TW202028427A - 矽層蝕刻劑組成物、製備其的方法及形成圖案的方法 - Google Patents
矽層蝕刻劑組成物、製備其的方法及形成圖案的方法 Download PDFInfo
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- TW202028427A TW202028427A TW109100598A TW109100598A TW202028427A TW 202028427 A TW202028427 A TW 202028427A TW 109100598 A TW109100598 A TW 109100598A TW 109100598 A TW109100598 A TW 109100598A TW 202028427 A TW202028427 A TW 202028427A
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- silicon layer
- etchant composition
- group
- nonionic surfactant
- amine compound
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- 239000000203 mixture Substances 0.000 title claims abstract description 94
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 63
- 239000010703 silicon Substances 0.000 title claims abstract description 63
- 238000000034 method Methods 0.000 title claims abstract description 51
- -1 amine compound Chemical class 0.000 claims abstract description 60
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- 125000005210 alkyl ammonium group Chemical group 0.000 claims abstract description 33
- 125000001165 hydrophobic group Chemical group 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000005530 etching Methods 0.000 claims description 44
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- 239000000126 substance Substances 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 7
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- QVOFCQBZXGLNAA-UHFFFAOYSA-M tributyl(methyl)azanium;hydroxide Chemical compound [OH-].CCCC[N+](C)(CCCC)CCCC QVOFCQBZXGLNAA-UHFFFAOYSA-M 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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Abstract
一種矽層蝕刻劑組成物、製備其的方法及形成圖案的方法,所述組成物包含約1重量%到約20重量%的烷基氫氧化銨;約1重量%到約30重量%的胺化合物;約0.01重量%到約0.2重量%的包括疏水基團及親水基團兩者的非離子表面活性劑;以及水,所有重量%都是基於所述矽層蝕刻劑組成物的總重量。
Description
各實施例有關一種矽層蝕刻劑組成物及使用所述矽層蝕刻劑組成物形成圖案的方法。相關申請的交叉參考
