TWI752516B - 使用表面保護材料來形成薄膜的方法 - Google Patents

使用表面保護材料來形成薄膜的方法 Download PDF

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TWI752516B
TWI752516B TW109119047A TW109119047A TWI752516B TW I752516 B TWI752516 B TW I752516B TW 109119047 A TW109119047 A TW 109119047A TW 109119047 A TW109119047 A TW 109119047A TW I752516 B TWI752516 B TW I752516B
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surface protection
protection material
chamber
metal precursor
adsorbed
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TW202118890A (zh
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李根守
金才玟
金哈娜
崔雄辰
鄭恩愛
李東炫
李明洙
文志原
張東學
魯賢植
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南韓商優吉尼科技材料股份有限公司
南韓商愛思開海力士有限公司
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Abstract

本發明揭露一種使用一表面保護材料來形成一薄膜的方法，該方法包含將該表面保護材料供給至一載置有一基板的腔室內，以使得該表面保護材料被吸附至該基板；藉由吹掃該腔室的內部將未被吸附之表面保護材料從該腔室內排出；將一金屬前驅物供給至該腔室內，以使得該金屬前驅物被吸附至該基板；藉由吹掃該腔室的內部將未被吸附之金屬前驅物從該腔室內排出；以及將一反應材料供給至該腔室內，以使得該反應材料與該被吸附之金屬前驅物進行反應以形成該薄膜。

