TWI410517B - Method for forming tantalum nitride film - Google Patents
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- TWI410517B TWI410517B TW095106850A TW95106850A TWI410517B TW I410517 B TWI410517 B TW I410517B TW 095106850 A TW095106850 A TW 095106850A TW 95106850 A TW95106850 A TW 95106850A TW I410517 B TWI410517 B TW I410517B
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- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
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- H01L23/522—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body
- H01L23/532—Arrangements for conducting electric current within the device in operation from one component to another, i.e. interconnections, e.g. wires, lead frames including external interconnections consisting of a multilayer structure of conductive and insulating layers inseparably formed on the semiconductor body characterised by the materials
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Abstract
Description
本發明係有關於鉭氮化物膜之形成方法，尤其是有關於，依照CVD法來形成對於做為配線膜用之障壁膜為有用的鉭氮化物膜的形成方法。The present invention relates to a method for forming a tantalum nitride film, and more particularly to a method for forming a tantalum nitride film which is useful as a barrier film for a wiring film in accordance with a CVD method.
近年來，半導體領域的薄膜製造技術中對於微細加工的要求日益加速，其也伴隨著各種問題的發生。In recent years, the demand for microfabrication in the thin film manufacturing technology in the semiconductor field has been accelerating, and it has been accompanied by various problems.
以半導體裝置中的薄膜配線加工為例，做為配線材料，基於阻抗率小等理由，銅的使用已為主流化。可是，由於銅具有難以蝕刻、且容易往基底層之絕緣膜中擴散之性質，因此會產生裝置信賴性降低這類問題。Taking thin film wiring processing in a semiconductor device as an example, as a wiring material, the use of copper has been mainstreamed for reasons such as a small impedance ratio. However, since copper has a property of being difficult to etch and easily diffusing into the insulating film of the underlying layer, there is a problem that the device reliability is lowered.
為了解決此問題，先前是藉由，在多層配線構造中的多層間連接孔的內壁表面，以CVD法等形成金屬薄膜(亦即導電性的障壁膜)，然後在其上形成銅薄膜而做為配線層，以使得銅薄膜和基底層的矽氧化膜等絕緣膜不會直接接觸，防止銅的擴散(例如，參照專利文獻1)。In order to solve this problem, a metal thin film (that is, a conductive barrier film) is formed by a CVD method or the like on the inner wall surface of the connection hole between the plurality of layers in the multilayer wiring structure, and then a copper thin film is formed thereon. As the wiring layer, the insulating film such as the tantalum oxide film of the copper thin film and the underlying layer is not in direct contact with each other, and diffusion of copper is prevented (for example, refer to Patent Document 1).
此時，伴隨上記多層配線化或圖案微細化，長寬比高的微細接觸孔或配線溝等，是被要求以薄的障壁膜，階梯覆蓋性(step coverage)良好地嵌埋。In this case, in the case of the above-described multilayer wiring or pattern refinement, a fine contact hole or a wiring groove having a high aspect ratio is required to be embedded in a thin barrier film with good step coverage.
【專利文獻1】日本特開2002－26124號公報(申請專利範圍等)[Patent Document 1] Japanese Laid-Open Patent Publication No. 2002-26124 (Application Patent Range, etc.)
在上記先前技術的情況中，要一邊確保和Cu配線膜之密著性，同時又要以CVD法形成做為障壁膜為有用之低阻抗的鉭氮化物(TaN)膜是有困難，具有如此問題。為了解決此問題，必須要開發能夠將原料氣體中之烷基等有機基切斷去除而減少C含有量，且，能夠切斷Ta和N之鍵結而提高Ta/N組成比的成膜製程。In the case of the prior art, it is difficult to ensure the adhesion to the Cu wiring film while forming a low-impedance tantalum nitride (TaN) film which is useful as a barrier film by the CVD method. problem. In order to solve this problem, it is necessary to develop a film forming process capable of cutting off an organic group such as an alkyl group in a material gas to reduce the C content, and cutting the bonding of Ta and N to increase the Ta/N composition ratio. .
於是，本發明之課題係為解決上記先前技術之問題點，提供一種依照CVD法，C、N含有量低，Ta/N組成比高，又，做為確保和配線膜(例如，Cu配線膜)之密著性的障壁膜是有用的低阻抗鉭氮化物膜的形成方法。Accordingly, the problem of the present invention is to solve the problems of the prior art described above, and to provide a low content of C and N in accordance with the CVD method, a high Ta/N composition ratio, and as a securing and wiring film (for example, a Cu wiring film). The adhesive barrier film is a useful method for forming a low-resistance tantalum nitride film.
本發明之鉭氮化物膜之形成方法，依照CVD法，在成膜室內，同時導入在鉭元素(Ta)的周圍配位有N=(R,R')(R及R'係表示碳原子數1~6個的烷基，其各自可為相同的基也可為互異的基)而成之配位化合物所成之原料氣體及鹵素氣體，在基板上形成由TaNx (Hal)y (R,R')z 化合物(式中、Hal係代表鹵素原子)所成之鹵化化合物膜，然後導入H原子氣體以將前記鹵化化合物膜中之Ta上所鍵結的N切斷去除，且，將鍵結在N上之鹵素原子或R(R')基切斷去除，形成富含鉭之鉭氮化物膜。上記配位化合物中的碳原子數若超過6，則會有膜中殘存過多碳的問題。In the method for forming a tantalum nitride film according to the present invention, N=(R, R') is coordinated around the tantalum element (Ta) in the film forming chamber according to the CVD method (R and R' represent a carbon atom. a raw material gas and a halogen gas formed by a coordination compound having a number of 1 to 6 alkyl groups each of which may be the same group or a mutually different group, and formed on the substrate by TaN x (Hal) y a halogenated compound film formed of a (R, R') z compound (wherein Hal represents a halogen atom), and then a H atom gas is introduced to cut off the N bonded on the Ta in the precursor halogenated compound film, and The halogen atom or the R(R') group bonded to N is cut off to form a germanium-rich nitride film. When the number of carbon atoms in the above-mentioned coordination compound exceeds 6, there is a problem that excessive carbon remains in the film.
其特徵為，前記含H原子氣體，是在成膜室內，藉由熱或電漿而轉換成自由基；令該自由基和鹵化化合物膜發生反應而形成富含鉭之鉭氮化物膜。It is characterized in that the H atom-containing gas is converted into a radical by heat or plasma in a film forming chamber; and the radical and the halogenated compound film are reacted to form a cerium-rich cerium nitride film.
若依據前記構成，則所得之膜中的C、N含有量會減少，Ta/N組成比會增大，又，可形成做為確保和配線膜(例如Cu配線膜)之密著性的Cu配線障壁膜是有用的低阻抗鉭氮化物膜。According to the above configuration, the content of C and N in the obtained film is reduced, the Ta/N composition ratio is increased, and Cu can be formed to ensure adhesion to the wiring film (for example, Cu wiring film). The wiring barrier film is a useful low impedance tantalum nitride film.
