TWI798816B - 選擇性材料及使用選擇性材料之選擇性形成薄膜的方法 - Google Patents

選擇性材料及使用選擇性材料之選擇性形成薄膜的方法 Download PDF

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TWI798816B
TWI798816B TW110133264A TW110133264A TWI798816B TW I798816 B TWI798816 B TW I798816B TW 110133264 A TW110133264 A TW 110133264A TW 110133264 A TW110133264 A TW 110133264A TW I798816 B TWI798816 B TW I798816B
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substrate
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TW202225443A (zh
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金才玟
金哈娜
崔雄辰
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南韓商Ｅｇｔｍ股份有限公司
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Abstract

揭露一種形成區域選擇性薄膜的方法，該方法包含：將選擇性材料供應至其中置有基材的腔室之內部，使得選擇性材料吸附至基材的非生長區域；沖洗腔室內部；將前驅物供應至腔室內部，使得前驅物吸附至基材的生長區域；沖洗腔室內部；以及將反應材料供應至腔室內部，使得反應材料與所吸附的前驅物發生反應以形成薄膜。

Description

選擇性材料及使用選擇性材料之選擇性形成薄膜的方法 發明領域
本發明係關於一種形成薄膜的方法，且更特定言之，使用選擇性材料選擇性形成薄膜的方法。
發明背景
隨著創新技術的發展，DRAM裝置繼續進行小型化，達到了10nm時代。相應地，為了改良效能及可靠性，即使電容器尺寸減小，亦須充分維持高電容及低漏電流特徵，並且崩潰電壓必須高。
為了增大習知高k材料的電容，正進行多種研究，並且存在一種利用晶種層來幫助介電層結晶的方法。
由此，即使在相對較低的溫度下亦可形成具有高介電常數的晶體結構，但問題在於晶種層甚至在介電膜不應沈積之處發生沈積，產生漏電流。
本發明之一目標係提供一種用於形成具有高電容之薄膜的方法。
本發明之另一目標係提供一種用於形成能夠最小化漏電流之薄膜的方法。
本發明之另一目標係提供一種用於形成薄膜的方法，該薄膜就區域而言具有選擇性。
本發明之其他目標自以下實施方式將變得更顯而易見。
發明概要
揭露一種形成區域選擇性薄膜的方法，該方法包含：將選擇性材料供應至其中置有基材的腔室之內部，使得選擇性材料吸附至基材的非生長區域；沖洗腔室內部；將前驅物供應至腔室內部，使得前驅物吸附至基材的生長區域；沖洗腔室內部；以及將反應材料供應至腔室內部，使得反應材料與所吸附的前驅物發生反應以形成薄膜。
生長區域可為氮化鈦膜或氮化鈮膜。
非生長區域可為氮化矽膜。
氮化矽膜可為選自SiN、SiCN、C摻雜SiN及SiON中的至少一者。
選擇性材料可由以下化學式1表示：
Figure 110133264-A0305-02-0004-1
在<化學式1>中，n各自獨立地為0至8的整數，R1至R3獨立地選自具有1至8個碳原子的烷基，R4選自氫、具有1至8個碳原子的烷基，及具有1至8個碳原子的烷氧基。
反應材料可選自O3、O2、H2O。
前驅物可為選自包括Al在內之第3族或包括Zr及Hf在內之第4族或包括Nb及Ta在內之第5族的至少一者。
薄膜可藉由金屬有機化學氣相沈積(MOCVD)或原子層沈積(ALD) 形成。
圖1為示意性地展現根據本發明之一實施例之薄膜形成方法的流程圖。
圖2為示意性地展現根據圖1之供應週期的圖。
圖3為示意性地說明根據圖1之薄膜形成方法的圖。
圖4為展現根據本發明之一實施例及比較實例1之藉由X射線光電子光譜(XPS)分析所得之Nb含量的圖。
較佳實施例之詳細說明
在下文中，將利用圖1至圖4來描述本發明之實施例。本發明之實施例可包括各種修改，且本發明之範圍不應解釋為受限於下述實施例。此等實施例係為了向本發明所屬領域中具通常知識者更詳細地解釋本發明而提供。因此，附圖中所示之各元件的形狀可以放大，以強調更清晰的描述。
在通篇本說明書中，除非另有陳述，否則當一個部件「包括」某一組件時，其意謂可進一步包括其他組件而非排除其他組件。
如通篇本說明書所用，當展現所述含義中固有的製造及材料容限時，術語「約」、「基本上」及其類似術語係在數值的意義上或接近於該數值的意義上使用，並且旨在防止肆無忌憚的侵權者對揭露內容(包括供理解本發明用的精確或絕對數字)進行不公正的利用。
在通篇本說明書中，術語「烷基」或「烷基基團」係指1至12個碳原子、1至10個碳原子、1至8個碳原子、1至5個碳原子、1至3個碳原子的直鏈或分支鏈烷基，其具有3至8個碳原子或3至5個碳原子。舉例而言，烷基包括甲基、乙基、正丙基(nPr)、異丙基(iPr)、正丁基(nBu)、三級丁基(tBu)、 異丁基(iBu)、二級丁基(sBu)、正戊基、三級戊基、異戊基、二級戊基、新戊基、3-戊基、己基、異己基、庚基、4,4-二甲基戊基、辛基、2,2,4-三甲基戊基、壬基、癸基、十一烷基、十二烷基及其異構體，但可不限於此。
