TW202210616A - 移除硬遮罩之方法 - Google Patents
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- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 51
- 239000007800 oxidant agent Substances 0.000 claims abstract description 29
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 14
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052796 boron Inorganic materials 0.000 claims abstract description 12
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- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 7
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- 229910052740 iodine Inorganic materials 0.000 claims description 6
- 239000011630 iodine Substances 0.000 claims description 6
- 235000011149 sulphuric acid Nutrition 0.000 claims description 5
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
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- 238000005530 etching Methods 0.000 abstract description 16
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- 239000000377 silicon dioxide Substances 0.000 abstract description 3
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
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- H01L21/31111—Etching inorganic layers by chemical means
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Abstract
本發明提供適用於蝕刻—亦即移除—已摻雜有諸如硼、氯或氮之元素之非晶碳硬遮罩的組合物及方法。該等組合物利用濃硫酸、水及至少一種氧化劑。在該方法之操作中，即使在存在諸如二氧化矽、氮化矽、氮化鉭及多晶矽之層的情況下，該組合物亦以良好選擇性來選擇性地移除經摻雜硬遮罩層。
Description
本發明大體上係關於微電子裝置製造之領域，且係關於用於蝕刻—亦即移除—摻硼非晶碳硬遮罩之方法。
處理半導體及微電子裝置涉及沈積材料層並藉由被稱作「蝕刻」之化學製程移除材料的各種步驟。藉由蝕刻，將薄遮罩層置放在經沈積材料層上方。接著在遮罩中形成開口，且曝露基板之選擇部分。接著使經遮蔽基板與蝕刻劑接觸，該蝕刻劑通過遮罩中之開口接觸底層基板之材料且以化學方式降解及移除基板之材料以在基板中形成開口(三維空間)。
許多較新類型之基板，諸如用以製備三維記憶體裝置之基板，經處理以形成具有高縱橫比之開口，例如延伸至基板中之深度顯著地大於開口之寬度尺寸(例如直徑)的開口。作為一個實例，3D NAND記憶體裝置之豎直延伸「通道孔」係藉由在深度方向上將豎直延伸開口蝕刻至經沈積膜之許多層之堆疊中而形成。通道孔之深度可比通道孔之直徑大二十倍、四十倍或五十倍，或更多。藉由蝕刻而在微電子裝置中形成此類型之高縱橫比特徵會需要高度專業化、準確且精確的蝕刻製程。
對於此類型之蝕刻步驟，將抗化學腐蝕「硬遮罩」置放在經沈積膜之多個層中之頂部層上方。有時被稱作「膜堆疊」之膜層為記憶體裝置之功能材料，且可為經沈積氧化矽、氮化矽、多晶矽或類似物之層。硬遮罩抵抗用以以化學方式降解及移除膜堆疊之材料以在基板中形成高縱橫比開口(例如通道孔)的蝕刻溶液。