前記原料氣體是從五二甲胺鉭(PDMAT)、三級戊醯亞胺三(二甲醯胺)鉭(TAIMATA)、五二乙胺鉭(PEMAT)、三級丙醯亞胺三(二甲醯胺)鉭(TBTDET)、三級丙醯亞胺三(甲乙醯胺)鉭(TBTEMT)、Ta(N(CH3 )2 )3 (NCH3 CH2 )2 (DEMAT)、TaX5 (X：從氯、溴及碘中選出之鹵素原子)中所選出之至少一種配位化合物之氣體，較為理想。The pre-recorded raw material gas is from pentamidine (PDMAT), tertiary pentamidine, triammine (TAIMATA), penta diethylamine (PEMAT), and tertiary acetonitrile (three). Methotrexate TB (TBTDET), tertiary acetonitrile imine (TBTEMT), Ta(N(CH 3 ) 2 ) 3 (NCH 3 CH 2 ) 2 (DEMAT), TaX 5 ( X: a gas of at least one coordination compound selected from the group consisting of halogen atoms selected from chlorine, bromine and iodine is preferred.
前記鹵素氣體，是從氟、氯、溴、碘中選出至少一種之氣體，較為理想。若使用此種鹵素氣體，則可生成上記TaNx (Hal)y (R,R')z 化合物。It is preferable that the halogen gas is at least one selected from the group consisting of fluorine, chlorine, bromine and iodine. When such a halogen gas is used, a compound of the above TaN x (Hal) y (R, R') z can be produced.
前記含H原子氣體是從H2 、NH3 、SiH4 中選出至少一種之氣體，較為理想。It is preferable that the gas containing H atoms is a gas selected from at least one of H 2 , NH 3 and SiH 4 .
若依據前記鉭氮化物膜之形成方法，則可獲得膜中的鉭和氮的組成比是滿足Ta/N≧2.0之低阻抗薄膜。According to the method for forming a nitride film, the composition ratio of bismuth and nitrogen in the film is a low-impedance film satisfying Ta/N ≧ 2.0.
本發明之鉭氮化物膜之形成方法，其又一特徵為，對於藉由上記形成方所得到之鉭氮化物膜，藉由使用以鉭為主構成成份之靶材的濺鍍，射入鉭粒子。藉此，可形成更富含鉭之充分滿足Ta/N≧2.0的鉭氮化物膜。Further, in the method for forming a tantalum nitride film of the present invention, the tantalum nitride film obtained by the above-described formation is injected by sputtering using a target having a composition of ruthenium as a main component. particle. Thereby, a niobium nitride film which is more rich in niobium and sufficiently satisfies Ta/N≧2.0 can be formed.
前記濺鍍是調整DC功率和RF功率，使得DC功率為低且RF功率為高而進行，較為理想。The pre-sputtering is performed by adjusting the DC power and the RF power so that the DC power is low and the RF power is high.
若依據本發明，則可依照CVD法，達到具有低C、N含有量、且高本發明Ta/N組成比，做為確保了和配線膜(例如Cu配線膜)之密著性的障壁膜是有用的低阻抗之鉭氮化物膜的效果。According to the present invention, it is possible to achieve a barrier film having a low C and N content and a high Ta/N composition ratio of the present invention in accordance with the CVD method, and ensuring adhesion to a wiring film (for example, a Cu wiring film). It is a useful low-impedance nitride film effect.
又，若依據本發明，則可達到對於藉由上記CVD法所獲得之鉭氮化物膜，藉由濺鍍法等之PVD法打入鉭，來形成更富含鉭之鉭氮化物膜之效果。Further, according to the present invention, it is possible to form a germanium nitride film obtained by the above-described CVD method, and to form a germanium-rich nitride film by a PVD method such as a sputtering method. .
然後，若依據本發明，則可達到能在上記障壁膜上，形成兼具優良密著性和平滑性的配線膜之效果。According to the present invention, it is possible to obtain an effect of forming a wiring film having both excellent adhesion and smoothness on the barrier film.
若依據本發明，則具有低C、N含有量、高Ta/N組成比之低阻抗的鉭氮化物膜，係可藉由依照熱CVD法或電漿CVD法等CVD法，在已被載置於成膜室亦即真空腔室內的基板上，令上記含鉭配位化合物所成之原料氣體和鹵素氣體發生反應，而在基板上形成TaNx (Hal)y (R,R')z 化合物膜，然後令該鹵化化合物膜，和被導入至真空腔室內的含H原子氣體藉由熱或電漿予以活性化所生成之H2 氣體或HN3 氣體由來之H自由基、NH3 氣體由来之NHx 自由基等之自由基，發生反應而形成之。According to the present invention, a ruthenium nitride film having a low C, N content and a high Ta/N composition ratio of low impedance can be carried by CVD according to a thermal CVD method or a plasma CVD method. It is placed on a substrate in a film forming chamber, that is, in a vacuum chamber, and reacts a raw material gas containing a ruthenium-containing complex compound with a halogen gas to form TaN x (Hal) y (R, R') z on the substrate. compound film, and then enabling the halogenated compound film, and is introduced into the vacuum chamber a gas containing H atoms to be by thermal or plasma of H radicals generated by activated H 2 gas or the origin of HN 3 gas, NH 3 gas Free radicals such as NH x radicals are formed by reaction.
作為原料氣體、鹵素氣體及含H原子氣體，係可直接導入上記腔室，也可和N2 氣或Ar氣等惰性氣體一同導入。關於這些反應體的量，鹵素氣體，係使用對原料氣體而言，例如，對原料氣體5sccm而為5sccm程度以下之流量，又，含H原子化合物氣體係使用對原料氣體使用較鹵素氣體為多量，例如對原料氣體5sccm而為100~1000sccm(H2 換算)之流量，較為理想。The raw material gas, the halogen gas, and the H-containing gas may be directly introduced into the upper chamber, or may be introduced together with an inert gas such as N 2 gas or Ar gas. For the amount of the reactants, the raw material gas is used, for example, at a flow rate of 5 sccm or less to the raw material gas of 5 sccm or less, and the H-containing compound gas system is used in a larger amount than the halogen gas for the raw material gas. For example, it is preferable that the flow rate of the raw material gas is 5 sccm and the flow rate is 100 to 1000 sccm (in terms of H 2 ).
上記二反應的溫度，係只要能發生反應的溫度即可，例如，原料氣體和鹵素氣體的鹵化反應時，一般係為300℃以下，理想為150~300℃；又，該鹵化反應之生成物和自由基的反應時，一般係為300℃以下，理想為150~300℃。真空腔室內的壓力當為最初之鹵化反應時為1~10Pa，其後的成膜反應時為1~100Pa，較為理想。The temperature of the second reaction is preferably a temperature at which the reaction can occur. For example, when the halogen reaction of the source gas and the halogen gas is carried out, the temperature is usually 300 ° C or lower, preferably 150 to 300 ° C. Further, the product of the halogenation reaction When reacting with a radical, it is generally 300 ° C or less, and preferably 150 to 300 ° C. The pressure in the vacuum chamber is 1 to 10 Pa in the initial halogenation reaction, and is preferably 1 to 100 Pa in the subsequent film formation reaction.
