JP2009016854A - Method of manufacturing semiconductor integrated circuit device - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To prevent the contamination of a wafer due to transition metals in semiconductor mass-production processes. <P>SOLUTION: A method includes (a) a step of preparing the wafer, (b) a step of accumulating a desired film containing transition metal elements on the wafer, (c) a step of removing the accumulated film from the outer edge of the reverse or main face of the wafer on which the film is accumulated, and (d) a step of executing desired treatment on the wafer where the film is removed from the outer edge of the reverse or main face. Furthermore, (c) the removing step includes (c1) a step of providing a predetermined space between the main face of the wafer and the stage to keep the main face of the water and the stage in a non-contact state so that a plurality of pins arranged on the stage support the wafer at its side faces, and (c2) a step of rotating the wafer integrally with the stage and supplying washing liquid to the reverse of the wafer while supplying inactive gas from the stage toward a peripheral portion on the main face of the wafer. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a technology for manufacturing a semiconductor integrated circuit device, and in particular, a lithography process for a wafer on which a film containing a transition metal such as ruthenium (Ru) is deposited when a large number of wafers are continuously processed over a plurality of processes. Further, the present invention relates to a technique that is effective when applied to a semiconductor manufacturing process performed in a mass production line that shares a lithography process for wafers belonging to other process groups.

  2. Description of the Related Art Conventionally, in industrial fields other than semiconductor manufacturing, a technique is known in which a platinum group element is dissolved and separated for the purpose of recovering the platinum group element contained in wastes.

Japanese Laid-Open Patent Publication No. 7-155782 (Ito et al.) (Patent Document 1) recovers precious metals such as gold and platinum group elements contained in waste electronic parts, precious metal-containing waste catalysts, waste jewelry, etc. by dissolving them in a solution. The technology is disclosed. To dissolve the noble metal, an aqueous solution of an interhalogen compound composed of two types of halogens (ClF, BrF, BrCl, ICl, ICl ₃ , IBr, etc.) and an aqueous solution of a halogenated oxo acid (iodic acid, bromic acid, or chloric acid) Is used in the range of 1: 9 to 9: 1. The noble metal dissolved in the solution is first separated as a halogenated complex, and then decomposes the halogenated complex (sodium hydroxide, sodium borohydride, hydrazine or salt thereof, sulfurous acid or salt thereof, bisulfite, etc.) Is added as a metal.

JP-A-7-224333 (Wada et al.) (Patent Document 2) discloses ruthenium (Ru), rhodium (Rh), palladium (Pd), etc. contained in an insoluble residue generated in a reprocessing step of spent nuclear fuel. Without soaking pretreatment such as liquid metal extraction by immersing a fission product alloy containing noble metals in a solution of hydroiodic acid (or hydrobromic acid) to which iodine alone (or bromine alone) is added A technique for dissolving as an aqueous solution is disclosed. Here, the dissolved solution has a concentration of hydroiodic acid (or hydrobromic acid) in the range of 5 to 57% by weight, and the concentration of simple iodine (or simple bromine) to be added is 0.00 per liter of the former aqueous solution. The range of 01 to 0.5 mol is preferred.
Japanese Patent Laid-Open No. 7-157832. JP 7-224333 A

A large-capacity DRAM (Dynamic Random Access Memory) of 1 Gbit or more has a relative dielectric constant of 100 or more for a capacitor insulating film of an information storage capacitor element (capacitor) in order to secure a stored charge amount of a miniaturized memory cell. An ABO ₃ type oxide, that is, a high dielectric material such as BST ((Ba, Sr) TiO ₃ ) which is a perovskite type double oxide is used. Still as a capacitor insulating film material of the next _{generation, PZT (PbZr X Ti 1-} X O 3), PLT (PbLa X Ti 1-X O 3), PLZT, SBT, such PbTiO _3, SrTiO _3, BaTiO ₃ perovskite The introduction of a ferroelectric material containing a type crystal structure is also being studied.

  When using the high / ferroelectric material as described above for the capacitor insulating film of the capacitor, the conductive film for the upper and lower electrodes sandwiching the capacitor insulating film is also a metal having a high affinity for the high / ferroelectric material. For example, it is necessary to use a conductive film containing a platinum group metal (Ru (ruthenium), Rh (rhodium), Pd (palladium), Os (osmium), Ir (iridium), Pt (platinum)) as a main constituent material. is there. In particular, ruthenium (Ru) is considered to be promising as an electrode material for capacitors in which the capacitive insulating film is composed of the above-mentioned high / ferroelectric material because it has excellent etching controllability and film stability. Yes.

  On the other hand, in the field of high-speed logic LSI, as a measure to prevent an increase in wiring resistance and a decrease in reliability due to the miniaturization of the wiring width, a wiring groove (and a through hole) is formed in the insulating film deposited on the substrate. After depositing a copper (Cu) film having an electric resistance lower than that of the Al film on the insulating film including the inside of the wiring groove (and the through hole), the unnecessary copper film outside the wiring groove is subjected to chemical mechanical polishing (CMP). The introduction of buried copper wiring by the so-called Damascene method, which is removed by the method, has been promoted. Introduction of this embedded copper wiring is being considered not only in logic LSIs but also in the memory field such as DRAM.

