TWI464779B - Methods for forming a ruthenium-based film on a substrate - Google Patents
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本案係請求2007年2月21日申請之美國臨時申請案第60/890,916號之利益，其全文以引用方式併入以為參考。The benefit of the U.S. Provisional Application Serial No. 60/890,916, filed on Feb. 21, 2007, which is incorporated herein by reference in its entirety, is incorporated by reference.
本發明大體而言係關於半導體製造之領域。更特定言之，本發明係關於在基材上形成含釕膜之方法。The present invention is generally related to the field of semiconductor fabrication. More specifically, the present invention relates to a method of forming a ruthenium-containing film on a substrate.
釕及諸如氧化釕之釕化合物是被視為有希望用作次世代DRAM中之電容器電極材料的材料。當前對於此等電容器電極係使用諸如氧化鋁、五氧化二鉭、氧化鉿及鈦酸鍶鋇(BST)之高介電常數材料(亦稱為高k材料)。然而，此等高k材料係藉由使用高達600℃之溫度而生產，此導致多晶矽、矽及鋁之氧化且造成電容的損失。另一方面，釕及氧化釕顯示出高抗氧化性及高傳導性，且適於應用為電容器電極材料。其亦有效地充當氧擴散障壁。亦已建議將釕用作鑭系元素氧化物之閘極金屬。另外，與鉑及其他貴金屬化合物相比，較易於藉由臭氧及藉由使用氧之電漿來蝕刻釕。釕作為使低k材料與鍍銅分離之障壁層及作為種子層之用途近來亦已吸引關注。Antimony and antimony compounds such as antimony oxide are considered to be promising materials for capacitor electrode materials in next generation DRAMs. High dielectric constant materials (also known as high k materials) such as alumina, tantalum pentoxide, yttria and barium strontium titanate (BST) are currently used for such capacitor electrodes. However, such high k materials are produced by using temperatures up to 600 ° C, which causes oxidation of polycrystalline germanium, antimony and aluminum and causes loss of capacitance. On the other hand, niobium and tantalum oxide exhibit high oxidation resistance and high conductivity, and are suitable for use as capacitor electrode materials. It also effectively acts as an oxygen diffusion barrier. It has also been proposed to use ruthenium as a gate metal for lanthanide oxides. In addition, it is easier to etch ruthenium by ozone and by using a plasma of oxygen than platinum and other precious metal compounds. The use of ruthenium as a barrier layer for separating low-k materials from copper plating and its use as a seed layer has recently attracted attention.
可在適當條件下自高純度四氧化釕(RuO4 )之前驅體沉積釕及氧化釕(RuO2 )之高品質膜。此前驅體亦可用於顯示出極佳傳導性及非常類似於該鈦酸鍶鋇及鈦酸鍶之三 維結構的諸如鍶釕氧化物之鈣鈦礦型材料之沉積(膜形成)。A high quality film of ruthenium and ruthenium oxide (RuO 2 ) can be deposited from high purity ruthenium tetroxide (RuO 4 ) before appropriate conditions. The precursor can also be used for deposition (film formation) of a perovskite-type material such as cerium oxide which exhibits excellent conductivity and is very similar to the three-dimensional structure of the barium titanate and barium titanate.
然而，高純度四氧化釕為強氧化劑，且被視為具有高毒性。另外，高純度四氧化釕具有約130℃之沸點，且因此帶來在高溫(高於約108℃)下***的風險。因此建議在低溫下儲存純四氧化釕以避免其分解(***)之可能性。However, high purity osmium tetroxide is a strong oxidant and is considered to be highly toxic. In addition, high purity osmium tetroxide has a boiling point of about 130 ° C and thus carries the risk of explosion at high temperatures (above about 108 ° C). It is therefore recommended to store pure osmium tetroxide at low temperatures to avoid the possibility of decomposition (explosion).
考慮到四氧化釕(RuO4 )之此等性質(尤其是在保存期間***的風險)，在作為反應物時，通常有必要將其在適當溶劑中稀釋。已知使用(例如)水、四氯化碳及烷烴作為此溶劑。In view of the nature of ruthenium tetroxide (RuO 4 ) (especially the risk of explosion during storage), it is often necessary to dilute it in a suitable solvent when acting as a reactant. It is known to use, for example, water, carbon tetrachloride, and an alkane as the solvent.
在水作為溶劑之情況下，另外有必要添加諸如NalO4 之穩定劑以防止RuO4 在保存期間反應及分解。另外，將該RuO4 水溶液用作釕基前驅體可能導致雜質引入至膜及工具(例如，反應腔室)中。In the case of water as a solvent, it is additionally necessary to add a stabilizer such as NalO 4 to prevent RuO 4 from reacting and decomposing during storage. Additionally, the use of the RuO 4 aqueous solution as a sulfhydryl precursor may result in the introduction of impurities into the membrane and tool (eg, the reaction chamber).
電子工業正放棄四氯化碳(歸因於其高毒性)，因此對於四氧化釕前驅體溶液而言，四氯化碳並非理想的溶劑選擇。The electronics industry is abandoning carbon tetrachloride (due to its high toxicity), so carbon tetrachloride is not an ideal solvent choice for osmium tetroxide precursor solutions.
諸如戊烷及辛烷之烷烴可用作RuO4 之溶劑，但當在膜生產中使用含有溶解之RuO4 的烷烴作為釕基前驅體時，烷烴(例如，戊烷)與RuO4 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。Alkanes such as pentane and octane can be used as a solvent for RuO 4 , but when an alkane containing dissolved RuO 4 is used as a sulfhydryl precursor in film production, an alkane (for example, pentane) and RuO 4 are used. The reaction causes the 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.
本文描述在半導體製程中於基材上提供膜之新穎方法 及調配物。所揭示之方法及調配物利用將四氧化釕之混合物溶解於至少兩種不可燃氟化溶劑之混合物中。This article describes a novel method of providing a film on a substrate in a semiconductor process And preparations. The disclosed methods and formulations utilize a mixture of osmium tetroxide dissolved in a mixture of at least two non-flammable fluorinated solvents.