一種常見類型之硬遮罩為非晶碳硬遮罩。此類型之硬遮罩作為連續層被沈積至微電子裝置基板上，且接著經蝕刻以在硬遮罩中形成開口。蝕刻底層基板之後續步驟接著係藉由將具有硬遮罩之基板曝露於能夠以化學方式降解膜堆疊之材料的氣態化學蝕刻劑來執行。氣態蝕刻劑穿過硬遮罩中之開口以接觸並蝕刻掉—亦即移除—基板之材料以在基板中產生開口。在已視需要而蝕刻掉基板材料之後，必須自基板移除硬遮罩以允許將基板進一步處理為成品微電子裝置。
產生展現高縱橫比之精確形成且良好界定之基板開口可極具挑戰性。蝕刻製程之常常被研究以用於改良整個製程之一個組成部分為硬遮罩，包括硬遮罩之組合物以及應用及移除硬遮罩之方法。
硬遮罩可由厚非晶碳膜或能夠耐受電漿蝕刻製程之多種類似材料組成。對於3D NAND結構，非晶碳為不完美的硬遮罩材料，此係因為非晶碳在曝露於反應性電漿達處理此類結構所需之時間長度時易遭受蝕刻。一種增加此類非晶碳膜之耐用性的方法包括使碳層摻雜有諸如硼、氯及氮之抗蝕刻元素。在硼摻雜之狀況下，使遮罩硬化，藉此形成碳化硼並使遮罩類似於陶瓷形態且因此抵抗化學蝕刻劑。接著最終使用利用O2
電漿或O2
電漿結合H2
電漿之(乾式)反應性離子蝕刻技術來移除此類遮罩。(參見例如美國專利第9,229,581號)。
然而，需要用於移除已摻雜有諸如硼之抗蝕刻元素之硬遮罩的經改良方法。
總體而言，本發明提供適用於蝕刻—亦即移除—已摻雜有諸如硼、氯或氮之元素之非晶碳硬遮罩的組合物及方法。該等組合物利用濃硫酸、水及至少一種氧化劑。在一個實施例中，該氧化劑係選自諸如碘酸鹽及過碘酸之含碘氧化劑。該等組合物可進一步包含除硫酸之外的額外酸。在本發明之方法中，可將該等組合物施加至合意地在高溫下移除之遮罩。在該方法之操作中，即使在存在諸如二氧化矽、氮化矽、氮化鉭及多晶矽之層的情況下，該組合物亦以良好選擇性來選擇性地移除經摻雜硬遮罩層。
因此，本發明之方法之效能非常適於包括具有96個層及更多層之3D-NAND結構之應用。
1. 在第一態樣中，本發明提供一種用於自微電子裝置移除非晶碳硬遮罩之方法，其中該硬遮罩已摻雜有選自硼、氯及氮之元素以形成經摻雜硬遮罩，該方法包含使該微電子裝置與包含以下各者之組合物接觸：
a. 按該組合物之總重量計，約50重量百分比至約98重量百分比之H2
SO4
；
b. 水；及
c. 按該組合物之總重量計，約0.1重量百分比至約30重量百分比之至少一種氧化劑。
在一個實施例中，該元素為硼。
在某些實施例中，該氧化劑係選自諸如碘酸鹽及過碘酸、硝酸、過氯酸及過錳酸鹽以及過硫酸鹽之氧化劑。在一個實施例中，該氧化劑之存在量為約1重量百分比至約15重量百分比或約5重量百分比至10重量百分比。在另一實施例中，該氧化劑為過碘酸，且該氧化劑之存在量為約5%至約8%。在另一實施例中，該氧化劑為過碘酸，且該氧化劑之存在量為約5%至約6%。
在一個實施例中，該含碘氧化劑係選自H5
IO6
、HIO4
或其混合物。
在一個實施例中，該組合物包含約65重量百分比至約85重量百分比之H2
SO4
。
在某些實施例中，該組合物進一步包含除H2
SO4
之外的酸。在某些實施例中，除H2
SO4
之外的酸係選自甲磺酸、三氟甲磺酸、硼酸及磷酸。
在某些實施例中，該組合物進一步包含至少一種界面活性劑。如本文中所使用，術語「界面活性劑」係指降低兩種液體之間或液體與固體之間的表面張力(或界面張力)之有機化合物，典型地為含有疏水基(例如烴(例如烷基)「尾端」)及親水基之有機兩親媒性化合物。有利地，界面活性劑係熱穩定的且在諸如本發明之蝕刻製程之條件的強酸性條件下保持離子性。實例包括全氟烷基磺酸及長鏈四級銨化合物(例如十二烷基三甲基硫酸氫銨)。亦可使用經氟化之非離子性界面活性劑，諸如Chemours' Capstone® FS-31/FS-35。亦可使用非離子性的未經氟化之界面活性劑，諸如聚(乙二醇)-聚(丙二醇)共聚物(「PEG-PPG」)。
蝕刻組合物中之界面活性劑之量可為結合蝕刻組合物之其他材料而將提供所需總體效能的量。舉例而言，組合物可含有一定量之界面活性劑，按組合物之總重量計，該量可在約0.001重量百分比至約10重量百分比之範圍內，例如約0.01重量百分比至約0.5重量百分比、1重量百分比、2重量百分比、7重量百分比或7重量百分比之界面活性劑。
本發明之組合物因此可用以藉由將此類組合物施加至微電子裝置之表面來蝕刻或移除此類摻硼、氯或氮非晶硬遮罩。取決於待移除膜之厚度，硫酸濃度及操作溫度可變化且最佳化。在一個實施例中，施加組合物係在約100℃至170℃之環境中進行。在一個實施例中，施加組合物係在約140℃至170℃之環境中進行。