2019年1月8號在韓國智慧財產權局提出申請且標題為:“矽層蝕刻劑組成物及使用其形成圖案的方法”的韓國專利申請第10-2019-0002488號全文併入本文供參考。
在例如動態隨機存取記憶體(dynamic random-access memory,DRAM)、反及閘(NAND)快閃記憶體裝置等半導體裝置中,儘管臨界尺寸(critical dimension,CD)最近急劇減小,但實現大容量的開發仍在繼續。
在此種半導體裝置中,例如可使用基於矽(例如,多晶矽)的層或圖案作為閘電極、電容器電極、導電觸點、佈線(wiring line)等的材料。
實施例可通過提供一種矽層蝕刻劑組成物來實現,所述矽層蝕刻劑組成物包含:約1重量%到約20重量%的烷基氫氧化銨;約1重量%到約30重量%的胺化合物;約0.01重量%到約0.2重量%的包括疏水基團及親水基團兩者的非離子表面活性劑;以及水,所有重量%都是基於所述矽層蝕刻劑組成物的總重量。
實施例可通過提供一種形成圖案的方法來實現,所述方法包括:通過蝕刻基板上的矽層形成虛設閘極;形成絕緣層以部分包圍所述虛設閘極;通過使用根據實施例的矽層蝕刻劑組成物移除所述虛設閘極;以及在通過移除所述虛設閘極而獲得的開口中形成閘極結構。
實施例可通過提供一種製備根據實施例的矽層蝕刻劑組成物的方法來實現,所述方法包括:通過將胺化合物與包括疏水基團及親水基團兩者的非離子表面活性劑混合來製備添加劑混合物;以及將所述添加劑混合物與烷基氫氧化銨的水溶液混合。
實施例可通過提供一種形成圖案的方法來實現,所述方法包括:通過蝕刻基板上的矽層形成虛設閘極;形成絕緣層以部分包圍所述虛設閘極;通過使用包含烷基氫氧化銨、胺化合物、包括疏水基團及親水基團兩者的非離子表面活性劑以及水的蝕刻劑組成物來移除所述虛設閘極;以及在通過移除所述虛設閘極而獲得的開口中形成閘極結構。
實施例可通過提供一種用於矽層蝕刻劑的添加劑混合物來實現,所述添加劑混合物包含:胺化合物;以及包括疏水基團及親水基團兩者的非離子表面活性劑。
實施例可通過提供一種製備矽層蝕刻劑組成物的方法來實現,所述方法包括:通過將胺化合物與包括疏水基團及親水基團兩者的非離子表面活性劑混合來製備根據實施例的添加劑混合物;以及將所述添加劑混合物與烷基氫氧化銨水溶液混合。
實施例可通過提供一種製備矽層蝕刻劑組成物的方法來實現,所述方法包括:通過將胺化合物與包括疏水基團及親水基團兩者的非離子表面活性劑混合來製備添加劑混合物;以及將所述添加劑混合物與烷基氫氧化銨水溶液混合。
在實施方式中,蝕刻劑組成物可包含例如烷基氫氧化銨、胺化合物及非離子表面活性劑。
在本文中所用的術語“矽層”可指包含多晶矽或非晶矽的層。
在下文中,將詳細闡述實施例。
>矽層蝕刻劑組成物>
根據示例性實施例的矽層蝕刻劑組成物(其在下文中可簡稱為蝕刻劑組成物)可包含例如烷基氫氧化銨、胺化合物、非離子表面活性劑及水(例如,餘量的水)。
可包含烷基氫氧化銨作為通過離解氫氧離子而移除矽層的主要蝕刻試劑。在實施方式中,烷基氫氧化銨可包括由化學式1表示的季烷基氫氧化銨(quaternary alkylammonium hydroxide)。
[化學式1]
在化學式1中,R1
、R2
、R3
及R4
可各自獨立地為例如C1到C8烷基或C6到C8芳基。在實施方式中,R1
、R2
、R3
及R4
可各自獨立地為例如C1到C4烷基。在實施方式中,R1
、R2
、R3
及R4
中的至少一者可為例如C1到C8烷基。如果R1
、R2
、R3
及R4
各自的碳數過度增加,那麼氫氧離子的解離可因空間位阻(steric hindrance)而受到抑制。
在實施方式中,烷基氫氧化銨可包括例如四甲基氫氧化銨、四乙基氫氧化銨、四丙基氫氧化銨、四丁基氫氧化銨、四己基氫氧化銨、四辛基氫氧化銨、苄基三乙基氫氧化銨、二乙基二甲基氫氧化銨、甲基三丁基氫氧化銨等。烷基氫氧化銨可單獨使用或組合使用。
在實施方式中,以蝕刻劑組成物的總重量計,烷基氫氧化銨可以例如約1重量%到約20重量%的量存在。在此範圍內,可確保氫氧離子的解離度或者從蝕刻劑組成物解離的氫氧離子的量,並且可實現足夠的蝕刻能力。在實施方式中,以蝕刻劑組成物的總重量計,烷基氫氧化銨可以例如約3重量%到約17重量%的量存在。
胺化合物可有助於調節或保持蝕刻劑組成物的酸鹼度(pH),並且可被添加作為蝕刻促進劑。舉例來說,胺化合物可有助於加速蝕刻劑組成物中氫氧離子的解離或生成,並且可有助於改善矽層的親水化或潤濕性。此外,胺化合物可有助於加速移除在蝕刻矽層期間產生的表面氫氣。