  However, when introducing a new transition metal or a material containing it, which has not been used in the conventional wafer process, such as the above-described platinum group metal, perovskite type high / ferroelectric or copper, into the semiconductor manufacturing process. Therefore, it is necessary to take measures to prevent contamination of the wafer by these transition metals. In particular, transition metals such as copper have a large diffusion coefficient in silicon (Si) and can easily reach the substrate in the annealing process (heat treatment process). I'm scared.

  For example, in the manufacturing process of general-purpose LSIs such as DRAMs, gates are used for lithography equipment (photoexposure equipment, EB exposure equipment), various inspection equipment, annealing (heat treatment) equipment, etc., in order to reduce capital costs by minimizing capital investment. The common device is used in the initial element forming process and the wiring process before forming the insulating film, and these shared devices are also used in the capacitor forming process using the new material as described above. That is, in these shared devices, after the wafer for performing the capacitor forming process is unloaded from the apparatus, the wafer for performing the initial element forming process and the wafer for performing the wiring process are loaded into the apparatus. The In addition, when the upper wiring of the capacitor is the buried copper wiring by the damascene method, a wafer for annealing (heat treatment) the copper film deposited on the upper layer of the capacitor is a wafer for performing other processes. It is carried back and forth to the shared device.

  Films containing transition metals such as platinum group metals, perovskite-type high / ferroelectric materials, or copper deposited on the device surface of the wafer using sputtering or CVD are also applied to the outer edge (edge) and back surface of the wafer. accumulate. Therefore, if the wafer is loaded into a shared device without sufficiently removing the transition metal-containing film deposited on the outer edge or back surface of the wafer, the wafer stage, wafer carrier, conveyor, etc. that are in contact with the outer edge or back surface of the wafer The transition metal-containing film adheres, and the wafer for executing the lower layer process (initial element forming process and wiring process before forming the gate insulating film) that is subsequently carried into the shared device is contaminated with the transition metal.

  Therefore, in a mass production line in which a lithography process for a wafer on which a transition metal-containing film as described above is deposited and a lithography process for a wafer belonging to another process group including a lower layer process are performed using a common apparatus, a transition metal-containing line is included. Prior to carrying the wafer on which the film is deposited into the common apparatus, a cleaning process for removing the transition metal-containing film deposited on the outer edge or the back surface of the wafer becomes indispensable.

  However, some of the transition metals described above, such as ruthenium, have not yet been established an effective cleaning method because no solution for dissolving the same has been found. As mentioned above, several platinum group metal solutions have been proposed in industrial fields other than semiconductor manufacturing, but these solutions are used in semiconductor mass production lines because ruthenium is dissolved very slowly. Can not do it.

  Further, as another measure for preventing contamination of the wafer with the transition metal, it is possible to prepare a dedicated device for performing the lithography process for the wafer on which the transition metal-containing film is deposited, in addition to the shared device. Not realistic.

  An object of the present invention is to form an initial element in a semiconductor mass production process in which a lithography apparatus, an inspection apparatus, an annealing (heat treatment) apparatus, etc. are shared in an initial element forming process, a wiring process, and a transition metal-containing film processing process before forming a gate insulating film. It is an object of the present invention to provide a technique for reliably preventing a defect in which a wafer executing a process or a wiring process is contaminated with a transition metal.

  The above and other objects and novel features of the present invention will be apparent from the description of this specification and the accompanying drawings.

  Of the inventions disclosed in the present application, the outline of typical ones will be briefly described as follows.

A manufacturing method of a semiconductor integrated circuit device which is one invention of the present application,
(A) a step of preparing a semiconductor wafer;
(B) depositing a desired film containing a transition metal element on the semiconductor wafer;
(C) removing the film deposited on the back surface of the semiconductor wafer or the outer edge of the main surface of the semiconductor wafer from the semiconductor wafer on which the film is deposited;
(D) performing a desired process on the semiconductor wafer from which the film on the outer surface of the back surface or the main surface has been removed;
Including
In the removing step in the step (c),
(C1) A predetermined interval is provided between the main surface of the semiconductor wafer and the stage so that the main surface of the semiconductor wafer and the stage are not in contact with each other, and the semiconductor is provided by a plurality of pins arranged on the stage. Supporting the side of the wafer;
(C2) supplying the cleaning liquid to the back surface of the semiconductor wafer while rotating the semiconductor wafer integrally with the stage and supplying an inert gas from the stage side toward the periphery of the main surface of the semiconductor wafer. ;
Is included.

The outline of the invention of the present application other than the above-described invention can be simply classified and described as follows. That is,
1. A mass production method of a semiconductor integrated circuit device comprising the following steps;
(A) a step of depositing a platinum group metal film on the device surface of the first wafer among the plurality of wafers flowing through the wafer process;
(B) removing the platinum group metal film on the outer edge or the back surface of the device surface of the first wafer on which the platinum group metal film is deposited;
(C) After the step (b), patterning the platinum group metal film on the device surface of the first wafer using an etching resistant mask pattern formed by a lithography process;
(D) depositing a film to be processed different from the platinum group metal film on the device surface of the second wafer among the plurality of wafers flowing through the wafer process;
(E) A step of patterning the film to be processed deposited on the device surface of the second wafer by the lithography step.

  2. 2. The method for mass production of a semiconductor integrated circuit device according to the item 1, wherein the platinum group metal film is a ruthenium film.

  3. 3. The method for mass production of a semiconductor integrated circuit device according to the item 1 or 2, wherein the step of patterning the film to be processed is a step below the step of patterning the platinum group metal film.

