TW200905725A

TW200905725A - Methods for forming a ruthenium-based film on a substrate

Info

Publication number: TW200905725A
Application number: TW97106011A
Authority: TW
Inventors: Bin Xia; Ashutosh Misra
Original assignee: Air Liquide
Priority date: 2007-02-21
Filing date: 2008-02-21
Publication date: 2009-02-01
Also published as: TWI464779B

Abstract

Methods for forming a film on a substrate in a semiconductor manufacturing process. A reaction chamber and a substrate in the chamber are provided. A ruthenium based precursor, which includes ruthenium tetroxide dissolved in a mixture of at least two non-flammable fluorinated solvents, is provided and a ruthenium containing film is produced on the substrate.

Description

200905725 九、發明說明：【相關申請案之交互參照】本案係請求2〇07年2月21曰申請之美國第續號之利益’其全文以引用方式併入以為二案背景 > 。【發明所屬之技術領域】本發明大體而言係關於半導體製造之領域。更特定二之，本發明係關於在基材上形成含釕膜之方法。【先前技術】釕及諸b氧化釕之釕化合物是被視為有希望用作▲世代DRAM中之電容器電極材料的材料。當 ^ :=)一氧…五氧化二鈕、氧化給及= )之回介電常數材料（亦稱為高k材料）。缺此等高k材料係藉由使用高達溫度致多晶石夕、石夕及銘之氧化且造成電容的損失。另一方面，了顯示出高抗氧化性及高傳導性，且適於應用為二Γ材料。其亦有效地充當氧擴散障壁。亦已建議主*严亍兀京减物之閘極金屬。另外，與鉑及其他二：:匕合物相比，較易於藉由臭氧及藉由使用氧之電漿、了釕作為使低k材料與鍍銅分離之障壁層及作為 a之用途近來亦已吸引關注。沉積:：田條件下自间純度四氧化17 ( Ru04 )之前驅體 g ψ I化釕（ru02 )之尚品質膜。此前驅體亦可用於出極佳傳導性及非常類似於該鈦酸㈣及鈦酸認之三 200905725 維結構的諸如锶釕氧化物成）。 $欽確型材料之沉積（膜形然而，高純度四氧化釕為強氧化劑，毒性。另外，古从由片被視為具有南此帶來在古、，7:又四氧化舒具有約13(rc之彿點，且因於約_)下***的風險。因此建議存純四氧化舒以避免其分解（***）之可能性。考慮到四氧化釕（Ru0) & π 、 4之此4性質（尤其是在保存 ::二乍的風險），在作為反應物時，通常有必要將其在、當〉谷劑中稀釋。已知 ' 作為此溶劑。（例如）水、四風化碳及烧烴 =作為溶劑之情況下，另外有必要添加諸如請4 』心疋Μ防止Ru〇4在保存期間反應及分解。另外，將只Ru〇4水/合液用作釕基前驅體可能導致雜質弓|入至膜及工具（例如，反應腔室）中。電T工業正放棄四氯化碳（歸因於其高毒性），因此200905725 IX. Invention Description: [Reciprocal Reference of Related Applications] This case is for the benefit of the US continuation number requested by February 21, 2007. The full text is incorporated by reference into the second case background > TECHNICAL FIELD OF THE INVENTION The present invention relates generally to the field of semiconductor fabrication. More specifically, the present invention relates to a method of forming a ruthenium-containing film on a substrate. [Prior Art] The ruthenium compound of bismuth and bismuth oxide is considered to be a material which is expected to be used as a capacitor electrode material in ▲generation DRAM. When ^ :=) an oxygen ... pentoxide oxide, oxidation gives =) back dielectric constant material (also known as high-k material). The lack of such high-k materials causes the loss of capacitance by using up to temperature to cause oxidation of polycrystalline shi, shixi and ming. On the other hand, it exhibits high oxidation resistance and high conductivity, and is suitable for use as a diterpene material. It also effectively acts as an oxygen diffusion barrier. It has also been suggested that the main * strict Yan Jing reduction of the gate metal. In addition, compared with platinum and other two:: chelates, it is easier to use ozone and plasma by using oxygen, ruthenium as a barrier layer for separating low-k materials from copper plating, and the use as a. Has attracted attention. Deposition: The quality film of the precursor g ψ I 钌 (ru02) before the pure tetraoxide 17 (Ru04). Previously, the precursor can also be used for excellent conductivity and very similar to the titanic acid (IV) and the titanic acid of the 200905725 dimensional structure such as cerium oxide. The deposition of the material of the Chin-type material (membrane shape, however, the high-purity osmium tetroxide is a strong oxidant, the toxicity. In addition, the ancient from the film is considered to have the south to bring in the ancient, 7: and the tetraoxide has about 13 (The Buddha point of rc, and the risk of explosion due to about _). Therefore it is recommended to store pure tetraoxide to avoid the possibility of decomposition (explosion). Considering ruthenium tetroxide (Ru0) & π, 4 4 properties (especially in the preservation:: risk of diterpenes), when used as a reactant, it is usually necessary to dilute it in the gluten. Known as 'the solvent. (for example) water, four weathered carbon And burning hydrocarbon = as a solvent, it is also necessary to add such as 请疋Μ to prevent Ru〇4 from reacting and decomposing during storage. In addition, only Ru〇4 water/liquid is used as the sulfhydryl precursor. Leading to impurity bowing into membranes and tools (eg, reaction chambers). The electric T industry is abandoning carbon tetrachloride (due to its high toxicity), so

對於四乳化釕前驅體溶液而言，四氯化碳並非理選擇。 W 諸如戊烷及辛烷之烷烴可用作Ru04之溶劑，但當在膜生產中使用含有溶解之Ru04的烷烴作為釕基前驅體二，烷烴（例如，戊烷）與Ru04之間的反應引起碳之併入。碳造成釕型膜之電阻的增大，因此，可將在膜生產期間出現的碳視為不理想的。【發明内容】本文描述在半導體製程中於基材上提供膜之新穎方法 200905725For a four-emulsified ruthenium precursor solution, carbon tetrachloride is not a rational choice. W Alkane such as pentane and octane can be used as a solvent for Ru04, but when an alkane containing dissolved Ru04 is used as a sulfhydryl precursor 2 in film production, a reaction between an alkane (for example, pentane) and Ru04 is caused. Incorporation of carbon. Carbon causes an increase in the electrical resistance of the ruthenium type film, and therefore, carbon which occurs during film production can be regarded as undesirable. SUMMARY OF THE INVENTION A novel method of providing a film on a substrate in a semiconductor process is described herein.

上提供膜之之水分。溶解於溶劑混合物中之四氧化釕， /刀。接著在基材上沉積含釕膜本發明之其他具體實例可包括中之一或多者：將四氧化釕之混合之基材。提供釕基可燃氟化溶劑之混及小於約100 ppm (但不限於）以下特徵The moisture of the membrane is provided on the membrane. The osmium tetroxide dissolved in the solvent mixture, / knife. Next, depositing a ruthenium-containing film on the substrate. Other specific examples of the present invention may include one or more of: a substrate in which osmium tetroxide is mixed. Provides a blend of sulfhydryl flammable fluorinated solvents of less than about 100 ppm (but not limited to)