配位化合物，係如上述，是在鉭元素(Ta)的周圍，配位了N＝(R,R')(R及R'係表示碳原子數1~6個的烷基，其各自可為相同的基也可為互異的基)而成者。該烷基係可為例如甲基、乙基、丙基、丁基、戊基、己基，無論直鏈或分岔者皆可。該配位化合物，通常，係在Ta的周圍，配位了4至5個N－(R,R')而成之化合物。The complex compound is as described above, and is coordinated with N=(R, R') around the lanthanum element (Ta) (R and R' represent an alkyl group having 1 to 6 carbon atoms, each of which may be The same base can also be a different base). The alkyl group may be, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group, and may be either a straight chain or a branched group. The coordination compound is usually a compound in which 4 to 5 N-(R, R') are coordinated around Ta.
上記本發明之方法，係依照CVD法，在身為成膜室的真空腔室內，例如，係可為導入原料氣體和鹵素氣體而進行鹵化反應而在基板上形成TaNx (Hal)y (R,R')z 化合物膜，然後導入含氫原子化合物氣體，令藉由熱或電漿所生成之自由基和上記還原化合物發生反應，以形成鉭氮化物膜，又，亦可為其後將該製程反覆進行所望次數，又或亦可為將上記鹵化反應反覆進行所望次數後，進行和自由基的反應。According to the method of the present invention, in the vacuum chamber which is a film forming chamber according to the CVD method, for example, a halogenation reaction can be carried out for introducing a source gas and a halogen gas to form TaN x (Hal) y (R) on the substrate. , R') z compound film, and then introduce a hydrogen atom-containing compound gas, so that the radical generated by the heat or the plasma reacts with the above-mentioned reducing compound to form a ruthenium nitride film, or it may be The process may be repeated in a desired number of times, or may be subjected to a reaction with a radical after repeating the above-mentioned halogenation reaction.
本發明之鉭氮化物之形成方法，係只要是能實施CVD法的成膜裝置，都可毫無特別限制地加以實施。例如，以下說明使用圖1所示之電漿CVD成膜裝置來實施本發明方法時的一實施形態。The method for forming the niobium nitride of the present invention can be carried out without any particular limitation as long as it is a film forming apparatus capable of performing the CVD method. For example, an embodiment in which the plasma CVD film forming apparatus shown in Fig. 1 is used to carry out the method of the present invention will be described below.
圖1所示的電漿CVD裝置，係由身為成膜室的真空腔室1所成，該真空腔室的側壁上係連接真空排氣系2，真空腔室的上方部係設置有利真空腔室呈絕緣狀態的電極3。該電極3所連接之高頻電源4是被配置在真空腔室1的外部，對電極施加高頻電力，就可在真空腔室內產生電漿。真空腔室1內，其下方部內載著加熱器等之加熱手段5的基板載置用平台6，是被配設成令其基板載置面和電極面彼此呈平行而對向。The plasma CVD apparatus shown in FIG. 1 is formed by a vacuum chamber 1 which is a film forming chamber, and a vacuum exhaust system 2 is connected to a side wall of the vacuum chamber, and a favorable vacuum is provided in an upper portion of the vacuum chamber. The chamber is in the insulated state of the electrode 3. The high-frequency power source 4 to which the electrode 3 is connected is disposed outside the vacuum chamber 1, and high-frequency power is applied to the electrode to generate plasma in the vacuum chamber. In the vacuum chamber 1, a substrate mounting stage 6 on which a heating means 5 such as a heater is placed in a lower portion thereof is disposed such that the substrate mounting surface and the electrode surface face each other in parallel.
電極3的內部，設有氣體室7，在對向於電極之基板載置用平台6的面上，開口了作為蓮蓬頭噴嘴機能的複數之孔8，從該孔將氣體導入至真空腔室內，而可供給至基板表面之構成；該電極係作為蓮蓬頭板之機能。A gas chamber 7 is provided inside the electrode 3, and a plurality of holes 8 functioning as showerhead nozzles are opened on the surface of the substrate mounting platform 6 facing the electrodes, and gas is introduced into the vacuum chamber from the holes. It can be supplied to the surface of the substrate; the electrode functions as a showerhead.
氣體室7係連接著氣體導入系9的一端，該氣體導入系的另一端係連接著分別充填著原料氣體或鹵素氣體或含H原子氣體等的複數氣瓶(未圖示)。此時，亦可為氣體室7係連接複數個氣體導入系9，其分別又連接至個別的氣瓶。雖未圖示，但是能夠以質流控制器來控制各氣體流量。The gas chamber 7 is connected to one end of the gas introduction system 9, and the other end of the gas introduction system is connected to a plurality of gas cylinders (not shown) each filled with a material gas, a halogen gas, a gas containing H atoms, and the like. At this time, a plurality of gas introduction systems 9 may be connected to the gas chamber 7, which are respectively connected to individual gas cylinders. Although not shown, the gas flow rate can be controlled by the mass flow controller.
原料氣體，雖然可用充填原料氣體的氣瓶來導入，但除此以外，亦可將上記含鉭有機金屬化合物收容在被加熱保溫的容器內，將做為緩衝氣體的Ar等惰性氣體，透過質流控制器而供給至容器內以使原料昇華，與該緩衝氣體一併將原料氣體導入至真空腔室內；亦可將透過氣化器等而被氣化之原料氣體導入至真空腔室內。The raw material gas may be introduced into a gas cylinder filled with a raw material gas, but in addition, the above-mentioned ruthenium-containing organometallic compound may be contained in a container that is heated and kept, and an inert gas such as Ar, which is a buffer gas, may be used. The flow controller is supplied to the container to sublimate the raw material, and the raw material gas is introduced into the vacuum chamber together with the buffer gas; and the material gas vaporized by the vaporizer or the like may be introduced into the vacuum chamber.
使用圖1所示之電漿CVD成膜裝置，來實施本發明之鉭氮化物形成方法的製程的一實施形態，係如以下所述。An embodiment of the process for forming the tantalum nitride forming method of the present invention by using the plasma CVD film forming apparatus shown in Fig. 1 is as follows.
首先，藉由真空排氣系2，將真空腔室1內真空排氣成所定壓力(例如10－ 4 ~10－ 5 Pa)，在基板載置用平台6上載置基板S後，對加熱手段5通電而將基板加熱至所定溫度(例如150~300℃)。其次，從氣體導入系9向氣體室7導入原料氣體和鹵素氣體，從孔8向基板S表面進行供給。作為該基板S，並無特別限制，例如，可為公知之基底密著層是設在絕緣層上者，或可為其表面經過脫氣處理等之前處理者。First, the vacuum chamber 2 evacuates the vacuum chamber 1 to a predetermined pressure (for example, 10 - 4 to 10 - 5 Pa), and after placing the substrate S on the substrate mounting platform 6, the heating means 5 energize and heat the substrate to a predetermined temperature (for example, 150 to 300 ° C). Next, the material gas and the halogen gas are introduced into the gas chamber 7 from the gas introduction system 9, and are supplied from the holes 8 to the surface of the substrate S. The substrate S is not particularly limited. For example, the known substrate adhesion layer may be provided on the insulating layer, or the surface may be subjected to a degassing treatment or the like.