  4). 4. The method for mass production of a semiconductor integrated circuit device according to any one of items 1 to 3, wherein the removal of the platinum group metal film is performed using a solution containing orthoperiodic acid.

  5). 5. The semiconductor integrated circuit device according to claim 1, wherein the platinum group metal film is removed using a solution containing orthoperiodic acid and a second acid. Mass production method.

  6). 6. The method for mass production of a semiconductor integrated circuit device according to the item 5, wherein the second acid is nitric acid.

  7. 6. The mass production method for a semiconductor integrated circuit device according to the item 6, wherein the concentration of orthoperiodic acid in the solution is 20 wt% to 40 wt%, and the concentration of nitric acid is 20 wt% to 40 wt%.

  8). 6. The mass production method of a semiconductor integrated circuit device according to the item 6, wherein the concentration of orthoperiodic acid in the solution is 25 wt% to 35 wt%, and the concentration of nitric acid is 25 wt% to 35 wt%.

  9. 6. The method for mass production of a semiconductor integrated circuit device according to the item 5, wherein the second acid is acetic acid.

  10. 10. The semiconductor integrated circuit according to any one of items 1 to 9, wherein the platinum group metal film is removed at least on substantially the entire back surface of each wafer and on the outer edge of the device surface. Method for mass production of equipment.

11. A mass production method of a semiconductor integrated circuit device comprising the following steps;
(A) a step of depositing a transition metal-containing film on the device surface of the first wafer among the plurality of wafers flowing through the wafer process;
(B) removing the transition metal-containing film on the outer edge or the back surface of the device surface of the first wafer on which the transition metal-containing film is deposited;
(C) after the step (b), patterning the transition metal-containing film on the device surface of the first wafer using an etching resistant mask pattern formed by a lithography process;
(D) depositing a film to be processed different from the transition metal-containing film on the device surface of the second wafer among the plurality of wafers flowing through the wafer process;
(E) A step of patterning the film to be processed deposited on the device surface of the second wafer by the lithography step.

  12 12. The method for mass production of a semiconductor integrated circuit device according to the item 11, wherein the transition metal-containing film is made of a perovskite type high dielectric material or ferroelectric material.

  13. 12. The method for mass production of a semiconductor integrated circuit device according to the item 12, wherein the perovskite type high-dielectric or ferroelectric is BST.

14 12. The mass production method of a semiconductor integrated circuit device according to the item 12, wherein the perovskite type high-dielectric or ferroelectric is any one of PZT, PLT, PLZT, SBT, PbTiO ₃ , SrTiO ₃ , and BaTiO _3. .

  15. 12. The method for mass production of a semiconductor integrated circuit device according to the item 11, wherein the transition metal is copper.

16. A mass production method of a semiconductor integrated circuit device comprising the following steps;
(A) a step of depositing a Ru film on the device surface of the first wafer among a plurality of wafers flowing through the wafer process;
(B) removing the Ru film on the outer edge or the back surface of the device surface of the first wafer on which the Ru film is deposited;
(C) After the step (b), forming the capacitor electrode by patterning the Ru film on the device surface of the first wafer using an etching-resistant mask pattern formed by a lithography process. ,
(D) a step of depositing a film to be processed different from the Ru film on the device surface of a second wafer among a plurality of wafers flowing through the wafer process;
(E) A step of patterning the film to be processed deposited on the device surface of the second wafer by the lithography step.

  17. 16. The method for mass production of a semiconductor integrated circuit device according to the item 16, wherein the step of patterning the film to be processed is a step below the step of patterning the Ru film.

  18. 18. The method for mass production of a semiconductor integrated circuit device according to 16 or 17, wherein the Ru film is removed using a solution containing orthoperiodic acid.

  19. 16. The method for mass production of a semiconductor integrated circuit device according to 16 or 17, wherein the Ru film is removed using a solution containing orthoperiodic acid and a second acid.

  20. 20. The method for mass production of a semiconductor integrated circuit device as described in 19 above, wherein the second acid is nitric acid.

  21. 20. The method for mass production of a semiconductor integrated circuit device according to the item 20, wherein the concentration of orthoperiodic acid in the solution is 20 wt% to 40 wt%, and the concentration of nitric acid is 20 wt% to 40 wt%.

  22. 20. The method for mass production of a semiconductor integrated circuit device according to the item 20, wherein the concentration of orthoperiodic acid in the solution is 25 wt% to 35 wt%, and the concentration of nitric acid is 25 wt% to 35 wt%.

23. A mass production method of a semiconductor integrated circuit device comprising the following steps;
(A) a step of depositing a Ru film on the device surface of the first wafer among a plurality of wafers flowing through the wafer process;
(B) using a solution containing orthoperiodic acid, removing the Ru film on the outer edge or the back surface of the device surface of the first wafer on which the Ru film is deposited;
(C) After the step (b), the Ru film on the device surface of the first wafer is patterned by using an etching-resistant mask pattern formed by a lithography process, thereby forming a capacitor electrode of the DRAM. The process of
(D) a step of depositing a film to be processed different from the Ru film on the device surface of a second wafer among a plurality of wafers flowing through the wafer process;
(E) A step of patterning the film to be processed deposited on the device surface of the second wafer by the lithography step.

  24. 24. The method for mass production of a semiconductor integrated circuit device according to the item 23, wherein the step of patterning the film to be processed is a step below the step of patterning the Ru film.