在實施方式中,胺化合物可包括例如1-氨基-2-丙醇、2-氨基-1-丁醇、3-氨基-1-丙醇、3-氨基-1,2-丙二醇、2,3-丁二醇、二乙烯三胺、異丙胺、甲基二乙醇胺、三乙胺、三甲胺、甲胺、乙胺、丙醇胺、乙醇胺、苯胺、2-氨基戊烷、二乙胺、二乙醇胺、N-甲基乙醇胺、N-甲基二乙醇胺、2-氨基-3-甲基-1-丁醇、3-氨基-2,2-二甲基-1-丙醇、三(羥甲基)氨基甲烷、2-氨基-2-甲基-1,3-丙二醇、3-甲氨基-1-丙醇、2-二甲氨基-2-甲基-1-丙醇、1-二甲氨基-2-丙醇、3-二甲氨基-1-丙醇、2-二甲氨基-1-丙醇、2-二乙胺基-1-丙醇、2-二乙胺基-1-乙醇、2-乙胺基-1-乙醇、1-(二甲氨基)-2-丙醇、二乙醇胺、N-丙基二乙醇胺、N-異丙基二乙醇胺、N-(2-甲基丙基)二乙醇胺、N-正丁基二乙醇胺、N-叔丁基乙醇胺、N-環己基二乙醇胺、N-十二烷基二乙胺、2-(二甲氨基)乙醇、2-二乙氨基乙醇、2-二丙氨基乙醇、2-丁氨基乙醇、2-叔丁基氨基乙醇、2-環氨基乙醇、2-氨基-2-戊醇、2-[雙(2-羥乙基)氨基]-2-甲基-1-丙醇、2-[雙(2-羥乙基)氨基]-2-丙醇、N,N-雙(2-羥丙基)乙醇胺、2-氨基-2-甲基-1-丙醇、三(羥甲基)氨基甲烷、三異丙醇胺、三甲基吡啶、二甲基吡啶等。這些胺化合物可單獨使用或組合使用。
在實施方式中,胺化合物可包括例如含羥基的胺化合物(例如,烷醇胺化合物)。
在實施方式中,以蝕刻劑組成物的總重量計,胺化合物可以例如約1重量%到約30重量%的量存在。將胺化合物的量保持在約1重量%或大於1重量%可有助於確保實現蝕刻加速及氣體移除的充分效果。將胺化合物的量保持在約30重量%或小於30重量%可有助於確保胺化合物不會過度吸附到矽層上,從而防止蝕刻速率的劣化。
非離子表面活性劑可有助於降低矽層的表面張力,並且可有助於抑制在蝕刻製程中產生的泡沫或氣泡。
在實施方式中,非離子表面活性劑可具有親水基團及疏水基團相結合的結構。
親水基團可有助於改善蝕刻劑組成物中非離子表面活性劑的滲透性。舉例來說,當非離子表面活性劑吸附在矽層表面上時,親水基團可同時加速氫氧離子的滲透。
親水基團可具有相對大於疏水基團的分子量,並且親水基團可改善對蝕刻劑組成物的整體親和力。在實施方式中,親水基團可包括例如聚氧伸烷基(polyoxyalkylene)、多羥基醇(polyhydroxy alcohol)、氟烷基磺醯胺銨(ammonium fluoroalkylsulfonamide)等。在實施方式中,親水基團可包括例如聚氧伸烷基。
在實施方式中,聚氧伸烷基結構中包含的烷基氧化物的重複次數可為2到8次(例如,聚氧伸烷基基團可包括2到8個烷基氧化物部分)。在此範圍內,可防止過度的空間位阻及分子量的過度增加,並且可易於確保與蝕刻劑組成物的充分相互作用。
疏水基團可有助於加速在矽層表面上的吸附,並且可移除或解吸在蝕刻製程中產生的泡沫或氣泡。為了有助於改善在矽層表面上的吸附,與親水基團相比,疏水基團可具有相對較低的分子量結構。
在實施方式中,疏水基團可包括例如脂族或芳族烴基。在實施方式中,疏水基團可包括例如環狀結構。舉例來說,為了有助於改善非離子表面活性劑對矽層周圍圖案之間空間的滲透性,疏水基團可包括脂環族環或芳族環。在實施方式中,疏水基團可包括例如芳環。
在實施方式中,疏水基團可包括例如丙基、異丙基、丁基、異丁基、仲丁基、叔丁基、苯基、萘基、乙基己基、癸基、月桂基、異十三烷基、十六烷基、油烯基、硬脂醯基(stearyl group)、烷基苯基(甲基苯基或辛基苯基)等。
在實施方式中,疏水基團可具有例如C3到C18結構。在實施方式中,疏水基團可具有例如C3到C10結構。在此範圍內,通過疏水基團的吸附/解吸來移除泡沫或氣泡可得到進一步改善。
在實施方式中,親水基團可通過醚鍵(-O-)連接到疏水基團。
在實施方式中,以蝕刻劑組成物的總重量計,非離子表面活性劑可以例如約0.01重量%到約0.2重量%的量存在。將非離子表面活性劑的量保持在約0.01重量%或大於0.01重量%可有助於確保實現移除泡沫或氣泡的充分效果。將非離子表面活性劑的量保持在約0.2重量%或小於0.2重量%可有助於確保在不降低蝕刻速率的情況下保持降低表面張力的效果。