真空腔室1內的壓力達到所定壓力而穩定後，從高頻電源4輸出頻率27.12MHz、電力密度0.2W/cm2 之高頻交流電壓。一旦來自該高頻電源的交流電壓施加至電極3，則作為陰極機能而構成的電極3和作為陽極機能而構成之基板保持器6上所載置之基板S表面之間，會產生原料氣體和鹵素氣體的電漿。在該電漿中會生成原料氣體及鹵素氣體的自由基，在基板S表面上引起鹵化反應，形成TaNx (Hal)y (R,R')z 化合物膜。在形成具有所定膜厚之鹵化化合物膜後，停止高頻電源4的動作，停止原料氣體和鹵素氣體的導入。After the pressure in the vacuum chamber 1 reaches a predetermined pressure and is stabilized, a high-frequency AC voltage having a frequency of 27.12 MHz and a power density of 0.2 W/cm 2 is output from the high-frequency power source 4. When an alternating voltage from the high-frequency power source is applied to the electrode 3, a material gas is generated between the electrode 3 configured as a cathode function and the surface of the substrate S placed on the substrate holder 6 configured as an anode function. Plasma of halogen gas. A radical of a source gas and a halogen gas is generated in the plasma, and a halogenation reaction is caused on the surface of the substrate S to form a TaN x (Hal) y (R, R') z compound film. After the formation of the halogenated compound film having a predetermined film thickness, the operation of the high-frequency power source 4 is stopped, and the introduction of the material gas and the halogen gas is stopped.
然後，向真空腔室1內透過氣體導入系9而導入含H原子氣體而進行活性化。亦即，如上記，令腔室內產生電漿，使該電漿中所發生的自由基，入射至如上記所形成之鹵化化合物膜的表面，將該鹵化化合物膜分解，將膜中之Ta上所鍵結之N切斷去除，且去除剩餘之N上所鍵結之R(R')基，形成富含鉭的鉭氮化物膜。形成具有所定膜厚之鉭氮化物膜後，停止高頻電源4的動作，並停止含H原子氣體的導入，將基板S搬出至真空腔室1外。Then, a gas containing H atoms is introduced into the vacuum chamber 1 through the gas introduction system 9 to be activated. That is, as described above, plasma is generated in the chamber, and radicals generated in the plasma are incident on the surface of the halogenated compound film formed as described above, and the halogenated compound film is decomposed to form a Ta on the film. The bonded N is cleaved off and the remaining R(R') groups on the remaining N are removed to form a germanium-rich germanium nitride film. After the niobium nitride film having a predetermined film thickness is formed, the operation of the high-frequency power source 4 is stopped, the introduction of the H-containing gas is stopped, and the substrate S is carried out to the outside of the vacuum chamber 1.
關於如上記所形成之鉭氮化物膜，以AES進行分析時的結果，C為2%以下，N為33~35%，Ta/N＝1.9~2.0，相對阻抗為450μ Ω．cm以下。Regarding the tantalum nitride film formed as described above, when analyzed by AES, C is 2% or less, N is 33 to 35%, Ta/N is 1.9 to 2.0, and relative resistance is 450 μΩ. Below cm.
如上記，電漿CVD法中，NH3 氣體或含H氣體等之反應氣體會在電漿中被活性化，因此就算是較低溫度也能形成薄膜。又，即使是熱CVD法，也能以公知的製程條件和上記同樣地形成富含鉭之鉭氮化物膜。As described above, in the plasma CVD method, a reaction gas such as NH 3 gas or an H-containing gas is activated in the plasma, so that a film can be formed even at a relatively low temperature. Further, even in the thermal CVD method, a niobium-rich tantalum nitride film can be formed in the same manner as in the above-described conventional processing conditions.
如上記對於已形成好具有所望膜厚之鉭氮化物膜的基板，例如，亦可依照公知的成膜法，使用Ar等濺鍍氣體，對靶材施加電壓而產生電漿，濺射靶材而在上記鉭氮化物膜之表面上，形成金屬薄膜、亦即配線膜側密著層(障壁膜側基底層)。As described above, for the substrate on which the tantalum nitride film having a desired film thickness is formed, for example, a sputtering gas such as Ar may be used in accordance with a known film formation method to apply a voltage to the target to generate a plasma, and the sputtering target may be used. On the surface of the upper nitride film, a metal thin film, that is, a wiring film side adhesion layer (a barrier film side underlayer) is formed.
經過以上工程而在基板12形成層積膜，然後，在上記配線膜側密著層之上，以公知的方法形成配線膜(例如Cu配線膜)。After the above process, a laminated film is formed on the substrate 12, and then a wiring film (for example, a Cu wiring film) is formed on the wiring film side adhesion layer by a known method.
順便一提，在本發明之鉭氮化物形成方法中，在該障壁膜形成前，需要進行將基板表面所吸附之氣體等雜質予以去除之公知的脫氣處理，又，在該基板上形成了障壁膜後，最終會形成例如由Cu所成之配線膜。因此，若將該成膜裝置，構成為透過可真空排氣之搬送室而至少連接著脫氣室及配線膜形成室，基板是可藉由搬送用機器人從搬送室往成膜裝置和脫氣室和配線膜形成室之間搬送的複合型配線膜形成裝置，則從前處理至配線膜形成止的一連串工程，都可用該裝置來實施。By the way, in the niobium nitride forming method of the present invention, before the formation of the barrier film, it is necessary to perform a known degassing treatment for removing impurities such as gas adsorbed on the surface of the substrate, and further, formed on the substrate. After the barrier film, a wiring film made of, for example, Cu is finally formed. Therefore, when the film forming apparatus is configured to be connected to at least the degassing chamber and the wiring film forming chamber through the vacuum evacuation transfer chamber, the substrate can be transferred from the transfer chamber to the film forming apparatus and degassed by the transfer robot. The composite wiring film forming apparatus that transports between the chamber and the wiring film forming chamber can be implemented by a series of processes from the pre-treatment to the formation of the wiring film.
對如上記所形成之鉭氮化物膜，藉由濺鍍法等之PVD法打入鉭粒子，就可形成更富含鉭之鉭氮化物膜。例如，可使用在真空腔室的上方，對向於基板保持器的位置處設置了靶材的公知之濺鍍裝置而加以實施。When the ruthenium nitride film formed as described above is impregnated with a ruthenium particle by a PVD method such as a sputtering method, a ruthenium-rich ruthenium nitride film can be formed. For example, it can be implemented by using a known sputtering apparatus in which a target is placed above the vacuum chamber and at a position facing the substrate holder.
此種濺鍍裝置的情況下，靶材上係連接著，將其表面予以濺射，使其放出靶材構成物質之粒子的電漿產生用之電壓施加裝置。此處所用靶材，係構成為以上記原料氣體中所含之金屬之構成元素(Ta)為主成份；又，電壓施加裝置，係由高頻發生裝置、連接至靶材的電極所構成。濺鍍氣體，係只要為公知的惰性氣體，例如氬氣、氙氣等即可。In the case of such a sputtering apparatus, a voltage applying device for generating plasma of particles of a target constituent material is sputtered on the target. The target material used herein is composed of the constituent element (Ta) of the metal contained in the raw material gas as a main component, and the voltage application device is composed of a high-frequency generating device and an electrode connected to the target. The sputtering gas may be any known inert gas such as argon gas or helium gas.
