TWI716452B - 以peald於溝槽中沉積介電膜的方法 - Google Patents
以peald於溝槽中沉積介電膜的方法 Download PDFInfo
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- TWI716452B TWI716452B TW105130130A TW105130130A TWI716452B TW I716452 B TWI716452 B TW I716452B TW 105130130 A TW105130130 A TW 105130130A TW 105130130 A TW105130130 A TW 105130130A TW I716452 B TWI716452 B TW I716452B
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- film
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- dielectric film
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- wet etching
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- 238000000034 method Methods 0.000 title claims abstract description 35
- 238000000151 deposition Methods 0.000 title claims abstract description 29
- 239000000758 substrate Substances 0.000 claims abstract description 48
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 239000002243 precursor Substances 0.000 claims abstract description 37
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 9
- 125000000524 functional group Chemical group 0.000 claims abstract description 5
- 238000001039 wet etching Methods 0.000 claims description 71
- 230000008021 deposition Effects 0.000 claims description 17
- 238000005530 etching Methods 0.000 claims description 16
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 150000004696 coordination complex Chemical class 0.000 claims description 2
- -1 dimethyl amide metal complex Chemical class 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000007789 gas Substances 0.000 description 37
- 239000012535 impurity Substances 0.000 description 15
- 230000008569 process Effects 0.000 description 15
- 239000012159 carrier gas Substances 0.000 description 13
- 238000001350 scanning transmission electron microscopy Methods 0.000 description 10
