TW417199B - Method of strengthening gate oxide layer - Google Patents

Method of strengthening gate oxide layer Download PDF

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TW417199B
TW417199B TW088109723A TW88109723A TW417199B TW 417199 B TW417199 B TW 417199B TW 088109723 A TW088109723 A TW 088109723A TW 88109723 A TW88109723 A TW 88109723A TW 417199 B TW417199 B TW 417199B
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oxide layer
gate oxide
strengthening
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scope
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TW088109723A
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Jenn-Gwo Hwu
Yen-Hao Hsih
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Nat Science Council
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Description

,Γ 417 19 9 五、發明說明（1) . 本案係為一種形成閘極氧化層的方法，應用於半導體 元件的製程上面，尤指一種強化閘極氧化層的方法。 隨著微電子技術的發展，半導體元件的尺寸也越來越 小。現今為了發展超大型積體電路ULSI (Ultra Large Scaled Integrated Circuit) 之次微米元件技術，半導體 元件閘極氧化層的厚度也隨之降低至100埃以下。在現今 製造閘極氧化層的方法中，以熱氧化法（t h e r m a 1 oxidation process) 最為普遍。而熱氧化製程的發展方 向，主要是集中在如何製造電性優良且厚度極薄的閘極氧 化層，以因應半導體元件越來越小的要求。也因此，如此薄 的閘極氧化層必須要具有較高的介電常數（d i e 1 e c t r i c ( constant),較低的氧化層電荷（oxide charge),與較高的 崩潰電壓(breakdown voltage)等 ° 在傳統的製程上，形成閘極氧化層的方法，不外乎下列 兩種方法：（1 )使用超高純度的氧氣來形成閘極氧化層，並 加上高溫氮氣的退火（a η n e a I i n g ) 步驟，或是（2 )使用 超高純度的笑氣（N20)取代氧氣直接成長氧化層並加上高 溫氮氣的退火步驟。並且為了符合生產的經濟要素與技術 條件，傳統的高溫爐設備成長氧化層的方式已經逐漸被快 速熱處理（rapid thermal processing) 的方法所取代。 而以如此方法所形成的閘極氧化層，雖然能承受更高的崩 潰電場（breakdown field) 與更高的崩潰電荷庫倫數 < (charge to breakdown), 但是卻具有厚度不均勻的缺 點，使得後續的製程上，產生了閘極氧化層穩定度不佳的問
第4頁 417199 五、發明說明（2) . 題。 職是之故，吾人鑑於習知技術的缺失，乃經悉心試驗與 研究並一本鍥而不捨的精神，終創作出本案之強化閘極氧 化層的方法。 以下為本案之簡要說明。 本案的主要目的在於提供一種強化閘極氧化層的方 法，以使所形成之閘極氧化層能承受更高的崩潰電場與崩 潰電何庫儉數。 根據本案之構想，該方法之步驟包括：（a)提供一晶 圓，（b)在該晶圓表面上形成一閘極氧化層，（c)提供一 具有高導電性的化學溶液，U)將該晶圓當作陰極，置入該（ 化學溶液中，（e )提供一陽極，置入該化學溶液中，（f )對 該晶圓通入一電子流，以電子通過該閘極氧化層來破壞該 閘極氧化層中鍵結不完全的鍵與比較差的該閘極氧化層， (g )以去離子水清洗該閘極氧化層表面殘留的該化學溶液， 以及（h )將該間極氧化層進行一退火（a η n e a丨i n g ) 處理以 使受損的該閘極氧化層重新鍵結。 根據本案構想，其中該步驟（a)夠包含了下列步驟： (a )將該晶圓以R C A 清洗步驟清洗完成。 根據本案構想，其中該步驟（b )之形成閘極氧化層之 方法，係為一採用快速熱處理（rapid thermal processing) 之熱氧化法。 根據本案之構想，其中該閘極氧化層係為二氧化矽 (Si02)。