CxHyFz〇tNu ;其不可燃氟化溶劑中之每一者具有通式 x>3 ； y + z<2x + 2； ζ>1 ； t>0 ； 0 ;且 t + u>0 其中父、7、2、1及11均為整數。溶劑混合物為曱基九氟丁醚及乙基九氟丁醚之混合物；溶劑混合物包含以體積計約10%到約90%之間，較佳地約30%之甲基九氟丁醚；溶劑混合物包含以體積計約10%到約9〇%之間，較_ 地約70%之乙基九氟丁醚； 8 200905725 荊驅體含有小於約1 ppm之水分；前驅體含有小於約i ppm之未締合或自由的氧（); 反應腔室中之壓力保持於約〇.〇1 t〇rr到約1〇〇〇 t〇rr 之間；將膜沉積至溫度保持於約50°C到約8〇(rc之間，較佳地約100°c與約600。(：之間的基材上；將氣體還原劑引入反應腔室中，且將含釕膜經由還原劑與前驅體之間的反應而沉積基材上；還原劑為氫、空氣或氧中之一者；同時將還原劑及前驅體引入腔室；將前驅體以液態引入蒸發器；至少部分蒸發前驅體以形成氣態前驅體；經由惰性氣體加壓而將液態前驅體引入蒸發器；在蒸發器中蒸發至少約99%的液態前驅體；在蒸發器中蒸發實質上全部液態前驅體；CxHyFz〇tNu; each of its nonflammable fluorinated solvents has the formula x>3; y + z<2x + 2; ζ>1;t>0;0; and t + u>0 where parent, 7 , 2, 1, and 11 are all integers. The solvent mixture is a mixture of decyl nonafluorobutyl ether and ethyl nonafluorobutyl ether; the solvent mixture comprises between about 10% and about 90% by volume, preferably about 30%, of methyl nonafluorobutyl ether; The mixture comprises from about 10% to about 9% by volume, more preferably about 70% ethyl nonafluorobutyl ether; 8 200905725 contains less than about 1 ppm moisture; the precursor contains less than about i ppm Unassociated or free oxygen (); the pressure in the reaction chamber is maintained between about 〇1 t〇rr to about 1〇〇〇t〇rr; the film is deposited until the temperature is maintained at about 50 ° C Up to about 8 〇 (between rc, preferably about 100 ° C and about 600 Å. ( between: on the substrate; a gas reducing agent is introduced into the reaction chamber, and the ruthenium-containing film is passed through the reducing agent and the precursor a reaction between the substrate; the reducing agent is one of hydrogen, air or oxygen; at the same time introducing a reducing agent and a precursor into the chamber; introducing the precursor into the evaporator in a liquid state; at least partially evaporating the precursor to form a gaseous precursor; introducing a liquid precursor into the evaporator via inert gas pressurization; evaporating at least about 99% of the liquid in the evaporator State precursor; evaporating substantially all of the liquid precursor in the evaporator;

乂、勺10 C到約8 0 c之間的溫度蒸發液態前驅體; 基材為適於半導體製造之矽型基材；及基材為以陶瓷為主之基材。月；I文已相田廣泛地概括了本發明之特徵及技術優勢，以便可較佳地理解隨後對本發明之詳細描述。後文將描述本毛明之額外特徵及優勢，其形成本發明之申請專利範圍的標的物項技術者應瞭解可易於利用所揭示之概念及特定具體實㈣為修改或設剌於執行本發明之相同目的的其他結構之基礎。熟習此項技術者亦應認識到該等 9 200905725 等效構造不脫離如所附申請專利範圍中所陳述的本發明之精神及範疇。為了進-步理解本發明之本質及目標，應結合隨附圖式而參考以下詳細描述，在隨附圖式中給予相似元件相同或類似的參考號碼，其中：圖1說明用於沉積含釕膜之裝置的_具體實例；且圖2說明用於沉積含釕膜之裝置的另—具體實例。【實施方式】大體而言，本發明係關於用於在半導體製程中於基材上提供膜之方法，其提供反應腔室及包含於腔室内的基材。提供釕基前驅體混合物，其中前驅體包二可燃氟化溶劑之混合物、溶解於溶劑混 I種不及小於約_ ppm之水分。接著結^物中之四氧化釘刀接者在基材上沉積含釕膜。 2地在前驅體混合物中使用不可燃溶劑，因為當在二…皿之環境中使用混合物時不可燃溶劑為較佳的不燃溶劑亦為較佳，因為一般而言，其將碳引入^ 材上之膜的^ …p A積於基因為氟存在於溶劑…使::;燃佳的，響弓丨入膜之組成中。將月顯負面影在本發明之—些具體實例中，溶劑混合、 /合劑所構A，可根據以下通式來描述其中每至）兩 CxHyFz〇tNu 其中： · y + z<2x + 2 ； 10 200905725 ζ>1 ； t>0 ； u>0 ；且 t + u > 0，且其中x、y、z、t及u均為整數。若干溶劑滿足此通式且適用於溶劑混合物中。此等溶劑係包括.曱基全氟丙醚；曱基九氟丁醚；乙基九氟丁醚； 1，1，1，2,2,3,4,5,5,5-十氟-3_甲氧基_4_(三氟甲基）_戊烷；3_ 乙氧基-1，1，1，2,3,4,4,5,5,6,6,6-十二氟_2-三氟曱基_己烷； C9F12N ； C12F27N ； C12F33N ； C6FI4 ； C8F16 ； C7F16 ； C5F10H2 ； C4F5H5 ’ 1，1，2,3,3 五氟丙烷；及 C3F7〇CFHCF2CH(CH3)OCF2CFH〇C4F9。在一具體實例中’溶劑混合物為甲基九氟丁醚與乙基九氟丁醚之混合物。此等兩種均可購自3M公司，且其以商標名稱 N〇vec HFE 7100 及 N〇vec HFE 7200 而售賣。 CJioH2亦可以商標名稱Vertrel購自Dup〇nt公司。在一些具體實例中，含沉積釕膜之基材係可變化。基材可為半導體基材，其可能已具有由其他半導體製造步驟而，儿積於其上的其他材料層。基材亦可為陶瓷基材（例如，二氧化矽等等）、金屬基材或聚合物基材。在一些具體實例中，基材具有不同形狀。基材可為平坦的，諸如典型半導體晶圓或用於併合電路之陶瓷基材。基材亦可為凸U球狀表面。基材亦可為奈米粒子或以大比表面積為特徵之另一材料。 11 200905725 依據膜形成條件及膜將形成於其上告禋埋扭从，〜签何的材枓而適度The liquid precursor is evaporating at a temperature between 10 C and about 80 ° C; the substrate is a ruthenium-type substrate suitable for semiconductor manufacturing; and the substrate is a ceramic-based substrate. The features and technical advantages of the present invention are summarized in the form of a detailed description of the present invention. The additional features and advantages of the present invention will be described hereinafter, and it is understood by those skilled in the art that the present invention is to be construed as being <RTIgt; The basis of other structures for the same purpose. Those skilled in the art will also recognize that the equivalents of the <RTIgt; 200905725</RTI> equivalents are not departing from the spirit and scope of the invention as set forth in the appended claims. For the purpose of further understanding of the nature of the present invention, the same referenced A specific example of a device for a membrane; and Figure 2 illustrates another specific example of a device for depositing a membrane containing ruthenium. [Embodiment] In general, the present invention relates to a method for providing a film on a substrate in a semiconductor process, which provides a reaction chamber and a substrate contained in the chamber. A sulfhydryl precursor mixture is provided, wherein the precursor comprises a mixture of flammable fluorinated solvents, dissolved in a solvent mixture of less than about _ppm. Next, the oxidized nail knives in the structure deposit a ruthenium-containing film on the substrate. The non-flammable solvent is used in the precursor mixture because it is preferred that the non-flammable solvent is a preferred non-flammable solvent when the mixture is used in the environment of the second dish, because in general, it introduces carbon into the material. The film of ... p A is accumulated in the gene for the presence of fluorine in the solvent ... so that::; burning, the bow into the film composition. In the specific examples of the present invention, the solvent mixture, / composition A, can be described according to the following formula: each of the two CxHyFz〇tNu where: · y + z < 2x + 2 ; 10 200905725 ζ>1;t>0;u>0; and t + u > 0, and wherein x, y, z, t, and u are integers. Several solvents satisfy this formula and are suitable for use in solvent mixtures. Such solvents include: mercapto perfluoropropyl ether; mercapto nonafluorobutyl ether; ethyl nonafluorobutyl ether; 1,1,1,2,2,3,4,5,5,5-decafluoro- 3_methoxy_4_(trifluoromethyl)-pentane; 3_ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro 2-trifluorodecyl-hexane; C9F12N; C12F27N; C12F33N; C6FI4; C8F16; C7F16; C5F10H2; C4F5H5 ' 1,1,2,3,3 pentafluoropropane; and C3F7〇CFHCF2CH(CH3)OCF2CFH〇C4F9. In one embodiment, the solvent mixture is a mixture of methyl nonafluorobutyl ether and ethyl nonafluorobutyl ether. Both of these are available from 3M Company and are sold under the trade names N〇vec HFE 7100 and N〇vec HFE 7200. CJioH2 is also available from Dup〇nt under the trade name Vertrel. In some embodiments, the substrate comprising the deposited ruthenium film can vary. The substrate can be a semiconductor substrate that may already have other layers of material that are otherwise formed by other semiconductor fabrication steps. The substrate can also be a ceramic substrate (e.g., ceria, etc.), a metal substrate, or a polymeric substrate. In some embodiments, the substrate has a different shape. The substrate can be flat, such as a typical semiconductor wafer or a ceramic substrate for a parallel circuit. The substrate may also be a convex U spherical surface. The substrate may also be a nanoparticle or another material characterized by a large specific surface area. 11 200905725 According to the film formation conditions and the film will be formed on it, the warning is buried, and the material is moderately signed.