蝕刻劑組成物可包含水,例如剩餘量或餘量的水(例如,去離子水)。在本文中所用的術語“剩餘量”或“餘量”可指依據組分或試劑的添加而變化的可變數。舉例來說,術語“剩餘量”或“餘量”可指除了以上已闡述的烷基氫氧化銨、胺化合物及非離子表面活性劑各自的量之外的剩餘量,或者除了烷基氫氧化銨、胺化合物、非離子表面活性劑及其他添加劑各自的量之外的剩餘量。
在實施方式中,蝕刻劑組成物可進一步包含添加劑,所述添加劑不抑制由烷基氫氧化銨、胺化合物及非離子表面活性劑提供的蝕刻能力、表面張力降低效果、氣泡移除效果等。在實施方式中,添加劑可包括例如蝕刻促進劑、腐蝕抑制劑、酸鹼度控制劑等。
在實施方式中,蝕刻劑組成物的酸鹼度可調節到例如約11到約14的範圍。在此酸鹼度範圍內,可抑制對其他絕緣結構、半導體圖案、基板等(除了作為蝕刻目標層的矽層)的損壞。
在實施方式中,蝕刻劑組成物可製備成2-液體型(2-liquid type)組成物。舉例來說,用於矽層蝕刻劑的初步蝕刻劑組成物或添加劑混合物可通過混合胺化合物及非離子表面活性劑來製備。然後可將用於矽層蝕刻劑的初步蝕刻劑組成物或添加劑混合物與烷基氫氧化銨水溶液混合。舉例來說,具有目標成分的蝕刻劑組成物可由相對濃縮的初步蝕刻劑組成物製備。
由於蝕刻劑組成物以上述2-液體型的方式製備,因此胺化合物與非離子表面活性劑可預先彼此混合並穩定。舉例來說,可防止活性抑制,否則會由於胺化合物及非離子表面活性劑預先與烷基氫氧化銨接觸而發生活性抑制。
如上所述,在根據示例性實施例的蝕刻劑組成物中,可通過烷基氫氧化銨與胺化合物之間的相互作用來增加矽層的蝕刻速率,並且可通過非離子表面活性劑與胺化合物之間的相互作用來實現表面張力的降低及潤濕性的改善。舉例來說,可防止由矽層表面上的泡沫或氣泡導致的不良蝕刻,並且可實現高蝕刻速率及蝕刻均勻性。
>圖案形成方法>
圖1到圖5示出根據示例性實施例在形成圖案的方法中各階段的示意性剖視圖。在實施方式中,如圖1到5所示,半導體邏輯裝置可包括使用矽層的多替換閘極(poly-replacement gate)或閘極最後製程(gate-last process)。
在實施方式中,蝕刻劑組成物可用於形成各種結構或圖案(例如,佈線、觸點及閘極)的製程。
參照圖1,可在基板100上以此所陳述的次序依序形成閘極絕緣層110及虛設閘極層120。
基板100可包含半導體材料,例如單晶矽、單晶鍺或III-V族化合物。
閘極絕緣層110可包含例如氧化矽、高介電常數(high-k)金屬氧化物等。虛設閘極層120可包含例如多晶矽或非晶矽。在實施方式中,可通過化學氣相沉積(chemical vapor deposition,CVD)製程、濺射製程、物理氣相沉積(physical vapor deposition,PVD)製程、原子層沉積(atomic layer deposition,ALD)製程等形成閘極絕緣層110。
參照圖2,可通過部分蝕刻虛設閘極層120及閘極絕緣層110來形成虛設閘極125及閘極絕緣圖案115。
舉例來說,可在虛設閘極層120上形成硬罩幕或光致抗蝕劑圖案。可通過使用硬罩幕或光致抗蝕劑圖案作為蝕刻罩幕的乾蝕刻製程形成虛設閘極125及閘極絕緣圖案115。
參照圖3,可在基板100上形成絕緣層130使得虛設閘極125的頂表面被暴露出。舉例來說,可沉積包括氧化矽、氮化矽、氮氧化矽、聚矽氧烷等的絕緣材料,隨後通過化學機械研磨(chemical mechanical polishing,CMP)製程平坦化絕緣材料使得虛設閘極125的頂表面被暴露出,從而形成絕緣層130。
參照圖4,可使用根據示例性實施例的前述蝕刻劑組成物來移除虛設閘極125。可在通過移除虛設閘極125獲得的空間中形成開口135。
如上所述,蝕刻劑組成物可通過烷基氫氧化銨與胺化合物之間的相互作用而對矽層具有改善的蝕刻速率,並且可有助於通過非離子表面活性劑與胺化合物之間的相互作用而防止在矽層表面上產生泡沫或氣泡。舉例來說,可在沒有蝕刻缺陷的情況下移除具有奈米級大小的虛設閘極125。
參照圖5,可在開口135中形成閘極結構。
舉例來說,可在絕緣層130上形成包含金屬氮化物(例如,氮化鈦或氮化鉭)的阻擋層及包含金屬(例如,鎢、鈷或銅)的閘極金屬層以填充開口135。接下來,可通過化學機械研磨製程平坦化閘極金屬層及阻擋層使得絕緣層130的頂表面被暴露出,從而形成包括阻擋圖案140及金屬閘極150的閘極結構。