五、發明說明（3) . 根據本案之構想，其中該閘極氧化層係為氮化矽 (Si3N4)。 根據本案之構想，其中該閘極氧化層係為五氧化二鈕 (Ta2 05 )。 根據本案之構想，其中該具有高導電性的化學溶液係 為一稀釋的氫就酸溶液（diluted HF solution),且其漢 度範圍為0 0 4 9 % 至0 . 9 8 %，而以0 · 2 4 5 % 為最佳。 根據本案之構想，其中該陽極係為一白金片 (platinum plate) ° 根據本案之構想，其中該電流之電流密度範圍為0. 1 /zA/cm2 至 10 yA/cm2，而以4 //A/cm2 為最佳 d 根據本案之構想，其中該退火處理，係使用快速熱處理 (rapid thermal processing) 〇 本案得藉由下列圖示詳細說明，俾得一更深入之瞭 解。 第一圖：為本案設備之簡單示意圖。 第二圖：為四個實驗樣本在時依性介電崩潰定電流破 壞測試的偉伯分布圖（W e i b u 1 1 p 1 〇 t)。其中電流密度為 2 0 mA /cm2 〇 第三圖：為實驗樣本1與樣本4的電流密度-電壓曲線 圖。 第四圖：為四個實驗組樣品在非時依性介電崩潰破壞 測試的偉伯分布圖（W e i b u Π ρ丨〇 t)。 第五圖：為本案的能階示意圖。
417199 五、發明說明（4) _ 本案圖示中所包含之各元件列示如下： 1 : K e t h 1 e y 2 2 0 電流源。 2 :白金片。 3 :石夕晶圓。 4 : 閘極氧化層。 5:濃度為0.2 4 5% 的稀釋氫氟酸溶液（diluted HF solution) ° 6 : 通過閘極氧化層之電子流。 7 :快速熱機台。 請參見第一圖。本圖係為本案設備的簡單示意圖。首 先，提供一矽晶圓3 ( s i 1 i c ο n w a i e r )，將該石夕晶圓3先以 （ R C A 清洗步驟清洗完成後，再置入一高溫氧氣的快速熱機 台7進行快速熱處理（rapid thermal processing)後形成 一閘極氧化層4 於矽晶圓3上。 再者，提供一濃度為0 . 2 4 5 %的稀釋氫氟酸溶液5 (d i 1 u t e d H F s ο 1 u t i ο η )為導電闻的化學溶液，將該表面上 長成一閘極氧化層4的石夕晶圓3當成電解用的陰極，採用白 金片2 (platinum plate)為電解用的陽極，置入該稀釋的 氫氟酸溶液5 (diluted HF solution)中，並以 Kethley 2 2 0 電流源1為本實施例中的電流源，如圖將該電流源1與 陽極2與陰極3所示的極性相連接後通入電子流進行破壞。 由於該稀釋的氫氟酸溶液5具有蝕刻性，它會蝕刻該閘 極氧化層4，更由於該稀釋的氫氟酸溶液5是種具高導電度 的化學溶液，一旦通入電流，馬上就會有強大的電子流6由
第7頁 417 1 99 五、發明說明（5) . 電流源1進入陰極3而通過該閘極氧化層4至陽極2。因為該 閘極氧化層4中品質比較差的區域其等效厚度比正常的閘 極氧化層來的薄，因此在石夕晶圓3與閘極氧化層4之介面會 累積較多的電子，而會有較少氫氟酸陰離子在此處累積，因 而蝕刻速度降低，使的往後的閘極氧化層厚度變的更均勻； 並且此處的氧化層會通過較多的電荷，而此電荷會將閘極 氧化層4中的未飽合鍵（unsaturated bonding)及鍵結不 完全的區域給破壞。 在完成破壞步驟後，該閘極氧化層4 _的未飽合鍵與鍵 結不完全的部份都已經受到破壞，這時再將該閘極氧化層4 置入一高溫It氣的快速熱機台7做退火（annealing)處理，（ 將這些被電子破壤的區域重新鍵結起來。由於閘極氧化層 生長後，在靠近矽晶圓與閘極氧化層的介面有很多鍵結不 完全之處，在高電場的情形下，於此處容易產生「電子陷 阱」（electron traps)。以高溫氮氣退火的技術，可以將 鍵結不完全的區域部份改善，以使該閘極氧化層4的穩定度 增加。 而在本實施例中，我們更進一步的設立了四個實驗樣 本以輔助說明本實施例中所形成的閘極氧化層的電氣特 性。第一個實驗樣本，是採用快速熱氧化法加上快速熱退 火以形成閘極氧化層；第二個實驗樣本，是採用快速熱氧化 法加上化學物質輔助電子破壞後熱退火處理，不過是以去 離子水（Dissociated water, H20)為電解的化學溶液；第 三個實驗樣本，是採用快速熱氧化法加上化學物質輔助電