Description

使用表面保護材料來形成薄膜的方法
發明領域
本發明係有關於形成一薄膜的方法。更具體地，本發明係有關於使用一表面保護材料來形成一薄膜的方法。
發明背景
在半導體製程領域中，沉積製程係將材料沉積在基板上的一重要製程，且隨著電子裝置之外觀持續縮小及裝置之密度增加，特徵的深寬比(aspect ratio)也跟著增加。因此，具有優良階梯覆蓋率(step coverage)之製程係備受關注，且原子層沉積(atomic layer deposition, ALD)相當受到重視。
在原子層沉積(ALD)製程期間，反應氣體被依序地供給至一載置有一基板的製程腔室。第一反應氣體被供給至該製程腔室且被吸附至該基板的表面。第二反應氣體被供給至該製程腔室以與該被吸附之第一反應氣體反應，以使得形成一薄膜。
本發明之一目的係提供形成一具有優良階梯覆蓋率之薄膜的方法。
本發明之另一目的係提供形成一薄膜的方法，其能夠顯著地改善可進行ALD製程的溫度範圍。
本發明之其他目的將由以下詳細說明變得更加明顯。
發明概要
本發明揭露一種使用一表面保護材料來形成一薄膜的方法，該方法包含將該表面保護材料供給至一載置有一基板的腔室內，以使得該表面保護材料被吸附至該基板；藉由吹掃(purging)該腔室的內部將未被吸附之表面保護材料從該腔室內排出；將一金屬前驅物供給至該腔室內，以使得該金屬前驅物被吸附至該基板；藉由吹掃該腔室的內部將未被吸附之金屬前驅物從該腔室內排出；以及將一反應材料供給至該腔室內，以使得該反應材料與該被吸附之金屬前驅物進行反應以形成該薄膜。
該表面保護材料可由以下化學式1表示： ＜化學式1＞
Figure 02_image001
其中n係1或2，且X係選自於CH2 、O、S、NH，且R係選自於一具有1至5個碳原子之烷基基團。
該表面保護材料可由以下化學式2表示： ＜化學式2＞
Figure 02_image003
其中n係1或2，且X係選自於CH2 、O、S、NH，且R係選自於一具有1至5個碳原子之烷基基團。
該表面保護材料可由以下化學式3表示： ＜化學式3＞
Figure 02_image005
該表面保護材料可由以下化學式4表示： ＜化學式4＞
Figure 02_image007
該反應材料可選自於水蒸氣(H2 O)、氧氣(O2 )及臭氧(O3 )。
該金屬前驅物可為一化合物，該化合物包括一包含Al之三價金屬、一包含Zr或Hf之四價金屬，及一包含Nb或Ta之五價金屬的至少一者。
較佳實施例之詳細說明
在下文中，將使用圖1至圖8描述本發明之實施態樣。本發明之實施態樣可包括多種修改，且本發明之範圍不應被視為限於以下描述之實施態樣。
在習知的沉積製程中，在一具有高深寬比(例如，40:1或更高)之溝槽結構(trench structure)中使用單一前驅物，沉積在該溝槽上部(或入口)之薄膜變得較厚，且沉積在該溝槽下部(或底部)之薄膜變得較薄。因此，該薄膜之階梯覆蓋率係差的且不均勻。
然而，下述表面保護材料與金屬前驅物係以相同方式表現，且相較於在該溝槽下部，該表面保護材料在該溝槽上部係在較高密度下被吸附以在接續製程中阻礙該金屬前驅物之吸附，因此該金屬前驅物與一反應材料進行反應以在該溝槽中形成具有均勻厚度之薄膜。
圖1係一流程圖，其示意性地展示根據本發明實施態樣之一種形成薄膜的方法，且圖2係一圖，其示意性地展示根據本發明實施態樣之一供給週期(supply cycle)。將一基板載置於一製程腔室內，並調整以下ALD製程條件。ALD製程條件可包括該基板或該製程腔室之溫度、在該製程腔室中之壓力、氣體流動速率，且該溫度係200至600°C。
將該基板暴露於該被供給至該腔室內部的表面保護材料，且該表面保護材料被吸附至該基板的表面。在一溝槽結構具有高深寬比(例如，40:1或更高)的案例中，該表面保護材料與該金屬前驅物在該沉積製程期間具有一類似行為，以使得該表面保護材料在該溝槽入口係在高密度下被吸附，且在該溝槽底部係在低密度下被吸附，以在接續製程中阻礙該金屬前驅物之吸附。
該表面保護材料可由以下化學式1表示： ＜化學式1＞
Figure 02_image001
其中n係1或2，且X係選自於CH2 、O、S、NH，且R係選自於一具有1至5個碳原子之烷基基團。
該表面保護材料可由以下化學式2表示： ＜化學式2＞
Figure 02_image003
其中n係1或2，且X係選自於CH2 、O、S、NH，且R係選自於一具有1至5個碳原子之烷基基團。
此外，更具體地，該化學式1可由以下化學式3表示： ＜化學式3＞
Figure 02_image005
此外，更具體地，該化學式2可由以下化學式4表示： ＜化學式4＞
Figure 02_image007
其後，將一吹掃氣體(例如，一諸如Ar之惰性氣體)供給至該腔室的內部以將未被吸附之表面保護材料或副產物排出。
其後，將該基板暴露於一被供給至該腔室內部的金屬前驅物，且該金屬前驅物被吸附至該基板的表面。該金屬前驅物可包括一諸如Al之第三族元素、一諸如Zr、Hf之第四族元素，或一諸如Nb或Ta之第五族元素。
舉例而言，相較於在該溝槽底部，上述表面保護材料在該溝槽入口係更密集地被吸附，且該金屬前驅物不會在該表面保護材料被吸附的位置被吸附。換句話說，在習知的沉積製程中，相較於在該溝槽底部，該金屬前驅物在該溝槽入口係更密集地被吸附以在該溝槽入口具有高密度。但是，在本發明中，相較於在該溝槽底部，該表面保護材料在該溝槽入口係更密集地被吸附以阻礙在該溝槽入口該金屬前驅物之吸附，因此，該金屬前驅物可以被均勻地吸附在該溝槽中而不會在該溝槽入口有過度吸附之情形，且可以改善下述薄膜之階梯覆蓋率。
其後，將一吹掃氣體(例如，一諸如Ar之惰性氣體)供給至該腔室的內部以將未被吸附之金屬前驅物或副產物排出。
其後，將該基板暴露於一被供給至該腔室內部的反應材料，且一薄膜係在該基板之表面上形成。該反應材料與該金屬前驅物進行反應以形成該薄膜，且該反應材料可以係水蒸氣(H2 O)、氧氣(O2 )及臭氧(O3 )。一金屬氧化物膜可藉由該反應而形成。此時，該反應材料氧化該被吸附之表面保護材料，且該被吸附之表面保護材料可從該基板之表面被分開並且移除。