在一具體實例中，在半導體製程中於基材上提供膜之方法包含提供反應腔室及包含於腔室內之基材。提供釕基前驅體，其中該前驅體包含至少兩種不可燃氟化溶劑之混合物、溶解於溶劑混合物中之四氧化釕，及小於約100 ppm之水分。接著在基材上沉積含釕膜。In one embodiment, a method of providing a film on a substrate in a semiconductor process includes providing a reaction chamber and a substrate contained within the chamber. A sulfhydryl precursor is provided wherein the precursor comprises a mixture of at least two non-flammable fluorinated solvents, osmium tetroxide dissolved in a solvent mixture, and less than about 100 ppm moisture. A ruthenium containing film is then deposited on the substrate.
本發明之其他具體實例可包括(但不限於)以下特徵中之一或多者：不可燃氟化溶劑中之每一者具有通式Cx Hy Fz Ot Nu ；其中x3; y+z2x+2; z1; t0; u0；且t+u0其中x、y、z、t及u均為整數。Other embodiments of the invention may include, but are not limited to, one or more of the following features: each of the non-flammable fluorinated solvents having the general formula C x H y F z O t N u ; 3; y+z 2x+2; z 1; t 0; u 0; and t+u 0 where x, y, z, t, and u are integers.
溶劑混合物為甲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90%之間，較佳地約70%之乙基九氟丁醚； 前驅體含有小於約1 ppm之水分；前驅體含有小於約1 ppm之未締合或自由的氧(O2 )；反應腔室中之壓力保持於約0.01 torr到約1000 torr之間；將膜沉積至溫度保持於約50℃到約800℃之間，較佳地約100℃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；以約10℃到約80℃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。The solvent mixture is a mixture of methyl 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; solvent The mixture comprises between about 10% and about 90% by volume, preferably about 70%, of ethyl nonafluorobutyl ether; the precursor contains less than about 1 ppm moisture; and the precursor contains less than about 1 ppm unassociated Or free oxygen (O 2 ); the pressure in the reaction chamber is maintained between about 0.01 torr to about 1000 torr; the film is deposited to a temperature maintained between about 50 ° C and about 800 ° C, preferably about 100 ° C. On a substrate between about 600 ° C; introducing a gas reducing agent into the reaction chamber, and depositing the ruthenium containing film on the substrate via a reaction between the reducing agent and the precursor; the reducing agent is hydrogen, air or oxygen One of the same; 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 the liquid precursor into the evaporator via pressurization with an inert gas; Evaporating at least about 99% of the liquid precursor in the evaporator; evaporating substantially in the evaporator All liquid precursors; evaporating the liquid precursor at a temperature between about 10 ° C and about 80 ° C; the substrate is a ruthenium-type substrate suitable for semiconductor fabrication; and the substrate is a ceramic-based substrate.
前文已相當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。後文將描述本發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。熟習此項技術者應瞭解可易於利用所揭示之概念及特定具體實例作為修改或設計用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 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。The features and technical advantages of the present invention are set forth in the <RTIgt; Additional features and advantages of the invention will be described hereinafter, which form the subject matter of the invention. Those skilled in the art will appreciate that the concept and specific embodiments disclosed may be readily utilized as a basis for modifying or designing other structures for the same purpose. Those skilled in the art should also recognize that The equivalent constructions do not depart from the spirit and scope of the invention as set forth in the appended claims.
為了進一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。For a better understanding of the nature and objects of the present invention, reference should be made to the accompanying drawings. A specific example of the device; and Figure 2 illustrates another specific example of a device for depositing a ruthenium containing film.
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內的基材。提供釕基前驅體混合物，其中前驅體包含至少兩種不可燃氟化溶劑之混合物、溶解於溶劑混合物中之四氧化釕及小於約100 ppm之水分。接著在基材上沉積含釕膜。In general, the present invention relates to a method for providing a film on a substrate in a semiconductor process that provides a reaction chamber and a substrate contained within the chamber. A sulfhydryl precursor mixture is provided wherein the precursor comprises a mixture of at least two non-flammable fluorinated solvents, osmium tetroxide dissolved in a solvent mixture, and less than about 100 ppm moisture. A ruthenium containing film is then deposited on the substrate.
較佳地在前驅體混合物中使用不可燃溶劑，因為當在高於室溫之環境中使用混合物時不可燃溶劑為較佳的。不可燃溶劑亦為較佳，因為一般而言，其將碳引入沉積於基材上之膜的風險最小化。一般而言，氟化溶劑為較佳的，因為氟存在於溶劑分子中使其不可燃，而不將明顯負面影響引入膜之組成中。Non-flammable solvents are preferably used in the precursor mixture because non-flammable solvents are preferred when the mixture is used in an environment above room temperature. Non-flammable solvents are also preferred because, in general, they minimize the risk of carbon being introduced into the film deposited on the substrate. In general, fluorinated solvents are preferred because the presence of fluorine in the solvent molecules renders them non-flammable without introducing significant negative effects into the composition of the film.
在本發明之一些具體實例中，溶劑混合物係由至少兩種溶劑所構成，可根據以下通式來描述其中每一者；Cx Hy Fz Ot Nu 其中：x3; y+z2x+2; z1; t0; u0；且t+u0，且其中x、y、z、t及u均為整數。In some embodiments of the invention, the solvent mixture is comprised of at least two solvents, each of which can be described according to the following general formula; C x H y F z O t N u wherein: x 3; y+z 2x+2; z 1; t 0; u 0; and t+u 0, and wherein x, y, z, t, and u are integers.
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：甲基全氟丙醚；甲基九氟丁醚；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-2-三氟甲基-己烷；C9 F12 N;C12 F27 N;C12 F33 N;C6 F14 ;C8 F16 ;C7 F16 ;C5 F10 H2 ;C4 F5 H5 ;1,1,2,3,3五氟丙烷；CF3CFHCF2CH2OCF2CFHOC3F7及C3F7OCFHCF2CH(CH3)OCF2CFHOC4F9。Several solvents satisfy this formula and are suitable for use in solvent mixtures. Such solvents include: methyl perfluoropropyl ether; methyl nonafluorobutyl ether; ethyl nonafluorobutyl ether; 1,1,1,2,2,3,4,5,5,5-decafluoro- 3-methoxy-4-(trifluoromethyl)-pentane; 3-ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-12 Fluor-2-trifluoromethyl-hexane; C 9 F 12 N; C 12 F 27 N; C 12 F 33 N; C 6 F 14 ; C 8 F 16 ; C 7 F 16 ; C 5 F 10 H 2 ; C 4 F 5 H 5 ; 1,1,2,3,3 pentafluoropropane; CF3CFHCF2CH2OCF2CFHOC3F7 and C3F7OCFHCF2CH(CH3)OCF2CFHOC4F9.