- 238000012546 transfer Methods 0.000 description 10
- 230000007423 decrease Effects 0.000 description 7
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
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- 238000005137 deposition process Methods 0.000 description 2
- 229910052732 germanium Inorganic materials 0.000 description 2
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 235000012431 wafers Nutrition 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- QKIUAMUSENSFQQ-UHFFFAOYSA-N dimethylazanide Chemical compound C[N-]C QKIUAMUSENSFQQ-UHFFFAOYSA-N 0.000 description 1
- 238000000572 ellipsometry Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
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- 150000002500 ions Chemical class 0.000 description 1
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- 238000005259 measurement Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 210000004180 plasmocyte Anatomy 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000000391 spectroscopic ellipsometry Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- MNWRORMXBIWXCI-UHFFFAOYSA-N tetrakis(dimethylamido)titanium Chemical compound CN(C)[Ti](N(C)C)(N(C)C)N(C)C MNWRORMXBIWXCI-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
本發明揭露藉由電漿增強原子層沉積(PEALD)於溝槽中沉積介電膜之方法,其包括在其中在一基板之頂表面上之沉積膜之濕式蝕刻率實質上等同於或高於在該溝槽之側壁處之沉積膜之濕式蝕刻率之條件下,藉由PEALD在一基板之溝槽中沉積一介電膜,其中饋入該反應空間內之一前驅物具有-N(CH3)2作為官能基。
Description
本發明通常係關於一種藉由電漿增加原子層沉積(PEALD)在一基板之溝槽中沉積一介電膜之方法。
在電漿增加原子層沉積(PEALD)製程中,由於基板之溝槽之側壁較該基板之頂表面進行較少的離子撞擊,因而在該側壁處之表面反應較該頂表面上不具活性,導致在側壁處之一膜之蝕刻率與該頂表面上之一膜之蝕刻率不同或較高之問題。
於習知技術中,藉由增加製程溫度或諸如此類,以改善在側壁上沉積之一介電膜之品質(例如:密度、硬度),可減少使得在側壁處之蝕刻率。然而,上述改善僅僅只是部份的,且在該側壁與該頂表面間之不同蝕刻率之問題並未充份地得到解決。
為提供本發明內容之目的,任何與相關技術關聯之問題及解決方案之討論已單獨包括在本揭露中,且不應視為承認在作出本發明時知曉任何或全部討論。
在本發明之某些具體實施例中,替代改善在一基板之溝槽之側壁處之一介電膜之品質,藉由降低在該基板之頂表面上之一介電膜之品