〜擇根據本發明之前驅體混合物的四氧㈣（RuQ 優勢據本發明的產了基前驅體之具體實令!係提供至少以下由於純淨形式之Ru〇j造成***風險，因此r⑽容 =化溶劑混合物中使得能夠在儲存或保存期間以穩定形式處理RU〇4而無***之風險。不可燃溶劑混合物不與Ru〇4反應，因此可避免在使存況下發生Μ4分解。此得以敎長期保存（儲孖）釕基丽驅體。二事實上可產生所要含釕膜，因為當以氣體形式使用此 :驅體及藉由㈣CVD產生膜時，対基前驅體中之不可物洛劑氟化溶劑不與Ru〇4反應。、 l: 各在當前釕基前驅體之情況下，不可燃溶劑混合物不與 § Ru〇4在反應腔室中分解時產生的活性Ru化合物反鹿，且溶劑混合物連同任何未反應之氣體自反應腔室排出:此使得有可能獲得所要含釕膜而其不含有諸如氧化物之不合萬要的化合物。 /目反’若藉由在水中溶解Ru04而形成釕基前驅體且接著藉由以氣體形式將該前驅體傳遞至反應腔室來執行藉由熱CVD進行之膜形成’則Ru〇4將經歷分解且產生活^ Ru。此活性Ru接著將與水反應從而產生物。此使得難以產生所要含釘膜。在一些具體； 12 200905725 基刖驅體實質上無水分含量，含有小於i 〇〇 ppm，較佳地小於1 ppm之水分。釕基前驅體中之不可燃溶劑混合物較佳係無毒的。此使得當使用氣體釕基前驅體藉由熱CVD而產生含釕膜時，有可能在安全環境中實施膜生產。釕基前驅體中之氟化溶劑混合物較佳係不可燃的且顯示出高熱穩定性，此使得在以氣體形式使用此釕基前驅體 (:以用於藉由熱CVD生產含釕膜時有可能避免將碳併入至膜中以及溶劑混合物所造成之分解、燃燒或***。根據各種具體實例，藉由以氣體形式將至少本發明之釕基4驅體引入至容納基材的反應腔室中而在基材上沉積含釕膜來形成含釕膜。根據此等方法，可能之含釕膜沉積包括（但不限於）：釕膜，氧化釘膜（Ru〇2膜），及 {；釕酸鹽膜。丑於形成訂膜之方法 —根據一具體實例，藉由將氣體形式之釕基前驅體及氣體遇原劑引入至容納基材之反應腔室中且藉由使前驅體與逛原劑反應而在基材上沉積釕來形成釕膜。在一些具體實例中’可藉由使用起泡器系統將釕基前驅體引入至反應腔室中。亦即，可將如上文所提及為液體之訂基刖驅體置於容器中且可藉由使用惰性氣體起泡管使惰性氣體（例如’ t、氬、氦等等）以泡狀進入此（可能 13 200905725 溫度受到控制）容器，此導致將惰性氣體中夾帶的本發明前驅體傳遞進入反應腔室。在-些具體實例中，可經由直接蒸發系統將釕基前驅體引入至反應腔室中。該系統在此項技藝中係習知的，且可包括液體質量流量控制器及蒸發器，諸如玻璃或金屬管。惰性氣體（例如，t、氬、氦等等）可用以對液相釕基前驅體加壓且使其自儲存容器流動通過液體流量控制器且進入蒸發器。若不使用惰性氣體來使液體流動，則可在前驅體儲存容器之下游（例如，在蒸發器出口處）產生真空（或較低壓環境）。在—些具體實例中，將蒸發器加熱至、力1 0 C到約80 c之間的溫度。蒸發器之溫度使得液相前驅體蒸發為氣相前驅體。在一些具體實例中，約99%，且幸X么地全部液相前驅體蒸發為氣相前驅體。接著將此氣相前驅體傳遞至反應腔室。在一些具體實例中，考慮中之還原劑將四氧化釕還原為釕金屬。此還原劑可特別地由氫（H2)來舉例說明，但不限於此。其他可能還原劑係包括肼及其衍生物及烴類（例烯L炔烴、芳環等）。可使用單一還原劑或兩種或兩種以上還原劑之組合。氫對於還原劑尤為較佳。在些具體實例中，可使用化學氣相沉積（CVD )或原子層沉積（ALD)以形成釕膜。在CVD為所使用之沉積方法的具體實例中，同時將根據本發明之氣體還原劑及氣體釕基前驅體引入反應腔室中還原劑與前驅體中之Ru〇4以氣相反應，導致將還原 14 200905725 ru〇4為釕，釕沉積於基材上。伴隨在氣體前驅體中之Ru〇4 之不可燃氟化溶劑混合物在此沉積期間不會分解，且因此4 亦得以避免其併入所得釕膜中。在此膜產生期間’反應腔室中的總壓力較佳係保持於約0.01加與1000 torr之間，且更佳係保持於約〇」t阶與10t〇rr之間。基材較佳係被加熱至約5〇。〇與8〇(rc之間，Selecting the tetraoxane (tetra) of the precursor mixture according to the present invention (RuQ Advantage According to the specific practice of the base precursor of the present invention, the system provides at least the following risk of explosion due to the pure form of Ru〇j, so r(10) capacity = The solvent mixture enables the treatment of RU〇4 in a stable form during storage or storage without the risk of explosion. The non-flammable solvent mixture does not react with Ru〇4, thus avoiding the decomposition of Μ4 under the conditions. Preservation (reservoir) 钌基丽驱体. 2 In fact, it can produce the desired ruthenium film, because when using this in the form of gas: the body and the film produced by (4) CVD, The solvent does not react with Ru〇4. l: In the case of the current sulfhydryl precursor, the non-flammable solvent mixture does not react with the active Ru compound which is produced when § Ru〇4 is decomposed in the reaction chamber, and the solvent The mixture is withdrawn from the reaction chamber along with any unreacted gases: this makes it possible to obtain the desired ruthenium film which does not contain an undesired compound such as an oxide. Ru04 forms a ruthenium-based precursor and then performs film formation by thermal CVD by transferring the precursor to the reaction chamber in a gaseous form. Then Ru〇4 will undergo decomposition and generate a living Ru. It will then react with water to produce a product. This makes it difficult to produce the desired nail film. In some specifics; 12 200905725 The base enthalpy drive has substantially no moisture content and contains less than i 〇〇 ppm, preferably less than 1 ppm moisture. The non-flammable solvent mixture in the ruthenium-based precursor is preferably non-toxic, which makes it possible to carry out film production in a safe environment when a gas-containing ruthenium precursor is used to produce a ruthenium-containing film by thermal CVD. The fluorinated solvent mixture is preferably non-flammable and exhibits high thermal stability, which makes it possible to use the ruthenium-based precursor in a gaseous form (for use in the production of a ruthenium-containing film by thermal CVD, it is possible to avoid carbon Incorporating into the membrane and decomposition, combustion or explosion caused by the solvent mixture. According to various embodiments, at least the sulfhydryl group 4 of the present invention is introduced into the reaction chamber containing the substrate by gas form A ruthenium-containing film is deposited on the substrate to form a ruthenium-containing film. According to such methods, possible ruthenium-containing film deposition includes, but is not limited to, ruthenium film, oxidized nail film (Ru〇2 film), and {; Acid film. Ugly method for forming a film - according to a specific example, by introducing a gas-based sulfhydryl precursor and a gas-producing agent into a reaction chamber containing a substrate and by making the precursor The virgin reacts to deposit ruthenium on the substrate to form a ruthenium film. In some embodiments, the ruthenium-based precursor can be introduced into the reaction chamber by using a bubbler system. That is, as mentioned above And placing the liquid substrate in the container and allowing the inert gas (eg, 't, argon, helium, etc.) to enter the bubble by using an inert gas bubbler tube (possible 13 200905725 temperature controlled) The container, which results in the transfer of the precursor of the invention entrained in the inert gas into the reaction chamber. In some embodiments, the sulfhydryl precursor can be introduced into the reaction chamber via a direct evaporation system. Such systems are well known in the art and may include a liquid mass flow controller and an evaporator such as a glass or metal tube. An inert gas (e.g., t, argon, helium, etc.) can be used to pressurize the liquid phase sulfhydryl precursor and flow it from the storage vessel through the liquid flow controller and into the evaporator. If no inert gas is used to flow the liquid, a vacuum (or lower pressure environment) can be created downstream of the precursor storage container (e.g., at the evaporator outlet). In some embodiments, the evaporator is heated to a temperature between 10 C and about 80 c. The temperature of the evaporator causes the liquid phase precursor to evaporate into a gas phase precursor. In some embodiments, about 99%, and fortunately all of the liquid precursor is vaporized into a gas phase precursor. This gas phase precursor is then passed to the reaction chamber. In some embodiments, the reducing agent under consideration reduces osmium tetroxide to a ruthenium metal. This reducing agent can be exemplified particularly by hydrogen (H2), but is not limited thereto. Other possible reducing agents include hydrazine and its derivatives and hydrocarbons (eg, alkyne, alkyne, etc.). A single reducing agent or a combination of two or more reducing agents may be used. Hydrogen is especially preferred for reducing agents. In some embodiments, chemical vapor deposition (CVD) or atomic layer deposition (ALD) can be used to form a tantalum film. In the specific example of the deposition method used for CVD, the gas reducing agent and the gas sulfhydryl precursor according to the present invention are simultaneously introduced into the reaction chamber, and the reducing agent reacts with Ru〇4 in the precursor in the gas phase, resulting in Reduction 14 200905725 ru〇4 is ruthenium, and ruthenium is deposited on the substrate. The non-flammable fluorinated solvent mixture accompanying Ru〇4 in the gas precursor does not decompose during this deposition, and thus 4 is also prevented from being incorporated into the resulting ruthenium film. The total pressure in the reaction chamber during the film generation period is preferably maintained between about 0.01 and 1000 torr, and more preferably between about t"t and 10t". The substrate is preferably heated to about 5 Torr. 〇 between 8 and rc (rc,