  25. 24. The method for mass production of a semiconductor integrated circuit device according to the item 24, wherein the step of patterning the film to be processed is a step of forming a gate electrode or a step of forming a bit line.

  26. 26. The mass production method for a semiconductor integrated circuit device according to any one of items 23 to 25, wherein the Ru film is removed using a solution containing orthoperiodic acid and nitric acid.

  27. 26. The method for mass production of a semiconductor integrated circuit device according to 26, wherein the concentration of orthoperiodic acid in the solution is 20 wt% to 40 wt%, and the concentration of nitric acid is 20 wt% to 40 wt%.

  28. 28. The method for mass production of a semiconductor integrated circuit device according to 27, wherein the concentration of orthoperiodic acid in the solution is 25 wt% to 35 wt%, and the concentration of nitric acid is 25 wt% to 35 wt%.

29. A mass production method of a semiconductor integrated circuit device comprising the following steps;
(A) depositing a transition metal-containing film made of a perovskite-type high-dielectric or ferroelectric on the device surface of the first wafer among a plurality of wafers flowing through the wafer process;
(B) removing the transition metal-containing film on the outer edge or the back surface of the device surface of the first wafer on which the transition metal-containing film is deposited;
(C) After the step (b), the capacitance of the DRAM capacitor is patterned by patterning the transition metal-containing film on the device surface of the first wafer using an etching-resistant mask pattern formed by a lithography process. Forming an insulating film;
(D) depositing a film to be processed different from the transition metal-containing film on the device surface of the second wafer among the plurality of wafers flowing through the wafer process;
(E) A step of patterning the film to be processed deposited on the device surface of the second wafer by the lithography step.

  30. 30. The method for mass production of a semiconductor integrated circuit device as described above in 29, wherein the perovskite type high dielectric material or ferroelectric material is BST.

  Hereinafter, general meanings of terms used in the present application will be described.

  1. “CMIS integrated circuit” refers to an integrated circuit made of complementary insulated gate FETs, and in addition to a general CMOS integrated circuit, a gate insulating film made of a dielectric material other than an oxide film such as silicon nitride or tantalum oxide. Including a device having

  2. The “device surface” is a main surface of a wafer on which an integrated circuit pattern corresponding to a plurality of chip regions is formed by photolithography. That is, it is the main surface on the opposite side to the “back surface”.

  3. “Built-in wiring” refers to single damascene, dual damascene, etc., in which a trench is formed in an insulating film, and a conductive film such as copper is buried in it. A wiring patterned by a wiring forming technique for removing a film.

  4). "Semiconductor integrated circuit wafer" or "semiconductor wafer" means a silicon single crystal substrate (generally almost circular), a sapphire substrate, a glass substrate, other insulating, anti-insulating, or semiconductor substrates used for manufacturing a semiconductor integrated circuit, and a composite thereof. A special substrate. In addition, “semiconductor integrated circuit device” (or “electronic device”, “electronic circuit device”, etc.) is not limited to those made on a single crystal silicon substrate, unless specifically stated otherwise. In addition, the above-mentioned various substrates, or those produced on other substrates such as SOI (Silicon On Insulator) substrates, TFT (Thin Film Transistor) liquid crystal manufacturing substrates, STN (Super Twisted Nematic) liquid crystal manufacturing substrates, and the like are included.

  5). The “chip forming portion” is a portion including a plurality of chip regions on the device surface of the wafer, and refers to an internal region excluding an “outer edge portion” that is not intended to produce peripheral chips.

6). “High dielectric” means a high dielectric material such as Ta ₂ O ₅ having a relative dielectric constant of 20 or more, or a high dielectric such as BST ((Ba, Sr) TiO ₃ ) having a relative dielectric constant exceeding 100. Body material.

7). “Ferroelectric material” refers to PZT, PLT, PLZT, SBT, PbTiO ₃ , SrTiO _3, BaTiO _{3 and the} like including a perovskite structure in a ferroelectric phase at room temperature.

8). “Transition metal” generally refers to elements from Group 3 to which Yttrium, Lanthanum and the like belong to Group 11 to which Copper belongs and the like in the periodic table. “Transition metal-containing film” refers to a film containing a transition metal or a material containing a transition metal as a main or secondary component (for example, Ru, RuO ₂ , Ta ₂ O _5, etc.). The “transition metal-containing film deposition process” refers to a process in which the transition metal-containing film is attached or deposited intentionally or unintentionally. Therefore, the etching process is included in addition to the process of depositing the insulating film and the metal film. In the present application, the “hazardous transition metal” is a transition metal used in a semiconductor process whose properties as a contamination have not been sufficiently verified at present, and is composed of, for example, a platinum group and a copper group only. The one selected from the group. Further, in the present application, in the case of “made of copper”, it is not limited to pure copper unless otherwise specified, and other components, additives, Needless to say, it includes impurities and the like.

  9. “White metal element” generally refers to ruthenium, rhodium, palladium, osmium, iridium, and platinum among the elements belonging to Group 10 to Group 10 of the Periodic Table.

  10. With regard to the wafer process, the “lower layer process group” is a series of processing film formation, resist film formation process, exposure, development, patterning of the film, etc. that pass before the process when attention is paid to one wafer. A set of processes. For example, the lower layer wiring process group is a lower layer process than the upper layer wiring process group. The opposite is called “upper layer process group”. However, it is not necessarily limited to a physical relationship.