在通篇本說明書中，術語「膜」可以包括但不限於「薄膜」。
習知製程中存在的問題在於，介電膜沈積於非生長區域(例如非金屬薄膜，諸如氮化矽膜)上，導致漏電流。然而，下述選擇性材料以高於金屬薄膜的密度被吸附至非金屬薄膜(例如氮化矽膜)上，並且選擇性材料阻礙了隨後所添加之金屬前驅物的吸附，使得晶種層僅可在金屬薄膜上形成。
圖1為示意性地展現根據本發明之一實施例之薄膜形成方法的流程圖，且圖2為示意性地展現根據圖1之供應週期的圖。圖3為示意性地說明根據圖1之薄膜形成方法的圖。
將基板裝載至加工室中，且調整以下ALD製程條件。ALD製程條件可包括基材或加工室之溫度、加工室中之壓力、氣體流速，且溫度為10至900℃。
將基材暴露於供應至腔室內部的選擇性材料，且選擇性材料被吸附至基材的非生長區域。非生長區域可為氮化矽層，且可為選自SiN、SiCN、C摻雜SiN及SiON中的至少一者。選擇性材料以高密度被吸附至非生長區域的表面，且在後續製程中阻礙了金屬前驅物的吸附。
選擇性材料可由以下化學式1表示：
Figure 110133264-A0305-02-0007-2
在<化學式1>中，n各自獨立地為0至8的整數，R1至R3獨立地選自具有1至8個碳原子的烷基，R4選自氫、具有1至8個碳原子的烷基，及具有1至8個碳原子的烷氧基。
隨後，將沖洗氣體(例如惰性氣體，諸如Ar)供應至腔室內部以排出未吸附之選擇性材料或副產物。
隨後將基材暴露於供應至腔室內部的金屬前驅物，且金屬前驅物被吸附至基材生長區域的表面且由於選擇性材料而不被吸附至非生長區域的表面。金屬前驅物可以包括第3族，諸如Al，或第4族，諸如Zr或Hf，或第5族，諸如Nb或Ta。
隨後，將沖洗氣體(例如惰性氣體，諸如Ar)供應至腔室內部以排出未吸附之金屬前驅物或副產物。
隨後，將基材暴露於供應至腔室內部之反應物，且在基材表面上形成薄膜。反應物與金屬前驅物發生反應而形成薄膜，且反應物可選自O3、O2、H2O。金屬氧化層可由反應物材料形成。
隨後，將沖洗氣體(例如惰性氣體，諸如Ar)供應至腔室內部以排出未反應的材料或副產物。
另一方面，前文已描述選擇性材料係在金屬前驅物之前供應，但選擇性材料可以在金屬前驅物之後供應或金屬前驅物可以在選擇性材料之前與之後供應。
實施例1
使用原甲酸三甲酯作為選擇性材料，分別在金屬薄膜(TiN)基材及非金屬薄膜(SiN)基材上形成氧化鈮膜。經由ALD製程形成氧化鈮膜，製程溫度為290℃，且反應物是臭氧氣體(O3)。
經由ALD製程形成氧化鈮膜的方法如下，且執行一個週期的以下製程(參照圖1至圖3)。
1)將選擇性材料供應至反應室以吸附至基材上。
2)向反應室中供應Ar氣體以排出未吸附的選擇性材料或副產物。
3)使用Ar作為載氣，將鈮前驅物(TBTDEN，三級丁基醯亞胺基參(二乙基醯胺基)鈮供應至反應室，且鈮前驅物被吸附至基材上。
4)向反應室中供應Ar氣體以排出未吸附的鈮前驅物或副產物。
5)藉由向反應室中供應臭氧氣體(O3)而形成氧化鈮膜。
6)向反應室中供應Ar氣體以排出未反應的物質或副產物。
比較實例1
在不使用上述選擇性材料的情況下，在金屬薄膜(TiN)基材及非金屬薄膜(SiN)基材上分別形成氧化鈮膜。經由ALD製程形成氧化鈮膜，製程溫度為290℃，且反應物為臭氧氣體(O3)。
經由ALD製程形成氧化鈮膜的方法如下，且執行一個週期的以下製程。
1)使用Ar作為載氣，將鈮前驅物(TBTDEN，三級丁基醯亞胺基參(二乙基醯胺基)鈮供應至反應室，且鈮前驅物被吸附至基材上。
2)向反應室中供應Ar氣體以排出未吸附的鈮前驅物或副產物。
3)藉由向反應室中供應臭氧氣體(O3)而形成氧化鈮膜。
4)向反應室中供應Ar氣體以排出未反應的物質或副產物。
比較實例2
除了將選擇性材料自原甲酸三甲酯改成乙醇之外，以與實施例1相同之方式形成氧化鈮膜。
圖4為展現根據本發明之一實施例及比較實例1之藉由X射線光電子光譜(XPS)分析所得之Nb含量的圖(基於30個週期)。在比較實例1中，Nb含量為SiN基材：TiN基材=1：1.2，而在實施例1中，Nb含量為SiN：TiN=1：3.2，以便增加選擇性。此結果可解釋為，選擇性材料被吸附於SiN基材上且抑制鈮前驅物沈積。
表1顯示本發明之一實施例基於比較實例1的厚度減小率。如下表1中所示，實施例1之氧化鈮膜在TiN基材上的厚度減小42%，而在SiN基材上的厚度減小82%，證實了選擇性增加。實施例1中之選擇性材料具有選擇性的原因在於，其在結構上與SiN基材相容，從而增強吸附力，此解釋為金屬薄膜在SiN基材上的晶核生長延遲。
Figure 110133264-A0305-02-0009-3
總之，選擇性材料經由選擇性吸附至非金屬薄膜而展現較高的厚度減小作用，且可賦予選擇性，以便在基材的所需區域上沈積介電膜，並且防止在不必要的區域中形成薄膜。因此，可以將漏電流最小化。
根據本發明，在選擇性材料被吸附至非生長區域的狀態下，前驅物被阻止吸附至非生長區域，藉此阻止在非生長區域中形成薄膜。另外，可使漏電流最小化。
本發明已參考實施例詳細解釋，但可包括其他實施例。因此，以下申請專利範圍中描述之技術構思及範疇不限於實施例。