且更佳係被加熱至約10(rc與40(rc之間。允許還原劑以充足量進人反應腔室以將前驅體中之Ru04還原為釕金屬。當使用（例如）氫作為還原劑時，前驅體使用至少4莫耳氯。在此情況下之副產物二…U〇4 在以ALD為使用之沉積方法的一些具體實例中最初將氣體釕基前驅體引入反應腔室中且藉由前驅體之吸收及分解而在基材上形成非常薄的氧化釕層（例如，單原子層）。接著以惰性氣體（例如，氮、氦、氬卜沖洗反應腔室的内部以移除未反應或未吸收之釕基前驅體（其包括上文特定之不可燃氟化溶劑混合物）。此沖洗之後為引入氣體還原劑至反應腔室中。進入之還原劑與形成於基材上的氧化釕之單原子層反應且將氧化釕還原為釕金屬。此導致在基材上形成釕之單原子層。當希望生長較厚釕膜時，可在自反應腔室沖洗未反應之還原劑及由還原劑產生之氣體反應產物之後重複以下程序：引入氣體釕基前驅體，沖洗/ 移除殘餘釕基前驅體，引入還原劑，沖洗/移除還原劑及氣體反應產物。在一些具體實例中，在使用ALD之情況下可藉由脈衝 15 200905725 傳遞而進行氣體釕基前驅體及還原劑之引 * 、 J 、例如）以約0.1 seem至1〇 seem之流動速率弓丨入氣體釕基前驅體歷時約0.01秒與10秒之間，且可（例如）以約〇 5 sam 至100 seem之流動速率引入還原劑歷時約〇〇1秒。亦可 (例如）以約100 seem至5000 sccm之流動速率引入沖洗氣體歷時約0. 〇 1秒與1 〇秒之間。在A L D期間’反應腔室中之總壓力車交佳係保持於約〇. i f ton·與1〇 torr之間，而基材溫度較佳係保持於約⑽。c盥 600°C 之間。 ” 里化釕膜（尺⑹二膜）之方上根據一些具體實例，以氣體形式將釕基前驅體引入容納基材之反應腔室中。可藉由起泡器系統或經由直接蒸發系統而以氣體形式將此釕基前驅體引入反應腔室。在此情況下，將基材加熱至使前驅體中㈣分解且產生固體氧 :匕：（二氧化釕）的溫度。ώ Ru〇4分解產生之固體氧化釘丨儿積於基材上。体隨太名Μ么伴奴在乳體則驅體中Rn〇4之不可辦氟化溶劑混合物在氧化舒之沉積期間不會分解，且因此亦、 =免其二入氧化㈣中。固體氧化釘（ru〇2)作為氣體More preferably, it is heated to about 10 (rc and 40 (rc). The reducing agent is allowed to enter the reaction chamber in a sufficient amount to reduce Ru04 in the precursor to the base metal. When using, for example, hydrogen as a reducing agent The precursor uses at least 4 moles of chlorine. In this case the by-products two...U〇4 are initially introduced into the reaction chamber in some specific examples of deposition methods using ALD. A very thin layer of ruthenium oxide (for example, a monoatomic layer) is formed on the substrate by absorption and decomposition of the precursor. The inside of the reaction chamber is then rinsed with an inert gas (for example, nitrogen, helium, or argon to remove the a reactive or unabsorbed sulfhydryl precursor comprising a specific non-flammable fluorinated solvent mixture as described above. This rinsing is followed by introduction of a gaseous reducing agent into the reaction chamber. Oxidation of the reducing agent and the formation of the substrate The monoatomic layer reacts and reduces yttrium oxide to ruthenium metal. This results in the formation of a monoatomic layer of ruthenium on the substrate. When it is desired to grow a thicker ruthenium film, the unreacted reducing agent can be washed from the reaction chamber and Produced by a reducing agent The bulk reaction product is then followed by the following procedure: introducing a gas sulfhydryl precursor, rinsing/removing the residual sulfhydryl precursor, introducing a reducing agent, rinsing/removing the reducing agent and the gaseous reaction product. In some embodiments, using ALD In this case, the gas sulfhydryl precursor and the reducing agent can be introduced by the pulse 15 200905725, and J, for example, the gas sulfhydryl precursor is entangled at a flow rate of about 0.1 seem to 1 〇seem for about 0.01 seconds. The reducing agent can be introduced, for example, between 10 seconds and at a flow rate of from about 5 sam to 100 seem for about 1 second. The flushing gas can also be introduced, for example, at a flow rate of about 100 seem to 5000 sccm. Between 1 sec and 1 sec. Between the ALD period, the total pressure in the reaction chamber is maintained at about 〇. between ton· and 1〇torr, and the substrate temperature is better. The system is maintained between about (10) and c 盥 600 ° C. The ruthenium-based precursor is introduced into the reaction chamber of the accommodating substrate in a gas form according to some specific examples. Can be via a bubbler system or via The ruthenium-based precursor is introduced into the reaction chamber in the form of a gas by an evaporation system. In this case, the substrate is heated to decompose the precursor in the precursor (4) to produce a solid oxygen: 匕: (cerium oxide). The solid oxidized nail produced by the decomposition of Ru〇4 accumulates on the substrate. The body is accompanied by the name of the scorpion in the body of the milk. The fluorinated solvent mixture of Rn〇4 is not allowed during the deposition of oxidized sulphate. Decomposes, and therefore also, = is freed from oxidation (4). Solid oxide nail (ru〇2) as a gas

