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

Abstract

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

Description

200905725 IX. Invention Description: [Reciprocal Reference of Related Applications] This case is for the benefit of the US continuation number requested by February 21, 2007. The full text is incorporated by reference into the second case background > TECHNICAL FIELD OF THE INVENTION The present invention relates generally to the field of semiconductor fabrication. More specifically, the present invention relates to a method of forming a ruthenium-containing film on a substrate. [Prior Art] The ruthenium compound of bismuth and bismuth oxide is considered to be a material which is expected to be used as a capacitor electrode material in ▲generation DRAM. When ^ :=) an oxygen ... pentoxide oxide, oxidation gives =) back dielectric constant material (also known as high-k material). The lack of such high-k materials causes the loss of capacitance by using up to temperature to cause oxidation of polycrystalline shi, shixi and ming. On the other hand, it exhibits high oxidation resistance and high conductivity, and is suitable for use as a diterpene material. It also effectively acts as an oxygen diffusion barrier. It has also been suggested that the main * strict Yan Jing reduction of the gate metal. In addition, compared with platinum and other two:: chelates, it is easier to use ozone and plasma by using oxygen, ruthenium as a barrier layer for separating low-k materials from copper plating, and the use as a. Has attracted attention. Deposition: The quality film of the precursor g ψ I 钌 (ru02) before the pure tetraoxide 17 (Ru04). Previously, the precursor can also be used for excellent conductivity and very similar to the titanic acid (IV) and the titanic acid of the 200905725 dimensional structure such as cerium oxide. The deposition of the material of the Chin-type material (membrane shape, however, the high-purity osmium tetroxide is a strong oxidant, the toxicity. In addition, the ancient from the film is considered to have the south to bring in the ancient, 7: and the tetraoxide has about 13 (The Buddha point of rc, and the risk of explosion due to about _). Therefore it is recommended to store pure tetraoxide to avoid the possibility of decomposition (explosion). Considering ruthenium tetroxide (Ru0) & π, 4 4 properties (especially in the preservation:: risk of diterpenes), when used as a reactant, it is usually necessary to dilute it in the gluten. Known as 'the solvent. (for example) water, four weathered carbon And burning hydrocarbon = as a solvent, it is also necessary to add such as 请 疋Μ to prevent Ru〇4 from reacting and decomposing during storage. In addition, only Ru〇4 water/liquid is used as the sulfhydryl precursor. Leading to impurity bowing into membranes and tools (eg, reaction chambers). The electric T industry is abandoning carbon tetrachloride (due to its high toxicity), so

For a four-emulsified ruthenium precursor solution, carbon tetrachloride is not a rational choice. W Alkane such as pentane and octane can be used as a solvent for Ru04, but when an alkane containing dissolved Ru04 is used as a sulfhydryl precursor 2 in film production, a reaction between an alkane (for example, pentane) and Ru04 is caused. Incorporation of carbon. Carbon causes an increase in the electrical resistance of the ruthenium type film, and therefore, carbon which occurs during film production can be regarded as undesirable. SUMMARY OF THE INVENTION A novel method of providing a film on a substrate in a semiconductor process is described herein.

The moisture of the membrane is provided on the membrane. The osmium tetroxide dissolved in the solvent mixture, / knife. Next, depositing a ruthenium-containing film on the substrate. Other specific examples of the present invention may include one or more of: a substrate in which osmium tetroxide is mixed. Provides a blend of sulfhydryl flammable fluorinated solvents of less than about 100 ppm (but not limited to)