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Novec HFE 7100及Novec HFE 7200而售賣。C5 F10 H2 亦可以商標名稱Vertrel購自DuPont公司。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 Novec HFE 7100 and Novec HFE 7200. C 5 F 10 H 2 is also available from DuPont under the trade name Vertrel.
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沉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。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 deposited thereon by other semiconductor fabrication steps. The substrate can also be a ceramic substrate (eg, ceria, etc.), a metal substrate, or a polymeric substrate.
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。基材亦可為凸起或球狀表面。基材亦可為奈米粒子或以大比表面積為特徵之另一材料。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 can also be a raised or spherical surface. The substrate may also be a nanoparticle or another material characterized by a large specific surface area.
依據膜形成條件及膜將形成於其上之基材的材料而適當選擇根據本發明之前驅體混合物的四氧化釕(RuO4 )濃度。The concentration of ruthenium tetroxide (RuO 4 ) of the precursor mixture according to the present invention is appropriately selected depending on the film formation conditions and the material of the substrate on which the film is to be formed.
根據本發明的釕基前驅體之具體實例係提供至少以下優勢。Specific examples of sulfhydryl precursors in accordance with the present invention provide at least the following advantages.
由於純淨形式之RuO4 會造成***風險，因此RuO4 溶解在氟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RuO4 而無***之風險。Since the pure form of RuO 4 poses a risk of explosion, the dissolution of RuO 4 in the fluorinated solvent mixture allows for the treatment of RuO 4 in a stable form during storage or storage without the risk of explosion.
不可燃溶劑混合物不與RuO4 反應，因此可避免在使用水之情況下發生RuO4 分解。此得以穩定長期保存(儲存)釕基前驅體。The non-flammable solvent mixture does not react with RuO 4 , so that decomposition of RuO 4 occurs in the case of using water. This stabilizes the long-term storage (storage) of the sulfhydryl precursor.
事實上可產生所要含釕膜，因為當以氣體形式使用此前驅體及藉由熱CVD產生膜時，釕基前驅體中之不可燃溶劑氟化溶劑不與RuO4 反應。In fact, the desired ruthenium film can be produced because the non-flammable solvent fluorinated solvent in the ruthenium-based precursor does not react with RuO 4 when the precursor is used in the form of a gas and the film is produced by thermal CVD.
在當前釕基前驅體之情況下，不可燃溶劑混合物不與當RuO4 在反應腔室中分解時產生的活性Ru化合物反應，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需要的化合物。In the case of the current ruthenium-based precursor, the non-flammable solvent mixture does not react with the active Ru compound produced when RuO 4 is decomposed in the reaction chamber, and the solvent mixture is discharged from the reaction chamber together with any unreacted gas. This makes it possible to obtain a desired ruthenium film which does not contain an undesirable compound such as an oxide.
相反，若藉由在水中溶解RnO4 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RuO4 將經歷分解且產生活性Ru。此活性Ru接著將與水反應從而產生不合需要之氧化物。此使得難以產生所要含釕膜。在一些具體實例中，釕 基前驅體實質上無水分含量，含有小於100 ppm，較佳地小於1 ppm之水分。On the contrary, if the sulfhydryl precursor is formed by dissolving RnO 4 in water and then the film formation by thermal CVD is performed by transferring the precursor to the reaction chamber in a gaseous form, RuO 4 will undergo decomposition and Produces active Ru. This active Ru will then react with water to produce an undesirable oxide. This makes it difficult to produce the desired ruthenium film. In some embodiments, the sulfhydryl precursor is substantially free of moisture and contains less than 100 ppm, preferably less than 1 ppm moisture.
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。The non-flammable solvent mixture in the sulfhydryl precursor is preferably non-toxic. This 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.
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***。The fluorinated solvent mixture in the ruthenium-based precursor is preferably non-flammable and exhibits high thermal stability, which makes it possible to avoid the use of the ruthenium-based precursor in the form of a gas for the production of a ruthenium-containing film by thermal CVD. Incorporating carbon into the membrane and decomposition, combustion or explosion caused by the solvent mixture.
根據各種具體實例，藉由以氣體形式將至少本發明之釕基前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。According to various embodiments, a ruthenium-containing film is formed by depositing at least a ruthenium-based precursor of the present invention into a reaction chamber containing a substrate in a gaseous form to deposit a ruthenium-containing film on the substrate.
根據此等方法，可能之含釕膜沉積包括(但不限於)：釕膜，氧化釕膜(RuO2 膜)，及釕酸鹽膜。According to such methods, it is possible that the ruthenium-containing film deposition includes, but is not limited to, a ruthenium film, a ruthenium oxide film (RuO 2 film), and a ruthenate film.
根據一具體實例，藉由將氣體形式之釕基前驅體及氣體還原劑引入至容納基材之反應腔室中且藉由使前驅體與還原劑反應而在基材上沉積釕來形成釕膜。According to a specific example, a ruthenium film is formed by introducing a sulfhydryl precursor in a gaseous form and a gas reducing agent into a reaction chamber containing a substrate and depositing ruthenium on the substrate by reacting the precursor with a reducing agent. .
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釕基前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，氮、氬、氦等等)以泡狀進入此(可能 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。In some embodiments, the sulfhydryl precursor can be introduced into the reaction chamber by using a bubbler system. That is, a sulfhydryl precursor as a liquid as mentioned above may be placed in a container and an inert gas (eg, nitrogen, argon, helium, etc.) may be bubbled into this by using an inert gas bubbler. (may The temperature is controlled by the vessel, which results in the transfer of the precursor of the invention entrained in the inert gas into the reaction chamber.
在一些具體實例中，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，氮、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)。在一些具體實例中，將蒸發器加熱至約10℃到約80℃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%，且較佳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。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 can include liquid mass flow controllers and evaporators such as glass or metal tubing. An inert gas (eg, nitrogen, argon, helium, etc.) can be used to pressurize the liquid phase ruthenium based precursor and flow it from the storage vessel through the liquid flow controller and into the evaporator. If an inert gas is not used to flow the liquid, a vacuum (or lower pressure environment) can be created downstream of the precursor storage vessel (eg, at the evaporator outlet). In some embodiments, the evaporator is heated to a temperature between about 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 preferably all, of the liquid precursor is vaporized into a gas phase precursor. This vapor phase precursor is then passed to the reaction chamber.