質,在該側壁處及在該頂表面上之該膜之蝕刻率實質上係匹配的。
某些具體實施例提供一種方法,其用於藉由控制在具有溝槽之基板上沉積一介電膜之製程中之製程參數(諸如:RF功率)使用具有-N(CH3)2作為官能基之一前驅物藉由PEALD使在一基板之溝槽之側壁處之膜品質與在該基板之頂表面上之膜品質實質上相等。在某些具體實施例中,藉由增加RF功率增加在該頂表面上之一膜之蝕刻率,藉以降低在該頂表面上沉積之該膜之品質,因而減少該側壁及該頂表面間之蝕刻率之差異。在某些具體實施例中,藉由控制沉積製程增加該頂表面上之膜中之雜質(例如:氮)量。一膜之蝕刻率與該膜中之雜質量相關,且藉由增加雜質量,可增加該蝕刻率。例如,可藉由調整RF功率控制該雜質量。藉由控制沉積製程,可藉由使在該側壁處之該膜中雜質量與在該頂表面上之該膜中雜質量實質上相等而減少該側壁與該頂表面間之蝕刻率之差異。
基於總結本發明之態樣及優於相關技術所達成之優點的目的,在本揭露中描述本發明之某些目的及優點。當然,應了解根據本發明之任何特定具體實施例可不必達成所有此等目標或優點。因此,例如,熟悉此技術之人士將認知本發明可以達到或最佳化本文教示之一優點或一群優點之方式下體現或進行,而不必達成如可在本文教示或建議之其它目標或優點。
本發明之其它態樣、特徵、及優點將由以下實施方式變得顯而易見。
1:基板
2:底電極
3:反應室
4:上電極
5:轉移室
6:排放管線
7:排放管線
11:內部
12:電接地
13:圓形管路
14:分離板
16:轉移區
20:HRF功率
21:氣體管線
22:氣體管線
24:密封氣體管線
本發明之此等及其它特徵現將參考較佳具體實施例之圖示描述,該等較佳具體實施例係意欲說明而非限制本發明。該等圖式基於說明性目的而大幅地簡化且不必按比例繪製。
圖1A係可用在本發明之一具體實施例中用於沉積一介電膜
之電漿增強原子層沉積(PEALD)裝置之示意圖。
圖1B說明使用可用於本發明之一具體實施例中之一流通系統(FPS)之前驅物供應系統之示意圖。
圖2說明根據本發明之一具體實施例之一PEALD製程順序。
圖3A係顯示根據本發明之一具體實施例一膜之N濃度與用於該膜之沉積之RF功率間之關係之圖。
圖3B係顯示根據本發明之一具體實施例一沉積膜之濕式蝕刻率相對於氧化膜之濕式蝕刻率與用於該膜之沉積之RF功率間之關係之圖。
圖4係顯示根據本發明之一具體實施例在該側壁處及在該頂表面上之一沉積膜之濕式蝕刻率(任意單位)相對於熱氧化膜之濕式蝕刻率與用於該膜之沉積之RF功率間之關係之圖。
圖5顯示根據一比較例形成之依形性介電膜之橫截面之掃描穿透式電子顯微術(STEM)之照片,其中(a)顯示如所沉積之膜,及(b)顯示在濕式蝕刻後之一膜。
圖6顯示根據本發明之一具體實施例形成之依形性介電膜之橫截面之掃描穿透式電子顯微術(STEM)之照片,其中(a)顯示如所沉積之一膜,及(b)顯示在濕式蝕刻後之一膜。
在本揭露中,「氣體」可包括蒸發固體及/或液體,且可由單一氣體或氣體混合物構成。同樣地,冠詞「一」或「一種」係指一種類或包括多種類之屬。在本揭露中,經由淋洗頭引入反應室之製程氣體可包括一前驅物及一反應氣體、基本上由其組成、或由其組成。反應氣體包括當對反應氣體施加RF功率時用於氧化前驅物之氣體。若在無RF功率下該反
應氣體對該前驅物不具反應性,則可將該反應氣體連續引入一反應空間中。可將該前驅物與載體氣體(諸如惰性氣體)一起引入。除該製程氣體外之一氣體(即未通過該淋洗頭引入之一氣體)可用於例如密封該反應空間,其包括諸如一惰性氣體之一密封氣體。在某些具體實施例中,「膜」意指實質上無針孔在垂直於厚度方向上之方向連續延伸以覆蓋整個目標或關注表面之一層,或僅係覆蓋目標或關注表面之一層。一膜可由具有某種特性之不連續單一膜或層,或多個膜或層構成,且相鄰膜或層之間之邊界可或可不為清晰的,且可基於物理、化學、及/或任何其它特性、形成製程或順序,及/或相鄰膜或層之功能或目的建立。此外,在本揭露中,任何二個數目之變數可構成變數之可作用範圍,因為可作用範圍可基於例行工作確定,且所指出之任何範圍可包括或排除端點。此外,任何所指出之變數之值(無論其等是否係以「約」指出)可係指精確值或近似值,且包括等效值,且在一些具體實施例中可指平均值、中值、代表值、多數等。在某些具體實施例中,術語「由...構成」及「具有」獨立地指稱「通常或廣泛地包含」、「包含」、「基本上由...組成」或「由...組成」。
