224a‧‧‧開口
224b‧‧‧底部
231‧‧‧第一磊晶層
232‧‧‧第二磊晶層
H‧‧‧高度
W‧‧‧寬度
α‧‧‧錐形角
為讓本發明之上述和其他目的、特徵、優點與實施例能更明顯易懂,所附圖式之說明如下:第1圖繪示本發明一實施方式之磊晶成長方法的流程圖。
第2A-2F圖繪示本發明一實施方式之磊晶成長方法中各製程階段的剖面示意圖。
第2G圖繪示本發明一實施方式之步驟150所形成的孔隙的上視示意圖。
第3A-3D圖繪示本發明另一實施方式之磊晶成長方法中製程階段的剖面示意圖。
第3E-3H圖繪示本發明另一實施方式之磊晶成長方法中製程階段的剖面示意圖。
第4A-4F圖繪示本發明又一實施方式之磊晶成長方法中製程階段的剖面示意圖。
第5A-5B圖繪示本發明再一實施方式之磊晶成長方法中製程階段的剖面示意圖。
100‧‧‧方法
110、120、130、140、150、160‧‧‧步驟
Claims (18)
- 一種具孔隙結構之磊晶成長方法,包含:提供一基材;形成一犧牲層於該基材上;圖案化該犧牲層,並在該基材上形成複數間隔排列之凸起物,並且裸露出該些凸起物間之基材表面;在該裸露出之基材上磊晶成長一第一磊晶層,使該第一磊晶層覆蓋該些凸起物之一部分,並露出每一該凸起物之頂面;蝕刻移除該些凸起物,形成複數露出該基材表面之孔隙;以及在該第一磊晶層上磊晶成長一第二磊晶層,使該些孔隙被該第一磊晶層及該第二磊晶層包覆。
- 如請求項1所述方法,其中該基材為一藍寶石基板或矽基板。
- 如請求項1所述方法,其中該第一磊晶層包含週期表IIIA族的氮化物半導體材料(group IIIA nitride semiconductor)。
- 如請求項3所述方法,其中該第二磊晶層包含週期表IIIA族的氮化物之半導體材料(group III nitride semiconductor)。
- 如請求項4所述方法,其中該第一、第二磊晶層是氮化鎵所構成。
- 如請求項5所述方法,其中該第一及該第二磊晶層是以氫化物氣相磊晶製程(hydride vapor phase epitaxy process)、有機金屬化學氣相沉積製程(metal organic chemical vapor deposition process)或分子束磊晶製程(molecular beam epitaxy process)形成。
- 如請求項6所述方法,其中該第二磊晶層成長時的水平方向成長速率大於第一磊晶層的水平方向成長速率。
- 如請求項7所述方法,其中該第二磊晶層成長時的溫度大於第一磊晶層的成長溫度。
- 如請求項7所述方法,其中該第二磊晶層成長時的壓力小於第一磊晶層的成長壓力。
- 如請求項1所述方法,其中該犧牲層為一無機材料層。
- 如請求項10所述方法,其中該犧牲層包含氧化矽或氮化矽。
- 如請求項1所述方法,其中每一凸出物之一最大高度為約0.5μm至約3μm,每一凸出物之一底部寬度為約0.5μm至約5μm。
- 如請求項12所述方法,其中形成該些凸起物之步驟中,每一凸起物之一錐形角(taper angle)為小於或等於約90度。
- 如請求項13所述方法,其中圖案化該犧牲層之步驟包含以感應耦合電漿反應離子蝕刻(Inductively Coupled Plasma Reactive Ion Etching,ICP RIE)該犧牲層。
- 如請求項1所述方法,其中該些凸出物是以濕式蝕刻法移除。
- 如請求項15所述方法,其中該溼式蝕刻法所用的蝕刻劑包含氟化銨(NH4 F)以及氟化氫(HF)。
- 如請求項1所述方法,其中每一該些孔隙之開口面積為每一該些孔隙底部面積的約5%至約50%。
- 如請求項1至請求項17中任一項所述方法,其中該基材表面更包括一緩衝層。
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CN109638129B (zh) * | 2018-12-11 | 2021-04-27 | 宁波安芯美半导体有限公司 | 发光二极管外延结构的制备方法 |
CN114864774B (zh) * | 2022-06-07 | 2023-10-20 | 淮安澳洋顺昌光电技术有限公司 | 图形化衬底的制备方法及具有空气隙的led外延结构 |
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