將如上記所得之鉭氮化物膜也就是形成有障壁膜之基板S載置於濺鍍室內後，向濺鍍室內導入Ar等惰性氣體並進行放電，將以原料氣體之構成成份的鉭為主構成成份之靶材加以濺射，對形成在基板上之薄膜中，入射濺鍍粒子的鉭粒子。如此，藉由濺鍍，就可從靶材向基板表面的薄膜中入射鉭，因此，可更為增加障壁膜中的鉭含有率，可獲得所望之低阻抗的富含鉭之鉭氮化物膜。此外，由於原料氣體係為有機鉭化合物，因此藉由上記濺鍍以使構成元素(鉭)入射至基板的表面，可促進分解而使C或N等雜質從障壁膜排出，而可獲得雜質少的低阻抗之障壁膜。The tantalum nitride film obtained as described above, that is, the substrate S on which the barrier film is formed is placed in a sputtering chamber, and an inert gas such as Ar is introduced into the sputtering chamber to be discharged, and the constituents of the raw material gas are mainly used. The target component is sputtered, and the ruthenium particles of the sputtered particles are incident on the film formed on the substrate. In this way, by sputtering, ruthenium can be incident from the target to the film on the surface of the substrate, so that the ruthenium content in the barrier film can be further increased, and a low-impedance yttrium-rich yttrium nitride film can be obtained. . Further, since the raw material gas system is an organic ruthenium compound, the constituent element (钽) is incident on the surface of the substrate by sputtering, and decomposition can be promoted to cause impurities such as C or N to be discharged from the barrier film, and less impurities can be obtained. Low impedance barrier film.
由於該濺鍍係藉由將鉭粒子打入鉭氮化物膜中以濺射除去C或N，來進行該膜的改質，而並非層積鉭膜，因此，必須要要不會形成鉭膜之條件、亦即可以鉭粒子進行蝕刻之條件下進行。因此，例如需要調整DC功率和RF功率，使得DC功率為低且RF功率為高。例如，DC功率設定在5kW以下，並將RF功率設高，例如400~800W，藉此就可達成不會形成鉭膜之條件。由於RF功率係依存於DC功率，因此藉由適宜調整DC功率和RF功率，就能調整膜的改質程度。又，濺鍍溫度，係通常的濺鍍溫度即可，例如可為和鉭氮化物膜之形成溫度相同的溫度。Since the sputtering is performed by sputtering the cerium particles into the cerium nitride film to remove C or N by sputtering, instead of laminating the ruthenium film, it is necessary to form the ruthenium film. The conditions, that is, the conditions under which the particles are etched can be carried out. Therefore, for example, it is necessary to adjust the DC power and the RF power such that the DC power is low and the RF power is high. For example, the DC power is set to 5 kW or less, and the RF power is set to be high, for example, 400 to 800 W, whereby the condition that the ruthenium film is not formed can be achieved. Since the RF power is dependent on the DC power, the degree of modification of the film can be adjusted by appropriately adjusting the DC power and the RF power. Further, the sputtering temperature may be a normal sputtering temperature, and may be, for example, the same temperature as the formation temperature of the tantalum nitride film.
如上記對於已形成好具有所望膜厚之障壁膜的基板S，例如，亦可依照公知的成膜法，導入Ar等濺鍍氣體，從電壓施加裝置對靶材施加電壓而產生電漿，濺射靶材而在上記障壁膜之表面上，形成金屬薄膜、亦即配線膜側密著層(障壁膜側基底層)。As described above, for the substrate S in which the barrier film having the desired film thickness is formed, for example, a sputtering gas such as Ar may be introduced according to a known film formation method, and a voltage may be applied to the target from the voltage application device to generate a plasma. On the surface of the upper barrier film, a metal thin film, that is, a wiring film side adhesion layer (a barrier film side underlayer) is formed on the surface of the upper barrier film.
經過以上工程而在基板S形成層積膜，然後，在上記配線膜側密著層之上，以公知的方法形成配線膜。After the above process, a laminated film is formed on the substrate S, and then a wiring film is formed by a known method on the wiring layer side adhesion layer.
圖2係模式性地圖示具備圖1所示之成膜裝置1的複合型配線膜形成裝置的構成圖。FIG. 2 is a view schematically showing a configuration of a composite wiring film forming apparatus including the film forming apparatus 1 shown in FIG. 1 .
該複合型配線膜形成裝置100，係由前處理部101和成膜處理部103和將之連接的中繼部102所構成。無論何者，在進行處理前，都會先將內部變成真空環境。The composite wiring film forming apparatus 100 is composed of a pre-processing unit 101, a film formation processing unit 103, and a relay unit 102 connected thereto. Either way, the interior is turned into a vacuum environment before processing.
首先，前處理部101中，將配置在搬入室101a中之處理前基板，藉由前處理部側搬出入機器人101b而搬入至脫氣室101c。在該脫氣室101c中加熱處理前基板，使表面的水分等蒸發而進行脫氣處理。其次，將該脫氣處理完之基板藉由搬出入機器人101b，搬入至還原處理室101d。該還原處理室101d內，加熱上記基板而進行藉由氫氣等還原性氣體將下層配線的鉭氧化物去除之退火處理。First, in the pre-processing unit 101, the pre-process substrate placed in the carry-in chamber 101a is carried into the degassing chamber 101c by the pre-processing unit side being carried into and out of the robot 101b. The front substrate is heated and treated in the degassing chamber 101c, and moisture or the like on the surface is evaporated to perform a degassing treatment. Next, the degassed substrate is carried into the reduction processing chamber 101d by the loading and unloading robot 101b. In the reduction processing chamber 101d, the substrate is heated and an annealing treatment for removing the tantalum oxide of the lower wiring by a reducing gas such as hydrogen is performed.
退火處理結束後，藉由搬出入機器人101b而從還原處理室101d取出上記基板，搬入至中繼部102。被搬入之基板，係以中繼部103，交付給成膜處理部103之成膜處理部側搬出入機器人103a。After the annealing process is completed, the upper substrate is taken out from the reduction processing chamber 101d by the loading and unloading robot 101b, and carried into the relay unit 102. The substrate to be carried in is transferred to the film forming processing unit side loading/unloading robot 103a by the relay unit 103.
被交付之上記基板，係被搬出入機器人103a搬入至成膜室103b。該成膜室103b，係相當於上記成膜裝置1。在成膜室103b形成了障壁膜及密著層的層積膜，係藉由搬出入機器人103a從成膜室103b中搬出，而搬入至配線膜室103c。此處，上記障壁膜(障壁膜上形成有密著層的時候則為密著層)之上，會形成配線膜。配線膜形成後，該基板藉由搬出入機器人103a而從配線膜室103c移動至搬出室103d，而搬出。The substrate is delivered to the upper substrate, and is carried into the film forming chamber 103b by the loading and unloading robot 103a. This film forming chamber 103b corresponds to the above-described film forming apparatus 1. The laminated film in which the barrier film and the adhesion layer are formed in the film forming chamber 103b is carried out from the film forming chamber 103b by the loading/unloading robot 103a, and is carried into the wiring film chamber 103c. Here, a wiring film is formed on the upper barrier film (the adhesion layer is formed on the barrier film when the adhesion layer is formed). After the formation of the wiring film, the substrate is moved out of the wiring film chamber 103c to the carry-out chamber 103d by the loading/unloading robot 103a, and is carried out.