在實施方式中,再次參照圖4,在移除虛設閘極125之後,也可移除閘極絕緣圖案115。在此種情形下,閘極絕緣圖案115可被設置為虛設閘極絕緣層。接下來,在開口135中形成閘極結構之前,可再次形成閘極絕緣層。
提供以下實例及比較例是為了突出一個或多個實施例的特性,但應理解,所述實例及比較例不應被解釋為限制實施例的範圍,比較例也不應被解釋為位於實施例的範圍外。此外,應理解,實施例並不僅限於在實例及比較例中描述的特定細節。
根據在表1(實例)及表2(比較例)中列出的量(重量%)混合了各組分,並且一般添加了餘量的水,從而製備實例及比較例中每一者的蝕刻劑組成物。
表1
烷基氫氧化銨 | 非離子表面活性劑 | 胺化合物 | |||||||
B-l | B-2 | B-3 | B-4 | B-5 | B-6 | B-7 | |||
實例1 | 8.4(A-1) | 0.09 | 17.2(C-l) | ||||||
實例2 | 8.4(A-1) | 0.09 | 11.4(C-2) | ||||||
實例3 | 8.4(A-1) | 0.09 | 21.7(C-3) | ||||||
實例4 | 15.6(A-1) | 0.08 | 17.2(C-l) | ||||||
實例5 | 15.6(A-1) | 0.08 | 11.4(C-2) | ||||||
實例6 | 15.6(A-1) | 0.08 | 21.7(C-3) | ||||||
實例7 | 3.2(A-1) | 0.13 | 17.2(C-l) | ||||||
實例8 | 3.2(A-1) | 0.13 | 11.4(C-2) | ||||||
實例9 | 3.2(A-1) | 0.13 | 21.7(C-3) | ||||||
實例10 | 16.8(A-1) | 0.16 | 17.2(C-l) | ||||||
實例11 | 16.8(A-1) | 0.16 | 11.4(C-2) | ||||||
實例12 | 16.8(A-1) | 0.16 | 21.7(C-3) | ||||||
實例13 | 8.1(A-1) | 0.03 | 17.2(C-l) | ||||||
實例14 | 8.1(A-1) | 0.03 | 11.4(C-2) | ||||||
實例15 | 8.1(A-1) | 0.03 | 21.7(C-3) | ||||||
實例16 | 1(A-l) | 0.08 | 17.2(C-l) | ||||||
實例17 | 10(A-l) | 0.08 | 17.2(C-l) | ||||||
實例18 | 20(A-l) | 0.08 | 17.2(C-l) | ||||||
實例19 | 15.6(A-1) | 0.01 | 17.2(C-l) | ||||||
實例20 | 15.6(A-1) | 0.10 | 17.2(C-l) | ||||||
實例21 | 15.6(A-1) | 0.20 | 17.2(C-l) | ||||||
實例22 | 15.6(A-1) | 0.08 | 1(C-l) | ||||||
實例23 | 15.6(A-1) | 0.08 | 10(C-l) | ||||||
實例24 | 15.6(A-1) | 0.08 | 20(C-l) | ||||||
實例25 | 15.6(A-1) | 0.08 | 30(C-l) | ||||||
實例26 | 15.6(A-2) | 0.08 | 17.2(C-l) | ||||||
實例27 | 15.6(A-3) | 0.08 | 17.2(C-l) | ||||||
實例28 | 15.6(A-4) | 0.08 | 17.2(C-l) | ||||||
實例29 | 14.3(A-1) | 0.15 | 17.2(C-l) | ||||||
實例30 | 10.1(A-l) | 0.12 | 17.2(C-l) | ||||||
實例31 | 15.6(A-1) | 0.08 | 12.0(C-4) | ||||||
實例32 | 15.6(A-1) | 0.08 | 8.7(C-5) |
表2
烷基氫氧化銨 | 表面活性劑 | 胺化合物 | ||||
B-2 | B-8 | B-9 | ||||
比較例1 | 0.1(A-1) | 0.08 | - | - | 17.2(C-1) | |
