TWI251620B - Process for CVD of Hf and Zr containing oxynitride films - Google Patents

Process for CVD of Hf and Zr containing oxynitride films Download PDF

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Publication number
TWI251620B
TWI251620B TW093113990A TW93113990A TWI251620B TW I251620 B TWI251620 B TW I251620B TW 093113990 A TW093113990 A TW 093113990A TW 93113990 A TW93113990 A TW 93113990A TW I251620 B TWI251620 B TW I251620B
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Taiwan
Prior art keywords
precursor
source
ch2ch3
oxynitride film
oxygen
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TW093113990A
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English (en)
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TW200426241A (en
Inventor
John D Loftin
Robert Daniel Clark
Arthur Kenneth Hochberg
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Air Prod & Chem
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Publication of TW200426241A publication Critical patent/TW200426241A/zh
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Publication of TWI251620B publication Critical patent/TWI251620B/zh

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/308—Oxynitrides
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/455—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating characterised by the method used for introducing gases into reaction chamber or for modifying gas flows in reaction chamber
    • C23C16/45514—Mixing in close vicinity to the substrate
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
    • C23C16/52—Controlling or regulating the coating process
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    • H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
    • H01L21/02181—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing hafnium, e.g. HfO2
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    • H01L21/02172—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides
    • H01L21/02175—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal
    • H01L21/02189—Forming insulating materials on a substrate characterised by the type of layer, e.g. type of material, porous/non-porous, pre-cursors, mixtures or laminates characterised by the material of the layer the material containing at least one metal element, e.g. metal oxides, metal nitrides, metal oxynitrides or metal carbides characterised by the metal the material containing zirconium, e.g. ZrO2
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    • 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
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  • Engineering & Computer Science (AREA)
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  • Physics & Mathematics (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Manufacturing & Machinery (AREA)
  • Computer Hardware Design (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Vapour Deposition (AREA)
  • Formation Of Insulating Films (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

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1251620 玫、發明說明： 【發明所屬之技術領域】 [0001] 半導體製造工業需要適合在半導體及絕緣或介電 質基材上沉積金屬、金屬混合物及金屬化合物之混合物形 成薄層、栓塞、微孔及圖案，用來製造適用於積體電路、 δ己憶元件及平面顯示元件之電的元件。 【先前技術】 [0002] 有各種已知用來將金屬、金屬化合物及它們的混合 物沉積到合適的電子材料基材上的技術，包括物理方法的 錢鍵、分子束磊晶成長、蒸鍍及雷射蒸鍍、合金以及化學 氣相沉積（電漿、光或雷射增強）。 [0003] 化學氣相沉積（CVD)在近年獲得偏愛，原因是它可 提供均句且均勻覆蓋的沉積，以及它能夠在極可控制的條 件下沉積一種陣列的物質。通常化學氣相沉積可以在一種 控制的方式下提供高沉積速率的高純度物質。 [0004] 鍅和銓的氧氮化物閘極介電質及錯 石夕閉極介電質可以藉由多種方法來產生，例如濺2積、 電漿沉積以及電子束，這些閘極比起普通的熱的氧化矽或 石夕的介電質層可提供較高的介電常數，而且它們可以更以 更厚。 [0 0 0 5 ]在先前技術中具有代矣 τ，、啕η表性的文早說明锆和铪金屬 膜’錯和給的氧氮化物以及咎 及氪和铪的虱虱化矽的介電質的 形成如下： 1251620 [〇0〇6]美國專利第6,5〇3,56丨號揭示一種熱的CVD方法， 由一種不含溶劑之兩種或更多金屬配位基複合物前驅物 (例如锆、铪、鋁、鍺等）的混合物在一種基材上沉積多種 金屬層，其中的配位基是選自烷基、醯亞胺化合物、醯胺 化合物、IS化物、硝酸鹽、氟。此方法是直接以液體注射 到一個急速蒸發區，使此種不含溶劑之混合物在沉積多種 金屬化合物層之前與氧氣混合。 [0007]美國專利第6,291，867號揭示利用電漿沉積來形成 錘和銓的氧氮化矽閘極介電質，其中的一個方法包括在基 材上以電漿沉積一種矽化錘，在一種含有氧氣及氮氣（例如 NO)的氣氛下進行退火。在另一個方法中，矽化矽層是在一 種非氧化的氣氛（包括NH3或是氮氣）下進行退火，然後再 於一種氧化的氣氛中進行退火。此專利揭示一種用來形成 石夕化物層的CVD方法。 [〇〇〇8]利用聚矽閘極電極之熱安定的cVD HfOxNy先進閘 極介電質，2002, IEEE 0·7803-7463·Χ/〇2/$ 17.00(C)—文中 揭不HfOxNy的形成，其中一種四二乙基胺铪前驅物隨著 載運氣體（NO以及氨藉由快速的熱的cvD被沉積，接著在 800到900 C下進行沉積後退火，此方法是在7〇〇到8〇〇°c 的溫度下生長HfOxNy。 [0009]在一個用來比較的例子中，使用〇2以及相同的前 驅物在500°C下沉積Hf〇2，接著再進行沉積後退火。 【發明内容】 6 1251620 [0 010]本發明是有關一種形成Zr和Hf的氧氮化物膜 (ZrOxNy及HfOxNy)以及Zr和Hf的氧氮化石夕膜 [Zr(Si)zOxNy及Hf(Si)zOxNy]之方法的改良，這些膜適合 用於電子的應用（如介電質閘極）。變數（X)、變數（y)及變數 z是大於0的正數，此方法的改良包括·· (a) 在一種化學氣相沉積的腔體中形成一種反應混合 物，這是藉由將一種含有Zr或Hf的前驅物、一種氧氣源 及一種氮氣源導入該化學氣相沉積的腔體所形成，在導入 化學氣相沉積腔體之前不把含有Zr或Hf的前驅物與氧氣 源及鼠氣源相混合；以及， (b) 在咼溫（例如介於3〇〇到700°C之間的溫度）的腔體中 將一種基材與此種反應混合物接觸，因而沉積出一種Zr和 Hf的氧氮化物膜。 [00 11 ]所述的方法可以達到幾項優點，它們包括： 一種產生優質的Zr/Hf的氧氮化物膜以及zr/Hf的氧氮 化矽膜的能力； 一種將顯著的氮成分導入此種氧氮化物膜的能力； 一種使用化學氣相沉積方法來達到沉積的能力， 一種在沉積Zr/Hf的氧氮化物膜及Zr/Hf的氧氮化矽膜 時使用一種低溫方法並且保持低的晶圓（基材）溫度的能力； 以及 一種在單一方法步驟中製造優質的膜的能力。 【實施方式】 7 1251620 [0013] I發明是有關-種在—種基材（例如梦晶圓）上沉積 用於半導體元件之Zr/Hf的氧氮化物maAZr/H_氧氮化 矽膜之方法的改良。在此種沉積Zr/Hf的氧氮化物膜的方 法中’在此種化學氣相沉積的腔體中形成由一種錯或給的 前驅物、-種氮氣源及-種氧氣源所組成之—種反應混合 物’而在製備Z"Hf的氧氮化石夕膜時，—種石夕的前驅物被 添加到反應混合物中。 < [0014] 有非常多種含有至少一種配位基之錘和铪的前驅 物可以被用於進行此方法，這些包括錘和铪的氯化物，鍅 和銓的醯胺化合物。其他適用於鍅和铪前驅物的配位基包 括1至8個碳的烷基以及烷氧化物；矽氧化物，_化物，氫 化物，亞醯胺化合物，疊氮化物，硝酸鹽，環戊二烯化合 物，以及羰基化合物，優選地，此種前驅物在環境條件下 是液體。 [0015] 特定之_化物的例子包括锆和銓的四氣化物，而特 定的醯胺化合物包括那些選自由二甲基醯胺基 Zf(N(CH3)2)4 或 Hf(N(CH3)2)4 ，二乙基醯胺基 Zr(N(CH2CH3)2)4 或 Hf[N(CH2CH3)2)]4 乙基甲基醯胺基
Zr[N(CH2CH3)(CH3)]4’ 或是 Hf[N(CH2CH3)(CH3)]4，或是， 丁基醯胺基，二丙基醯胺基，甲基丙基醯胺基，乙基丙基 醯胺基，所組成的族群。特定的烷氧化物是選自甲氧基， 乙氧基，丙氧基，及丁氧基Zr(OC4H9)4或是Hf(〇C4H9)4的 基團。 [0016] 當想要Zr-Si及Hf-Si的氧氮化物膜時，有非常多 1251620 種Si的前驅物可以被使用，優選地，“前 刖^物的配位基血 製造Zr/Hf的氧氮切膜時所使用錯和給的前㈣相同或 相似。矽的醯胺化合物的一種形式是（H)xSi(NRlR2)4_x，其 中R1及R2是1至8個碳的烷基，而χ是整數〇,丨，2或3。 矽的醯胺化合物的一種特定形式是選自由
Si[N(CH2CH3)2]4，Si[N(CH2CH3)(CH3)]4 ^ Si[N(CH3)2]4， HSi[N(CH2CH3)2]3 所組成的族群，HSi[N(CH2CH3)(cH3)]3， HSi[N(CH3)2]3 或是 H2Si[NH(C4H9)]2。用來形成 Zr_Si 及
Hf-Si的氧氮化物膜之矽的前驅物的含量是隨膜的設計者 的意見，亦即當製造Zr-Si&Hf_Si的氧氮化物膜時，冗是 正的。 [0017]在本文所描述的CVD方法中，優選的配位基是醯 胺化合物，它提供在基材（例如矽晶圓）上產生鍅和铪的氧 氮化物膜及锆和铪的氧氮化矽膜的沉積的能力，它是在低 的基材溫度下沉積，例如4〇〇到500。〇，通常是在1〇Τ〇Η， 或是低於lOTorr。 [〇〇18]常見的氧氣及氮氣源可以被用於Zr/Hf的氧氮化物 膜及Zr/Hf-Si-氧氮化物膜的形成。氧氣源包括氧氣，水， N〇2，NO，ΝΑ，臭氧及空氣，而氮氣源包括醯胺化合物， 氨’ NO，空氣，ν2〇，Ν〇2，Μ#〕等等。