其後，將一吹掃氣體(例如，一諸如Ar之惰性氣體)供給至該腔室的內部以將該表面保護材料/未反應材料或副產物排出。
另一方面，先前描述該表面保護材料係在該金屬前驅物之前被供給。或者，該表面保護材料可以係在該金屬前驅物之後被供給，或該金屬前驅物可以係在該表面保護材料之前及之後被供給。 比較實施例
在不使用上述表面保護材料的情況下，在一矽基板上形成一氧化鉿膜。透過ALD製程形成一氧化鉿膜，該製程溫度係300至360°C，且該反應材料係臭氧氣體(O3 )。
以下係透過ALD製程形成該氧化鉿膜之製程，且以下製程係以一個週期進行。 1)    使用Ar作為一載體氣體，在室溫下將該鉿前驅物供給至該反應腔室，且該鉿前驅物被吸附至該基板上。 2)    將Ar氣體供給至該反應腔室內以將未被吸附之鉿前驅物或副產物排出。 3)    藉由將臭氧氣體(O3 )供給至該反應腔室以形成單層(monolayer)。 4)    將Ar氣體供給至該反應腔室內以將未反應之物質或副產物排出。
圖3係一根據本發明比較實施例且根據該製程溫度展示該氧化鉿膜之GPC的圖。如圖3所顯示，直到該基板溫度為320°C時才顯示ALD行為，但是該GPC係在320至340°C區段中增加2.6%，且該GPC係當該基板溫度增加至320°C以上才增加。 實施例1
使用MTHF(2-甲基四氫呋喃)作為一表面保護材料，在一矽基板上形成一氧化鉿膜。透過ALD製程形成一氧化鉿膜，該製程溫度係300至360°C，且該反應材料係臭氧氣體(O3 )。
以下係透過ALD製程形成一氧化鉿膜之製程，且以下製程係以一個週期進行(參見圖1及圖2)。 1)    將一表面保護材料(MTHF)供給至該反應腔室以被吸附至該基板上。 2)    將Ar氣體供給至該反應腔室內以將未被吸附之表面保護材料或副產物排出。 3)    使用Ar作為一載體氣體，在室溫下將該鉿前驅物供給至該反應腔室，且該鉿前驅物被吸附至該基板上。 4)    將Ar氣體供給至該反應腔室內以將未被吸附之鉿前驅物或副產物排出。 5)    藉由將臭氧氣體(O3 )供給至該反應腔室以形成單層。 6)    將Ar氣體供給至該反應腔室內以將未反應之物質或副產物排出。
圖4係一根據本發明實施例1展示該表面保護材料之DSC的圖。由於在400℃以下未檢測到該表面保護材料的分解峰(向上方向)，可見該表面保護材料即使在高溫下被使用也具有表面保護效果而不會被分解。
圖5係一根據本發明比較實施例及實施例1且根據該製程溫度展示該氧化鉿膜之GPC的圖。看到在320°C至340°C區段，在比較實施例的案例中，該GPC增加2.6%，然而在使用MTHF作為該表面保護材料之實施例1的案例中，該GPC增加1.2%以降低該GPC增加，且該ALD窗口(ALD window)擴大到340°C。 實施例2
除了將該表面保護材料從MTHF改為CPME(環戊基甲基醚)之外，以與實施例1相同方式在一矽基板上形成一氧化鉿膜。
圖6係一根據本發明實施例2展示該表面保護材料之DSC的圖。由於在400℃以下未檢測到該表面保護材料的分解峰(向上方向)，可見該表面保護材料即使在高溫下被使用也具有表面保護效果而不會被分解。
圖7係一根據本發明比較實施例及實施例1及實施例2且根據該製程溫度展示該氧化鉿膜之GPC的圖，以及圖8係一根據在本發明比較實施例及實施例1及實施例2中溫度之增加而展示GPC增加速率的表。看到在320°C至340°C區段，在比較實施例的案例中，該GPC增加2.6%，然而在使用MTHF作為該表面保護材料之實施例1的案例中，該GPC增加1.2%以降低該GPC之增加，且該ALD窗口擴大到340°C，以及在使用CPME作為一表面保護材料之實施例2的案例中，該GPC增加0.48%以降低該GPC之增加，且該ALD窗口擴大到340°C。
總而言之，該表面保護材料根據溫度之上升而緩和該GPC之增加，且其增加可進行ALD製程的溫度範圍。此外，在一溝槽結構具有高深寬比(例如，40:1或更高)的案例中，該表面保護材料與該金屬前驅物在該沉積製程期間具有一類似行為，以使得該表面保護材料在該溝槽入口係在高密度下被吸附，且在該溝槽底部係在低密度下被吸附，以在接續製程中阻礙該金屬前驅物之吸附。因此，該金屬前驅物可以均勻地被吸附該溝槽中。
具體地，以下係根據本發明之比較實施例及實施例1及實施例2之該等氧化鉿膜的階梯覆蓋率，且相較於比較實施例，在實施例1及實施例2的案例中，可看到階梯覆蓋率被顯著地改善。
表1
  階梯覆蓋率 (@300℃)
比較實施例 84.7
實施例1 89.8
實施例2 88.2
根據本發明，可形成一具有優良階梯覆蓋率之薄膜。該表面保護材料與該金屬前驅物在該沉積製程期間具有一類似行為。在一溝槽結構具有高深寬比(例如，40:1或更高)的案例中，該表面保護材料在該溝槽入口係在高密度下被吸附，且該表面保護材料在該溝槽底部係在低密度下被吸附，以使得藉由該保護材料阻礙該金屬前驅物之吸附。因此，該金屬前驅物可以在該溝槽中被均勻地吸附。
此外，該表面保護材料可根據溫度之上升而緩和該GPC之增加，因此增加可進行ALD製程的溫度範圍(ALD窗口)。
已參照實施態樣詳細地解釋本發明，但是其他實施態樣亦可被包括。 因此，在以下發明申請專利範圍中所描述之技術思想及範圍不限於該等實施態樣。
圖1係一示意性地展示根據本發明實施態樣之一種形成一薄膜的方法的流程圖。
圖2係一示意性地展示根據本發明實施態樣之一供給週期(supply cycle)的圖。
圖3係一根據本發明比較實施例且根據該製程溫度展示該氧化鉿膜之GPC的圖。
圖4係一根據本發明實施例1展示該表面保護材料之DSC的圖。
圖5係一根據本發明比較實施例及實施例1且根據該製程溫度展示該氧化鉿膜之GPC的圖。
圖6係一根據本發明實施例2展示該表面保護材料之DSC的圖。
圖7係一根據本發明比較實施例及實施例1及實施例2且根據該製程溫度展示該氧化鉿膜之GPC的圖。
圖8係一根據在本發明比較實施例及實施例1及實施例2中溫度之增加而展示GPC增加速率的表。