  11. “Lithography process” means, for example, in the case of light exposure, after a film formation process, a process of applying a photoresist to the wafer, and a process of exposing and developing the photoresist (baking if necessary) Including processes). A “shared relationship” for a lithography process refers to a relationship in which wafers belonging to different process groups pass through a lithography process comprising the same equipment. In this case, it is not necessary to share all devices even if they are the same equipment. Any one apparatus, for example, an exposure apparatus (light exposure apparatus or EB exposure apparatus) may be shared.

  12 With regard to the wafer line, “mass production” generally refers to a wafer with a throughput of about 1000 wafers / day. However, in the present application, in consideration of an increase in the diameter of the wafer, about 100 wafers / day is also included. To do. In this case, it goes without saying that the varieties need not be the same.

  13. “Chemical Mechanical Polishing (CMP)” means that the surface to be polished is generally in contact with a polishing pad made of a relatively soft cloth-like sheet material and the like, while being supplied with slurry, In this application, CML (Chemical Mechanical Lapping) that performs polishing by moving the surface to be polished relative to the hard grindstone surface is also included.

  Among the inventions disclosed in the present application, effects obtained by typical ones will be briefly described as follows.

  Initial device formation using the above devices in semiconductor mass production processes that share lithography equipment, inspection equipment, annealing (heat treatment) equipment, etc. in the initial device formation process, wiring process, and transition metal-containing film processing process before gate insulating film formation It is possible to reliably prevent transition metal contamination of the wafer in which the process and the wiring process are performed.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings. Note that components having the same function are denoted by the same reference symbols throughout the drawings for describing the embodiment, and the repetitive description thereof will be omitted. In the following embodiments, the description of the same or similar parts will not be repeated in principle unless particularly necessary.

  Further, in the following embodiments, when necessary for convenience, the description will be divided into a plurality of sections or embodiments, but they are not irrelevant to each other unless otherwise specified. The other part or all of the modifications, details, supplementary explanations, and the like are related. In the following embodiments, when referring to the number of elements (including the number, numerical value, quantity, range, etc.), unless explicitly stated or in principle clearly limited to a specific number It is not limited to the specific number, and may be a specific number or more. Further, in the following embodiments, it is needless to say that the constituent elements (including element steps and the like) are not necessarily indispensable unless otherwise specified and apparently essential in principle. Yes.

  Similarly, in the following embodiments, when referring to the shapes and positional relationships of components and the like, the shapes and the like of the components are substantially the same unless explicitly stated or otherwise apparent in principle. Including those that are approximate or similar to. The same applies to the above numerical values and ranges.

  A method for manufacturing a DRAM according to an embodiment of the present invention will be described in the order of steps with reference to FIGS.

  First, as shown in FIG. 1, an element isolation trench 2 is formed on the main surface of a semiconductor substrate (wafer) 1 made of single crystal silicon having a p-type resistivity of about 10 Ωcm, for example, and then a p-type well 3 is formed on the substrate 1. Form. The element isolation trench 2 is formed by dry etching the substrate 1 in the element isolation region, and then depositing a silicon oxide film 4 on the substrate 1 including the inside of the trench by a CVD method. It is formed by polishing by chemical mechanical polishing (CMP) and leaving it in the groove. The p-type well 3 is formed by ion-implanting an n-type impurity such as P (phosphorus) into the substrate 1 and then annealing (heat treatment) the substrate 1 to diffuse the n-type impurity.

  Next, after cleaning the surface of the p-type well 3 using a hydrofluoric acid (HF) cleaning solution, the substrate 1 is wet-oxidized to form a clean gate oxide film 5 on the surface of the p-type well 3.

  Next, as shown in FIG. 2, a gate electrode 6 (word line WL) is formed on the gate oxide film 5, and then a low impurity concentration n-type semiconductor region is formed in the p-type well 3 on both sides of the gate electrode 6. 7 is formed.

  For the gate electrode 6 (word line WL), for example, a polycrystalline silicon film doped with an n-type impurity such as P is deposited on the substrate 1 by the CVD method, and then a WN (tungsten nitride) film and a W (tungsten) film are formed thereon. A film is deposited by a sputtering method, and a silicon nitride film 8 is further deposited thereon by a CVD method, and then these films are formed by dry etching using a photoresist film as a mask. The n-type semiconductor region 7 is formed by ion implantation of an n-type impurity such as arsenic (As) into the p-type well 3.

  Next, as shown in FIG. 3, a silicon nitride film 9 and a silicon oxide film 10 are deposited on the substrate 1 by a CVD method, and then the surface of the silicon oxide film 10 is planarized by a chemical mechanical polishing method.

  Next, as shown in FIG. 4, using the photoresist film (not shown) as a mask, the silicon oxide film 10 and the silicon nitride film 9 above the n-type semiconductor region 7 are dry-etched to form contact holes 11 and 12. After the formation, as shown in FIG. 5, a plug 13 made of a polycrystalline silicon film is formed inside the contact holes 11 and 12. For example, the plug 13 is formed by depositing a polycrystalline silicon film doped with n-type impurities such as P on the inside of the contact holes 11 and 12 and the upper part of the silicon oxide film 10 by the CVD method, and then polycrystalline the upper part of the silicon oxide film 10. The silicon film is formed by removing the silicon film by a chemical mechanical polishing (or etch back) method and leaving it inside the contact holes 11 and 12.