為了容易操作及 控制’氧氣及氨分別是優選的氧氣及氮氣源。氮氣/氧氣源 (NO)通常需要較高的加工溫度。 [0019]利用化學氣相沉積在一種基材（例如矽晶圓）上成功 沉積優質的Zr/Hf氧氮化物膜及Zr/Hf_Si•氧氮化物膜的關 1251620 鍵是由氧氣源及氣氣源分開傳送前驅物到化學氣相沉積反 應的腔體，亦即不事先混合，使用分開傳送管線能夠排除 前驅物在進入反應腔體之前與質子氮氣源以及與氧氣源混 合。事先將前驅物與氧氣或氮氣源混合雖然在CVD方法中 是常見的，但是被發現會導致在到達腔體之前進行反應， 當它發生時’沉積會沒有效率而且難以控制。 ^ [0020]實施本文所實現的一個優點是有可能在氧氮化物 膜中一貫地得到高含量的氮，在一個原子的基礎上，氮的 含量（亦即Zr〇XNy或Hf0xNy分子式中的y數值）從低的1 % 到一般的5。/。以及在這之上，通常y的範圍可以在1〇到3〇% 之間。雖然藉由控制在反應混合物中的氧含量可以產生其 他X的數值，但在膜中的X數值的範圍是在4〇到5〇之間。 [002 1 ]以下的實施例是用於說明本發明的各種具體實例。 實施例1 利用 Hf[N(CH2CH3)2]4，Si[N(CH3)2]4，〇2，及 NH3 沉積含 有Hf，Si，氧及氮的膜 [0022] — 種由重量比為 ι:2 之 Hf[N(CH2CH3)2]4 及
Si[N(CH3)2]4所組成之液體前驅物的混合物經由液體傳送 被運送到一個加熱的蒸發器，並且利用一種20〇sccm流動 的掃除氣體He經由一個位於基材上方的注射環（可以被提 高或降低）被傳送到一個CVD反應腔體，一種由高達 15sccm的〇2，高達i5sccm的nh3以及高達3〇〇sccm之He 稀釋氣體所組成的氧化劑混合物被分開地傳送到腔體，而 1251620 且氧化劑混合物的入口位置與前驅物注射環藉由一個擴散 板分開’此種擴散板可被提高或降低。此種前驅物與氧化 劑在一個被加熱的基材上（300-700°C)反應並製造出含有 Hf ’ Si，〇，及N(以RBS測定）的膜。利用一種壓力控制閥 使腔體的壓力保持在ITorr，使用5到i0sccm的〇2及 1.85sccm的NH3以及O.lmL/min的前驅物的流動，在圖工 中所表現的膜的成分在不出的估計晶圓溫度下（亦即41〇， 430及450°C)被實現。 [0023]圖1中的結果顯示膜所含有的氮含量大於1〇個原 子百分率，並高達大約28個原子百分率的氮。此圖1也顯 示保持C VD腔體在低的晶圓溫度（例如從41 〇到45 0°C )是 可行的。 實施例2 利用 Hf[N(CH3)2]4 ’ Si[N(CH3)2]4 ’ 〇2 及 NH3 沉積含有 Hf，
Si，氧及氮的膜 [0024] — 種由重量比為 5:7 之 Hf[N(CH2CH3)2]4 及
Si[N(CH3)2]4所組成之液體前驅物的混合物經由液體傳送 被運送到一個加熱的蒸發器，並且利用一種2〇〇sccm流動 的掃除氣體He經由一個位於基材上方的注射環（可以被提 高或降低）被傳送到一個CVD反應腔體，—種由高達 30sccm的02，高達5sccm的NH3以及高達2〇〇SCcm之He 稀釋氣體所組成的氧化劑混合物被分開地傳送到腔體，而 且氧化劑混合物的入口位置與前驅物注射環藉由一個擴散 11 1251620 板分開，此種擴散板可被提南或降低。此種前驅物與氧化 劑在一個被加熱的基材上（300-70(rc)反應並製造出含有 Hf，Si，Ο，及N(以RBS測定）的膜。利用一種壓力控制閥 使腔體的壓力保持在1到1.5T0rr，在基材溫度估計為4〇〇 到500°C之間下，使用15到30sccm的〇2，185到5sccm 的NH3以及0·1到〇.2mL/min的前驅物的流動可以得到適 當的沉積速率及膜品質。 實施例3 利用Hf[N(CH2CH3)2]4，〇2及而3沉積含有Hf，氧及氮的膜 [0025] 採用實施例1的步驟，除了 Hf[N(CH2CH3)2]4是經 由液體傳送被運送到一個加熱的蒸發器，並且利用一種 200seem流動的掃除氣體He經由一個位於基材上方的注射 環（可以被提高或降低）被傳送到一個CVD反應腔體，並且 發生沉積並製造出一種铪的氧氮化物膜。 比較例4 [0026] 採用實施例1的步驟，但是依照一般cvd方法的 步驟’其中此種前驅物流及含有氨的氧化劑流經由一個喷 淋頭一起被運送。 [0027] 當嘗試這樣的組態時，通常不是沒有沉積，就是在 導入膜中的氮不是沒有就是只有微少量。雖然不想被束 縛，我們可推斷這個結果是由於與氮氣源反應的困難性。 12 1251620 貫施例5 [0028]重覆實施例3的步驟’除了使用專用的噴淋頭，其 中氨與前驅物是分離的’亦即含有前驅物及氨的流體是細 由噴淋頭中交互的洞所傳送，如同實施例…樣會發生 膜的沉積。 實施例6