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(例如，烯烴、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。In some embodiments, the reducing agent under consideration reduces osmium tetroxide to a ruthenium metal. This reducing agent may be specifically exemplified by hydrogen (H 2 ), but is not limited thereto. Other possible reducing agents include hydrazine and its derivatives and hydrocarbons (eg, olefins, alkynes, aromatic rings, etc.). A single reducing agent or a combination of two or more reducing agents may be used. Hydrogen is especially preferred for reducing agents.
在一些具體實例中，可使用化學氣相沉積(CVD)或原子層沉積(ALD)以形成釕膜。In some embodiments, chemical vapor deposition (CVD) or atomic layer deposition (ALD) can be used to form a tantalum film.
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RuO4 以氣相反應，導致將還原 RuO4 為釕，釕沉積於基材上。伴隨在氣體前驅體中之RuO4 之不可燃氟化溶劑混合物在此沉積期間不會分解，且因此亦得以避免其併入所得釕膜中。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. The reducing agent reacts with the RuO 4 in the precursor in a gas phase, resulting in the reduction of RuO 4 to ruthenium, which is deposited on the substrate. The non-flammable fluorinated solvent mixture accompanying RuO 4 in the gas precursor does not decompose during this deposition, and thus also avoids its incorporation into the resulting ruthenium film.
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 torr與1000 torr之間，且更佳係保持於約0.1 torr與10 torr之間。基材較佳係被加熱至約50℃與800℃之間，且更佳係被加熱至約100℃與400℃之間。允許還原劑以充足量進入反應腔室以將前驅體中之RuO4 還原為釕金屬。當使用(例如)氫作為還原劑時，前驅體中之每1莫耳RuO4 使用至少4莫耳氫。在此情況下之副產物為H2 O。During this film generation, the total pressure in the reaction chamber is preferably maintained between about 0.01 torr and 1000 torr, and more preferably between about 0.1 torr and 10 torr. The substrate is preferably heated to between about 50 ° C and 800 ° C, and more preferably between about 100 ° C and 400 ° C. The reducing agent is allowed to enter the reaction chamber in a sufficient amount to reduce RuO 4 in the precursor to the base metal. When, for example, hydrogen is used as the reducing agent, at least 4 moles of hydrogen is used per 1 mole of RuO 4 in the precursor. The by-product in this case is H 2 O.
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)沖洗反應腔室的內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。In some embodiments of the deposition method for use with ALD, a gas sulfhydryl precursor is initially introduced into the reaction chamber and a very thin layer of ruthenium oxide is formed on the substrate by absorption and decomposition of the precursor (eg, Monoatomic layer). The interior of the reaction chamber is then rinsed with an inert gas (eg, nitrogen, helium, argon) to remove unreacted or unabsorbed sulfhydryl precursors (including the particular non-flammable fluorinated solvent mixture above). This rinse is followed by introduction of a gaseous reducing agent into the reaction chamber. The incoming reducing agent reacts with the monoatomic layer of cerium oxide formed on the substrate and reduces cerium oxide to the cerium metal. This results in the formation of a monoatomic layer of tantalum on the substrate. When it is desired to grow a thicker ruthenium film, the following procedure can be repeated after flushing the unreacted reducing agent and the gaseous reaction product produced by the reducing agent from the reaction chamber: introducing a gas sulfhydryl precursor, rinsing/removing the residual sulfhydryl precursor Body, introducing a reducing agent, flushing/removing the reducing agent and the gaseous reaction product.
在一些具體實例中，在使用ALD之情況下可藉由脈衝 傳遞而進行氣體釕基前驅體及還原劑之引入。可(例如)以約0.1 sccm至10 sccm之流動速率引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0.5 sccm至100 sccm之流動速率引入還原劑歷時約0.01秒。亦可(例如)以約100 sccm至5000 sccm之流動速率引入沖洗氣體歷時約0.01秒與10秒之間。In some specific examples, the pulse can be pulsed using ALD. The introduction of the gas sulfhydryl precursor and the reducing agent is carried out. The gas sulfhydryl precursor can be introduced, for example, at a flow rate of from about 0.1 sccm to 10 sccm for between about 0.01 seconds and 10 seconds, and the reducing agent can be introduced, for example, at a flow rate of from about 0.5 sccm to 100 sccm. 0.01 seconds. The flushing gas can also be introduced, for example, at a flow rate of from about 100 sccm to 5000 sccm for between about 0.01 seconds and 10 seconds.
在ALD期間，反應腔室中之總壓力較佳係保持於約0.1 torr與10 torr之間，而基材溫度較佳係保持於約100℃與600℃之間。During ALD, the total pressure in the reaction chamber is preferably maintained between about 0.1 torr and 10 torr, while the substrate temperature is preferably maintained between about 100 and 600 °C.
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RuO4 分解且產生固體氧化釕(二氧化釕)的溫度。由RuO4 分解產生之固體氧化釕沉積於基材上。伴隨在氣體前驅體中RuO4 之不可燃氟化溶劑混合物在氧化釕之沉積期間不會分解，且因此亦得以避免其併入氧化釕膜中。固體氧化釕(RuO2 )作為氣體RuO4 之分解催化劑。因此，一旦氣體RuO4 在加熱時分解且由此分解產生之固體氧化釕沉積於基材上，氣體RuO4 即可令人滿意地分解(即使在降低加熱溫度時)。According to some embodiments, the sulfhydryl precursor is introduced into the reaction chamber containing the substrate in the form of a gas. The ruthenium-based precursor can be introduced into the reaction chamber in gaseous form by a bubbler system or via a direct evaporation system. In this case, the substrate is heated to a temperature at which RuO 4 in the precursor is decomposed and solid cerium oxide (cerium oxide) is produced. The solid cerium oxide produced by the decomposition of RuO 4 is deposited on the substrate. The non-flammable fluorinated solvent mixture accompanying RuO 4 in the gas precursor does not decompose during the deposition of cerium oxide, and thus also avoids its incorporation into the cerium oxide film. Solid ruthenium oxide (RuO 2 ) acts as a decomposition catalyst for the gas RuO 4 . Therefore, once the solid RuO 4 which is decomposed by heating and thus decomposed is deposited on the substrate, the gas RuO 4 can be satisfactorily decomposed (even when the heating temperature is lowered).