  Subsequently, the substrate 1 is annealed (heat treatment), and the n-type impurity in the polycrystalline silicon film constituting the plug 13 is diffused into the substrate 1 (n-type semiconductor region 7), whereby a high impurity concentration n-type semiconductor region is obtained. 14 (source, drain) are formed. The n-channel type memory cell selecting MISFET Qs constituting a part of the DRAM memory cell is completed through the steps so far.

  Next, as shown in FIG. 6, a silicon oxide film 15 is deposited on the silicon oxide film 10 by a CVD method, and then the silicon oxide film 15 is dry-etched to form a through hole 16 on the contact hole 11. After that, a plug 17 is formed inside the through hole 16, and a bit line BL is formed above the plug 17.

  The plug 17 is formed, for example, by depositing a TiN (tungsten nitride) film and a W film inside the through hole 16 and on the silicon oxide film 15 by a CVD method or a sputtering method, and then a TiN film and a W film on the silicon oxide film 15. Is removed by chemical mechanical polishing and left inside the through hole 16. The bit line BL is formed by, for example, depositing a W film on the silicon oxide film 15 by sputtering and then dry etching the W film using the photoresist film as a mask. The bit line BL is electrically connected to one of the source and drain (n-type semiconductor region 14) of the memory cell selection MISFET Qs via the plug 17 in the through hole 16 and the plug 13 in the contact hole 11.

  Next, as shown in FIG. 7, a silicon oxide film 18 is deposited on the upper portion of the silicon oxide film 15 by a CVD method, and a TiN film 19 is deposited on the upper portion of the silicon oxide film 18 by a sputtering method. The silicon oxide film 18 is dry-etched to form a through hole 20 above the contact hole 12, and a plug 21 is formed inside the through hole 20. For example, the plug 21 deposits a polycrystalline silicon film doped with an n-type impurity such as P on the inside of the through hole 20 and on the TiN film 19 by the CVD method, and then etches the polycrystalline silicon film on the TiN film 19. It is formed by removing it by the back method and leaving it inside the through hole 20. At this time, the polycrystalline silicon film constituting the plug 21 is over-etched, and the surface of the plug 21 is set back below the surface of the TiN film 19.

  Next, as shown in FIG. 8, a barrier metal 22 is formed on the plug 21. For example, the barrier metal 22 is formed by depositing a WN film in the through hole 20 and on the TiN film 19 by a sputtering method, and then removing the WN film on the TiN film 19 by a chemical mechanical polishing (or etch back) method. It is formed by leaving inside the through hole 20.

  The barrier metal 22 above the plug 21 prevents a reaction between the lower electrode material (Ru) of the information storage capacitor element and the plug 21 (polycrystalline silicon film) deposited on the TiN film 19 in the next step, It is formed for the purpose of preventing oxidation of the plug 21 (polycrystalline silicon film) due to oxygen in the capacitor insulating film material (BST). The barrier metal 22 can be made of TiN, TaN (tantalum nitride), TaSiN, WSiN, TiSiN or the like in addition to WN.

  Next, as shown in FIG. 9, a Ru film 23, which is a lower electrode material of the information storage capacitor element, is deposited on the TiN film 19 by sputtering.

  By the way, in the manufacturing process of a general-purpose LSI such as DRAM, in order to reduce the manufacturing cost by suppressing the capital investment as much as possible, as shown in FIG. 10, a lithography apparatus (light exposure apparatus, EB exposure apparatus), various inspection apparatuses , An annealing (heat treatment) apparatus is shared by the initial element formation process and the wiring process before the gate insulating film is formed, and a new transition that is not used in the conventional wafer process such as the Ru film 23 or the BST film described later. These shared devices are also used in the process of forming an information storage capacitor element for processing a metal or a material containing it. Therefore, in these shared apparatuses, after the wafer (substrate) 1 on which the Ru film 23 or the BST film is deposited is unloaded from the apparatus, the wafer 1 for executing the initial element forming process or the wiring process is included in the apparatus. It is brought in. Here, the wiring process means the process of forming the gate electrode 6 and the bit line BL shown in FIGS. 2 to 8 and the process of forming the wiring above the information storage capacitor element to be described later.

  FIG. 11 is a cross-sectional view showing the periphery of the wafer 1 on which the Ru film 23 is deposited. As shown in the figure, when the Ru film 23 is deposited on the device surface (main surface) of the wafer (substrate) 1 by using the sputtering method, the Ru film 23 is not only formed on the chip formation portion and the outer edge portion of the device surface but also on the side surface ( (The edge portion) is also deposited, and a part thereof adheres to the back surface of the wafer 1. For this reason, when the wafer 1 is loaded into the common apparatus without sufficiently removing the Ru film 23 on the side surface and the back surface, the Ru film 23 adheres to the surface of the wafer stage, wafer carrier, conveyor, etc. in contact with the side surface or the back surface of the wafer 1. Then, the wafer 1 in the lower layer process group (initial element forming process and wiring process before forming the gate insulating film) which is subsequently carried into the shared device is contaminated with Ru.

  Therefore, in this embodiment, prior to the step of carrying the wafer 1 on which the Ru film 23 is deposited into the common apparatus to form the lower electrode, the unnecessary Ru film 23 deposited on the side surface and the back surface of the wafer 1 is as follows. Remove by various methods.