CxHyFz〇tNu; each of its nonflammable fluorinated solvents has the formula x>3; y + z<2x + 2; ζ>1;t>0;0; and t + u>0 where parent, 7 , 2, 1, and 11 are all integers. The solvent mixture is a mixture of decyl nonafluorobutyl ether and ethyl nonafluorobutyl ether; the solvent mixture comprises between about 10% and about 90% by volume, preferably about 30%, of methyl nonafluorobutyl ether; The mixture comprises from about 10% to about 9% by volume, more preferably about 70% ethyl nonafluorobutyl ether; 8 200905725 contains less than about 1 ppm moisture; the precursor contains less than about i ppm Unassociated or free oxygen (); the pressure in the reaction chamber is maintained between about 〇1 t〇rr to about 1〇〇〇t〇rr; the film is deposited until the temperature is maintained at about 50 ° C Up to about 8 〇 (between rc, preferably about 100 ° C and about 600 Å. ( between: on the substrate; a gas reducing agent is introduced into the reaction chamber, and the ruthenium-containing film is passed through the reducing agent and the precursor a reaction between the substrate; the reducing agent is one of hydrogen, air or oxygen; at the same time introducing a reducing agent and a precursor into the chamber; introducing the precursor into the evaporator in a liquid state; at least partially evaporating the precursor to form a gaseous precursor; introducing a liquid precursor into the evaporator via inert gas pressurization; evaporating at least about 99% of the liquid in the evaporator State precursor; evaporating substantially all of the liquid precursor in the evaporator;

The liquid precursor is evaporating at a temperature between 10 C and about 80 ° C; the substrate is a ruthenium-type substrate suitable for semiconductor manufacturing; and the substrate is a ceramic-based substrate. The features and technical advantages of the present invention are summarized in the form of a detailed description of the present invention. The additional features and advantages of the present invention will be described hereinafter, and it is understood by those skilled in the art that the present invention is to be construed as being <RTIgt; The basis of other structures for the same purpose. Those skilled in the art will also recognize that the equivalents of the <RTIgt; 200905725</RTI> equivalents are not departing from the spirit and scope of the invention as set forth in the appended claims. For the purpose of further understanding of the nature of the present invention, the same referenced A specific example of a device for a membrane; and Figure 2 illustrates another specific example of a device for depositing a membrane containing ruthenium. [Embodiment] In general, the present invention relates to a method for providing a film on a substrate in a semiconductor process, which provides a reaction chamber and a substrate contained in the chamber. A sulfhydryl precursor mixture is provided, wherein the precursor comprises a mixture of flammable fluorinated solvents, dissolved in a solvent mixture of less than about _ppm. Next, the oxidized nail knives in the structure deposit a ruthenium-containing film on the substrate. The non-flammable solvent is used in the precursor mixture because it is preferred that the non-flammable solvent is a preferred non-flammable solvent when the mixture is used in the environment of the second dish, because in general, it introduces carbon into the material. The film of ... p A is accumulated in the gene for the presence of fluorine in the solvent ... so that::; burning, the bow into the film composition. In the specific examples of the present invention, the solvent mixture, / composition A, can be described according to the following formula: each of the two CxHyFz〇tNu where: · y + z &lt; 2x + 2 ; 10 200905725 ζ&gt;1;t&gt;0;u&gt;0; and t + u &gt; 0, and wherein x, y, z, t, and u are integers. Several solvents satisfy this formula and are suitable for use in solvent mixtures. Such solvents include: mercapto perfluoropropyl ether; mercapto nonafluorobutyl ether; ethyl nonafluorobutyl ether; 1,1,1,2,2,3,4,5,5,5-decafluoro- 3_methoxy_4_(trifluoromethyl)-pentane; 3_ethoxy-1,1,1,2,3,4,4,5,5,6,6,6-dodecafluoro 2-trifluorodecyl-hexane; C9F12N; C12F27N; C12F33N; C6FI4; C8F16; C7F16; C5F10H2; C4F5H5 ' 1,1,2,3,3 pentafluoropropane; and C3F7〇CFHCF2CH(CH3)OCF2CFH〇C4F9. In one embodiment, the solvent mixture is a mixture of methyl nonafluorobutyl ether and ethyl nonafluorobutyl ether. Both of these are available from 3M Company and are sold under the trade names N〇vec HFE 7100 and N〇vec HFE 7200. CJioH2 is also available from Dup〇nt under the trade name Vertrel. In some embodiments, the substrate comprising the deposited ruthenium film can vary. The substrate can be a semiconductor substrate that may already have other layers of material that are otherwise formed by other semiconductor fabrication steps. The substrate can also be a ceramic substrate (e.g., ceria, etc.), a metal substrate, or a polymeric substrate. In some embodiments, the substrate has a different shape. The substrate can be flat, such as a typical semiconductor wafer or a ceramic substrate for a parallel circuit. The substrate may also be a convex U spherical surface. The substrate may also be a nanoparticle or another material characterized by a large specific surface area. 11 200905725 According to the film formation conditions and the film will be formed on it, the warning is buried, and the material is moderately signed.