在此氧化釕沉積期間，反應腔室內的總壓力較佳係約0.01 torr與1000 torr之間，且更佳係約0.1 torr與5 torr之間。基材較佳係被加熱至約150℃，且更佳係被加熱至 約350℃與400℃之間的溫度。During this yttrium oxide deposition, the total pressure within the reaction chamber is preferably between about 0.01 torr and 1000 torr, and more preferably between about 0.1 torr and 5 torr. Preferably, the substrate is heated to about 150 ° C, and more preferably heated to A temperature between about 350 ° C and 400 ° C.
可由諸如矽基材之半導體基材來舉例說明如上文描述送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k膜、高k膜、C摻雜之二氧化矽膜、氮化鈦膜、銅膜、氮化鉭膜、鉬膜、鎢膜及鐵電膜。本發明提供之釕膜及氧化釕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，諸如碳及諸如氟之鹵素的雜質之併入完全不會出現於此等釕膜、含氧化釕或含釕膜。另外，孕核期在本發明中不必要或者非常短暫，此使得釕膜及氧化釕膜在相應較短時間段沉積(在ALD之情況下自初始早期階段開始，對於CVD為若干分鐘)。The substrate fed to the film formation method as described above can be exemplified by a semiconductor substrate such as a tantalum substrate. For example, the following can be used to form the semiconductor substrate: low-k film, high-k film, C-doped yttria film, titanium nitride film, copper film, tantalum nitride film, molybdenum Film, tungsten film and ferroelectric film. The tantalum film and the tantalum oxide film provided by the present invention exhibit excellent adhesion to these films and will not crack even when subjected to chemical mechanical polishing (CMP). Further, the incorporation of impurities such as carbon and a halogen such as fluorine does not occur at all in the ruthenium film, ruthenium oxide or ruthenium containing film. In addition, the gestational phase is not necessary or very short in the present invention, which causes the ruthenium film and the ruthenium oxide film to be deposited in a correspondingly shorter period of time (in the case of ALD, from the initial early stage, for CVD for several minutes).
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。Turning now to Figure 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11、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)，且在基座上安裝諸如矽基材的單一半導體基材(未圖示)。基座之內部裝備用於將半導體基材加熱至指定反應溫度之加熱器。在批次工具之情況下，在反應腔室11中係容納5至200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器之結構不同的結構。The apparatus illustrated in Figure 1 is provided with a reaction chamber 11, a feed source 12 for the ruthenium based 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 susceptor. 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 200 semiconductor substrates are housed in the reaction chamber 11. The heater in the batch tool can have a different structure than the heater in the single wafer tool.
釕基前驅體之進料源12藉由使用上文已描述之起泡器 系統或直接蒸發系統而將釕基前驅體引入反應腔室11，且藉由管線L1而連接至惰性氣體進料源14。管線L1具備關斷閥V1且在關斷閥V1之下游具備流動速率控制器，例如，質量流量控制器MFC1。經由管線L2將釕基前驅體自進料源12引入反應腔室11。自上游側起在所考慮之管線L2中提供以下各項：UV分光計UVS、壓力計PG1、關斷閥V2及關斷閥V3。UV分光計UVS起作用以確認前驅體(特定是RuO4 )在管線L2中之存在且偵測其濃度。The ruthenium-based precursor feed source 12 introduces the ruthenium-based precursor into the reaction chamber 11 by using a bubbler system or a direct evaporation system as described above, and is connected to the inert gas feed source via line L1. 14. The line L1 is provided with a shut-off valve V1 and has a flow rate controller downstream of the shut-off valve V1, for example, a mass flow controller MFC1. The sulfhydryl precursor is introduced into the reaction chamber 11 from the feed source 12 via line L2. From the upstream side, the following items are provided in the considered line L2: UV spectrometer UVS, pressure gauge PG1, shut-off valve V2 and shut-off valve V3. The UV spectrometer UVS acts to confirm the presence of the precursor (specifically RuO 4 ) in line L2 and to detect its concentration.
還原劑氣體之進料源13包含保持氣體形式之還原劑的容器。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。The feed source 13 of reducing agent gas comprises a vessel holding 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.
惰性氣體進料源14包含保持氣體形式之惰性氣體的容器。可經由管線L4將惰性氣體自此進料源引入反應腔室11。自上游側起在所考慮之管線L4中提供以下各項：關斷閥V6、質量流量控制器MFC3及壓力計PG2。管線L4與關斷閥V4上游之管線L3接合。管線L1於關斷閥V6之上游自管線L4分叉。The inert gas feed source 14 contains a vessel that holds an inert gas in the form of a gas. Inert gas can be introduced into the reaction chamber 11 from this feed source via line L4. From the upstream side, the following items are provided in the considered line L4: shut-off valve V6, mass flow controller MFC3 and pressure gauge PG2. Line L4 is engaged with line L3 upstream of shut-off valve V4. Line L1 branches off from line L4 upstream of shut-off valve V6.
於關斷閥V1上游之管線L5自管線L1分出支路。此管線L5在關斷閥V2與V3之間與管線L2接合。關斷閥V7及質量流量控制器MFC4以自上游側之給定序列而配置於管線L5中。The line L5 upstream of the shut-off valve V1 branches off the branch line L1. This line L5 is engaged with the line L2 between the shut-off valves V2 and V3. The shut-off valve V7 and the mass flow controller MFC4 are disposed in the line L5 in a given sequence from the upstream side.
到達反應腔室11之管線L6在關斷閥V3與V4之間分叉。在此管線L6中提供關斷閥V8。The line L6 reaching the reaction chamber 11 branches between the shut-off valves V3 and V4. A shut-off valve V8 is provided in this line L6.