在其中未具體指明條件及/或結構之本揭露中,熟悉本技術者考量本揭露作為實驗事件可容易地提供此等條件及/或結構。
在所有所揭露之具體實施例中,任何在具體實施例中所用之元件可以用於所欲目的之其任何等效元件替代,包括本文明確地、必要地、或本質上地揭露者。進一步地,本發明可同樣地應用在裝置及方法中。
在此揭露中,在某些具體實施例中任可所定義之意義不必排除普通及習知之意義。
在某些具體實施例中,術語「前驅物」通常指參與化學反應之化合物,其產生另一化合物,且尤其構成一膜基質或一膜之主要骨幹之化合物,而該術語「反應物」係指活化一前驅物、改質一前驅物、或催化一前驅物之反應的一化合物。
該介電膜包括但不限於金屬氧化物膜,其由諸如氧化鈦、或多元素材料之類所構成,其具有約10至約100、通常約50至約60之介電常數。在某些具體實施例中,藉由電漿增強ALD或其它電漿輔助循環沉積方法,該介電膜在溝槽、通孔、或其它包括側壁及底表面之凹入物(總稱為「溝槽」)中形成。溝槽可具有約10nm至約1,000nm,通常約100nm至約500nm之深度,及約1至約10、通常約2至約3之深寬比。該沉積之介電膜之厚度可係在約2nm至約500nm、通常約10nm至約100nm、更通常約15nm至約30nm之範圍中(一所需膜厚度可根據膜之應用及目的等等適當地選擇)。
該等具體實施例將就較佳具體實施例說明。然而,本發明不限於該等較佳具體實施例。
在一具體實施例中,一種用於藉由電漿增強原子層沉積(PEALD)在溝槽中沉積一介電膜之方法包含:(i)測定在施加至一反應空間(其中藉由PEALD在一基板之溝槽中沉積一介電膜)之RF功率與在該溝槽之側壁上沉積之該膜之一部份之一濕式蝕刻率之間之第一關係,及該RF功率與在該基板之頂表面上沉積之該膜之一部份的一濕式蝕刻率間之第二關係,其中饋入該反應空間內之一前驅物具有-N(CH3)2作為一官能基;(ii)測定RF功率,其對應於在該溝槽之側壁上沉積之該膜之部份的第一濕式蝕刻率,及在該基板之頂表面上沉積之該膜之部份之第二濕式蝕刻率,其中該第二濕式蝕刻率實質上等同於或高於根據步驟(i)中之第一及第二關係之第一濕式蝕刻率;及(iii)在等同於第一及第二關係中所用之條件的條件下藉由PEALD在一基板之溝槽中沉積一介電膜,其中RF功率係步驟(ii)中測定者。
在此揭露中,「實質上相同」、「實質上相等」、或諸如此類在某些具體實施例中可係指無形差異或熟習此技術者所認知之差異諸如少於10%、少於5%、少於1%、或其任何範圍者(通常,該差異係±5%)。並且,在此揭露中,「實質上較高」、「實質上不同」、或諸如此類在某些具體實施
例中可係指物質差異或熟習此技術者所認知之差異諸如至少5%、10%、20%、30%、40%、50%、60%、70%、80%、或其任何範圍者。
在某些具體實施例中,在一基板之頂表面上沉積之膜之濕式蝕刻率呈用於該膜之沉積之RF功率之函數而變化,且當使用具有-N(CH3)2作為官能基之一前驅物時,該膜之濕式蝕刻率隨著RF功率增加沿具有一頂點之一向下拋物線變化。即,當RF功率相對弱時,該濕式蝕刻率隨RF功率增加而減少,即,沉積膜之品質改善。然而,當RF功率進一步增加時,更多電漿到達頂表面,且雜質濃度亦開始增加。通常,該濕式蝕刻率之變化對應於雜質濃度之變化。結果,該濕式蝕刻率在到達最小值(最低頂點)後開始增加。在由最低頂點獲得之頂表面上之膜品質呈現為最高。然而,當該頂表面上之膜品質在最低頂點處為最高時,在側壁處之膜品質並非最高,即,在側壁處之膜之濕式蝕刻率係相對高的。由於電漿不易到達側壁,相對於在頂表面上之膜品質,在側壁之膜品質未明顯受到RF功率強度的影響。在某些具體實施例中,在側壁處之該膜之濕式蝕刻率隨RF功率增加而逐漸減少。因此,雖然當RF功率相對低時,在側壁處之該膜之濕式蝕刻率高於該頂表面上之該膜之濕式蝕刻率,隨著RF功率增加,在該頂表面之膜之濕式蝕刻率之最低頂點後之某點處,在該頂表面上之該膜之濕式蝕刻率與在該側壁處之該膜之濕式蝕刻率變得實質上相等,此係因為在該側壁處之該膜之濕式蝕刻率逐漸減少的同時,在該頂表面之該膜之濕式蝕刻率繼續增加(表示在該頂表面上之該膜之濕式蝕刻率與RF功率之間之關係之線,與表示在該側壁處之該膜之濕式蝕刻率與RF功率之間之關係之線相交)。