[〇〇29]採用實施例i的步驟，除了铪前驅物是氯化铪。雖 然這些前驅是可接受的，但它們使用上並非沒有問題，這 些前驅物在一般的條件下是固體的，所以存在著將其傳送 到化學氣相沉積腔體的困難性。此外，與氨一起使用這些 前驅物會導致在腔體中形成氯化銨粒子，不利於積體電路 的製造。 【圖式簡單說明】 [0012]圖1疋給的氧氮化石夕膜沉積在不同的基材溫度下的 成分百分比的圖示。 13

Claims (1)

  1. I251620 2005年6月修正 拾、申請專利範圍： L 一種形成一選自由Zr和Hf的氧氮化物膜所組成之族 群的金屬氧氮化物膜的沉積方法，此方法包括： A·在一個化學氣相沉積腔體中形成一種反應混合物， 它是藉由 (a) 將一種選自由含有Zr和Hf的前驅物所組成之族 群的前驅物以氣態的形式傳送到該化學氣相沉 積腔體；並且， (b) 將一種氧氣源及一種氮氣源分開傳送到腔體，這 樣該氧氣源及該氮氣源在傳送到化學氣相沉積 腔體之前不會與前驅物發生混合；以及， B.在該化學氣相沉積腔體中，將所獲得的反應混合物 與一基材接觸，以產生金屬氧氮化物膜的沉積，該 基材被加熱到一昇高溫度。 2·如申請專利範圍第1項的方法，其中的金屬前驅物是 在10 Torr或低於1 〇 Torr的壓力下，以氣態的形式傳 送到該化學氣相沉積腔體。 3·如申請專利範圍第1項的方法，其中的基材在一 30〇 到70(TC之間的溫度下被加熱。 4 · 如申請專利範圍第1項的方法，其中的金屬前驅物是 一種Zr或Hf的醯胺化合物。 5· 如申請專利範圍第4項的方法，其中的Zr或Hf的醯 胺化合物是選自由 Zr[N(CH2CH3)2]4，Zr[N(CH2CH3)(CH3)]4， Zr[N(CH3)2]4，HfIN(CH2CH3)2]4，HfIN(CH2CH3)(CH3)]4，或 14 1251620 2005年6月修正 6. 7. 8. 9. 10. 11. 12. 13. Hf[N(CH3)2]4所組成之族群。 如申請專利範圍第5項的方法，其中的氧氣及氮氣源 是 NO，N2〇 或 n〇2。 如申請專利範圍第4項的方法，其中的氧氣源是〇2， H2〇，〇3，或 h202。 如申請專利範圍第7項的方法，其中的氮氣源是NH3或 n2h4。 如申請專利範圍第5項的方法，其中的氧氣源是〇2 以及氮氣源是NH3。 如申請專利範圍第5項的方法，其中一種矽的前驅物 被加入化學氣相沉積腔體中以形成一種Zr或Hf的氧 氮化矽膜。 如申請專利範圍第1 0項的方法，其中矽的前驅物是一 種石夕的醯胺化合物。 如申請專利範圍第11項的方法，其中矽的醯胺化合物 的形式是（HhSUNRiR2)"，其中Ri及f是1至8個 碳的烧基，並且X是整數〇，1，2或3。 如申請專利範圍第12項的方法，其中矽的醯胺化合物 是選自由 Si[N(CH2CH3)2]4，Si[N(CH2CH3)(CH3)]4，Si[N(CH3)2]4， HSi[N(CH2CH3)2]3，HSi[N(CH2CH3)(CH3)]3，HSi[N(CH3)2]3 或 H2Si[NH(C4H9)]2K 組成之族群。 一種形成選自由Zr的氧氮化矽膜及Hf的氧氮化矽膜 所組成之族群的金屬氧氮化矽膜的沉積方法，此方法 15 14. 1251620 包括： 2005年6月修正 前驅物以氣態的形式傳送到 (a)將一選自由含有Zr的 物所組成之族群的 化學氣相沉積腔體； 前驅物及含有Hf的前驅 (b) 將一 $有Sl的前驅物以* 初从虱悲的形式與該含有 Zr或Hf的前驅物分開咬 4疋與Zr或Hf的前驅物 以一混合物方式傳送到該腔體； (c) 將一種氧氣源及一種氣a π 種鼠瑕^源與該含有Zr，Hf 和Si的前驅物分開的方式傳送到該腔體；以及 (d) 在該腔體中’將—基材與所獲得的反應混合物 接觸，該基材被加熱到一介於3〇〇到7〇〇它之間 的溫度，並且在該基材上沉積出Zr的氧氮化矽膜 或Hf的氧氮化矽膜。 15. 如申明專利範圍第14項的方法，其中含有Zr或Hf 和石夕的前驅物是以氣態的形式在1 〇 T〇rr或低於1 〇 Torr下被傳送到一化學沉積腔體。 I6·如申請專利範圍第15項的方法，其中的含有Zr或Hf 和Si的前驅物是Zr的醯胺化合物或Hf的醯胺化合物 以及石夕的醯胺化合物。 17*如申請專利範圍第16項的方法，其中的醯胺化合物是 選自由 N(CH2CH3)2，N(CH2CH3)(CH3)，N(CH3)2 及 N(CH2CH3)2 所 組成之族群。 1 8 ·如申請專利範圍第1 7項的方法，其中的氧氣源是〇2 以及氮氣源是nh3。 16
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