Selecting the tetraoxane (tetra) of the precursor mixture according to the present invention (RuQ Advantage According to the specific practice of the base precursor of the present invention, the system provides at least the following risk of explosion due to the pure form of Ru〇j, so r(10) capacity = The solvent mixture enables the treatment of RU〇4 in a stable form during storage or storage without the risk of explosion. The non-flammable solvent mixture does not react with Ru〇4, thus avoiding the decomposition of Μ4 under the conditions. Preservation (reservoir) 钌基丽驱体. 2 In fact, it can produce the desired ruthenium film, because when using this in the form of gas: the body and the film produced by (4) CVD, The solvent does not react with Ru〇4. l: In the case of the current sulfhydryl precursor, the non-flammable solvent mixture does not react with the active Ru compound which is produced when § Ru〇4 is decomposed in the reaction chamber, and the solvent The mixture is withdrawn from the reaction chamber along with any unreacted gases: this makes it possible to obtain the desired ruthenium film which does not contain an undesired compound such as an oxide. Ru04 forms a ruthenium-based precursor and then performs film formation by thermal CVD by transferring the precursor to the reaction chamber in a gaseous form. Then Ru〇4 will undergo decomposition and generate a living Ru. It will then react with water to produce a product. This makes it difficult to produce the desired nail film. In some specifics; 12 200905725 The base enthalpy drive has substantially no moisture content and contains less than i 〇〇 ppm, preferably less than 1 ppm moisture. The non-flammable solvent mixture in the ruthenium-based precursor is preferably non-toxic, which makes it possible to carry out film production in a safe environment when a gas-containing ruthenium precursor is used to produce a ruthenium-containing film by thermal CVD. The fluorinated solvent mixture is preferably non-flammable and exhibits high thermal stability, which makes it possible to use the ruthenium-based precursor in a gaseous form (for use in the production of a ruthenium-containing film by thermal CVD, it is possible to avoid carbon Incorporating into the membrane and decomposition, combustion or explosion caused by the solvent mixture. According to various embodiments, at least the sulfhydryl group 4 of the present invention is introduced into the reaction chamber containing the substrate by gas form A ruthenium-containing film is deposited on the substrate to form a ruthenium-containing film. According to such methods, possible ruthenium-containing film deposition includes, but is not limited to, ruthenium film, oxidized nail film (Ru〇2 film), and {; Acid film. Ugly method for forming a film - according to a specific example, by introducing a gas-based sulfhydryl precursor and a gas-producing agent into a reaction chamber containing a substrate and by making the precursor The virgin reacts to deposit ruthenium on the substrate to form a ruthenium film. In some embodiments, the ruthenium-based precursor can be introduced into the reaction chamber by using a bubbler system. That is, as mentioned above And placing the liquid substrate in the container and allowing the inert gas (eg, 't, argon, helium, etc.) to enter the bubble by using an inert gas bubbler tube (possible 13 200905725 temperature controlled) The container, which results in the transfer of the precursor of the invention entrained in the inert gas into the reaction chamber. In some embodiments, the sulfhydryl precursor can be introduced into the reaction chamber via a direct evaporation system. Such systems are well known in the art and may include a liquid mass flow controller and an evaporator such as a glass or metal tube. An inert gas (e.g., t, argon, helium, etc.) can be used to pressurize the liquid phase sulfhydryl precursor and flow it from the storage vessel through the liquid flow controller and into the evaporator. If no inert gas is used to flow the liquid, a vacuum (or lower pressure environment) can be created downstream of the precursor storage container (e.g., at the evaporator outlet). In some embodiments, the evaporator is heated to a temperature between 10 C and about 80 c. The temperature of the evaporator causes the liquid phase precursor to evaporate into a gas phase precursor. In some embodiments, about 99%, and fortunately all of the liquid precursor is vaporized into a gas phase precursor. This gas phase precursor is then passed to the reaction chamber. In some embodiments, the reducing agent under consideration reduces osmium tetroxide to a ruthenium metal. This reducing agent can be exemplified particularly by hydrogen (H2), but is not limited thereto. Other possible reducing agents include hydrazine and its derivatives and hydrocarbons (eg, alkyne, alkyne, etc.). A single reducing agent or a combination of two or more reducing agents may be used. Hydrogen is especially preferred for reducing agents. In some embodiments, chemical vapor deposition (CVD) or atomic layer deposition (ALD) can be used to form a tantalum film. In the specific example of the deposition method used for CVD, the gas reducing agent and the gas sulfhydryl precursor according to the present invention are simultaneously introduced into the reaction chamber, and the reducing agent reacts with Ru〇4 in the precursor in the gas phase, resulting in Reduction 14 200905725 ru〇4 is ruthenium, and ruthenium is deposited on the substrate. The non-flammable fluorinated solvent mixture accompanying Ru〇4 in the gas precursor does not decompose during this deposition, and thus 4 is also prevented from being incorporated into the resulting ruthenium film. The total pressure in the reaction chamber during the film generation period is preferably maintained between about 0.01 and 1000 torr, and more preferably between about t"t and 10t". The substrate is preferably heated to about 5 Torr. 〇 between 8 and rc (rc,