在某些具體實施例中,僅藉由調整用於沉積一膜之RF功率(其它製程參數未改變),提供實質上等同於或高於第一濕式蝕刻率(即,在側壁處沉積之一膜之濕式蝕刻率)的第二濕式蝕刻率(即,在該頂表面上沉積之一膜之濕式蝕刻率),使得可改善在濕式蝕刻後之該膜的依形性。在某些
具體實施例中,在濕式蝕刻後之該膜的依形性係在約90%至約110%,理想上約95%至約100%之範圍中。該依形性定義為在一基板之溝槽之側壁處(或該底表面處)之一膜的厚度對該基板之頂表面上之該膜的厚度之比率。第一濕式蝕刻率取決於在該基板上沉積之膜之依形性選擇。若該依形性係約100%,則第一及第二濕式蝕刻率可實質上相等,使得在濕式蝕刻後之該膜的依形性可保持約100%。在某些具體實施例中,所沉積之膜之依形性係在約80%至約100%之範圍中。習知上,在濕式蝕刻後之依形性低於所沉積膜之依形性約5%至約10%。相反地,在本發明之某些具體實施例中,在濕式蝕刻後之依形性高於所沉積膜之依形性約5%至約15%(通常約10%)。在某些具體實施例中,替代改善在該基板之溝槽之側壁處之膜之品質,藉由降低在該基板之頂表面上之膜之品質而達成上述結果。
在某些具體實施例中,該前驅物係二甲基醯胺金屬錯合物。在某些具體實施例中,在該金屬錯合物中之金屬係鈦。可使用其它金屬,諸如鍺。在某些具體實施例中,該前驅物係選自由肆(二甲基醯胺)鈦、肆(二甲基醯胺)鍺組成之群組之一或多個化合物。
在某些具體實施例中,用於步驟(iii)中之RF功率(即RF功率決定步驟)係在每基板面積約0.02W/cm2至約1.4W/cm2、通常約0.07W/cm2至約0.7W/cm2、更常0.3W/cm2至約0.4W/cm2之範圍中。
上文中,該等測量步驟如下:(1)將一膜沉積於其上之一基板切割成尺寸為5 x 5cm之片;(2)藉由光譜橢圓偏振術測量該膜之厚度;(3)將該基板片浸入具有1:100氫氟酸濃度之溶液五分鐘;(4)使用純水徹底清洗該基板片並以一吹風器將其乾燥;及(5)藉由光譜橢圓偏振術測量該膜之厚度;及計算該濕式蝕刻率,其定義為在步驟(2)中測量之厚度及步驟(5)中測量之厚度間之差與在步驟(2)中測量之膜厚度的比例。並且,使熱氧化膜(TOX)沉積於上之一基板進行上述相同步驟,並計算該膜之濕式蝕刻率對TOX之濕式蝕刻率之比例。
在某些具體實施例中,由於濕式蝕刻率程度與該膜中雜質濃度相關,該方法可基於該雜質濃度進行如下:(a)在第一條件下沉積一膜,並測量在該頂表面上之膜之雜質濃度(T1)及在該側壁處之膜之雜質濃度(S1),其中T1<S1;(b)在第二條件下沉積一膜,其中諸如RF功率之製程參數係改變自第一條件之製程參數(例如:增加RF功率),及測量在該頂表面上之該膜之雜質濃度(T2)及在該側壁處之膜之雜質濃度(S2),其中T1<T2,且S1>S2;及(c)重覆步驟(b)直至測定最佳條件,其中T2S2(「」表示實質上相同)。
在某些具體實施例中,該膜係藉由PEALD在下表2中所示之條件下沉積。
圖2說明根據本發明之一具體實施例之一PEALD製程順序。在此揭示中,每一欄之寬度未必代表實際時間長度,且在每一列中之該線之升高水平代表開啟(ON)狀態,而在每一列中該線下方水平代表關閉(OFF)狀態。沉積循環包括以下步驟:依此順序將前驅物饋送至一反應區、清洗該反應區、將RF功率施加至該反應區、及清洗該反應區,其中在整個沉積循環步驟中連續地供應一清洗/載體氣體至該反應區,並在整個沉積循環步驟中將用於沉積之反應氣體連續地供應至該反應區。在該沉積循環
中,可重覆饋送前驅物、清洗該反應區、將RF功率施加至該反應區、及清洗該反應區之步驟p次(p係150至350,通常250至300之整數),取決於該膜之目標膜厚度及目標組成及品質,儘管所述重覆步驟並非為必須的。
在本揭露中,該字詞「連續地」指以下之至少一者:未破壞真空下,未暴露於空氣,未開放一室,作為一原位製程,未中斷為順序中之一步驟、未改變主要製程條件,取決於該具體實施例。在某些具體實施例中,諸如在本內容中無形或非實質之諸步驟間之延遲或其它步驟之一輔助步驟不算作一步驟,因此,該字詞「連續地」不排除插入一輔助步驟。