本發明之組合物可被容易調配為在使用時或在使用之前混合的單封裝調配物或多部分調配物，例如，多部分調配物之個別部分可在工具處、在工具上游之儲存槽中或在將經混合調配物直接遞送至工具之裝運封裝中混合。舉例而言，單一裝運封裝可包括可由使用者在製造廠混合在一起之至少兩個單獨容器或囊，且經混合調配物可經直接遞送至工具。至少兩個容器或囊中之一者可包括可為固體之氧化劑，而至少兩個容器中之另一者可包括硫酸溶液。在一個實施例中，至少兩個容器或囊中之一者包括氧化劑，而至少兩個容器或囊中之第二者包括硫酸。在另一實施例中，至少兩個容器或囊中之一者包括氧化劑，而至少兩個容器或囊中之第二者包括硫酸與除硫酸之外的另一酸之混合物。在每一狀況下，若將添加水，則可在離開製造商之前將水添加至一個及/或兩個容器，可在使用之前在製造廠添加水，或此兩者之組合，如熟習此項技術者容易判定。裝運封裝及該封裝之內部容器或囊必須適合於儲存及裝運該等組合物組分，例如由Advanced Technology Materials公司(美國康涅狄格州丹柏立(Danbury))提供之封裝。
替代地，該組合物之濃縮物可在一個容器中被調配及封裝以用於裝運且用於在使用之前及/或期間與現場硫酸及視情況為除硫酸之外的酸混合，其中本文中描述該使用方法。舉例而言，該濃縮物可包含至少一種氧化劑、水，且其中按濃縮物之總重量計，該氧化劑之濃度可在約0.1 wt%至約30 wt%或約1 wt%至約15 wt%之範圍內。當存在時，該濃縮物中之硫酸之量按濃縮物之總重量計可在約50 wt%至約96 wt%之範圍內。在較佳實施例中，用於與現場酸組合之濃縮物包含以下各者、由以下各者組成或基本上由以下各者組成：至少氧化劑、水及視情況為除硫酸之外的至少一種酸。在另一實施例中，用於與現場酸組合之濃縮物包含以下各者、由以下各者組成或基本上由以下各者組成：至少一種含碘氧化劑、水及除硫酸之外的至少一種酸。熟習此項技術者在知曉低pH組合物中需要多少氧化劑且濃縮物中存在多少酸的情況下會容易判定濃縮物對現場酸之比率。
另一態樣係關於一種套組，該套組在一或多個容器中包括經調適以形成如本文中所描述之任一態樣之組合物的一或多種組分。套組之容器必須適合於儲存及裝運該等組合物，例如NOWPak®容器(Advanced Technology Materials公司，美國康涅狄格州丹柏立)。容納本文中所描述之組合物之組分的一或多個容器較佳地包括用於使該一或多個容器中之組分處於流體連通以用於摻合及施配的構件。舉例而言，參看NOWPak®容器，可向該一或多個容器中之襯墊之外部施加氣體壓力，以使該襯墊之內容物之至少一部分排放且因此使能夠進行流體連通以用於摻合及施配。替代地，可向習知可加壓容器之頂部空間施加氣體壓力，或可使用泵以使能夠進行流體連通。另外，系統較佳地包括施配通口以用於將經摻合移除組合物施配至製程工具。
實質上化學惰性、無雜質、可撓性及彈性聚合膜材料，諸如PTFE或PTFA，較佳地用以製造用於該一或多個容器之襯墊。處理合意的襯墊材料，而無需共擠出或障壁層，且無需可不利地影響對於待安置於襯墊中之組分之純度要求的任何顏料、UV抑制劑或處理劑。合意的襯墊材料之清單包括包含原始聚四氟乙烯(PTFE)、PFA、Halar®等等之膜。在某些實施例中，此類襯墊材料之厚度在約5密耳(0.005吋)至約30密耳(0.030吋)之範圍內，例如20密耳(0.020吋)之厚度。
關於套組之容器，以下專利及專利申請案之揭示內容之各別全文特此以引用之方式併入本文中：名為「APPARATUS AND METHOD FOR MINIMIZING THE GENERATION OF PARTICLES IN ULTRAPURE LIQUIDS」之美國專利第7,188,644號；名為「RETURNABLE AND REUSABLE, BAG-IN-DRUM FLUID STORAGE AND DISPENSING CONTAINER SYSTEM」之美國專利第6,698,619號；2008年5月9日以John E. Q. Hughes之名義申請的名為「SYSTEMS AND METHODS FOR MATERIAL BLENDING AND DISTRIBUTION」之國際申請案第PCT/US08/63276號；及2008年12月8日以John E. Q. Hughes等人之名義申請的名為「SYSTEMS AND METHODS FOR DELIVERY OF FLUID-CONTAINING PROCESS MATERIAL COMBINATIONS」之國際申請案第PCT/US08/85826號。