More preferably, it is heated to about 10 (rc and 40 (rc). The reducing agent is allowed to enter the reaction chamber in a sufficient amount to reduce Ru04 in the precursor to the base metal. When using, for example, hydrogen as a reducing agent The precursor uses at least 4 moles of chlorine. In this case the by-products two...U〇4 are initially introduced into the reaction chamber in some specific examples of deposition methods using ALD. A very thin layer of ruthenium oxide (for example, a monoatomic layer) is formed on the substrate by absorption and decomposition of the precursor. The inside of the reaction chamber is then rinsed with an inert gas (for example, nitrogen, helium, or argon to remove the a reactive or unabsorbed sulfhydryl precursor comprising a specific non-flammable fluorinated solvent mixture as described above. This rinsing is followed by introduction of a gaseous reducing agent into the reaction chamber. Oxidation of the reducing agent and the formation of the substrate The monoatomic layer reacts and reduces yttrium oxide to ruthenium metal. This results in the formation of a monoatomic layer of ruthenium on the substrate. When it is desired to grow a thicker ruthenium film, the unreacted reducing agent can be washed from the reaction chamber and Produced by a reducing agent The bulk reaction product is then followed by the following procedure: introducing a gas sulfhydryl precursor, rinsing/removing the residual sulfhydryl precursor, introducing a reducing agent, rinsing/removing the reducing agent and the gaseous reaction product. In some embodiments, using ALD In this case, the gas sulfhydryl precursor and the reducing agent can be introduced by the pulse 15 200905725, and J, for example, the gas sulfhydryl precursor is entangled at a flow rate of about 0.1 seem to 1 〇seem for about 0.01 seconds. The reducing agent can be introduced, for example, between 10 seconds and at a flow rate of from about 5 sam to 100 seem for about 1 second. The flushing gas can also be introduced, for example, at a flow rate of about 100 seem to 5000 sccm. Between 1 sec and 1 sec. Between the ALD period, the total pressure in the reaction chamber is maintained at about 〇. between ton· and 1〇torr, and the substrate temperature is better. The system is maintained between about (10) and c 盥 600 ° C. The ruthenium-based precursor is introduced into the reaction chamber of the accommodating substrate in a gas form according to some specific examples. Can be via a bubbler system or via The ruthenium-based precursor is introduced into the reaction chamber in the form of a gas by an evaporation system. In this case, the substrate is heated to decompose the precursor in the precursor (4) to produce a solid oxygen: 匕: (cerium oxide). The solid oxidized nail produced by the decomposition of Ru〇4 accumulates on the substrate. The body is accompanied by the name of the scorpion in the body of the milk. The fluorinated solvent mixture of Rn〇4 is not allowed during the deposition of oxidized sulphate. Decomposes, and therefore also, = is freed from oxidation (4). Solid oxide nail (ru〇2) as a gas