在圖2中所說明之順序中,使用連續供應之載體氣體以脈衝供應該前驅物。使用流通系統(FPS)完成此程序,其中載體氣體管線提供有具有前驅物儲存器(瓶)之改道管線,且切換主要管線及改道管線,其中當一載體氣體僅意欲饋送至一反應室時,關閉該改道管線,而當意欲饋送該載體氣體及一前驅物氣體兩者至該反應室中時,關閉該主要管線,且該載體氣體流經該改道管線並與該前驅物氣體一起自該瓶流出。在此方式下,該載體氣體可連續地流入該反應室內,並可藉由切換該主要管線及該改道管線脈衝地攜載該前驅物氣體。圖1B示例說明根據本發明之一具體實施例使用一流通系統(FPS)之一前驅物供應系統(黑色閥係指該等閥係關閉的)。如圖1B所示,當饋送一前驅物至一反應室中時(未顯示),首先,一載體氣體(諸如Ar(或He))流經具有閥b及c之一氣體管線,及接著進入一瓶(儲存器)20。該載體氣體自該瓶20流出同時攜載對應於該瓶20內之蒸氣壓之一量的一前驅物氣體,並流經具有閥f及e之一氣體管線,且接著與該前驅物一起饋送至該反應室中。上文中,關閉閥a及d。當僅饋送該載體氣體(惰性氣體)至該反應室中時,如圖1B中之(b)中所示,該載體氣體流經具閥a之氣體管線同時旁流至該瓶20。在上文中,閥b、c、d、e、及f關閉。
可在一載體氣體之輔助下提供該前驅物。由於ALD為自限制吸附反應製程,所沉積之前驅物分子數係以反應表面位點數測定且與飽
和後之前驅物暴露無關,且該前驅物之供應係使得藉以每一循環之該等反應表面位點飽和。可原位產生沉積電漿,例如,於整個沉積循環中連續流動之氨氣中。在其它具體實施例中,該電漿可遠端地產生並提供至該反應室。
如上所提及,每一沉積循環之每一脈衝或階段較佳地係自限制。在每一階段中供應過量之反應劑以飽和該易受影響之結構表面。表面飽和確保所有可得之反應位點之反應劑佔據(例如,受到物理尺寸或「立體阻礙」限制)且因此確保優異之階梯覆蓋。在某些具體實施例中,可減少一或多個反應物之脈衝時間使得未達成完全飽和且在該基板表面上吸附少於單層。
可使用例如包括圖1A所示之裝置之任何適合裝置進行該製程循環。圖1A係可用在本發明之某些具體實施例中之PEALD裝置之示意圖,希望連同經程式化以進行以下描述之順序控制。在本圖式中,藉由平行地並彼此相對地在反應室3之內部11(反應區)中提供一對導電平板電極4、2,向一側施加HRF功率(13.56MHz或27MHz)20,及電接地另一側12,在電極間激發電漿。在較低之台2(低電極)上提供一溫度調節器,且其上所置之基板1之溫度在所給溫度下保持恆定。上方電極4亦用作一淋洗板,且將反應氣體(及惰性氣體)及前驅物氣體分別通過一氣體管線21及一氣體管線22,及通過該淋洗板4引入該反應室3內。此外,在該反應室3中,提供具一排放管線7之圓形管路13,在該反應室3之內部11中之氣體通過其排放。另外,置於該反應室3下之轉移室5提供有一密封氣體管線24以經由該轉移室5之內部16(轉移區)將密封氣體引入該反應室3之內部11內,其中提供用於分開該反應區及該轉移區之一分離板14(一晶圓通過一閘閥轉移至該轉移室5或自其轉移,該閘閥自該圖省略)。該轉移室亦提供有排放管線6。在某些具體實施例中,該多元素膜之沉積及表面處理係在相同反應空間中進行,使得可在未暴露該基板至空氣或其它含氧氣氛下連續地
進行所有該等步驟。在某些具體實施例中,可使用一遠端電漿單元以激發一氣體。
在某些具體實施例中,在圖1A中所示之裝置中,可使用在圖1B(先前所述)中說明之切換一惰性氣體流及一前驅物氣體流之系統,以在無該反應室之實質上波動之壓力下脈衝式地引入該前驅物氣體。
在某些具體實施例中,可使用雙室反應器(用於加工彼此緊密放置之晶圓的兩區或腔室),其中可經由一共用管線供應一反應氣體及惰性氣體,而經由未共用管線供應一前驅物氣體。
熟悉本技術者將了解本裝置包括一或多個控制器(未示出),其經程式化或是經組態以使得進行本文他處所描述之沈積及反應器清潔程序。該(等)控制器與各種電源、加熱系統、幫浦、機器人及反應器之氣體流量控制器或閥連通,如熟悉本技術者所了解。
本發明進一步地參照以下工作實施例解釋。然而,該等實施例未意欲限制本發明。在其中未具體指明條件及/或結構之實施例中,熟悉本技術者考量本揭露作為例行實驗事件可容易地提供此等條件及/或結構。並且,應用在該特定實施例中之數字在某些具體實施例中可以至少±50%之範圍修正,且該等數字為近似值。