比較例2 | 0.5(A-l) | 0.08 | - | - | 17.2(C-1) | |
比較例3 | 21(A-1) | 0.08 | - | - | 17.2(C-1) | |
比較例4 | 25(A-1) | 0.08 | - | - | 17.2(C-1) | |
比較例5 | 15.6(A-1) | 0.005 | - | - | 17.2(C-1) | |
比較例6 | 15.6(A-1) | 0.25 | - | - | 17.2(C-1) | |
比較例7 | 15.6(A-1) | 0.08 | - | - | 0.5(C-1) | |
比較例8 | 15.6(A-1) | 0.08 | - | - | 31(C-1) | |
比較例9 | 15.6(A-1) | 0.08 | - | - | 35(C-1) | |
比較例10 | 15.6(A-1) | - | - | - | - | |
比較例11 | - | 0.08 | - | - | - | |
比較例12 | - | - | - | - | 17.2(C-1) | |
比較例13 | 15.6(A-1) | 0.08 | - | - | - | |
比較例14 | 15.6(A-1) | - | - | - | 17.2(C-1) | |
比較例15 | - | 0.08 | - | - | 17.2(C-1) | |
比較例16 | 15.6(A-1) | - | 0.08 | - | 17.2(C-1) | |
比較例17 | 15.6(A-1) | - | - | 0.08 | 17.2(C-1) | |
表1及表2中採用的組分如下。
A-1)四甲基氫氧化銨
A-2)四乙基氫氧化銨
A-3)四丙基氫氧化銨
A-4)四丁基氫氧化銨
B-1)聚氧乙烯苯基醚,n=2個烷基氧化物部分
B-2)聚氧乙烯苯基醚,n=4個烷基氧化物部分
B-3)聚氧乙烯β-萘基醚
B-4)聚氧乙烯2-乙基己基醚
B-5)聚氧乙烯癸基醚
B-6)聚氧乙烯月桂基醚
B-7)聚氧乙烯油烯基醚
B-8)十二烷基硫酸鈉
B-9)月桂基三甲基溴化銨
C-1)1-氨基-2-丙醇
C-2)2-氨基-1-丁醇
C-3)N-甲基乙醇胺
C-4)二乙烯三胺
C-5)三乙醇胺
實驗例
1)評估表面氣泡
通過將矽晶片切割成1.5公分×1.5公分的大小並浸入實例及比較例各自的蝕刻劑組成物中1分鐘而製備了樣品,其中在矽晶片上形成有厚度為1900 Å的多晶矽層。此處,在多晶矽層上產生的表面氣泡觀察及評估如下。
>評估標準>
◎:以多晶矽層的表面積計,氣泡覆蓋面積等於或小於1%
○:氣泡覆蓋面積大於1%且等於或小於10%
△:氣泡覆蓋面積大於10%且等於或小於20%
×:氣泡覆蓋面積大於20%
2)評估多晶矽層的潤濕性
測量了每個實例及比較例的蝕刻劑組成物相對於多晶矽層的表面的接觸角(C/A),從而評估潤濕性。評估標準如下。
>評估標準>
◎:C/A等於或小於10°
○:C/A大於10°且等於或小於20°
△:C/A大於20°且等於或小於30°
×:C/A大於30°
3)評估多晶矽層的蝕刻速率
將上面沉積有厚度為1,900 Å的多晶矽層的矽晶片切割成1.5公分×1.5公分的大小,從而製備樣本。在70℃及400 rpm的條件下,將樣本浸入含有實例及比較例各自的蝕刻劑組成物的浴中10秒鐘。接下來,從浴中取出樣本,用水清洗並風乾,隨後使用掃描電子顯微鏡(scanning electron microscope,SEM)測量多晶矽層的厚度,且然後通過計算從多晶矽層的初始厚度的厚度變化來計算多晶矽層的蝕刻速率。
>評估標準>
◎:蝕刻速率等於或大於3,500 Å/min
○:蝕刻速率小於3,500 Å/min且等於或大於2,500 Å/min
△:蝕刻速率小於2,500 Å/min且等於或大於1,500 Å/min
×:蝕刻速率小於1,500 Å/min
4)評估泡沫破裂率
通過使用氣泡發生器由實例及比較例中每一者的蝕刻劑組成物人工產生泡沫10秒鐘,隨後檢查泡沫破裂趨勢。評估標準如下。
>評估標準>
◎:泡沫破裂率等於或大於5%/sec
○:泡沫破裂率小於5%/秒且等於或大於3%/sec
△:泡沫破裂率小於3%/sec且等於或大於1%/sec
×:泡沫破裂率小於1%/sec
評估結果示出於表3及表4中。
[表3]
表面氣泡 | 潤濕性 | 蝕刻速率 | 泡沫破裂率 | |