五、發明說明（6) _ 子破壞，不過是以氫氟酸溶液（H F )為電解的化學溶液。第 四個實驗樣本即是本實施例，乃是採用快速熱氧化法加上 化學物質輔助電子破壞後熱退火處理，而以氫氟酸溶液 (HF)為電解的化學溶液。 請參見第二圖。本圖是四個實驗樣本在時依性介電崩 潰定電流破壞（time-dependent dielectric breakdown constant current stressing)湏1J 試的偉伯分佈圖 (Weibull plot),其縱座標為-In (1-F)的自然對數值，橫 座標為崩潰電荷庫倫數。由此圖中可以看出本實施例的實 驗樣本4具有比習用方法的實驗樣本1多一倍以上的崩潰電 荷庫倫數。而實驗樣本2因為採用去離子水（H20)來當電解/ 溶液，而去離子水的導電度遠不及氫氟酸溶液，無法選擇性 的通過閘極氧化層比較弱的區域，因而影響了電子通過氧 化層的路徑，造成樣本2曲線分散的效果。 請參見第三圖。本圖是典型的電流密度與電壓圖，其 中縱座標為電流密度J;橫座標為閘極氧化層的電壓V，以樣 本1與樣本4的曲線來作比較，發現到F - N t u η n e 1 i n g 發生 的區域，樣本1發生的時間比樣本4還要早。但是在兩個樣 本崩潰前，樣本1的電流密度反而比樣本4來的小。這代表 樣本1在量測J - V時在崩潰前的高電場，會產生較多的電子 陷阱，使得後來要穿過閘極氧化層的電子，因為負電荷相排, 斥，比較不容易穿過去，電流密度比樣本4來的小。在高電 ' 場下能含有較少的電子陷阱，往往在時依性介電崩潰定電 流破壞測試中能容忍較多的電子通過氧化層，這印證了樣
ί 41719 9 五、發明說明（7) _ 本4具有較佳的穩定度。 請參見第四圖。本圖是四個實驗樣本在非時依性介電 崩潰破壞(time-zero dielectric breakdown stressing)測試的偉伯分佈圖（Weibull plot)，其縱座標 為 1 - F )的自然對數值，橫座標為崩潰電場。本圖類 似於第二圖，其中樣本4具有較高的崩潰電場，且樣本2的曲 線也分散開來，代表著若去離子水不能夠有效的讓電子通 過品質較差的閘極氧化層，反而會去破壞原本品質已經报 好的閘極氧化層，而高溫熱退火又不足以將這樣被破壞的 閘極氡化層完全鍵結回來，導致樣本2的測試結果有好有壞 的分布。 請參見第五圖《本圖是本實施例的能階示意圖，其表 示氧化層受到電子破壞之情形。 縱上所述，本案乃是利用一具有高導電性的化學溶液 將一表面長成一閘極氧化層的晶圓通入電子流，利用電子 通過品質較差或是鍵結不完全的閘極氧化層來破壞該閘極 氧化層，再用高溫氮氣退火的技術將該閘極氧化層重新鍵 結，如此形成的閘極氧化層不但穩定度提昇，更能承受更高 的崩潰電場與崩潰電荷庫倫數。 是以，本案得由熟習此技藝之人士任施匠思而為諸般 修飾，然皆不脫如附申請專利範圍所欲保護者。
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Claims (1)

  1. 六、申請專利範圍 _ 1 . 一種強化閘極氧化層的方法，應用於半導體元件的製程 上，其包含下列步驟： (a ) 提供一晶圓； (b ) 在該晶圓表面上形成一閘極氧化層； (c) 提供一具有高導電性的化學溶液； (d ) 將該晶圓當作陰極，置入該化學溶液中； (e ) 提供一陽極，置入該化學溶液中； (f ) 對該晶圓通入一電子流進行破壞，以電子通過該晶圓 上的該閘極氧化層來破壞該閘極氧化層中鍵結不完全的鍵 與比較差的該閘極氧化層； (g)以去離子水清洗該閘極氧化層表面殘留的該化學溶 液；以及 (h ) 將該閘極氧化層進行一退火（a η n e a 1 i n g ) 處理以使受 損的該閘極氧化層重新鍵結。 2. 如申請專利範圍第1項所述之強化閘極氧化層的方法， 其中該步驟（a )更包含下列步驟： (a ) 將該晶圓以R C A 清洗步驟清洗完成。 3. 如申請專利範圍第1項所述之強化閘極氧化層的方法， 其中步驟（b ) 之形成該閘極氧化層之方法係為一熱氧化 法。 4. 如申請專利範圍第3項所述之強化閘極氧化層的方法， 其中該熱氧化法係使用快速熱處理（r a p i d t h e r m a 1 processing) ° 5. 如申請專利範圍第1項所述之強化閘極氧化層的方法，
    六、申請專利範圍 . 其中該閘極氧化層係為二氧化矽（S i 02)。 6. 如申請專利範圍第1項所述之強化閘極氧化層的方法， 其中該閘極氧化層係為氮化矽（Si3N4)。 7. 如申請專利範圍第1項所述之強化閘極氧化層的方法， 其中該間極氧化層係為五氧化二钽（T a2 05 )。 8. 如申請專利範圍第1項所述之強化閘極氧化層的方法， 其中該具有高導電性的化學溶液係為一稀釋的氫氟酸溶液 (diluted HF solution)。 9. 如申請專利範圍第8項所述之強化閘極氧化層的方法， 其中該稀釋的氫氟酸溶液的濃度範圍為0. 0 4 9% 至0. 98 °/〇， 而以0 . 2 4 5 為最佳= 10. 如申請專利範圍第1項所述之強化閘極氧化層的方法， 其中該陽極係為一白金片（platinum plate)。 11. 如申請專利範圍第1項所述之強化閘極氧化層的方法， 其中該電流之電流密度範圍為0 . 1 # A / c m2至1 0 # A / cm2, 而以4 " A / c m2最最佳。 12. 如申請專利範圍第1項所述之強化閘極氧化層的方法， 其中該退火處理，係使用快速熱處理（rapid thermal processing) a
    第12頁
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