到達泵PMP之管線L7係提供於反應腔室11之底部，且自上游側起在所考慮之此管線L7中提供以下各項：壓力計PG3、用於調節背壓之蝶形閥BV及熱阱15。熱阱15包含在圓周上具備加熱器之管。由於氣體前驅體中之RuO4 藉由熱分解而轉化為固體氧化釕，因此可藉由轉化至固體氧化釕(其沉積於管之內壁上)而自氣流消除引入此熱阱15之RuO4 。A line L7 reaching the pump PMP is provided at the bottom of the reaction chamber 11, and from the upstream side, the following items are provided in the line L7 under consideration: a pressure gauge PG3, a butterfly valve BV for regulating back pressure, and heat Well 15. The heat sink 15 includes a tube having a heater on the circumference. Since 4 by thermal decomposition of the precursor gas RuO converted to solid ruthenium oxide, and thus may be converted to a solid by ruthenium oxide (which is deposited on the inner wall of the pipe) from the gas stream and introduced to eliminate this heat sink 15 of RuO 4 .
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V1、V2及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L6的L5將來自惰性氣體進料源14之惰性氣體引入反應腔室11。In order to generate the diaphragm by using the apparatus illustrated in Fig. 1, first, the shutoff valves V1, V2, and V5 are closed and the switches V6, V7, V3, V4, and V8 are opened. When the pump PMP is operated, the inert gas from the inert gas feed source 14 is introduced into the reaction chamber 11 via line L4 and through L5 of line L6.
接著打開關斷閥V5且自還原劑氣體進料源13將還原劑氣體引入反應腔室11，接著打開關斷閥V1及V2及將來自惰性氣體進料源14之惰性氣體經由管線L1引入至釕基前驅體之進料源12中。此導致將氣體前驅體(RuO4 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11中。將還原劑氣體及RuO4 在反應腔室11中反應，導致釕金屬沉積在半導體基材上。The switch valve V5 is then switched and the reductant gas is introduced into the reaction chamber 11 from the reductant gas feed source 13, then the switch valves V1 and V2 are switched and the inert gas from the inert gas feed source 14 is introduced via line L1. The sulfhydryl precursor is fed into the source 12. This results in the introduction of a gaseous precursor (RuO 4 and the non-flammable solvent specified above, preferably a fluorinated solvent) into the reaction chamber 11 via line L2 and line L6. The reducing agent gas and RuO 4 are reacted in the reaction chamber 11 to cause the base metal to deposit on the semiconductor substrate.
為了藉由使用圖1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以使惰性氣體流入反應腔室。在此狀態中時，打開關斷閥V1、V2且 經由管線L4及管線L1自惰性氣體進料源14將惰性氣體引入釕基前驅體之進料源12，導致將氣體前驅體(RuO4 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11中。由於正在加熱反應腔室11，引入反應腔室11之RuO4 經歷至沉積於基材上的固體氧化釕之熱分解。In order to produce a solid yttria film by using the apparatus illustrated in Figure 1, the apparatus is prepared by closing the shut-off valves V5 and V4 and V6 and keeping the valves closed (since no reducing agent will be used). The pump PMP is activated to create a vacuum environment, and the switches are closed to valves V3, V7 and V8 to allow inert gas to flow into the reaction chamber. In this state, the switch opens the valves V1, V2 and introduces the inert gas from the inert gas feed source 14 into the feed source 12 of the ruthenium-based precursor via line L4 and line L1, resulting in the gas precursor (RuO 4 and The non-flammable solvent specified above, preferably a fluorinated solvent, is introduced into the reaction chamber 11 via line L2 and line L6. Since the reaction chamber 11 is being heated, RuO 4 introduced into the reaction chamber 11 undergoes thermal decomposition to solid cerium oxide deposited on the substrate.
現轉向圖2，描述可用以實施藉由ALD進行之膜沉積方法的裝置之說明性實例。Turning now to Figure 2, an illustrative example of a device that can be used to implement a film deposition process by ALD is described.
圖2中說明之裝置具有一結構，其中管線L8提供於圖1所說明之裝置中；此管線L8自身具備關斷閥V2'，且在關斷閥V2'之下游具備與熱阱15相同之熱阱15'。因此向與圖1中相同之彼等元件指派相同的參考符號，且將不再詳細描述此等元件。所安裝之管線L8之一端連接至紫外分光計UVS與壓力計PG1之間的管線L2，而另一端連接至熱阱15與泵PMP之間的管線L7。The apparatus illustrated in FIG. 2 has a structure in which a line L8 is provided in the apparatus illustrated in FIG. 1; this line L8 itself has a shut-off valve V2', and has the same heat sink 15 downstream of the shut-off valve V2'. Heat sink 15'. Therefore, the same reference numerals are assigned to the same elements as those in FIG. 1, and such elements will not be described in detail. One end of the installed line L8 is connected to the line L2 between the ultraviolet spectrometer UVS and the pressure gauge PG1, and the other end is connected to the line L7 between the heat trap 15 and the pump PMP.
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14之惰性氣體且使其經由管線L6進入反應腔室11。惰性氣體經由管線L1通過釕基前驅體之進料源12導致在L2及L8中氣體前驅體(RuO4 及不可燃氟化溶劑混合物)伴隨惰性氣體的流動。In order to generate the diaphragm by ALD using the apparatus illustrated in Fig. 2, the shutoff valves V2 and V5 are first closed and the switches V6, V7, V3, V4, V8 and V9 are opened, as are the valves V1 and V2'. When the pump PMP is operating, a vacuum condition is created in the different lines, wherein the inert gas from the inert gas feed source 14 is introduced via L4 and L5 and passed into the reaction chamber 11 via line L6. The inert gas is passed through line L1 through feed source 12 of the ruthenium-based precursor to cause a gas precursor (RuO 4 and a non-flammable fluorinated solvent mixture) to accompany the flow of the inert gas in L2 and L8.