如此上，若將上記障壁膜形成前後的工程、亦即脫氣工程和配線膜形成工程以一連串方式進行而構成上記複合型配線膜形成裝置100，則可提升作業效率。In this way, the above-described process before and after the formation of the barrier film, that is, the degassing process and the wiring film formation process, is performed in a series of ways to form the composite wiring film forming apparatus 100, the work efficiency can be improved.
此外，上記複合型配線膜形成裝置100的構成，雖然是在前處理部101中設置脫氣室101c和還原處理室101d各1間，在成膜處理部103中設置成膜室103b和配線膜室103c各1間，但並非被限定於此構成。In the pre-processing unit 101, the pre-processing unit 101 is provided with one between the degassing chamber 101c and the reduction processing chamber 101d, and the film forming chamber 103b and the wiring film are provided in the film forming processing unit 103. Each of the chambers 103c is one, but is not limited to this configuration.
因此，例如，將前處理部101及成膜處理部103的形狀設計成多角形狀，且各個面上設置複數個上記脫氣室101c及還原處理室101、以及成膜室103b及配線膜室103c，則可更為提升處理能力。Therefore, for example, the shape of the pretreatment unit 101 and the film formation processing unit 103 is designed to have a polygonal shape, and a plurality of upper degassing chambers 101c and reduction processing chambers 101, and a film forming chamber 103b and a wiring film chamber 103c are provided on each surface. , can improve processing power.
本實施例中，係使用圖1所示的成膜裝置1，使用五二甲胺鉭(MO)氣體作為原料氣體，作為鹵素氣體是使用氟氣及作為反應氣體是使用NH3 氣體，來形成鉭氮化物膜。In the present embodiment, the film forming apparatus 1 shown in Fig. 1 is used, and a dimethyl hydrazine (MO) gas is used as a material gas, a fluorine gas is used as a halogen gas, and a NH 3 gas is used as a reaction gas. Niobium nitride film.
依照公知的方法，在具有SiO2 絕緣膜之基板S表面之脫氣前處理工程實施後，將基板S搬入至藉由真空排氣系2真空排氣成10－ 5 Pa的真空腔室1內。作為該基板雖然沒有特別限制，但例如，亦可使用依照通常的成膜法，使用Ar濺鍍氣體，向具有Ta為主構成成份之靶材施加電壓而產生電漿，濺射靶材而在表面形成有基板側密著層之基板。After the degassing pretreatment process on the surface of the substrate S having the SiO 2 insulating film is carried out in accordance with a known method, the substrate S is carried into the vacuum chamber 1 which is evacuated to a vacuum of 10 - 5 Pa by the vacuum exhaust system 2 . Although the substrate is not particularly limited, for example, an Ar sputtering gas may be used in accordance with a usual film formation method, and a voltage may be applied to a target having Ta as a main component to generate a plasma, and the sputtering target may be used. A substrate having a substrate-side adhesion layer is formed on the surface.
將基板S搬入真空腔室1內，將基板S載置於基板載置用平台6上後，將該基板以加熱器5加熱至250℃，從氣體導入系9往氣體室7導入上記原料氣體5sccm、上記鹵素氣體5sccm，從孔8朝向基板S表面供給。After the substrate S is carried into the vacuum chamber 1 and the substrate S is placed on the substrate mounting platform 6, the substrate is heated to 250 ° C by the heater 5, and the raw material gas is introduced from the gas introduction system 9 to the gas chamber 7. 5 sccm and a halogen gas of 5 sccm were supplied from the hole 8 toward the surface of the substrate S.
真空腔室1內的壓力達到所定壓力而穩定後，從高頻電源4輸出頻率27.12MHz、電力密度0.2W/cm2 之高頻交流電壓，在電極3和基板S表面之間，就會產生原料氣體和鹵素氣體的電漿。在該電漿中會生成原料氣體及鹵素氣體的自由基，藉由在基板S表面上的鹵化反應，形成TaNx (Hal)y (R,R')z 化合物膜。在形成具有所定膜厚之鹵化化合物膜後，停止高頻電源4的動作，停止原料氣體和鹵素氣體的導入。After the pressure in the vacuum chamber 1 reaches a predetermined pressure and is stabilized, a high-frequency AC voltage having a frequency of 27.12 MHz and a power density of 0.2 W/cm 2 is output from the high-frequency power source 4, and is generated between the electrode 3 and the surface of the substrate S. A plasma of a material gas and a halogen gas. A radical of a source gas and a halogen gas is generated in the plasma, and a TaN x (Hal) y (R, R') z compound film is formed by a halogenation reaction on the surface of the substrate S. After the formation of the halogenated compound film having a predetermined film thickness, the operation of the high-frequency power source 4 is stopped, and the introduction of the material gas and the halogen gas is stopped.
然後，向真空腔室1內透過氣體導入系9而導入上記含H原子氣體，如上記，令腔室內產生電漿，使該電漿中所產生的自由基，入射至如上記所形成之鹵化化合物膜的表面而發生反應。藉由該反應，該鹵化化合物膜中的Ta－N鍵結會被切斷去除，且N上所鍵結的R(R')基會被切斷去除。其結果，形成了富含鉭之鉭氮化物膜。形成具有所定膜厚之鉭氮化物膜後，停止高頻電源4的動作，並停止含H原子氣體的導入，將基板S搬出至真空腔室1外。Then, a gas containing H atoms is introduced into the vacuum chamber 1 through the gas introduction system 9, and as described above, plasma is generated in the chamber, and the radical generated in the plasma is incident on the halogenation formed as described above. The surface of the compound film reacts. By this reaction, the Ta-N bond in the halogenated compound film is cut off, and the R(R') group bonded to N is cut off. As a result, a niobium-rich niobium film is formed. After the niobium nitride film having a predetermined film thickness is formed, the operation of the high-frequency power source 4 is stopped, the introduction of the H-containing gas is stopped, and the substrate S is carried out to the outside of the vacuum chamber 1.
如此所得之障壁膜的組成，係Ta/N＝1.9，C含有量為2%以下，N含有量為33%。The composition of the barrier film thus obtained was Ta/N = 1.9, the C content was 2% or less, and the N content was 33%.
此外，為了比較，針對使用了上記原料氣體(MO氣體)和鹵素氣體(氟氣)的情形，及使用了上記原料氣體和反應氣體(H2 ；但是，反應氣體由來之H自由基的照射時間是設為3秒、5秒、10秒而進行)的情形，依據上記方法來進行成膜。Further, for comparison, the case where the above-mentioned source gas (MO gas) and halogen gas (fluorine gas) are used, and the above-mentioned source gas and reaction gas (H 2 ; however, the irradiation time of the H radical derived from the reaction gas are used. In the case where it is set to 3 seconds, 5 seconds, and 10 seconds, film formation is performed according to the above method.