Ru04之匀解催化劑。因此，—曰 —軋體Ru04在加熱時分解且由此为解產生之固體氧化釕沉々即可令人滿;f地分解（；土％ Ru04 广鮮（即使在降低加熱溫度時）。在此氧^化釘沉箱里日卩卩 — 』間，反應腔室内的總壓力較佳係约 1η Γ11000 t〇^5t〇rr 3基材較佳係被加熱至約15(rc’且更佳係被加熱至 16 200905725 約350°C與40(TC之間的溫度。可由諸如石夕基材之半導體基材來舉例說明如上文描述达入於膜形成方法的基材。舉例而言，可將以下各項用於形成於此半導體基材上：低让膜 '高k膜、C摻雜之二氧化石夕膜、氮化鈦膜、銅膜、氮化组膜、銦m、鶴膜及鐵電膜本毛月提之舒膜及氧化釘膜顯示出對此等膜極佳的黏附性且即使在受到化學機械研磨（CMP)時，將不脫裂。此外，諸如碳及諸如氟之_素的雜f之併人完全不會出現於此等釕膜、含氧化釕或含釕膜。另夕卜，孕核期在本發明中不必要或者非常短暫，此使得針膜及氧化釕膜在相應較短日7間段"“貝（在ALD之情況下自初始早期階段開始，對於CVD為若干分鐘）。現轉向圖1，描述可用以實施藉由CVD進行之膜沉積方法的裝置之說明性實例。Ru04 homopolymerization catalyst. Therefore, the crucible Ru04 is decomposed upon heating and thus the solid cerium oxide deposited by the solution can be filled; the decomposition of f (the soil % Ru04 is bright (even when the heating temperature is lowered). In the oxygenation chamber, the total pressure in the reaction chamber is preferably about 1η Γ11000 t〇^5t〇rr 3 and the substrate is preferably heated to about 15 (rc' and better It is heated to 16 200905725 at a temperature between about 350 ° C and 40 (TC. The substrate that reaches the film formation method as described above can be exemplified by a semiconductor substrate such as a Shi Xi substrate. For example, The following items are used to form the semiconductor substrate: a low-k film, a high-k film, a C-doped dioxide film, a titanium nitride film, a copper film, a nitride film, an indium m, a crane film, and The ferroelectric film of the film and the oxidized nail film showed excellent adhesion to these films and will not crack even when subjected to chemical mechanical polishing (CMP). In addition, such as carbon and such as fluorine _ 素素杂杂杂、、、、、、、、、、、、、、、、、、、、、、、、、、、、 It is unnecessary or very short in the Ming Dynasty, which makes the needle film and the yttrium oxide film in the 7th segment of the corresponding shorter day "" (in the case of ALD, since the initial early stage, for CVD for several minutes). 1. An illustrative example of a device that can be used to perform a film deposition process by CVD is described.

圖1中所說明之裝置具備反應腔室i i、釕基前驅體之進料源12、還原劑氣體之進料源13及通常用作載體氣體及/或稀釋氣體之惰性氣體的進料源14。在單晶圓工具之情況下，在反應腔室11中提供基座（未圖示），且在美座上安裝諸如矽基材的單一半導體基材（未圖示）。基座之内部裝備用於將半導體基材加熱至指定反應溫度之^熱器。在批次工具之情況下，在反應腔室11中係容納5至2〇〇個半導體基材。批次工具中之加熱器可具有與單晶圓工具中之加熱益之結構不同的結構。釕基前驅體之進料源12藉由使用上文已描述之起泡器 17 200905725 系統或直接蒸發系統而將釕基前驅體引入反應腔室11，The apparatus illustrated in Figure 1 is provided with a reaction chamber ii, a feed source 12 for the sulfhydryl precursor, a feed source 13 for the reductant gas, and a feed source 14 for the inert gas typically used as a carrier gas and/or diluent gas. . In the case of a single wafer tool, a susceptor (not shown) is provided in the reaction chamber 11, and a single semiconductor substrate (not shown) such as a ruthenium substrate is mounted on the pedestal. The interior of the susceptor is equipped with a heater for heating the semiconductor substrate to a specified reaction temperature. In the case of a batch tool, 5 to 2 semiconductor substrates are housed in the reaction chamber 11. The heater in the batch tool can have a different structure than the heating benefit in a single wafer tool. The thiol precursor feed source 12 introduces the ruthenium based precursor into the reaction chamber 11 by using the bubbler 17 200905725 system or direct evaporation system as described above.