Ru04 homopolymerization catalyst. Therefore, the crucible Ru04 is decomposed upon heating and thus the solid cerium oxide deposited by the solution can be filled; the decomposition of f (the soil % Ru04 is bright (even when the heating temperature is lowered). In the oxygenation chamber, the total pressure in the reaction chamber is preferably about 1η Γ11000 t〇^5t〇rr 3 and the substrate is preferably heated to about 15 (rc' and better It is heated to 16 200905725 at a temperature between about 350 ° C and 40 (TC. The substrate that reaches the film formation method as described above can be exemplified by a semiconductor substrate such as a Shi Xi substrate. For example, The following items are used to form the semiconductor substrate: a low-k film, a high-k film, a C-doped dioxide film, a titanium nitride film, a copper film, a nitride film, an indium m, a crane film, and The ferroelectric film of the film and the oxidized nail film showed excellent adhesion to these films and will not crack even when subjected to chemical mechanical polishing (CMP). In addition, such as carbon and such as fluorine _ 素 素 杂 杂 杂 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 It is unnecessary or very short in the Ming Dynasty, which makes the needle film and the yttrium oxide film in the 7th segment of the corresponding shorter day &quot;" (in the case of ALD, since the initial early stage, for CVD for several minutes). 1. An illustrative example of a device that can be used to perform a film deposition process by CVD is described.

The apparatus illustrated in Figure 1 is provided with a reaction chamber ii, a feed source 12 for the sulfhydryl precursor, a feed source 13 for the reductant gas, and a feed source 14 for the inert gas typically used as a carrier gas and/or diluent gas. . In the case of a single wafer tool, a susceptor (not shown) is provided in the reaction chamber 11, and a single semiconductor substrate (not shown) such as a ruthenium substrate is mounted on the pedestal. The interior of the susceptor is equipped with a heater for heating the semiconductor substrate to a specified reaction temperature. In the case of a batch tool, 5 to 2 semiconductor substrates are housed in the reaction chamber 11. The heater in the batch tool can have a different structure than the heating benefit in a single wafer tool. The thiol precursor feed source 12 introduces the ruthenium based precursor into the reaction chamber 11 by using the bubbler 17 200905725 system or direct evaporation system as described above.

