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TWI425666B - Growth of semi - polarized nitrides - Google Patents

Growth of semi - polarized nitrides Download PDF

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TWI425666B
TWI425666B TW100114580A TW100114580A TWI425666B TW I425666 B TWI425666 B TW I425666B TW 100114580 A TW100114580 A TW 100114580A TW 100114580 A TW100114580 A TW 100114580A TW I425666 B TWI425666 B TW I425666B
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semi
polarized
growing
nitride
wall surface
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TW100114580A
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TW201244164A (en
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Jen Inn Chyi
Hsueh Hsing Liu
Hsien Yu Lin
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Univ Nat Central
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Description

半極化氮化物的成長方法
本發明為有關一種半極化氮化物，尤指一種半極化氮化物的成長方法。
發光二極體由於具有環保、省電、體積小、重量輕、壽命長、低電壓電流操作、耐衝擊的優點，現已逐漸的取代傳統的螢光燈管以及鎢絲燈泡，廣泛的應用於頭燈、方向燈、指示燈、照明設備與顯示器當中，而發光二極體為一種固態元件，在現今的技術中，主要為使用具有直接能隙和高崩潰電壓的氮化物材料所製成，然而，傳統成長於c面(c-plane)方向的氮化鎵發光二極體，會因內建電場的關係，使得量子井能帶結構產生歪斜，進而影響電子、電洞波函數的重疊機率降低，使得發光效率減弱，因此，發展不具有內建電場的非極性與半極性氮化鎵材料，以有效提升發光二極體的內部量子效率，已為相關人士所努力的目標。
習知半極化氮化鎵的製造方法，如日本專利公開第2008305977號所示，揭露半極化氮化鎵材料成長在矽基板上的技術，此技術先在偏軸傾斜7°的(001)矽基板(7-degree off(001)Si substrate)上，定義平行於<-110>方向的脊狀週期遮罩圖形，該遮罩圖形的材質為二氧化矽，然後，使用氫氧化鉀溶液對該矽基板進行蝕刻，以形成具有兩個傾斜面的凹槽，該兩傾斜面分別為一與該矽基板的主要平面相交的(111)結晶面，以及一與該矽基板的主要平面相交的(-1-11)結晶面。接著，將二氧化矽覆蓋在該矽基板除(111)結晶面外之其餘部分，並以該矽基板的(111)結晶面做為成長區域，成長(1-101)結晶面的氮化鎵薄膜在該矽基板的(111)結晶面上，以形成半極化氮化鎵薄膜。此種成長方法係將氮化鎵厚膜成長在該矽基板(111)結晶面外露之全部面積，因氮化鎵與矽基板(111)結晶面之間有晶格不匹 配的現象，且彼此間的熱膨脹係數差異甚大，故將產生約-50%的舒張應力，常導致氮化鎵薄膜沿著<110>方向龜裂的問題。
本發明的主要目的，在於減少半極化的氮化鎵薄膜中，氮化鎵和矽基板之間因為熱應力而產生的龜裂現象，本發明的另一目的，在於降低成長氮化鎵薄膜所產生的缺陷，而獲得較好的氮化鎵薄膜品質。
為達上述目的，本發明提供一種半極化氮化物的成長方法，先在一矽基板上形成複數個凹槽，該凹槽分別具有一第一壁面以及一第二壁面，該第一壁面與該矽基板之表面間夾一傾斜角度。接著，於該矽基板之表面、該第一壁面與該第二壁面上形成一緩衝層，位於該第一壁面上之該緩衝層具有複數成長區域及一與該成長區域互補且位於該成長區域之間之非成長區域；於該緩衝層上形成一露出該成長區域且覆蓋該非成長區域的覆蓋層。最後，將一半極化氮化物成長於該緩衝層之成長區域，並令該半極化氮化物覆蓋於該覆蓋層之上。
由以上可知，本發明將位於該第一壁面上的該緩衝層之部分面積區分為該成長區域，並將其他部分定義為該非成長區域，而僅在分散的該成長區域磊晶成長該半極化氮化物，藉此降低該半極化氮化物與該緩衝層形成鍵結之面積，以減輕氮化物和矽基板之間因為熱應力及晶格不匹配而產生的龜裂現象，進而提升半極化氮化物的薄膜品質。
有關本發明的詳細說明及技術內容，現就配合圖式說明如下：請參閱「圖1A」至「圖1F」所示，為本發明一實施例的半極化氮化物製造流程示意圖，如圖所示：本發明提供一種半極化氮化物的成長方法，包括以下步驟：首先請參閱「圖1A」，於一矽基板10上形成一週期性的遮罩圖形50，該矽基板10之表面與該矽基板10之(001)結晶 面夾一介於5°至10°之間的角度。在此實施例中，先選擇一偏軸傾斜7°的(001)矽基板10(7-degree off(001)Si substrate)，並透過曝光顯影製程而於該矽基板10上定義出平行於<-110>方向之條狀週期性的該遮罩圖形50，該遮罩圖形50由二氧化矽所構成。