藉由管線L1而連接至惰性氣體進料源14。管線li具且 V1且在關斷閥v!之下游具備流動速率控制器，例如關質罝流量控制器MFC1。經由管線L2將釕基前驅體自進料源12引入反應腔室u。自上游側起在所考慮之管線乙之中提供以下各項：UV分光計uvs、壓力計pGl、關斷閱W 及關斷閥V3。UV分光計謂起作用以確認前驅體（特定是Ru〇4)在管線L2中之存在且偵測其濃度。 —遇原劑氣體之進料源13包含保持氣體形式之還原劑的 ::。允許還原劑氣體經由管線L3自進料源13進入反應腔室11。在管線L3中提供關斷閥V4。管線L3連接至管線L2。。。惰性氣體進料源14包含保持氣體形式之惰性氣體的容可A·由官線L4將惰性氣體自此進料源引入反應腔室 1 1。自上游側起在所考慮之管線L4中提供以下各項：關斷闊V6、質量流量控制器MFC3及壓力計pG2。管線L4 與關斷閥V4 h被·> & i ’f之e線L3接合。管線L1於關斷閥V6 之上游自管線L4分又。其於關斷闊V1上游之管線L5自管線L1分出支路。此 s、、泉L5在關斷閥V2與v3之間與管線L2接合。關斷閥v? :質量流量控制器MFC4以自上游侧之給定序列而配置於 ^線L5中。又至！達反應腔室11之管線L6在關斷閥V3與V4之間分在此管線L6中提供關斷閥V8。 18 200905725 到達豕PMP之管線L7係提供於反應腔室丨1之底部，且自上游側起在所考慮之此管、線U中提供以下各項··壓力計PG3、用於調節㈣之蝶形閥βν及㈣i5。熱_ μ ，含在圓周上具備加熱器之管。由於氣體前驅體中之副藉由熱77解而轉化為gj體氧化^了，因此可藉由轉化至固體氧化釕（其沉積於管之内壁上“自氣流消除引入此熱阱 15 之 Ru04。為了藉由使用圖1中所說明之裝置來產生釕膜，首先關閉關斷閥Vi、V2& V5且打開關斷閥V6、V7、V3、V4 及V8。在操作泵PMp時’經由管線L4及通過管線"的 L5將來自惰性氣體進料源、14 t惰性氣體引入反應腔室 11° j a㈡疋你削軋體進料源13將還原劑氣體引入反應腔室n，接荽轩 1 按者打開關斷閥V1及V2及將按者打開關斷閥來自惰性氣體進料源14之惰性氣體經由管線u引入至釕基前驅體之進料源12中。此導致將氣體前驅體（Ru〇4及上文規定之不可燃溶劑，較佳地為氟化溶劑）、經由管線L2 及管線L6引入至反應腔室u巾。將還原劑氣體及㈣在反應腔室U中反應’導致釕金屬沉積在半導體基材上。為了藉由使用目丨中所說明之裝置產生固體氧化釕膜’藉由關閉關斷閥V5以及V4與V6且保持此等閥關閉 (因為將不使用還原劑）而準備好此裝置。啟動泵pMp以產生真空環境，且打開關斷閥V3、V7及V8 體流入反應腔室。在此狀態中時，打開關斷閥以使惰性氣 VI、V2 且 19 200905725 經由管線L4及管線u自弓丨入4了 A a s「贴乳體進料源14將惰性氣體引入釕基刚驅體之進料源i2，、 m 1 ^ m 及上文規定之不可燃溶劑導致將氣體前驅體（Ru〇4 L2及管線L6弓丨入至反應腔室广/為氟化溶劑）經由管線室11，引入反應腔室Uuu(^由於正在加熱反應腔體氧化釕之熱分解。 “星歷至沉積於基材上的固現轉向圖2，描述可用以宭也精由ALD進行之膜沉積 f. 方去的I置之說明性實例。圖2中說明之裝置具有—έ 甘am ώ 、，'°構，其中官線L8提供於圖1所說明之装置中；此瞢綠τ 線L8自身具備關斷閥V2,，且在關斷閥V2’之下游具備與熱牌15相同之熱牌π。因此向與圖i中相同之彼等元件指派相同的參考符號，且將不再砰細描述此等元件。所安裝之管線L8之一端連接至紫外分光計UVS與壓力彳PG1之間的管線L2，而另一端連接至熱阱1 5與泵PMP之間的管線L7。為了使用圖2中所說明之裝置藉由ALD產生釕膜首先關閉關斷閥V2及V5且打開關斷閥V6、V7、V3、V4、 V8及V9,如同關斷閥V1及V2，。當泵pMp運作時，在不同管線中產生真空狀態，其中經由L4及L5引入來自惰性氣體進料源1 4之惰性氣體且使其經由管線L6進入反應腔室1 1。惰性氣體經由管線L1通過釕基前驅體之進料源 U導致在L2及L8中氣體前驅體（ru〇4及不可燃氟化溶劑混合物）伴隨惰性氣體的流動。在執行此初始準備之後，關閉關斷閥V2,且打開關斷 20 200905725It is connected to the inert gas feed source 14 by line L1. The line has a V1 and has a flow rate controller downstream of the shut-off valve v!, such as the shut-off 罝 flow controller MFC1. The sulfhydryl precursor is introduced into the reaction chamber u from the feed source 12 via line L2. From the upstream side, the following items are provided among the considered pipelines B: UV spectrometer uvs, pressure gauge pGl, shut-off W and shut-off valve V3. The UV spectrometer acts to confirm the presence of the precursor (specifically Ru〇4) in line L2 and to detect its concentration. - The feed source 13 of the source gas contains a :: of a reducing agent in the form of a gas. The reducing agent gas is allowed to enter the reaction chamber 11 from the feed source 13 via line L3. A shut-off valve V4 is provided in line L3. Line L3 is connected to line L2. . . The inert gas feed source 14 contains a capacity to maintain an inert gas in the form of a gas. A. The inert gas is introduced into the reaction chamber 11 from the feed source by the line L4. From the upstream side, the following items are provided in the considered line L4: the shut-off wide V6, the mass flow controller MFC3 and the pressure gauge pG2. The line L4 is engaged with the shut-off valve V4h by the e-line L3 of >& i 'f. Line L1 is again separated from line L4 upstream of shut-off valve V6. It branches off the pipeline L1 from the pipeline L5 upstream of the wide V1. This s, spring L5 is engaged with the line L2 between the shutoff valves V2 and v3. Shut-off valve v?: The mass flow controller MFC4 is disposed in the line L5 in a given sequence from the upstream side. Again! A line L6 of the reaction chamber 11 is provided between the shut-off valves V3 and V4 to provide a shut-off valve V8 in this line L6. 18 200905725 The line L7 that reaches the 豕PMP is provided at the bottom of the reaction chamber 丨1, and from the upstream side, the following items are provided in the tube and line U under consideration. · Pressure gauge PG3, butterfly for adjustment (4) Shape valve βν and (4) i5. Heat _ μ, containing a tube with a heater on the circumference. Since the by-product in the gas precursor is converted to gj body by heat solution, it can be converted to solid yttria (which is deposited on the inner wall of the tube) to eliminate Ru04 introduced into the heat sink 15 from the gas stream. In order to produce the diaphragm by using the apparatus illustrated in Figure 1, the shut-off valves Vi, V2 & V5 are first closed and the switches V6, V7, V3, V4 and V8 are opened. When operating the pump PMp 'via line L4 And through the pipeline " L5 from the inert gas feed source, 14 t inert gas into the reaction chamber 11 ° j a (two) 疋 your rolling body feed source 13 to introduce reducing agent gas into the reaction chamber n, connected to Xuan Xuan 1 The switcher valves V1 and V2 are opened and the switch is shut off. The inert gas from the inert gas feed source 14 is introduced via line u into the feed source 12 of the ruthenium based precursor. This results in a gas precursor ( Ru〇4 and the non-flammable solvent specified above, preferably a fluorinated solvent), introduced into the reaction chamber via line L2 and line L6. The reducing agent gas and (iv) react in the reaction chamber U' Bismuth metal is deposited on the semiconductor substrate. The illustrated apparatus produces a solid yttria membrane 'prepared by closing the shut-off valves V5 and V4 and V6 and keeping the valves closed (since no reducing agent will be used). Start the pump pMp to create a vacuum environment and open The shut-off valves V3, V7 and V8 flow into the reaction chamber. In this state, the switch is opened to open the valve to make the inert gas VI, V2 and 19 200905725 into the 4 through the pipeline L4 and the pipeline u. The milk feed source 14 introduces an inert gas into the feed source i2 of the ruthenium-based rigid body, m 1 ^ m and the non-flammable solvent specified above, resulting in the gas precursor (Ru〇4 L2 and the line L6 bowed) To the reaction chamber is wide / is a fluorinated solvent) via the line chamber 11, into the reaction chamber Uuu (^ due to the thermal decomposition of the reaction chamber yttrium oxide is being heated. "The ephemeris to the solidification of the deposition on the substrate. Figure 2 Describes an illustrative example of the I-position that can be used for film deposition by ALD. The device illustrated in Figure 2 has -έ 甘am ώ ,, '°, where the official line L8 is provided In the device described in 1; the green τ line L8 itself has a shut-off valve V2, and is in the off The downstream of the valve V2' is provided with the same hot card π as the hot card 15. Therefore, the same reference numerals are assigned to the same components as those in Fig. i, and the components will not be described in detail. The installed pipeline L8 One end is connected to the line L2 between the ultraviolet spectrometer UVS and the pressure 彳PG1, and the other end is connected to the line L7 between the heat sink 15 and the pump PMP. In order to produce the ruthenium film by ALD using the apparatus illustrated in Fig. 2 First, close the shut-off valves V2 and V5 and open the switches V6, V7, V3, V4, V8 and V9, as if the valves V1 and V2 were closed. When the pump pMp is operated, a vacuum state is generated in the different lines, wherein the inert gas from the inert gas feed source 14 is introduced via L4 and L5 and is introduced into the reaction chamber 11 via line L6. The inert gas is passed through line L1 through the feed source U of the ruthenium based precursor to cause the flow of the gaseous precursor (ru 〇 4 and the non-flammable fluorinated solvent mixture) with the inert gas in L2 and L8. After performing this initial preparation, close the shut-off valve V2 and switch off the switch 20 200905725