Claims (6)

  1. 一種形成一區域選擇性薄膜的方法，該方法包含：將選擇性材料供應至其中置有基材的腔室之內部，以便該選擇性材料被吸附至該基材之一非生長區域；沖洗該腔室之內部；將一前驅物供應至該腔室之內部，以便該前驅物被吸附至該基材之一生長區域；沖洗該腔室之內部；將一反應材料供應至該腔室之內部，以便該反應材料與被吸附的該前驅物發生反應而形成該薄膜，其中該選擇性材料係由以下化學式1表示：
    Figure 110133264-A0305-02-0011-4
     在<化學式1>中，n各自獨立地為0至8的一整數，R1至R3獨立地選自一具有1至8個碳原子的烷基，R4選自氫、一具有1至8個碳原子的烷基，及一具有1至8個碳原子的烷氧基。
  2. 如請求項1之方法，其中該生長區域為氮化鈦膜或氮化鈮膜。
  3. 如請求項1之方法，其中該非生長區域為氮化矽膜。
  4. 如請求項1之方法，其中該反應材料選自O3、O2及H2O中的至少一者。
  5. 如請求項1之方法，其中該前驅物為選自包括Al在內之第3族或包括Zr及Hf在內之第4族或包括Nb及Ta在內之第5族的至少一者。
  6. 如請求項1之方法，其中該薄膜係藉由金屬有機化學氣相沈積(MOCVD)或原子層沈積(ALD)形成。
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