請搭配參閱「圖1B」，於該矽基板10上形成複數凹槽11，複數該凹槽11間隔並排，並各具有一第一壁面111以及一第二壁面112，在此實施例中，利用蝕刻溶液對該矽基板10上未被遮罩圖形50所覆蓋的部分進行蝕刻，而形成複數該凹槽11，以及該凹槽11所具有的該第一壁面111、該第二壁面112以及一與該第一壁面111及該第二壁面112相接的底面113，該蝕刻溶液可為氨水(NH4OH)、氫氧化鉀(KOH，potassium hydroxide)水溶液、氫氧化四鉀基銨(TMAH，tetramethylammonium hydroxide)水溶液、EDP(ethylenediamine pyrocatechol)水溶液、聯氨(N2H4)、氫氧化鈉(NaOH)、氫氧化鋰(LiOH)或氫氧化銫(CsOH)等，而該第一壁面111為該矽基板10的(111)結晶面，並與該底面113所延伸之平面形成58.7°至64.7°之間的夾角，在此以61.7°為一實施例說明，該第二壁面112為該矽基板10的(-1-11)結晶面，並與該底面113所延伸之平面形成44.7°至50.7°之間的夾角，在此以47.7°為一較佳實施例說明。
接續，請參閱「圖1C」，於已形成複數該凹槽11的該矽基板10上形成一緩衝層20，位於該第一壁面111上之該緩衝層20具有複數成長區域21及複數與該成長區域21互補之非成長區域22，此實施例中是利用去氧化層溶液，例如氫氟酸(HF)或是氧化物蝕刻緩衝液(BOE，Buffer oxidation etchant)，對該矽基板10進行表面清洗，隨後，成長一層厚度為20與100奈米之間的該緩衝層20於該矽基板10上，該緩衝層20位於該第一壁面111的部分預設有該成長區域21以及與該成長區域21互補之非成長區域22，其中，該非成長區域22位 於相鄰的該成長區域21之間。在本發明中，該緩衝層20之材料可為含氮化鎵、氮化鋁或氮化銦的二元、三元及四元化合物，亦可使用如氧化鋅(ZnO)化合物等晶格常數與上述材料相近似的材料，以減少該矽基板10與所欲成長的一半極化氮化物40之間因晶格不匹配所產生的應力問題，而影響該半極化氮化物40磊晶的品質。並且，該緩衝層20可選擇使用分子束磊晶法、有機金屬化學氣相磊晶法或者氫化物氣相磊晶法來成長形成，或是以上述方法搭配使用形成，此外，該緩衝層20可選擇為單層結構、雙層結構或是多層結構，以達到最佳的緩衝效果。在此實施例中，該緩衝層20則以有機金屬化學氣相磊晶法形成單層結構的氮化鋁鎵為一較佳的實施例。
接著請搭配參閱「圖1D」及「圖1E」，在該矽基板10上形成該緩衝層20後，於該緩衝層20上形成一覆蓋層30，該覆蓋層30覆蓋於該緩衝層20上，且露出複數該成長區域21，其中，該覆蓋層30包含一第一覆蓋層31以及一第二覆蓋層32。進一步說明，先於該緩衝層20上形成呈長條狀的該第一覆蓋層31，該第一覆蓋層31的長度方向與該凹槽11的長度方向不平行，在本實施例中，該第一覆蓋層31的長度方向與該凹槽11的長度方向相互垂直，且該第一覆蓋層31位於該第一壁面111上的部分覆蓋該非成長區域22。於形成該第一覆蓋層31後，再於該矽基板10表面上的該緩衝層20，及該緩衝層20上的該第一覆蓋層31上形成該第二覆蓋層32，令該第二覆蓋層32及該第一覆蓋層31相疊形成之該覆蓋層30僅露出該成長區域21。換言之，整個緩衝層20上，僅該成長區域21未被該覆蓋層30罩覆，並且相鄰的兩該成長區域21之間隔著部分的該第一覆蓋層31。在此實施例中，該第一覆蓋層31及該第二覆蓋層32的材質為二氧化矽或氮化矽，可先利用曝光顯影製程定義出該第一覆蓋層31，且該第一覆蓋層31的長度方向與該凹槽11的長度方向相互垂直，並遮蔽該非成長區域22，接著該第二覆蓋層32可利用電漿輔助化學氣相沈 積法、電子槍蒸鍍法、熱阻式蒸鍍法或離子濺鍍法形成，並覆蓋於該緩衝層20上，只露出該成長區域21，因而形成複數間隔排列的該成長區域21，在此實施例中，該第二覆蓋層32為利用電子槍蒸鍍法而形成。
最後，請搭配參閱「圖1F」，於形成該覆蓋層30後，再將一半極化氮化物40自複數該成長區域21進行成長，並令該半極化氮化物40覆蓋於該覆蓋層30之上，其中該半極化氮化物40為選自含氮化鎵、氮化鋁或氮化銦在內的二元、三元或四元化合物所組成的群組，可選擇利用分子束磊晶法、有機金屬化學氣相磊晶法或氯化物氣相磊晶法成長。此步驟係由該緩衝層20上所具有的複數該成長區域21開始成長磊晶，而後進而相連形成該半極化氮化物40的半導體層，遮覆於該覆蓋層30之上，在此實施例中，該半極化氮化物40利用有機金屬化學氣相磊晶法，由該緩衝層20上之複數該成長區域21，成長出具有(1-101)面的半極化氮化鎵半導體層。須進一步說明的是，由於該緩衝層20無法完全的緩衝該矽基板10與該半極化氮化物40之間因晶格不匹配及熱應力不匹配所產生的應力問題，該覆蓋層30將該緩衝層20定義出分散的複數該成長區域21，再利用複數該成長區域21成長該半極化氮化物40，以達到分散來自於晶格不匹配及因而衍生之熱應力所產生之舒張應力的方向，改善該半極化氮化物40因舒張應力產生的龜裂現象。
綜上所述，由於本發明利用該覆蓋層於該緩衝層上定義複數個分散的該成長區域，藉此減少該半極化氮化物與該緩衝層形成鍵結之面積以及半極化氮化物和矽基板之間對應的成長面積，進而降低半極化氮化物與矽基板之間因晶格不匹配及熱應力不匹配而產生的舒張應力，並分散該舒張應力所產生的方向，改善因舒張應力而產生的龜裂現象，進而提升半極化氮化物的薄膜品質，因此本發明極具進步性及符合申請發明專利的要件，爰依法提出申請，祈 鈞局早日賜准專利，實感德便。
以上已將本發明做一詳細說明，惟以上所述者，僅為本發明的一較佳實施例而已，當不能限定本發明實施的範圍。即凡依本發明申請範圍所作的均等變化與修飾等，皆應仍屬本發明的專利涵蓋範圍內。
10‧‧‧矽基板
11‧‧‧凹槽
111‧‧‧第一壁面
112‧‧‧第二壁面
113‧‧‧底面
20‧‧‧緩衝層
21‧‧‧成長區域
22‧‧‧非成長區域
30‧‧‧覆蓋層
31‧‧‧第一覆蓋層
32‧‧‧第二覆蓋層
40‧‧‧半極化氮化物
50‧‧‧遮罩圖形
圖1A-圖1F，為本發明一實施例的半極化氮化物製造流程示意圖。
10‧‧‧矽基板
111‧‧‧第一壁面
112‧‧‧第二壁面
20‧‧‧緩衝層
30‧‧‧覆蓋層
32‧‧‧第二覆蓋層
40‧‧‧半極化氮化物