在下表3所示之條件下使用圖2中說明之順序及圖1A及1B中說明之PEALD裝置在300-mm基板上形成氧化鈦膜,該基板具有圖案化表面,其具有約2之深寬比及約320nm之開口深度。
測量在該基板之頂表面上沉積之每一膜之一部份的濕式蝕刻率。結果顯示在圖3B中,其中該濕式蝕刻率以WERR/[TOX]表示,即,該膜之濕式蝕刻率對熱氧化膜之濕式蝕刻率之比例。如圖3B中所示,該膜之濕式蝕刻率隨RF功率增加沿具有頂點之向下拋物線變化。即,當RF功率相對弱時,該濕式蝕刻率隨RF功率增加而減少,即,沉積膜之品質改善。該濕式蝕刻率在到達最小值(最低頂點)後開始增加。在最低頂點處獲得之該頂表面上之膜品質呈現最高,因此,隨著RF功率增加,該濕式蝕刻率增加,
降低在該頂表面上沉積之膜品質。亦對一些該等膜測量氮濃度,且結果顯示於圖3A。通常該濕式蝕刻率之變化對應於雜質濃度之變化。
在與實施例1中相同的條件下沉積膜,且不僅測量在該頂表面上亦測量該側壁處之各膜之濕式蝕刻率。結果顯示在圖4中。如圖3B中所示,在到達最小值(最低頂點)後,該濕式蝕刻率開始增加,且圖4顯示在最低頂點後之濕式蝕刻率。在由最低頂點處獲得之頂表面上之膜品質呈現為最高。儘管該頂表面上之膜品質在最低頂點處為最高,在側壁處之膜品質並不高,即,在側壁處之膜之濕式蝕刻率係相對高的。由於電漿不易到達側壁,相對於在頂表面上之膜品質,在側壁處之膜品質未明顯受到RF功率強度的影響。在側壁處之該膜之濕式蝕刻率隨RF功率增加而逐漸減少,如圖4所示。因此,儘管當RF功率相對低時,在側壁處之該膜之濕式蝕刻率高於該頂表面上之該膜之濕式蝕刻率,隨著RF功率增加,在該頂表面之膜之濕式蝕刻率之最低頂點後之某點處,在該頂表面上之該膜之濕式蝕刻率與在該側壁處之該膜之濕式蝕刻率變得實質上相等,此係因為在該側壁處之該膜之濕式蝕刻率逐漸減少的同時,在該頂表面上之該膜之濕式蝕刻率繼續增加,如在圖4中所示。即,表示在該頂表面上之該膜之濕式蝕刻率與RF功率之間之關係之線,與表示在該側壁處之該膜之濕式蝕刻率與RF功率之間之關係之線在約500W處相交。
當RF功率係200W時,以掃描穿透式電子顯微術(STEM)分析在溝槽中沉積之膜。圖5顯示該膜之橫截面之STEM照片,其中(a)顯示如所沉積之膜,及(b)顯示在濕式蝕刻後之膜。如圖5所示,所沉積之膜的依形性在較高側壁處係89%,在較低側壁處係96%,及在底部係97%,而在濕式蝕刻後之該膜的依形性在較高側壁處係83%,在較低側壁處係90%,及在底部係89%,即,在濕式蝕刻後該膜之依形性減少約6%至約8%。
並且,當RF功率係500W時,以掃描穿透式電子顯微術(STEM)分析在溝槽中沉積之膜。圖6顯示該膜之橫截面之STEM照片,其中(a)顯示如所沉積之膜,及(b)顯示在濕式蝕刻後之膜。如圖6所示,所沉積之膜的依形性在較高側壁處係83%,在較低側壁處係89%,及在底部係90%,而在濕式蝕刻後之該膜的依形性在較高側壁處係93%,在較低側壁處係100%,及在底部係99%,即,在濕式蝕刻後該膜之依形性增加約10%至約12%。如上所述,藉由增加RF功率降低在頂表面上之該膜品質(此處,在濕式蝕刻後之厚度減少,在當RF功率係500W時大於當RF功率係200W時),成功地改善在濕式蝕刻後之該膜的依形性。
熟悉本技術之人士應了解可在不背離本發明之精神下進行許多及各種修正。因此,應清楚了解本發明之形式僅作說明之用,且並未意欲限制本發明之範疇。
1:基板
2:底電極
3:反應室
4:上電極
5:轉移室
6:排放管線
7:排放管線
11:內部
12:電接地
13:圓形管路
14:分離板
16:轉移區
20:HRF功率
21:氣體管線
22:氣體管線
24:密封氣體管線
Claims (11)