It is connected to the inert gas feed source 14 by line L1. The line has a V1 and has a flow rate controller downstream of the shut-off valve v!, such as the shut-off 罝 flow controller MFC1. The sulfhydryl precursor is introduced into the reaction chamber u from the feed source 12 via line L2. From the upstream side, the following items are provided among the considered pipelines B: UV spectrometer uvs, pressure gauge pGl, shut-off W and shut-off valve V3. The UV spectrometer acts to confirm the presence of the precursor (specifically Ru〇4) in line L2 and to detect its concentration. - The feed source 13 of the source gas contains a :: of a reducing agent in the form of a gas. The reducing agent gas is allowed to enter the reaction chamber 11 from the feed source 13 via line L3. A shut-off valve V4 is provided in line L3. Line L3 is connected to line L2. . . The inert gas feed source 14 contains a capacity to maintain an inert gas in the form of a gas. A. The inert gas is introduced into the reaction chamber 11 from the feed source by the line L4. From the upstream side, the following items are provided in the considered line L4: the shut-off wide V6, the mass flow controller MFC3 and the pressure gauge pG2. The line L4 is engaged with the shut-off valve V4h by the e-line L3 of &gt;&amp; i 'f. Line L1 is again separated from line L4 upstream of shut-off valve V6. It branches off the pipeline L1 from the pipeline L5 upstream of the wide V1. This s, spring L5 is engaged with the line L2 between the shutoff valves V2 and v3. Shut-off valve v?: The mass flow controller MFC4 is disposed in the line L5 in a given sequence from the upstream side. Again! A line L6 of the reaction chamber 11 is provided between the shut-off valves V3 and V4 to provide a shut-off valve V8 in this line L6. 18 200905725 The line L7 that reaches the 豕PMP is provided at the bottom of the reaction chamber 丨1, and from the upstream side, the following items are provided in the tube and line U under consideration. · Pressure gauge PG3, butterfly for adjustment (4) Shape valve βν and (4) i5. Heat _ μ, containing a tube with a heater on the circumference. Since the by-product in the gas precursor is converted to gj body by heat solution, it can be converted to solid yttria (which is deposited on the inner wall of the tube) to eliminate Ru04 introduced into the heat sink 15 from the gas stream. In order to produce the diaphragm by using the apparatus illustrated in Figure 1, the shut-off valves Vi, V2 & V5 are first closed and the switches V6, V7, V3, V4 and V8 are opened. When operating the pump PMp 'via line L4 And through the pipeline &quot; L5 from the inert gas feed source, 14 t inert gas into the reaction chamber 11 ° j a (two) 疋 your rolling body feed source 13 to introduce reducing agent gas into the reaction chamber n, connected to Xuan Xuan 1 The switcher valves V1 and V2 are opened and the switch is shut off. The inert gas from the inert gas feed source 14 is introduced via line u into the feed source 12 of the ruthenium based precursor. This results in a gas precursor ( Ru〇4 and the non-flammable solvent specified above, preferably a fluorinated solvent), introduced into the reaction chamber via line L2 and line L6. The reducing agent gas and (iv) react in the reaction chamber U' Bismuth metal is deposited on the semiconductor substrate. The illustrated apparatus produces a solid yttria membrane 'prepared by closing the shut-off valves V5 and V4 and V6 and keeping the valves closed (since no reducing agent will be used). Start the pump pMp to create a vacuum environment and open The shut-off valves V3, V7 and V8 flow into the reaction chamber. In this state, the switch is opened to open the valve to make the inert gas VI, V2 and 19 200905725 into the 4 through the pipeline L4 and the pipeline u. The milk feed source 14 introduces an inert gas into the feed source i2 of the ruthenium-based rigid body, m 1 ^ m and the non-flammable solvent specified above, resulting in the gas precursor (Ru〇4 L2 and the line L6 bowed) To the reaction chamber is wide / is a fluorinated solvent) via the line chamber 11, into the reaction chamber Uuu (^ due to the thermal decomposition of the reaction chamber yttrium oxide is being heated. "The ephemeris to the solidification of the deposition on the substrate. Figure 2 Describes an illustrative example of the I-position that can be used for film deposition by ALD. The device illustrated in Figure 2 has -έ 甘am ώ ,, '°, where the official line L8 is provided In the device described in 1; the green τ line L8 itself has a shut-off valve V2, and is in the off The downstream of the valve V2' is provided with the same hot card π as the hot card 15. Therefore, the same reference numerals are assigned to the same components as those in Fig. i, and the components will not be described in detail. The installed pipeline L8 One end is connected to the line L2 between the ultraviolet spectrometer UVS and the pressure 彳PG1, and the other end is connected to the line L7 between the heat sink 15 and the pump PMP. In order to produce the ruthenium film by ALD using the apparatus illustrated in Fig. 2 First, close the shut-off valves V2 and V5 and open the switches V6, V7, V3, V4, V8 and V9, as if the valves V1 and V2 were closed. When the pump pMp is operated, a vacuum state is generated in the different lines, wherein the inert gas from the inert gas feed source 14 is introduced via L4 and L5 and is introduced into the reaction chamber 11 via line L6. The inert gas is passed through line L1 through the feed source U of the ruthenium based precursor to cause the flow of the gaseous precursor (ru 〇 4 and the non-flammable fluorinated solvent mixture) with the inert gas in L2 and L8. After performing this initial preparation, close the shut-off valve V2 and switch off the switch 20 200905725