閥V2，且將氣體前驅體之脈衝傳遞至反應腔室丨丨中。在此之後同時關閉關斷閥V2且打開關斷閥V2I，此導致氣體前驅體（其將於熱阱15,中分解）伴隨惰性氣體經由管線L8 之通過。藉由自L4及經由L6的L5向反應腔室u引入惰性氣體而進行的反應腔室内部之沖洗導致自反應腔室i i 内部移除未反應之前驅體（包括溶劑混合物）及所產生之副產物。接著打開關斷閥V5且將還原劑氣體之脈衝自還原劑氣體進料源13連同來自惰性氣體進料源14之惰性氣體傳遞至反應腔室Η中。在此之後關閉關斷閥V5，導致惰性氣體之脈衝傳遞至反應腔室丨丨中及反應副產物、未反應之還原㈣等自反應腔t !之移除等。可重複此處理循環直至獲得具有所要厚度之釕膜。威釕酸鹽膜之方法在一些具體實例中’藉由將氣體形式的上文規定之釕基前驅體及氣體有冑金屬化合物引入保持基材之反應腔室且使：驅體與有機金屬化合物在存在氧化氣體的情況下反 c且藉此使釕酸鹽沉積於基材表面上而形成釕酸鹽膜。如上文所述，可藉由起泡器系統或直接蒸發系統而將対基前驅體引入反應腔室。田（例如）待產生BaRuOx之鐵電膜時，為β_二酮/鋇錯合物之Ba(DPM)2可作為有機金屬化合物。當待產生 SrRu〇x之鐵電膜時，為卜二酮/鳃錯合物之Sr(DpM)2可用作有機金屬化合物。此處，DpM為特戊醯曱烷 (dipival〇ylmethanate )或 2,2,6,6-四曱基-3,5-庚二酸酯 21 200905725 (TMHD)之縮寫。含氧氣體可為（例如）氧氣、臭氧或N2〇。在一些具體實例巾，可使用CVD來形成上文提及之鐵屯膜在4 ^况下，將氣體形式之釕基前驅體及氣體形式之有機金屬金屬引入反康胪玄 ,Λ ^ X ., 久愿腔至。接者，前驅體中之Ru04 與有機金屬化合物以氣相右翁左— 札相在虱存在之情況下反應，此導致 (例如）BaRuOx (或 SrR 〇 ) )之形成及其在基材上之沉 / 積。然而’同日寺’伴隨在氣體前驅體中RU〇4之不可燃氟化洛劑混合物在鐵電膜之沉籍如P丨丁 A \ * % ^ l /儿槓期間不會分解，藉此亦避免併入膜中。反應腔室中之溫度較佳係約45(TC與800。〇之間，此為此等氣體之反應溫度。由此方法產生之对酸鴎腔Γ Y丨一 j馱凰胰（例如，BaRu〇x及SrRu〇x) 顯示出鐵電性質，且可用於广t、 x ^ 』用於（例如）電容器中。此外，由於可精由此方法產生薄鐵雷膜，田士山姑+ 頌电膜因此此等膜可用作電極材料，就如同Ru膜及Ru〇膜一般。取具體而§，此等鐵電膜 (特定言之，S飯〇x)可用作單獨鐵電之上部及下部電極材料（或用作鐵電與電極材料之間的緩衝層）。此等膜（為氧化物）可防止氧及Pb〇相料諸如鑭欽酸錯（PLT) 及錯鈦酸錯（PZT)之鐵電物質的擴散，且同日寺，用相同之約鈦礦結構作為此等鐵電”，可：：料與此等鐵電物質之界面處&釉θ 电極材介面處的黏附’且可尤其防止在此界面處可能發生的低介雪赍 ^ 低，丨電㊉數層之產生且可防止或減少劣化。尺錢 22 200905725 實施例 k I、以下非限制性實施例來進一步說明本發明之具體實例。然而，該等實施例不欲為完全包括性的，且不欲限制本文描述的本發明之範疇。實施你丨1 : 將溶解於48%之HFE-7100及52%之HFE-7200之溶劑混合物中由四氧化釕所製成之釕前驅體以各種基直接蒸發以決定對應於完全直接蒸發（經界定為在蒸= 中無液體殘留）的前驅體液體流動速率。纟用高純度氮作為載體氣體以對液體前驅體加壓且使其流入蒸發器中。在祭發器之出口處的基底真空壓力為67 t〇rr，且使用以玻璃 Μ珠填充之玻璃U形管作為蒸發器。樣本 1 2 3 4 [Ru041 % 0.42% 1.5% 1.5% 1.5% 溫度C 50 50 30 30 壓力（torr) 67 67 67 67 Ar (seem) 278 278 278 278 前驅體流動速率（ml/min、 1.8 1.6 1.8 1.6 ' 完全蒸發？" 是是是是雖然已展示並描述了本發明之具體實例，但可在不脫離本發明之精神或教示的情況下由熟習此項技術者對其進行修改。本文描述之具體實例僅為例示性且非限制性。組合物及方法之許多變化及修改為可能的且處於本發明之範疇内。因此，本發明之範疇不限於本文描述之具體實例，而是僅由隨後的申請專利範圍所限制，申請專利範圍之範 23 200905725 疇將包括申請專利範圍之標的物的所有等效物。【圖式簡單說明】圖1說明用於沉積含釕膜之裝置的一具體實例；且圖2說明用於沉積含釕膜之裝置的另一具體實例。【主要元件符號說明】 11 :反應腔室 12 :進料源 1 3 :進料源 1 4 :進料源 15 :熱阱 15’ ：熱阱 BV :蝶形閥 L1 :管線 L2 :管線 L3 :管線 L4 :管線 L5 :管線 L6 :管線 L7 :管線 L8 :管線 MFC1 :質量流量控制器 MFC3 :質量流量控制器 MFC4 :質量流量控制器 PG1 :壓力計 24 200905725 PG2 :壓力計 PG3 :壓力計 PMP :泵 UVS : UV分光計 V1 :關斷閥 V2 :關斷閥 V2':關斷閥 V3 :關斷閥 V4 :關斷閥 V5 :關斷閥 V6 :關斷閥 V7 :關斷閥 V8 :關斷閥 V9 :關斷閥Valve V2 and delivers a pulse of gas precursor into the reaction chamber bore. After that, the shut-off valve V2 is simultaneously closed and the switch is opened by the valve V2I, which causes the gas precursor (which will decompose in the heat sink 15,) to accompany the passage of the inert gas via the line L8. Flushing inside the reaction chamber by introducing inert gas from L4 and L5 through L6 causes removal of unreacted precursor (including solvent mixture) from the interior of reaction chamber ii and the resulting pair product. The switch is then interrupted by valve V5 and the pulse of reductant gas is passed from the reductant gas feed source 13 along with the inert gas from the inert gas feed source 14 to the reaction chamber. After this, the shut-off valve V5 is closed, causing the pulse of the inert gas to be transferred to the reaction chamber, the reaction by-product, the unreacted reduction (four), and the like from the reaction chamber. The cycle can be repeated until a ruthenium film having the desired thickness is obtained. The method of deuterate film in some embodiments by introducing a sulfhydryl precursor and a gaseous rhodium metal compound as defined above in a gaseous form into a reaction chamber holding the substrate and: driving the body with an organometallic compound In the presence of an oxidizing gas, a cyanate film is formed by anti-c and thereby depositing a bismuth salt on the surface of the substrate. As described above, the sulfhydryl precursor can be introduced into the reaction chamber by a bubbler system or a direct evaporation system. In the case of, for example, a ferroelectric film of BaRuOx to be produced, Ba(DPM) 2 which is a β-diketone/ruthenium complex can be used as an organometallic compound. When a ferroelectric film of SrRu〇x is to be produced, Sr(DpM)2 which is a diketone/oxime complex can be used as an organometallic compound. Here, DpM is an abbreviation for dipival〇ylmethanate or 2,2,6,6-tetradecyl-3,5-pimelate 21 200905725 (TMHD). The oxygen containing gas can be, for example, oxygen, ozone or N2 hydrazine. In some specific examples, CVD can be used to form the above-mentioned iron ruthenium film. In the case of 4 ^, the gas-based sulfhydryl precursor and the gaseous form of organometallic metal are introduced into the anti-Kang Xuan, Λ ^ X. , long-awaited. In the precursor, the Ru04 in the precursor reacts with the organometallic compound in the presence of ruthenium in the presence of ruthenium, which results in the formation of, for example, BaRuOx (or SrR 〇) and its presence on the substrate. Shen / product. However, 'Tongri Temple' is accompanied by a non-flammable fluorinated agent mixture of RU〇4 in the gas precursor, which does not decompose during the period of the ferroelectric film, such as P 丨 A A \ * % ^ l / 儿Avoid incorporation into the membrane. The temperature in the reaction chamber is preferably about 45 (TC and 800. Torr, which is the reaction temperature of the gas for this purpose. The method for producing the acid 鴎 cavity Γ Y丨一j 驮胰 pancreas (for example, BaRu 〇x and SrRu〇x) show ferroelectric properties and can be used in a wide range of x, x ^ for use in, for example, capacitors. In addition, due to the fine iron film that can be produced by this method, the Tianshishan + 颂 electric film is therefore The film can be used as an electrode material, just like the Ru film and the Ru film. Take the specific and §, these ferroelectric films (specifically, S rice cooker x) can be used as the upper and lower electrode materials of the separate ferroelectric (or used as a buffer between ferroelectric and electrode materials.) These films (which are oxides) prevent oxygen and Pb bismuth materials such as bismuth acid (PLT) and arsenate (PZT) iron. The diffusion of electrical materials, and the same day, using the same titanium ore structure as the ferroelectric", can:: the interface with the ferroelectric material at the interface & glaze θ electrode interface at the interface 'and In particular, it prevents the occurrence of low-medium snow at this interface, the generation of ten layers of electricity and the prevention or reduction of degradation. 。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。。 Implementation 丨1: The ruthenium precursor prepared from osmium tetroxide in a solvent mixture of 48% HFE-7100 and 52% HFE-7200 is directly evaporated in various bases to determine the corresponding direct evaporation (via Defined as the precursor liquid flow rate in the absence of liquid residue in the evaporation = 纟 High purity nitrogen is used as the carrier gas to pressurize the liquid precursor and flow it into the evaporator. The substrate vacuum at the exit of the ceremon The pressure was 67 t〇rr and a glass U-tube filled with glass beads was used as the evaporator. Sample 1 2 3 4 [Ru041 % 0.42% 1.5% 1.5% 1.5% Temperature C 50 50 30 30 Pressure (torr) 67 67 67 67 Ar (seem) 278 278 278 278 Precursor flow rate (ml/min, 1.8 1.6 1.8 1.6 'complete evaporation?" Yes, although specific examples of the invention have been shown and described, Deviation from the essence of the invention The present invention is described by way of example only, and is not intended to be limiting, and many variations and modifications of the compositions and methods are possible and are within the scope of the invention. Therefore, the scope of the invention is not limited to the specific examples described herein, but is only limited by the scope of the following claims, and the scope of the patent application is intended to include all equivalents of the subject matter of the claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 illustrates a specific example of a device for depositing a ruthenium-containing film; and Fig. 2 illustrates another specific example of a device for depositing a ruthenium-containing film. [Main component symbol description] 11: Reaction chamber 12: Feed source 1 3: Feed source 1 4: Feed source 15: Heat sink 15': Heat trap BV: Butterfly valve L1: Line L2: Line L3: Pipeline L4: Pipeline L5: Pipeline L6: Pipeline L7: Pipeline L8: Pipeline MFC1: Mass Flow Controller MFC3: Mass Flow Controller MFC4: Mass Flow Controller PG1: Pressure Gauge 24 200905725 PG2: Pressure Gauge PG3: Pressure Gauge PMP: Pump UVS: UV spectrometer V1: Shut-off valve V2: Shut-off valve V2': Shut-off valve V3: Shut-off valve V4: Shut-off valve V5: Shut-off valve V6: Shut-off valve V7: Shut-off valve V8: Off Broken valve V9: shut-off valve