Claims (10)

  1. 一種半極化氮化物的成長方法，包括以下步驟：在一矽基板上形成複數個凹槽，該凹槽分別具有一第一壁面以及一第二壁面，該第一壁面與該矽基板之表面間夾一傾斜角度；於該矽基板之表面、該第一壁面與該第二壁面上形成一緩衝層，位於該第一壁面上之該緩衝層具有複數成長區域及複數與該成長區域互補且位於該成長區域之間的非成長區域；於該緩衝層上形成一露出該成長區域且覆蓋該非成長區域的覆蓋層；以及將一半極化氮化物成長於該緩衝層之成長區域並令該半極化氮化物覆蓋該覆蓋層。
  2. 如申請專利範圍第1項所述的半極化氮化物的成長方法，其中該矽基板之表面與該矽基板之(001)結晶面間夾一介於5°至10°的角度。
  3. 如申請專利範圍第1項所述的半極化氮化物的成長方法，其中該第一壁面為該矽基板的(111)結晶面。
  4. 如申請專利範圍第1項所述的半極化氮化物的成長方法，其中該第二壁面為該矽基板的(-1-11)結晶面。
  5. 如申請專利範圍第1項所述的半極化氮化物的成長方法，其中該凹槽更具有一與該第一壁面及該第二壁面相接的底面。
  6. 如申請專利範圍第1項所述的半極化氮化物的成長方法，其中該半極化氮化物及該緩衝層之材料為選自由氮化鎵、氮化鋁及氮化銦所組成的群組。
  7. 如申請專利範圍第1項所述的半極化氮化物的成長方法，其中成長該半極化氮化物之方法選自由分子束磊晶法、有機金屬化學氣相磊晶法及氯化物氣相磊晶法所組成之群組。
  8. 如申請專利範圍第1項所述的半極化氮化物的成長方法，其中該緩衝層的厚度介於0.5奈米與該凹槽深度之間。
  9. 如申請專利範圍第1項所述的半極化氮化物的成長方法，其中成長該緩衝層之方法選自分子束磊晶法、有機金屬化學氣相磊晶法及氯化物氣相磊晶法所組成之群組。
  10. 如申請專利範圍第1項所述的半極化氮化物的成長方法，其中該覆蓋層的材質為二氧化矽或氮化矽。
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