  FIG. 12 is a schematic cross-sectional view showing an example of a cleaning device used for removing the Ru film 23 deposited on the side surface and the back surface of the wafer 1, and FIG. 13 is a plan view showing a stage of this cleaning device.

  In the central portion of the processing chamber 101 of the cleaning apparatus 100, a stage 102 on which the wafer 1 is placed is installed. Four pins 103 that come into contact with the side surface of the wafer 1 are arranged on the upper surface of the stage 102 at equal intervals. These pins 103 themselves can be rotated in a horizontal plane. The wafer 1 is held horizontally by being pinched by these pins 103 with its back surface facing up. The wafer 1 supported by the pins 103 is in a non-contact state with the stage 102 except for four points on the side surface in contact with the pins 103.

  Below the processing chamber 101, a driving unit 104 that rotates the stage 102 in a horizontal plane and a gas supply unit 105 that is filled with an inert gas such as nitrogen are installed. Nitrogen gas in the gas supply unit 105 is supplied to the upper surface of the stage 102 through the pipe 106 below the stage 102.

  As shown in FIG. 14, the four pins 103 arranged on the upper surface of the stage 102 can move horizontally in a direction away from the wafer 1. When the wafer 1 is held by the four pins 103, these pins 103 are moved to a position away from the wafer 1 in advance, and the wafer 1 is first floated by supplying the nitrogen gas to the lower surface of the wafer 1. In this state, the pins 103 are pressed against the side surface of the wafer 1.

  A cleaning tank 108 is installed above the stage 102. The cleaning tank 108 is filled with a cleaning liquid 107 for removing the Ru film 23 deposited on the side surface and the back surface of the wafer 1. The cleaning liquid 107 is supplied to the upper surface (back surface) of the wafer 1 through the nozzle 109 and cleans the back surface and side surfaces of the wafer 1 that rotates while being held by the pins 103. At this time, by controlling the rotational speed of the stage 102, the cleaning liquid 107 can be made to wrap around the outer edge portion of the lower surface (device surface) of the wafer 1.

  Next, the composition of the cleaning liquid 107 will be described. First, Ru etching rates by various cleaning solutions used in a semiconductor manufacturing process are shown in FIG. As a sample, a 3 cm × 4 cm square silicon chip on which a 100 nm thick Ru film was deposited was used, and the thickness of the Ru film etched per minute was measured. As shown in the figure, the Ru etching rate was 0.1 nm / min or less when any cleaning solution was used. Note that 0.1 nm / min is the measurement limit value of the instrument used here. From this result, it can be seen that Ru cannot be removed by a known cleaning solution used in the semiconductor manufacturing process.

Next, the dissolution mechanism of Ru will be described. In order to remove the Ru film 23, it is necessary to use a chemical solution capable of dissolving Ru, but in order to dissolve Ru, it is necessary to oxidize Ru. The oxidation reaction of Ru is as shown in the following formula:
Ru + 4H ₂ O → RuO ₄ + 8H ⁺ + 8e ⁻ (pH = 0)
Ru + 8OH ⁻ → RuO ₄ + 4H ₂ O + 8e ⁻ (pH = 14)
The required redox potential (E) at this time is 1.13 V in an acidic aqueous solution (pH = 0) and 0.30 V in an alkaline aqueous solution (pH = 14). Therefore, in order to oxidize Ru, an oxidizing agent having a redox potential of 1.13 V or higher in an acidic aqueous solution or 0.30 V or higher in an alkaline aqueous solution is required.

  FIG. 16 shows the etching rate of Ru at a predetermined concentration of various oxidizing agents (excluding iodine) having a redox potential larger than the above value. The sample used and the method for measuring the etching rate are the same as those in FIG.

As shown in the figure, orthoperiodic acid (H ₅ IO ₆ ) is the only oxidizing agent that exhibits an acidic and high etching rate. Further, there are three kinds of oxidizing agents which are alkaline and exhibit a high etching rate: hypochlorous acid, metaperiodic acid and orthoperiodic acid. However, among oxidants that are alkaline and have a high etching rate, hypochlorous acid and metaperiodic acid are salts of alkali metals such as sodium (Na), so in semiconductor manufacturing processes that dislike contamination with alkali metals. I can not use it. Accordingly, among these oxidants, the only oxidant that can be used as the cleaning solution 107 for the Ru film 23 is substantially orthoperiodic acid. The advantage of the oxidizing agent used in the acidic state is that, unlike the oxidizing agent used in the alkaline state, a salt is not generated with the solute.

  FIG. 17 is a graph showing a relationship between various orthoperiodic acid aqueous solutions (temperature: 60 ° C.) and Ru etching rate (nm / min). As shown in the figure, it is understood that when the orthoperiodic acid concentration in the aqueous solution is about 10 wt% or more, the etching rate of Ru increases almost in proportion to the concentration of orthoperiodic acid. Therefore, when the orthoperiodic acid aqueous solution is used as the cleaning liquid 107 for the Ru film 23, the concentration of orthoperiodic acid may be in the range of about 10 wt% to the saturated concentration.

  In addition, the present inventors have found that the etching rate of Ru can be further increased by mixing nitric acid into the orthoperiodic acid aqueous solution.