在執行此初始準備之後，關閉關斷閥V2'且打開關斷 閥V2，且將氣體前驅體之脈衝傳遞至反應腔室11中。在此之後同時關閉關斷閥V2且打開關斷閥V2'，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11引入惰性氣體而進行的反應腔室內部之沖洗導致自反應腔室11內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11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11中及反應副產物、未反應之還原劑等等自反應腔室11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。After performing this initial preparation, close the shut-off valve V2' and switch off Valve V2, and a pulse of the gas precursor is delivered to the reaction chamber 11. After this, the shut-off valve V2 is simultaneously closed and the switch is closed by the valve V2', which causes the gas precursor (which will decompose in the heat trap 15') to accompany the passage of the inert gas via the line L8. The flushing of the inside of the reaction chamber by introducing an inert gas from the L4 and the L5 via L6 causes the unreacted precursor (including the solvent mixture) and the resulting pair to be removed from the inside of the reaction chamber 11. product. Switching valve V5 is then switched off and a pulse of reductant gas is passed from reductant gas feed source 13 along with inert gas from inert gas feed source 14 to reaction chamber 11. After this, the shut-off valve V5 is closed, causing a pulse of inert gas to be transferred into the reaction chamber 11 and removal of reaction by-products, unreacted reducing agents, and the like from the reaction chamber 11. This processing cycle can be repeated until a ruthenium film having the desired thickness is obtained.
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機金屬化合物引入保持基材之反應腔室且使前驅體與有機金屬化合物在存在氧化氣體的情況下反應且藉此使釕酸鹽沉積於基材表面上而形成釕酸鹽膜。In some embodiments, by introducing a sulfhydryl precursor and a gaseous organometallic compound as defined above in a gaseous form into a reaction chamber holding the substrate and reacting the precursor with the organometallic compound in the presence of an oxidizing gas and Thereby, the niobate is deposited on the surface of the substrate to form a niobate film.
如上文所述，可藉由起泡器系統或直接蒸發系統而將釕基前驅體引入反應腔室。As described above, the sulfhydryl precursor can be introduced into the reaction chamber by a bubbler system or a direct evaporation system.
當(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SrRuOx 之鐵電膜時，為β-二酮/鍶錯合物之Sr(DPM)2 可用作有機金屬化合物。此處，DPM為特戊醯甲烷(dipivaloylmethanate)或2,2,6,6-四甲基-3,5-庚二酸酯 (TMHD)之縮寫。When, for example, a ferroelectric film of BaRuO x is to be produced, Ba(DPM) 2 which is a β-diketone/yttrium complex can be used as the organometallic compound. When a ferroelectric film of SrRuO x is to be produced, Sr(DPM) 2 which is a β-diketone/ruthenium complex can be used as the organometallic compound. Here, DPM is an abbreviation for dipivaloylmethanate or 2,2,6,6-tetramethyl-3,5-pimelate (TMHD).
含氧氣體可為(例如)氧氣、臭氧或N2 O。The oxygen containing gas can be, for example, oxygen, ozone or N 2 O.
在一些具體實例中，可使用CVD來形成上文提及之鐵電膜，在該情況下，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應腔室。接著，前驅體中之RuO4 與有機金屬化合物以氣相在氧存在之情況下反應，此導致(例如)BaRuOx (或SrRuOx )之形成及其在基材上之沉積。然而，同時，伴隨在氣體前驅體中RuO4 之不可燃氟化溶劑混合物在鐵電膜之沉積期間不會分解，藉此亦避免併入膜中。In some embodiments, CVD can be used to form the ferroelectric film mentioned above, in which case a sulfhydryl precursor in gaseous form and an organometallic metal in gaseous form are introduced into the reaction chamber. Next, RuO 4 in the precursor reacts with the organometallic compound in the vapor phase in the presence of oxygen, which results in, for example, the formation of BaRuO x (or SrRuO x ) and its deposition on the substrate. At the same time, however, the non-flammable fluorinated solvent mixture accompanying RuO 4 in the gas precursor does not decompose during deposition of the ferroelectric film, thereby also avoiding incorporation into the film.
反應腔室中之溫度較佳係約450℃與800℃之間，此為此等氣體之反應溫度。The temperature in the reaction chamber is preferably between about 450 ° C and 800 ° C, which is the reaction temperature of the gas.
由此方法產生之釕酸鹽膜(例如，BaRuOx 及SrRuOx )顯示出鐵電性質，且可用於(例如)電容器中。此外，由於可藉由此方法產生薄鐵電膜，因此此等膜可用作電極材料，就如同Ru膜及RuO2 膜一般。具體而言，此等鐵電膜(特定言之，SrRuOx )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)。此等鐵電膜(為氧化物)可防止氧及PbO相對於諸如鑭鈦酸鉛(PLT)及鋯鈦酸鉛(PZT)之鐵電物質的擴散，且同時，藉由採用相同之鈣鈦礦結構作為此等鐵電物質，可增大在電極材料與此等鐵電物質之界面處的黏附，且可尤其防止或減少在此界面處可能發生的低介電常數層之產生且可防止或減少劣化。The ruthenate film produced by this method (e.g., BaRuO x and SrRuO x) exhibit ferroelectric properties and may be used (for example) capacitor. Further, since a thin ferroelectric film can be produced by this method, these films can be used as an electrode material, just like a Ru film and a RuO 2 film. Specifically, such ferroelectric films (specifically, SrRuO x ) can be used as the upper and lower electrode materials of the separate ferroelectric (or as a buffer layer between the ferroelectric and electrode materials). These ferroelectric films (which are oxides) prevent the diffusion of oxygen and PbO relative to ferroelectric materials such as lead lanthanum titanate (PLT) and lead zirconate titanate (PZT), and at the same time, by using the same calcium titanium As such ferroelectric materials, the mineral structure can increase the adhesion at the interface between the electrode material and the ferroelectric substances, and can particularly prevent or reduce the occurrence of a low dielectric constant layer which may occur at the interface and can prevent Or reduce degradation.
提供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。The following non-limiting examples are provided to further illustrate specific examples of the invention. However, the embodiments are not intended to be exhaustive or to limit the scope of the invention described herein.
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蒸發器溫度直接蒸發以決定對應於完全直接蒸發(經界定為在蒸發器中無液體殘留)的前驅體液體流動速率。使用高純度氬作為載體氣體以對液體前驅體加壓且使其流入蒸發器中。在蒸發器之出口處的基底真空壓力為67 torr，且使用以玻璃微珠填充之玻璃U形管作為蒸發器。The ruthenium precursor prepared from osmium tetroxide dissolved in a solvent mixture of 48% HFE-7100 and 52% HFE-7200 is directly evaporated at various evaporator temperatures to determine the corresponding direct evaporation (defined as Precursor liquid flow rate without liquid residue in the evaporator. High purity argon is used as a carrier gas to pressurize the liquid precursor and flow it into the evaporator. The substrate vacuum pressure at the outlet of the evaporator was 67 torr, and a glass U-tube filled with glass beads was used as the evaporator.