針對上記方法所得到的各個薄膜，算出相對阻抗ρ(μ Ω．cm)。該相對阻抗係以4探針法來測定薄片阻抗(Rs)，以SEM測定膜厚(T)，基於式：ρ＝Rs．T而算出。The relative impedance ρ (μ Ω·cm) was calculated for each film obtained by the above method. The relative impedance is measured by the 4-probe method to determine the sheet resistance (Rs), and the film thickness (T) is determined by SEM, based on the formula: ρ=Rs. Calculated by T.
將原料氣體(MO氣體)以氟氣轉換(鹵化)後照射反應氣體(H自由基)10秒而進行成膜時，可獲得低於使用MO氣體和氟氣而成膜時(106μ Ω．cm)、使用MO氣體和氟氣和反應氣體(H自由基照射3秒)而成膜時(3×105μ Ω．cm)、及使用MO氣體和氟氣和反應氣體(H自由基照射5秒)而成膜時(4800μ Ω．cm)的相對阻抗(450μ Ω．cm)。When the material gas (MO gas) is converted (halogenated) with fluorine gas and then irradiated with a reaction gas (H radical) for 10 seconds to form a film, it is possible to form a film lower than the film using MO gas and fluorine gas (106 μ Ω·cm). ), when using MO gas and fluorine gas and reaction gas (H radical irradiation for 3 seconds) to form a film (3 × 105 μ Ω · cm), and using MO gas and fluorine gas and reaction gas (H radical irradiation for 5 seconds) The relative impedance (450 μ Ω·cm) at the time of film formation (4800 μΩ·cm).
由此可知，由於MO氣體和鹵素氣體的成膜所獲得的膜係含鹵素，因此會生成高阻抗的膜，該膜若以H自由基處理，則相對阻抗會隨著該處理時間而變化，處理時間越長則相對阻抗越是降低。從該結果可知，理想為將H自由基處理進行10秒以上，則可有效地去除鹵素、R,R'基及N。From this, it is understood that since the film obtained by the formation of the MO gas and the halogen gas contains halogen, a film of high impedance is formed, and if the film is treated with H radicals, the relative impedance changes with the processing time. The longer the processing time, the lower the relative impedance. From the results, it is understood that the halogen, R, R' group and N can be effectively removed by performing the H radical treatment for 10 seconds or more.
如上記，使用了MO氣體和鹵素氣體和含H原子氣體(自由基)的成膜時，雖然藉由鹵素而將原料氣體之Ta－N－(R,R')鍵結的N和R之鍵結之一部份切斷而選擇性地去除R，但是接著藉由H自由基照射而使高阻抗的鹵化Ta系化合物中的Ta和N之鍵結、N和鹵素原子之鍵結及殘餘之N和R,R'基(烷基)之鍵結予以切斷，而去除鹵素原子、C及N，因此可減少C、N之含有比率，其結果為，使所形成之膜組成為富含鉭，呈現出膜的相對阻抗降低。As described above, when a film of MO gas, a halogen gas, and a gas containing a H atom (radical) is used, the N and R of the Ta-N-(R, R') bonded to the source gas by halogen are used. One of the bonds is partially cut to selectively remove R, but then the bonding of Ta and N in the high-resistance halogenated Ta-based compound, the bonding of N and the halogen atom, and the residue are caused by H radical irradiation. The bond between N and R, R' group (alkyl group) is cut, and the halogen atom, C and N are removed, so that the content ratio of C and N can be reduced, and as a result, the formed film composition is rich. With yttrium, the relative impedance of the film is reduced.
對於如上記所得之具有所望膜厚之障壁膜的基板，例如，亦可依照公知的濺鍍成膜方法，使用Ar等濺鍍氣體，對靶材施加電壓而產生電漿，濺射靶材而在上記障壁膜之表面上，形成金屬薄膜、亦即作為基底層之配線膜側密著層(S6)。For the substrate having the barrier film having a desired film thickness obtained as described above, for example, a sputtering method can be used, a sputtering gas such as Ar can be used, a voltage can be applied to the target to generate a plasma, and the target can be sputtered. On the surface of the upper barrier film, a metal thin film, that is, a wiring film side adhesion layer as a base layer is formed (S6).
在令經由以上工程而形成有層積膜之基板S上，亦即上記障壁膜側密著層之上，依照公知的製程條件，形成Cu配線膜。可確認到各膜彼此的接著性係為優良。On the substrate S on which the laminated film was formed through the above process, that is, on the barrier film side adhesion layer, a Cu wiring film was formed in accordance with a known process condition. It was confirmed that the adhesion between the respective films was excellent.
本實施例中，對實施例1所得之鉭氮化物膜，使用公知的濺鍍裝置，藉由濺鍍法打入鉭粒子，形成了更富含鉭之鉭氮化物膜。In the present embodiment, the tantalum nitride film obtained in Example 1 was formed by sputtering using a known sputtering apparatus to form a germanium-rich nitride film rich in germanium.
在濺鍍裝置內導入濺鍍氣體，從電壓施加裝置對靶材施加電壓而放電，以產生電漿，濺射以鉭為主構成成份之靶材，向形成在基板S上之薄膜中入射濺鍍粒子的鉭粒子。該濺鍍條件係為，DC功率：5kW，RF功率：600W。又，濺鍍溫度，係在－30~150℃下進行。A sputtering gas is introduced into the sputtering apparatus, and a voltage is applied from the voltage application device to discharge the target material to generate a plasma, and a target material composed of ruthenium as a main component is sputtered, and the sputtering is performed on the film formed on the substrate S. Particles of ruthenium particles. The sputtering conditions were DC power: 5 kW, and RF power: 600 W. Further, the sputtering temperature is carried out at -30 to 150 °C.
藉由佈植上記鉭粒子的濺鍍，可更為增加障壁膜中的鉭含有率，可獲得所望之低阻抗的富含鉭之鉭氮化物膜。此外，藉由使鉭入射至基板S的表面薄膜中，可促進薄膜的分解而使C或N等雜質從膜中排出，而可獲得雜質少的低阻抗之障壁膜。如此所獲得之薄膜係為，Ta/N＝3.4，C及N的含有量為：C＝0.1%以下，N＝23%，及所得到之薄膜的相對阻抗為：250μ Ω．cm。By sputtering the implanted particles, the germanium content in the barrier film can be further increased, and a low-impedance germanium-rich germanium nitride film can be obtained. Further, by causing ruthenium to enter the surface film of the substrate S, decomposition of the film can be promoted, and impurities such as C or N can be discharged from the film, and a low-resistance barrier film having less impurities can be obtained. The film thus obtained was Ta/N=3.4, and the contents of C and N were: C=0.1% or less, N=23%, and the relative impedance of the obtained film was 250 μΩ. Cm.
如上記般地形成所望膜厚之改質鉭氮化物膜後，例如，亦可導入Ar濺鍍氣體，依照公知的濺鍍成膜製程條件而從電壓施加裝置向靶材施加電壓而產生電漿，濺射靶材而在上記障壁膜之表面上形成金屬薄膜、亦即作為基底層的配線膜側密著層。After the modified niobium nitride film having a desired film thickness is formed as described above, for example, an Ar sputtering gas may be introduced, and a voltage may be applied from the voltage application device to the target in accordance with a known sputtering deposition process condition to generate a plasma. The sputtering target is formed on the surface of the upper barrier film to form a metal thin film, that is, a wiring film side adhesion layer as a base layer.