因此，在另一態樣中，本發明提供一種套組，該套組在一或多個容器中包含上文所敍述之一或多種組分a.、b.及c.，其經調適以形成本發明之組合物，如本文中所描述。
本發明可進一步藉由其較佳實施例之以下實例進行說明，但應理解，除非另有特定指示，否則僅出於說明之目的而包括此等實例且此等實例不意欲限制本發明之範疇。
實例
調配物實例1至3：
*DIW =去離子水
*MSA =甲磺酸
*BHM =硼硬遮罩
| 重量% | *DIW | *MSA | H5 IO6 | H2 SO4 | 溫度(℃) | *BHM蝕刻速率(Å/分鐘) |
| 實例1 | 1.95 | 1 | 2.6 | 94.45 | 145 | 388.9 |
| 1.95 | 1 | 2.6 | 94.45 | 155 | 451.7 | |
| 實例2 | 1.89 | 1 | 5.66 | 91.45 | 155 | 943.4 |
| 實例3 | 19.38 | 1 | 5.87 | 73.75 | 155 | 467.3 |
以下實例1描述用於製備及測試調配物實例1至3之通用方法。
實例A—蝕刻組合物之製備
將H5
IO6
之50重量%樣本與水及甲磺酸組合。向此混合物中緩慢添加96% H2
SO4
，其中用於冷卻之冰水浴作為控制放熱反應之方式。燒杯測試之總溶液重量在250ml的三頸玻璃瓶中為300 g。用加熱包加熱所得溶液，同時將溫度控制為155℃。始終將攪拌維持在360 rpm。
實例B—試片測試：
將晶圓切割成1.5×3 cm2
大小，且藉由Teflon™帶將試片緊固在Teflon™ (聚四氟乙烯)樣本固持器上。毯覆式晶圓之處理時間為30 min至60 min，且圖案晶圓(50%過度蝕刻)為120 min。在蝕刻製程之後，用去離子水洗滌試片達1分鐘且用氮氣將其吹乾。藉由橢偏儀來量測膜損失，且藉由掃描電子顯微術(SEM)檢查圖案晶圓。
下表比較實例3之調配物的摻硼非晶形膜之蝕刻速率與其他表面組合物之蝕刻速率：
在155℃下進行測試達30分鐘，同時用磁性攪拌棒以360 rpm進行攪拌。使用橢偏儀來量測膜損失。
BPSG =硼磷矽玻璃
經摻雜多晶矽=摻硼多晶矽
| 蝕刻速率(Å/分鐘) | 選擇性 | |
| 摻硼非晶碳膜 | 467.3 | |
| W矽化物 | 0.3 | 1540 |
| SiCN | 0.5 | 8873 |
| SiN | -0.2 | ＞4000 |
| SiO2 | -0.5 | ＞4000 |
| BPSG | -0.03 | ＞4000 |
| 經摻雜多晶矽 | -0.22 | ＞4000 |
| TaN | -0.1 | ＞4000 |
在如此描述了本發明之若干說明性實施例的情況下，熟習此項技術者將容易瞭解，可在此處隨附的申請專利範圍之範疇內製作及使用另外其他實施例。此文件所涵蓋之本發明之諸多優點已在前文描述中進行闡述。然而，應理解，本發明在許多方面中僅係說明性的。在不超出本發明之範疇的情況下，可進行細節改變，尤其係在部分之形狀、大小及配置方面。當然，本發明之範疇係以表達隨附申請專利範圍的語言進行界定。
Claims (10)
- 一種用於自微電子裝置移除非晶碳硬遮罩之方法，其中該硬遮罩已摻雜有選自硼、氯及氮之元素以形成經摻雜硬遮罩，該方法包含使該微電子裝置與包含以下各者之組合物接觸： a. 按該組合物之總重量計，約50重量百分比至約98重量百分比之H2 SO4 ； b. 水；及 c. 按該組合物之總重量計，約0.1重量百分比至約30重量百分比之至少一種氧化劑。
- 如請求項1之方法，其中該元素為硼。
- 如請求項1之方法，其中氧化劑為含碘氧化劑。
- 如請求項1之方法，其中該含碘氧化劑係選自H5 IO6 、HIO4 或其混合物。
- 如請求項1之方法，其中該氧化劑之用量在約1重量百分比至約15重量百分比之範圍內。
- 如請求項1之方法，其中該氧化劑係選自過硫酸鹽、硝酸、過氯酸及過錳酸鹽。
- 如請求項1之方法，其中該組合物包含約65重量百分比至約85重量百分比之H2 SO4 。
- 如請求項1之方法，其進一步包含除含碘氧化劑之外的氧化劑。
- 如請求項1之方法，其進一步包含至少一種界面活性劑。
- 如請求項1之方法，其中該裝置及該組合物經加熱至約100℃至170℃之溫度。
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