- 一種用於藉由電漿增強原子層沉積(PEALD)於一溝槽沉積一介電膜之方法,其包含:(i)(a)取得多重基板,在每個基板上於沉積條件下在反應空間中通過PEALD形成一電介膜於每個基板的一溝槽中,其中作為施加給各個基板的RF功率,RF功率是唯一變化的變量,所述溝槽是從該基板的一頂表面向內的凹陷,且具有一底部和連接該頂表面和該底部的一側壁;(b)在共同蝕刻介電膜的條件下對所述多重基板上所形成的介電質膜進行濕蝕刻;(c)獲得一第一標準曲線,其代表施加至該反應空間之RF功率與在該溝槽之側壁上沉積之該膜之一部份之一濕式蝕刻率之間之第一關係,所測量該濕式蝕刻率的濕蝕刻條件為:以1:100稀釋的氫氟酸為蝕刻液,蝕刻溫度為17℃,樣品尺寸為5x5cm2,及蝕刻時間為5分鐘,及獲得一第二標準曲線,其代表該RF功率與在該基板之頂表面上沉積之該膜之一部份之一濕式蝕刻率之間之第二關係,其中饋入該反應空間之一前驅物具有-N(CH3)2作為一官能基,所述PEALD在沉積條件下施行,其中在該第一標準曲線和該第二標準曲線相交的範圍內,RF功率用作唯一變量;(ii)選擇RF功率,其對應於在該溝槽之側壁上沉積之該膜之部份的第一濕式蝕刻率及在該基板之頂表面上沉積之該膜之部份的第二濕式蝕刻率,其中基於步驟(i)中所獲得的該第一及第二標準曲線該第二濕式蝕刻率大於90%的第一濕式蝕刻率;及(iii)藉由PEALD在用於步驟(i)沉積條件的條件下在一基板之溝槽中沉積一介電膜,其中RF功率係在步驟(ii)中所測定者。
- 如申請專利範圍第1項之方法,其中在步驟(iii)中所用之RF 功率經選擇使得第二濕式蝕刻率等於根據步驟(i)中之第一及第二關係之第一濕式蝕刻率。
- 如申請專利範圍第1項之方法,其中該前驅物係二甲基醯胺金屬錯合物。
- 如申請專利範圍第3項之方法,其中在該金屬錯合物中之金屬係鈦。
- 如申請專利範圍第1項之方法,其中用於步驟(iii)中之RF功率係在該基板每單位面積之約0.07W/cm2至約0.7W/cm2之範圍中。
- 如申請專利範圍第1項之方法,其中該溝槽具有約100nm至約500nm之深度及約1至約5之深寬比。
- 如申請專利範圍第1項之方法,其中在步驟(iii)中沉積之該介電膜具有約10nm至約100nm之厚度。
- 如申請專利範圍第1項之方法,其進一步包含(iv)蝕刻在步驟(iii)中沉積之該介電膜。
- 如申請專利範圍第8項之方法,其中在步驟(iii)中沉積之該介電膜具有第一依形性且在步驟(iv)中蝕刻之該介電膜具有第二依形性,其中該第二依形性高於第一依形性。
- 如申請專利範圍第9項之方法,其中該第二依形性係約90% 至約110%。
- 一種用於藉由電漿增強原子層沉積(PEALD)在反應空間中一基板的一溝槽中沉積一介電膜之方法,所述溝槽是從該基板的一頂表面向內的凹陷,且具有一底部和連接該頂表面和該底部的一側壁,該方法包含在該基板之該溝槽中沉積一初始介電膜,並接者以濕蝕刻該初始介電膜,其中沉積該初始介電膜的步驟係藉由PEALD在施加RF功率條件,RF功率是唯一變化的變量,及選擇RF功率係在該基板每單位面積之約0.07W/cm2至約0.7W/cm2之範圍使得在該基板之頂表面上之沉積膜之濕式蝕刻率等大於90%的在該溝槽之側壁處之沉積膜之濕式蝕刻率,所測量該濕式蝕刻率的濕蝕刻條件為:以1:100稀釋的氫氟酸為蝕刻液,蝕刻溫度為17℃,樣品尺寸為5x5cm2,及蝕刻時間為5分鐘,其中饋入該反應空間內之一前驅物具有-N(CH3)2作為官能基。
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2016
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- 2016-10-13 KR KR1020160133156A patent/KR20170044602A/ko not_active Application Discontinuation
- 2016-10-14 CN CN201610898822.5A patent/CN106591801B/zh active Active
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CN106591801B (zh) | 2021-01-05 |
TW201725281A (zh) | 2017-07-16 |
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US9909214B2 (en) | 2018-03-06 |
CN106591801A (zh) | 2017-04-26 |
KR20170044602A (ko) | 2017-04-25 |
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