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內。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 疇將包括申請專利範圍之標的物的所有等效物。While the invention has been shown and described with respect to the specific embodiments of the present invention, it may be modified by those skilled in the art without departing from the scope of the invention. The specific examples described herein are illustrative only and not limiting. 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 appended claims. Domains will include all equivalents of the subject matter of the patent application.
11‧‧‧反應腔室11‧‧‧Reaction chamber
12‧‧‧進料源12‧‧‧ Feed source
13‧‧‧進料源13‧‧‧ Feed source
14‧‧‧進料源14‧‧‧ Feed source
15‧‧‧熱阱15‧‧‧Hot trap
15'‧‧‧熱阱15'‧‧‧Hot trap
BV‧‧‧蝶形閥BV‧‧‧Butterfly Valve
L1‧‧‧管線L1‧‧‧ pipeline
L2‧‧‧管線L2‧‧‧ pipeline
L3‧‧‧管線L3‧‧‧ pipeline
L4‧‧‧管線L4‧‧‧ pipeline
L5‧‧‧管線L5‧‧‧ pipeline
L6‧‧‧管線L6‧‧‧ pipeline
L7‧‧‧管線L7‧‧‧ pipeline
L8‧‧‧管線L8‧‧‧ pipeline
MFC1‧‧‧質量流量控制器MFC1‧‧‧ Mass Flow Controller
MFC3‧‧‧質量流量控制器MFC3‧‧‧ Mass Flow Controller
MFC4‧‧‧質量流量控制器MFC4‧‧‧ Mass Flow Controller
PG1‧‧‧壓力計PG1‧‧‧ pressure gauge
PG2‧‧‧壓力計PG2‧‧‧ pressure gauge
PG3‧‧‧壓力計PG3‧‧‧ pressure gauge
PMP‧‧‧泵PMP‧‧‧ pump
UVS‧‧‧UV分光計UVS‧‧‧UV spectrometer
V1‧‧‧關斷閥V1‧‧‧Shutdown valve
V2‧‧‧關斷閥V2‧‧‧Shutdown valve
V2'‧‧‧關斷閥V2'‧‧‧Shutdown valve
V3‧‧‧關斷閥V3‧‧‧Shutdown valve
V4‧‧‧關斷閥V4‧‧‧Shutdown valve
V5‧‧‧關斷閥V5‧‧‧Shutdown valve
V6‧‧‧關斷閥V6‧‧‧Shutdown valve
V7‧‧‧關斷閥V7‧‧‧Shutdown valve
V8‧‧‧關斷閥V8‧‧‧Shutdown valve
V9‧‧‧關斷閥V9‧‧‧Shutdown valve
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。Figure 1 illustrates a specific example of a device for depositing a ruthenium-containing film; and Figure 2 illustrates another specific example of a device for depositing a ruthenium-containing film.
11‧‧‧反應腔室11‧‧‧Reaction chamber
12‧‧‧進料源12‧‧‧ Feed source
13‧‧‧進料源13‧‧‧ Feed source
14‧‧‧進料源14‧‧‧ Feed source
15‧‧‧熱阱15‧‧‧Hot trap
BV‧‧‧蝶形閥BV‧‧‧Butterfly Valve
L1‧‧‧管線L1‧‧‧ pipeline
L2‧‧‧管線L2‧‧‧ pipeline
L3‧‧‧管線L3‧‧‧ pipeline
L4‧‧‧管線L4‧‧‧ pipeline
L5‧‧‧管線L5‧‧‧ pipeline
L6‧‧‧管線L6‧‧‧ pipeline
L7‧‧‧管線L7‧‧‧ pipeline
MFC1‧‧‧質量流量控制器MFC1‧‧‧ Mass Flow Controller
MFC3‧‧‧質量流量控制器MFC3‧‧‧ Mass Flow Controller
MFC4‧‧‧質量流量控制器MFC4‧‧‧ Mass Flow Controller
PG1‧‧‧壓力計PG1‧‧‧ pressure gauge
PG2‧‧‧壓力計PG2‧‧‧ pressure gauge
PG3‧‧‧壓力計PG3‧‧‧ pressure gauge
PMP‧‧‧泵PMP‧‧‧ pump
UVS:UV‧‧‧分光計UVS: UV‧‧‧ Spectrometer
V1‧‧‧關斷閥V1‧‧‧Shutdown valve
V2‧‧‧關斷閥V2‧‧‧Shutdown valve
V3‧‧‧關斷閥V3‧‧‧Shutdown valve
V4‧‧‧關斷閥V4‧‧‧Shutdown valve
V5‧‧‧關斷閥V5‧‧‧Shutdown valve
V6‧‧‧關斷閥V6‧‧‧Shutdown valve
V7‧‧‧關斷閥V7‧‧‧Shutdown valve
V8‧‧‧關斷閥V8‧‧‧Shutdown valve
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| US5378492A (en) * | 1992-10-12 | 1995-01-03 | Mashiko; Kenzo | Latent fingerprint detection method |
| US20040241321A1 (en) * | 2002-06-04 | 2004-12-02 | Applied Materials, Inc. | Ruthenium layer formation for copper film deposition |
| WO2006035281A1 (en) * | 2004-09-28 | 2006-04-06 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Precursor for film formation and method for forming ruthenium-containing film |
| US20060162658A1 (en) * | 2005-01-27 | 2006-07-27 | Applied Materials, Inc. | Ruthenium layer deposition apparatus and method |
-
2008
- 2008-02-21 TW TW097106011A patent/TWI464779B/en active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5378492A (en) * | 1992-10-12 | 1995-01-03 | Mashiko; Kenzo | Latent fingerprint detection method |
| US20040241321A1 (en) * | 2002-06-04 | 2004-12-02 | Applied Materials, Inc. | Ruthenium layer formation for copper film deposition |
| WO2006035281A1 (en) * | 2004-09-28 | 2006-04-06 | L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude | Precursor for film formation and method for forming ruthenium-containing film |
| US20060162658A1 (en) * | 2005-01-27 | 2006-07-27 | Applied Materials, Inc. | Ruthenium layer deposition apparatus and method |
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| TW200905725A (en) | 2009-02-01 |
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