實例1 | ○ | ○ | ◎ | ◎ |
實例2 | ○ | ○ | ◎ | ◎ |
實例3 | ○ | ○ | ◎ | ◎ |
實例4 | ◎ | ◎ | ◎ | ◎ |
實例5 | ○ | ◎ | ◎ | ◎ |
實例6 | ○ | ○ | ◎ | ◎ |
實例7 | ◎ | ○ | ○ | ○ |
實例8 | ◎ | ○ | ○ | ○ |
實例9 | ◎ | ○ | ○ | ○ |
實例10 | ○ | ○ | ○ | △ |
實例11 | ○ | ○ | ○ | △ |
實例12 | ○ | ○ | ○ | △ |
實例13 | △ | ○ | ○ | △ |
實例14 | △ | ○ | ○ | △ |
實例15 | △ | ○ | ○ | △ |
實例16 | ◎ | △ | △ | ◎ |
實例17 | ◎ | ◎ | ◎ | ◎ |
實例18 | ◎ | ◎ | △ | ◎ |
實例19 | △ | △ | ◎ | ◎ |
實例20 | ◎ | ◎ | ○ | ◎ |
實例21 | ◎ | ◎ | △ | ○ |
實例22 | △ | △ | ○ | ◎ |
實例23 | ○ | ○ | ○ | ◎ |
實例24 | ◎ | ◎ | ◎ | ◎ |
實例25 | ◎ | ◎ | △ | ◎ |
實例26 | ◎ | ◎ | ○ | ◎ |
實例27 | ◎ | ◎ | △ | ◎ |
實例28 | ◎ | ◎ | △ | ◎ |
實例29 | △ | ◎ | △ | △ |
實例30 | △ | ◎ | △ | △ |
實例31 | △ | ◎ | △ | △ |
實例32 | △ | ◎ | △ | △ |
[表4]
表面氣泡 | 潤濕性 | 蝕刻速率 | 泡沫破裂率 | |
比較例1 | ◎ | △ | X | ◎ |
比較例2 | ◎ | △ | X | ◎ |
比較例3 | ◎ | ◎ | X | ◎ |
比較例4 | ◎ | ◎ | X | ◎ |
比較例5 | X | ○ | ◎ | ◎ |
比較例6 | ◎ | ◎ | X | X |
比較例7 | △ | X | ○ | ◎ |
比較例8 | ◎ | ◎ | X | ◎ |
比較例9 | ◎ | ◎ | X | ◎ |
比較例10 | X | X | ◎ | ◎ |
比較例11 | ◎ | △ | X | ◎ |
比較例12 | ○ | ○ | △ | ◎ |
比較例13 | △ | X | ○ | ◎ |
比較例14 | X | △ | ◎ | ◎ |
比較例15 | X | X | X | ◎ |
比較例16 | △ | △ | △ | △ |
比較例17 | △ | △ | △ | △ |
參照表3及表4,實例的蝕刻劑組成物(包括上述組分及量)整體上相對於多晶矽層保持了改善的蝕刻速率,並且高效地抑制了表面氣泡及泡沫。
在將實例1到實例9的蝕刻劑組成物與實例10到實例15的蝕刻劑組成物進行比較時,蝕刻劑組成物在非離子表面活性劑的疏水基團包括芳環的情況下表現出更好的氣泡移除及泡沫破裂效果。
其中疏水基團的碳數稍微增加(碳數大於10)的實例29及實例30的蝕刻劑組成物表現出略微劣化的泡沫破裂效果。
綜上所述,當已經通過直接蝕刻金屬層而形成閘電極或佈線時,由於蝕刻解析度的限制,可能不容易形成具有預期精細大小的圖案,並且已經考慮了使用多晶矽層的製程。
當打算執行高可靠性半導體裝置製程時,製程良率或尺寸可靠性可能會因細小雜質或製程副產物而劣化。舉例來說,當執行蝕刻製程時,蝕刻均勻性可能會因從蝕刻劑產生的氣泡而劣化。
舉例來說,當執行矽層蝕刻製程時,蝕刻劑組成物可有助於改善蝕刻速率,同時保持蝕刻穩定性及可靠性用於形成細小圖案。
舉例來說,一些多晶矽層蝕刻劑可包括氫氧化銨,並且可考慮進行組分調整用於穩定形成細小圖案。
一個或多個實施例可提供一種表現出改善的蝕刻穩定性及蝕刻速率的矽層蝕刻劑組成物。
實施例提供一種蝕刻劑組成物,所述蝕刻劑組成物可具有改善的穩定性及效率,並且能夠蝕刻矽層。
此外,實施例可提供一種使用上述蝕刻劑組成物形成圖案的方法。
本文中已公開了各示例性實施例,且儘管採用了特定術語,然而所述術語僅被用於且被解釋為一般性及說明性意義,而非用於限制目的。在一些情況下,如在本申請提出申請時對於所屬領域中的普通技術人員來說將顯而易見,除非另外具體地指明,否則結合特定實施例闡述的特徵、特性和/或元件可單獨使用或者與結合其他實施例闡述的特徵、特性和/或元件組合使用。因此,所屬領域中的技術人員應理解,在不背離以上申請專利範圍所述的本發明的精神及範圍的條件下,可作出形式及細節上的各種改變。