Valve V2 and delivers a pulse of gas precursor into the reaction chamber bore. After that, the shut-off valve V2 is simultaneously closed and the switch is opened by the valve V2I, which causes the gas precursor (which will decompose in the heat sink 15,) to accompany the passage of the inert gas via the line L8. Flushing inside the reaction chamber by introducing inert gas from L4 and L5 through L6 causes removal of unreacted precursor (including solvent mixture) from the interior of reaction chamber ii and the resulting pair product. The switch is then interrupted by valve V5 and the pulse of reductant gas is passed from the reductant gas feed source 13 along with the inert gas from the inert gas feed source 14 to the reaction chamber. After this, the shut-off valve V5 is closed, causing the pulse of the inert gas to be transferred to the reaction chamber, the reaction by-product, the unreacted reduction (four), and the like from the reaction chamber. The cycle can be repeated until a ruthenium film having the desired thickness is obtained. The method of deuterate film in some embodiments by introducing a sulfhydryl precursor and a gaseous rhodium metal compound as defined above in a gaseous form into a reaction chamber holding the substrate and: driving the body with an organometallic compound In the presence of an oxidizing gas, a cyanate film is formed by anti-c and thereby depositing a bismuth salt on the surface of the substrate. As described above, the sulfhydryl precursor can be introduced into the reaction chamber by a bubbler system or a direct evaporation system. In the case of, for example, a ferroelectric film of BaRuOx to be produced, Ba(DPM) 2 which is a β-diketone/ruthenium complex can be used as an organometallic compound. When a ferroelectric film of SrRu〇x is to be produced, Sr(DpM)2 which is a diketone/oxime complex can be used as an organometallic compound. Here, DpM is an abbreviation for dipival〇ylmethanate or 2,2,6,6-tetradecyl-3,5-pimelate 21 200905725 (TMHD). The oxygen containing gas can be, for example, oxygen, ozone or N2 hydrazine. In some specific examples, CVD can be used to form the above-mentioned iron ruthenium film. In the case of 4 ^, the gas-based sulfhydryl precursor and the gaseous form of organometallic metal are introduced into the anti-Kang Xuan, Λ ^ X. , long-awaited. In the precursor, the Ru04 in the precursor reacts with the organometallic compound in the presence of ruthenium in the presence of ruthenium, which results in the formation of, for example, BaRuOx (or SrR 〇) and its presence on the substrate. Shen / product. However, 'Tongri Temple' is accompanied by a non-flammable fluorinated agent mixture of RU〇4 in the gas precursor, which does not decompose during the period of the ferroelectric film, such as P 丨 A A \ * % ^ l / 儿Avoid incorporation into the membrane. The temperature in the reaction chamber is preferably about 45 (TC and 800. Torr, which is the reaction temperature of the gas for this purpose. The method for producing the acid 鴎 cavity Γ Y丨一j 驮 胰 pancreas (for example, BaRu 〇x and SrRu〇x) show ferroelectric properties and can be used in a wide range of x, x ^ for use in, for example, capacitors. In addition, due to the fine iron film that can be produced by this method, the Tianshishan + 颂 electric film is therefore The film can be used as an electrode material, just like the Ru film and the Ru film. Take the specific and §, these ferroelectric films (specifically, S rice cooker x) can be used as the upper and lower electrode materials of the separate ferroelectric (or used as a buffer between ferroelectric and electrode materials.) These films (which are oxides) prevent oxygen and Pb bismuth materials such as bismuth acid (PLT) and arsenate (PZT) iron. The diffusion of electrical materials, and the same day, using the same titanium ore structure as the ferroelectric", can:: the interface with the ferroelectric material at the interface &amp; glaze θ electrode interface at the interface 'and In particular, it prevents the occurrence of low-medium snow at this interface, the generation of ten layers of electricity and the prevention or reduction of degradation. 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 Implementation 丨1: The ruthenium precursor prepared from osmium tetroxide in a solvent mixture of 48% HFE-7100 and 52% HFE-7200 is directly evaporated in various bases to determine the corresponding direct evaporation (via Defined as the precursor liquid flow rate in the absence of liquid residue in the evaporation = 纟 High purity nitrogen is used as the carrier gas to pressurize the liquid precursor and flow it into the evaporator. The substrate vacuum at the exit of the ceremon The pressure was 67 t〇rr and a glass U-tube filled with glass beads was used as the evaporator. Sample 1 2 3 4 [Ru041 % 0.42% 1.5% 1.5% 1.5% Temperature C 50 50 30 30 Pressure (torr) 67 67 67 67 Ar (seem) 278 278 278 278 Precursor flow rate (ml/min, 1.8 1.6 1.8 1.6 'complete evaporation?&quot; Yes, although specific examples of the invention have been shown and described, Deviation from the essence of the invention The present invention is described by way of example only, and is not intended to be limiting, and many variations and modifications of the compositions and methods are possible and are within the scope of the invention. Therefore, the scope of the invention is not limited to the specific examples described herein, but is only limited by the scope of the following claims, and the scope of the patent application is intended to include all equivalents of the subject matter of the claims. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 illustrates a specific example of a device for depositing a ruthenium-containing film; and Fig. 2 illustrates another specific example of a device for depositing a ruthenium-containing film. [Main component symbol description] 11: Reaction chamber 12: Feed source 1 3: Feed source 1 4: Feed source 15: Heat sink 15': Heat trap BV: Butterfly valve L1: Line L2: Line L3: Pipeline L4: Pipeline L5: Pipeline L6: Pipeline L7: Pipeline L8: Pipeline MFC1: Mass Flow Controller MFC3: Mass Flow Controller MFC4: Mass Flow Controller PG1: Pressure Gauge 24 200905725 PG2: Pressure Gauge PG3: Pressure Gauge PMP: Pump UVS: UV spectrometer V1: Shut-off valve V2: Shut-off valve V2': Shut-off valve V3: Shut-off valve V4: Shut-off valve V5: Shut-off valve V6: Shut-off valve V7: Shut-off valve V8: Off Broken valve V9: shut-off valve