Claims (6)

  1. 一種使用一表面保護材料來形成一薄膜的方法，該方法包含：將該表面保護材料供給至一載置有一基板的腔室內，以使得該表面保護材料被吸附至該基板；藉由吹掃該腔室的內部將未被吸附之表面保護材料從該腔室內排出；將一金屬前驅物供給至該腔室內，以使得該金屬前驅物被吸附至該基板；藉由吹掃該腔室的內部將未被吸附之金屬前驅物從該腔室內排出；以及將一反應材料供給至該腔室內，以使得該反應材料與該被吸附之金屬前驅物進行反應以形成該薄膜，其中該表面保護材料係由以下化學式1或以下化學式2表示：
    Figure 109119047-A0305-02-0013-1
    Figure 109119047-A0305-02-0013-2
     其中n係1或2，且X係選自於CH2、O、S、NH，且R係選自於一具有1至5個碳原子之烷基基團。
  2. 如請求項1之方法，其中該表面保護材料係2-甲基四氫呋喃(MTHF)或CPME(環戊基甲基醚)。
  3. 如請求項1之方法，其中該表面保護材料係由以下化學式3表示：
    Figure 109119047-A0305-02-0014-3
  4. 如請求項1之方法，其中該表面保護材料係由以下化學式4表示：
    Figure 109119047-A0305-02-0014-4
  5. 如請求項1之方法，其中該反應材料係選自於水蒸氣(H2O)、氧氣(O2)及臭氧(O3)。
  6. 如請求項1之方法，其中該金屬前驅物係一化合物，該化合物包括一包含Al之三價金屬、一包含Zr或Hf之四價金屬，及一包含Nb或Ta之五價金屬的至少一者。
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