100:基板
110:閘極絕緣層
115:閘極絕緣圖案
120:虛設閘極層120
125:虛設閘極
130:絕緣層
135:開口
140:阻擋圖案
通過參照所附圖式詳細闡述示例性實施例,各特徵對於所屬領域中的技術人員將為顯而易見的,在所附圖式中:
圖1到圖5示出根據示例性實施例在形成圖案的方法中各階段的示意性剖視圖。
100:基板
115:閘極絕緣圖案
130:絕緣層
135:開口
Claims (21)
- 一種矽層蝕刻劑組成物,包含: 約1重量%到約20重量%的烷基氫氧化銨; 約1重量%到約30重量%的胺化合物; 約0.01重量%到約0.2重量%的包括疏水基團及親水基團兩者的非離子表面活性劑;以及 水, 所有重量%都是基於所述矽層蝕刻劑組成物的總重量。
- 如申請專利範圍第2項所述的矽層蝕刻劑組成物,其中R1 、R2 、R3 及R4 各自獨立地為C1到C4烷基。
- 如申請專利範圍第1項所述的矽層蝕刻劑組成物,其中所述非離子表面活性劑的所述親水基團包括聚氧伸烷基。
- 如申請專利範圍第4項所述的矽層蝕刻劑組成物,其中所述非離子表面活性劑的所述疏水基團包括C3到C10烴基。
- 如申請專利範圍第5項所述的矽層蝕刻劑組成物,其中所述非離子表面活性劑的所述疏水基團包括脂環族環或芳環。
- 如申請專利範圍第1項所述的矽層蝕刻劑組成物,其中所述非離子表面活性劑的所述疏水基團及所述親水基團通過醚鍵彼此連接。
- 如申請專利範圍第1項所述的矽層蝕刻劑組成物,其中所述胺化合物包括含羥基的胺化合物。
- 如申請專利範圍第1項所述的矽層蝕刻劑組成物,其中所述矽層蝕刻劑組成物具有11到14的酸鹼度。
- 一種形成圖案的方法,所述方法包括: 通過蝕刻基板上的矽層形成虛設閘極; 形成絕緣層以部分包圍所述虛設閘極; 通過使用如申請專利範圍第1項所述的矽層蝕刻劑組成物移除所述虛設閘極;以及 在通過移除所述虛設閘極而獲得的開口中形成閘極結構。
- 一種製備如申請專利範圍第1項所述的矽層蝕刻劑組成物的方法,所述方法包括: 通過將所述胺化合物與包括疏水基團及親水基團兩者的所述非離子表面活性劑混合來製備添加劑混合物;以及 將所述添加劑混合物與所述烷基氫氧化銨的水溶液混合。
- 一種形成圖案的方法,所述方法包括: 通過蝕刻基板上的矽層形成虛設閘極; 形成絕緣層以部分包圍所述虛設閘極; 通過使用包含烷基氫氧化銨、胺化合物、包括疏水基團及親水基團兩者的非離子表面活性劑以及水的蝕刻劑組成物來移除所述虛設閘極;以及 在通過移除所述虛設閘極而獲得的開口中形成閘極結構。
- 如申請專利範圍第12項所述的方法,其中所述蝕刻劑組成物包含: 約1重量%到約20重量%的所述烷基氫氧化銨; 約1重量%到約30重量%的所述胺化合物; 約0.01重量%到約0.2重量%的所述非離子表面活性劑;以及 水, 所有重量%都是基於所述蝕刻劑組成物的總重量。
- 如申請專利範圍第12項所述的方法,其中形成所述閘極結構包括形成阻擋圖案及金屬閘極使得所述阻擋圖案包含金屬氮化物,所述阻擋圖案及所述金屬閘極以此所陳述的次序依序堆疊在所述開口中。
- 如申請專利範圍第12項所述的方法,其中所述非離子表面活性劑的所述親水基團包括聚氧伸烷基。
- 如申請專利範圍第15項所述的方法,其中所述非離子表面活性劑的所述疏水基團包括C3到C10脂環族環或芳環。
- 如申請專利範圍第17項所述的方法,其中R1 、R2 、R3 及R4 各自獨立地為C1到C4烷基。
- 一種用於矽層蝕刻劑的添加劑混合物,所述添加劑混合物包含: 胺化合物;以及 包括疏水基團及親水基團兩者的非離子表面活性劑。
- 一種製備矽層蝕刻劑組成物的方法,所述方法包括: 通過將所述胺化合物與包括所述疏水基團及所述親水基團兩者的所述非離子表面活性劑混合來製備如申請專利範圍第19項所述的添加劑混合物;以及 將所述添加劑混合物與烷基氫氧化銨水溶液混合。
- 一種製備矽層蝕刻劑組成物的方法,所述方法包括: 通過將胺化合物與包括疏水基團及親水基團兩者的非離子表面活性劑混合來製備添加劑混合物;以及 將所述添加劑混合物與烷基氫氧化銨水溶液混合。
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