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Claims (1)

200905725 X. Patent application: 1. A method for forming a film on a substrate in a semiconductor process, comprising: raising a substrate, a reaction chamber, and a substrate contained in the chamber; The body 'wherein the precursor comprises: 1) a mixture of at least two non-flammable fluorinated solvents, each solvent having the general formula CxHyF2〇tNu, wherein: Ο x&gt;3; a) b) n) Υ + ζ&lt;2χ + 2 ; iii) z &gt;1; iv) t &gt;〇; v ) u 2 〇; and vi) t + u 2 〇; and wherein x, y, z, t and u are integers; 2) a oxidized nail in the solvent mixture; and 3) less than about 1 〇〇 ppm of moisture; and c) depositing a ruthenium-containing film on the substrate. 2. The method of claim 1, wherein the solvent mixture comprises a mixture of methyl nonafluorobutyl ether and ethyl nonafluorobutyl ether. 3) The method of claim 2, wherein the solvent mixture comprises: a) from about 10% to about 90 by volume. /. Methyl nonafluorobutyl ether; and b) between about 1% and about 90% by volume of ethyl nonafluorophene. 4. The method of claim 3, wherein the solvent mixture package 26 200905725 comprises: a) about 30% by volume b) about 70% by volume of ethyl nonafluorobutyl ether. 5. The method of claim 1 wherein the precursor comprises less than about 1 ppm moisture. 6. The method of claim </ RTI> wherein the precursor further comprises less than about 1 pprn of unassociated oxygen. / / As in the patent application scope &quot; page method, wherein the pressure in the reaction chamber is maintained between 〇 1 t〇rr to 1〇〇〇 t〇rr. 8. The method of applying for a patent, wherein the film deposition step is carried out at a substrate temperature between 50 C and 80 (TC). 9. The method of applying the patent range 帛8, wherein the film deposition step is known The substrate temperature between 100C and about 6〇〇t is carried out. ίο. If the square basin gas reducing agent of the scope of claim i is introduced into the reaction chamber and to the small Α, 匕3 will be handled _ ' to ^邛The method of claim 10, wherein the reducing agent is hydrogen, as in the method of claim 10, wherein the reducing agent is hydrogen. The reducing agent is air-rolled or oxygen. 13 · If the method of applying for patents on the same day 4 _ 11 cofferdam 10 items, the system and the step include the threshold to introduce the hardogen and the precursor into the chamber. The method of claim 1, wherein the method further comprises: introducing: the precursor into the evaporator, wherein the precursor is initially in a liquid state; and “the precursor is to form at least a portion of the precursor in a gaseous state; and 27 200905725 C) Introduce a gaseous precursor into the reaction chamber. The method of claim 14, further comprising introducing the liquid precursor into the evaporator by pressurizing the liquid precursor with an inert gas. The method of claim 14, further comprising evaporating at least about The method of claim 14, wherein the entire liquid precursor is evaporated to form a gaseous precursor. The method of claim 14 further comprising The precursor is evaporated at a temperature of between about 10 ° C and about 80 ° C. 19. The method of claim 1 wherein the substrate is a tantalum substrate suitable for semiconductor fabrication. The method of item 1, wherein the substrate is a ceramic-based material. XI. Schema: as shown in the next page 28