在令經由以上工程而形成有層積膜之基板S上，亦即上記配線膜側密著層之上，依照公知的製程條件，形成Cu配線膜。可確認到各膜彼此的接著性係為優良。On the substrate S on which the laminated film is formed through the above process, that is, on the wiring film side adhesion layer, a Cu wiring film is formed in accordance with a known process condition. It was confirmed that the adhesion between the respective films was excellent.
除了作為原料氣體，不用五二甲胺鉭而改用三級戊醯亞胺三(二甲醯胺)鉭以外，依照實施例1而實施成膜製程，獲得富含鉭的低阻抗之鉭氮化物膜。所獲得之膜中，Ta/N＝1.8，C含有量：3%，N含有量35.7%，相對阻抗係為550μ Ω．cm。In addition to being a raw material gas, a film-forming process was carried out in accordance with Example 1 except that the dimethyl dimethyl hydrazine was used instead of the dimethyl quinone imine tris(dimethylamine) ruthenium to obtain a ruthenium-rich low-impedance ruthenium nitrogen. Chemical film. In the obtained film, Ta/N=1.8, C content: 3%, N content 35.7%, and relative resistance was 550 μΩ. Cm.
除了作為鹵素氣體不用氟氣而改用氯氣、溴氣或碘氣，又，作為生成H自由基的氣體是使用H2 以外，依照實施例1實施成膜製程後發現，獲得和實施例1同樣的結果。The same procedure as in Example 1 was carried out except that chlorine gas, bromine gas or iodine gas was used instead of fluorine gas as a halogen gas, and a gas formation process was carried out in the same manner as in Example 1 except that H 2 was used as the gas for generating the H radical. the result of.
若依據本發明，則可依照CVD法，形成C、N含有量低，Ta/N組成比高，做為確保和Cu膜密著性的障壁膜是有用的低阻抗之鉭氮化物膜。因此，本發明係可適用於半導體裝置領域的薄膜形成製程中。According to the present invention, it is possible to form a low-impedance tantalum nitride film which is low in the content of C and N and has a high Ta/N composition ratio in accordance with the CVD method, and as a barrier film for ensuring adhesion to the Cu film. Therefore, the present invention is applicable to a thin film forming process in the field of semiconductor devices.
1．．．真空腔室1. . . Vacuum chamber
2．．．真空排氣系2. . . Vacuum exhaust system
3．．．電極3. . . electrode
4．．．高頻電源4. . . High frequency power supply
5．．．加熱手段5. . . Heating means
6．．．基板載置用平台6. . . Substrate mounting platform
7．．．氣體室7. . . Gas chamber
8．．．孔8. . . hole
9．．．氣體導入系9. . . Gas introduction system
S．．．基板S. . . Substrate
[圖1]用來實施本發明之成膜方法的成膜裝置之一例的模式性構成圖。Fig. 1 is a schematic configuration diagram showing an example of a film forming apparatus for carrying out the film forming method of the present invention.
[圖2]內建有用來實施本發明之成膜方法的成膜裝置的複合型配線膜形成裝置的模式性構成圖。Fig. 2 is a schematic configuration diagram of a composite wiring film forming apparatus in which a film forming apparatus for carrying out the film forming method of the present invention is incorporated.
1．．．真空腔室1. . . Vacuum chamber
2．．．真空排氣系2. . . Vacuum exhaust system
3．．．電極3. . . electrode
4．．．高頻電源4. . . High frequency power supply
5．．．加熱手段5. . . Heating means
6．．．基板載置用平台6. . . Substrate mounting platform
7．．．氣體室7. . . Gas chamber
8．．．孔8. . . hole
9．．．氣體導入系9. . . Gas introduction system
S．．．基板S. . . Substrate
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| TW095106850A TWI410517B (en) | 2005-03-03 | 2006-03-01 | Method for forming tantalum nitride film |
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| JP (1) | JP4931174B2 (en) |
| KR (1) | KR100911643B1 (en) |
| CN (1) | CN101091005B (en) |
| TW (1) | TWI410517B (en) |
| WO (1) | WO2006093263A1 (en) |
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| JP2009111251A (en) * | 2007-10-31 | 2009-05-21 | Tohoku Univ | Semiconductor device, and manufacturing method thereof |
| WO2011162255A1 (en) * | 2010-06-22 | 2011-12-29 | 株式会社アルバック | Process for production of barrier film, and process for production of metal wiring film |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5989999A (en) * | 1994-11-14 | 1999-11-23 | Applied Materials, Inc. | Construction of a tantalum nitride film on a semiconductor wafer |
| US20030124262A1 (en) * | 2001-10-26 | 2003-07-03 | Ling Chen | Integration of ALD tantalum nitride and alpha-phase tantalum for copper metallization application |
| WO2004010471A2 (en) * | 2002-07-19 | 2004-01-29 | Aviza Technology, Inc. | In-situ formation of metal insulator metal capacitors |
| US20040219784A1 (en) * | 2001-07-19 | 2004-11-04 | Sang-Bom Kang | Methods for forming atomic layers and thin films including tantalum nitride and devices including the same |
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| KR100200739B1 (en) * | 1996-10-16 | 1999-06-15 | 윤종용 | Method for forming barrier metal wiring |
| US6265311B1 (en) * | 1999-04-27 | 2001-07-24 | Tokyo Electron Limited | PECVD of TaN films from tantalum halide precursors |
| US6410432B1 (en) * | 1999-04-27 | 2002-06-25 | Tokyo Electron Limited | CVD of integrated Ta and TaNx films from tantalum halide precursors |
| JP2003342732A (en) * | 2002-05-20 | 2003-12-03 | Mitsubishi Materials Corp | Solution raw material for organometallic chemical vapor deposition method containing tantalum complex and tantalum-containing thin film produced by using the same |
| JP2005203569A (en) * | 2004-01-15 | 2005-07-28 | Semiconductor Leading Edge Technologies Inc | Fabrication process of semiconductor device and semiconductor device |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5989999A (en) * | 1994-11-14 | 1999-11-23 | Applied Materials, Inc. | Construction of a tantalum nitride film on a semiconductor wafer |
| US20040219784A1 (en) * | 2001-07-19 | 2004-11-04 | Sang-Bom Kang | Methods for forming atomic layers and thin films including tantalum nitride and devices including the same |
| US20030124262A1 (en) * | 2001-10-26 | 2003-07-03 | Ling Chen | Integration of ALD tantalum nitride and alpha-phase tantalum for copper metallization application |
| WO2004010471A2 (en) * | 2002-07-19 | 2004-01-29 | Aviza Technology, Inc. | In-situ formation of metal insulator metal capacitors |
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| Publication number | Publication date |
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| CN101091005B (en) | 2010-05-19 |
| JP2006241525A (en) | 2006-09-14 |
| KR20070085593A (en) | 2007-08-27 |
| CN101091005A (en) | 2007-12-19 |
| WO2006093263A1 (en) | 2006-09-08 |
| TW200641176A (en) | 2006-12-01 |
| JP4931174B2 (en) | 2012-05-16 |
| KR100911643B1 (en) | 2009-08-10 |
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