2525

Claims

200905725 十、申請專利範固： 1· 一種在半導體製程中於基材上形成膜之方法，其係包含：提i、反應腔至及包含於腔室内之基材；提ί、釘基$驅體’其中前驅體包含： 1 )至少兩種不可燃氟化溶劑之混合物，每一溶劑具有通式CxHyF2〇tNu，其中： Ο x>3 ； a) b) n) Υ + ζ<2χ + 2； iii) z > 1 ; iv) t > 〇 ; v ) u 2 〇 ;且 vi) t + u 2 〇 ;且其中x、y、z、t及u均為整數； 2) 洛解於溶劑混合物中之四氧化釘；及 3) 小於約l〇〇ppm之水分；及 c )在基材上沉積含釕膜。 2·如申請專利範圍帛i項之方法，其中溶劑混合物包含甲基九氟丁醚及乙基九氟丁醚之混合物。 3_如申請專利範圍第2項之方法，其中溶劑混合物包含： a) 以體積計約10%到約90。/。之間的甲基九氟丁醚；及 b) 以體積計約1〇%到約90%之間的乙基九氟丁峻。 4.如申請專利範圍第3項之方法’其中溶劑混合物包 26 200905725 含： a)以體積計約30%之 b)以體積計約70%之乙基九氟丁醚。 5·如申請專利範圍第1項之方法’其中前驅體包含小於約1 ppm之水分。 6·如申請專利範圍第丨項之方法，其中前驅體進—步包含小於約1 pprn之未締合氧。 /·如申請專利範圍帛"頁之方法，其中反應腔室中之壓力係保持於〇〇1 t〇rr到1〇〇〇 t〇rr之間。 8·如申請專利_ "員之方法，其中膜沉積步驟传於50C到80(TC之間的基材溫度進行。 9.如申請專利範圍帛8項之方法，其中膜沉積步驟係知約100C到約6〇〇t之間的基材溫度進行。 ίο.如申請專利範圍第i項之方盆氣體還原劑引入該反應腔室中及至小Α ,匕3將务辦_ ’ 至^邛分藉由使前驅體與乳體還原劑反應而在該基材上沉積含舒膜。如申請專利範圍第10項之方法，其中還原劑為氫。 ^如申請專利範圍第10項之方法，其中還原劑為空軋或氧。 13 ·如申請專利範圊筮同日4 _ 11圍帛10項之方法，其係、進〆步包含门犄將硬原劑及前驅體引入腔室中。士申明專利乾圍第1項之方法，其係進一步包含 ;:前：體引入蒸發器，其中前驅體初始為液態；、、“驅體以形成至少部分處於氣態的前驅體；及 27 200905725 C)將氣態前驅體引入反應腔室。 15.如申請專利範圍第14項之方法，其係進一步包含藉由以惰性氣體對液態前驅體加壓而將液態前驅體引入蒸發器。 16_如申請專利範圍第14項之方法，其係進一步包含蒸發至少約99%的液態前驅體。 17.如申請專利範圍第14項之方法，其中將整個液態前驅體蒸發以形成氣態前驅體。 1 8 ·如申請專利範圍第14項之方法，其係進一步包含以約1 0°C到約80°C之間的溫度蒸發前驅體。 19. 如申請專利範圍第1項之方法，其中基材為適於半導體製造之矽基材。 20. 如申請專利範圍第1項之方法，其中基材為以陶瓷為主之材料。十一、圖式：如次頁 28200905725 X. Patent application: 1. A method for forming a film on a substrate in a semiconductor process, comprising: raising a substrate, a reaction chamber, and a substrate contained in the chamber; The body 'wherein the precursor comprises: 1) a mixture of at least two non-flammable fluorinated solvents, each solvent having the general formula CxHyF2〇tNu, wherein: Ο x>3; a) b) n) Υ + ζ<2χ + 2 ; iii) z >1; iv) t >〇; v ) u 2 〇; and vi) t + u 2 〇; and wherein x, y, z, t and u are integers; 2) a oxidized nail in the solvent mixture; and 3) less than about 1 〇〇 ppm of moisture; and c) depositing a ruthenium-containing film on the substrate. 2. The method of claim 1, wherein the solvent mixture comprises a mixture of methyl nonafluorobutyl ether and ethyl nonafluorobutyl ether. 3) The method of claim 2, wherein the solvent mixture comprises: a) from about 10% to about 90 by volume. /. Methyl nonafluorobutyl ether; and b) between about 1% and about 90% by volume of ethyl nonafluorophene. 4. The method of claim 3, wherein the solvent mixture package 26 200905725 comprises: a) about 30% by volume b) about 70% by volume of ethyl nonafluorobutyl ether. 5. The method of claim 1 wherein the precursor comprises less than about 1 ppm moisture. 6. The method of claim </ RTI> wherein the precursor further comprises less than about 1 pprn of unassociated oxygen. / / As in the patent application scope " page method, wherein the pressure in the reaction chamber is maintained between 〇 1 t〇rr to 1〇〇〇 t〇rr. 8. The method of applying for a patent, wherein the film deposition step is carried out at a substrate temperature between 50 C and 80 (TC). 9. The method of applying the patent range 帛8, wherein the film deposition step is known The substrate temperature between 100C and about 6〇〇t is carried out. ίο. If the square basin gas reducing agent of the scope of claim i is introduced into the reaction chamber and to the small Α, 匕3 will be handled _ ' to ^邛The method of claim 10, wherein the reducing agent is hydrogen, as in the method of claim 10, wherein the reducing agent is hydrogen. The reducing agent is air-rolled or oxygen. 13 · If the method of applying for patents on the same day 4 _ 11 cofferdam 10 items, the system and the step include the threshold to introduce the hardogen and the precursor into the chamber. The method of claim 1, wherein the method further comprises: introducing: the precursor into the evaporator, wherein the precursor is initially in a liquid state; and “the precursor is to form at least a portion of the precursor in a gaseous state; and 27 200905725 C) Introduce a gaseous precursor into the reaction chamber. The method of claim 14, further comprising introducing the liquid precursor into the evaporator by pressurizing the liquid precursor with an inert gas. The method of claim 14, further comprising evaporating at least about The method of claim 14, wherein the entire liquid precursor is evaporated to form a gaseous precursor. The method of claim 14 further comprising The precursor is evaporated at a temperature of between about 10 ° C and about 80 ° C. 19. The method of claim 1 wherein the substrate is a tantalum substrate suitable for semiconductor fabrication. The method of item 1, wherein the substrate is a ceramic-based material. XI. Schema: as shown in the next page 28