  FIG. 18 is a graph showing the relationship between the nitric acid concentration and the etching rate when Ru is etched using an aqueous solution (temperature 60 ° C.) obtained by adding nitric acid to an orthoperiodic acid aqueous solution having a concentration of 47 wt%. Same as used in FIG. 15). As shown in the figure, when the nitric acid concentration is in the range of ˜2 mol / l, the etching rate of Ru increased almost in proportion to the amount of nitric acid added.

  In addition, FIG. 19 shows that an aqueous solution of orthoperiodic acid 10 having four concentrations (20 wt%, 30 wt%, 40 wt%, 50 wt%) is 0 (no addition), 1, 2, It is a graph which shows the relationship between the nitric acid mixing ratio and etching rate when etching Ru using the aqueous solution (temperature of 60 degreeC) added by the ratio of 5 and 10 (a sample is the same as what was used in the said FIG. 15). . In any case, the addition of nitric acid significantly increased the Ru etching rate compared to orthoperiodic acid alone.

  FIG. 20 is a graph in which the concentration of orthoperiodic acid and nitric acid is recalculated as weight% in the example of FIG. 19, and the Ru etching rate is displayed as a contour line (unit: nm / min). As shown in the figure, an aqueous solution having an orthoperiodic acid concentration of 20 wt% to 40 wt% and a nitric acid concentration of 20 wt% to 40 wt% has little fluctuation in the Ru etching rate. In particular, it can be seen that an aqueous solution having an orthoperiodic acid concentration of 25 wt% to 35 wt% and a nitric acid concentration of 25 wt% to 35 wt% indicated by a broken line in the figure shows a small variation in Ru etching rate of about 10%.

  Therefore, when an aqueous solution containing orthoperiodic acid and nitric acid is used as the cleaning liquid 107 for the Ru film 23, the orthoperiodic acid concentration and the nitric acid concentration are in the range of 20 wt% to 40 wt%, respectively. By using an aqueous solution having an iodic acid concentration and a nitric acid concentration in the range of 25 wt% to 35 wt%, it is possible to suppress fluctuations in the etching rate of Ru due to a change in the concentration of the cleaning liquid 107 and to increase a process margin. Become. That is, the orthoperiodic acid + nitric acid mixed aqueous solution in the above concentration range is a cleaning solution suitable for a mass production process for continuously processing a large number of wafers.

The reason why the etching rate of Ru is increased by mixing nitric acid with the orthoperiodic acid aqueous solution is estimated as follows. That is, orthoperiodic acid (H ₅ IO ₆ ) is in an ionization equilibrium state represented by the following formula in an aqueous solution.

H ₅ IO ₆ ⇔ H ₄ IO ₆ ⁻ + H ^{+
_{H 4 IO 6 - ⇔ H 3}} IO 6 2- + H +
H ₃ IO ₆ ²⁻ ⇔ H ₂ IO ₆ ^{3 −} + H ⁺
H ₄ IO ₆ ⁻ ⇔ IO ₄ ⁻ + H ₂ O
2H ₃ IO ₆ ²⁻ ⇔ H ₂ I ₂ O ₁₀ ⁴⁻ + 2H ₂ O
Of these molecules and ionic species contained in the aqueous solution, only orthoperiodic acid (H ₅ IO ₆ ) has the ability to oxidize Ru. When nitric acid is added to this orthoperiodic acid aqueous solution, since the concentration of protons (H ⁺ ) derived from nitric acid is increased in the aqueous solution, the above equilibrium advances to the left side. As a result, it is presumed that the concentration of orthoperiodic acid (H ₅ IO ₆ ) that can oxidize Ru increases, and the etching rate of Ru increases.

  Therefore, the etching rate of Ru can be increased by adding not only nitric acid but also an acid that advances the above-mentioned equilibrium toward the left side. For example, FIG. 21 shows a change in the etching rate of Ru when various commercially available acids are added to an orthoperiodic acid aqueous solution. As shown in the figure, it is understood that the etching rate of Ru increases even when acetic acid is added as well as nitric acid.

Examples of the acid that increases the etching rate of Ru include carboxylic acids represented by acetic acid and HCOOH (formic acid);
Hydrohalic acids such as HF (hydrogen fluoride), HBr (hydrogen bromide), HI (hydrogen iodide);
Halogenated oxoacids such as HClO ₃ (chloric acid), HClO ₄ (perchloric acid), HBrO ₃ (brominated acid), HBrO ₄ (perbrominated acid);
Group 6 element hydrides such as polyhydrogen sulfide such as H ₂ S (hydrogen sulfide), H ₂ S ₃ and H ₂ S ₄ , H ₂ Se (hydrogen selenide) and H ₂ Te (hydrogen telluride);
H ₂ S ₂ O _{3 (thiosulfate), H 2 S 2 O 7} ( _disulfate), H 2 SO ₆ (polythionic _acid), H 2 SO _{5 (persulfate), H 2 S 2 O 8} ( peroxodisulfate ) Sulfur oxoacids such as H ₂ SeO ₄ (selenic acid), H ₆ TeO ₆ (telluric acid);
Polyphosphoric acids such as H ₃ PO ₄ (orthophosphoric acid), H ₄ P ₂ O ₇ (pyrophosphoric acid), H ₅ P ₃ O ₁₀ (triphosphoric acid), H ₆ P ₄ O ₁₃ (tetraphosphoric acid), (HPO ₃ ) Phosphorus oxoacids represented by _n (cyclo-phosphate);
Examples thereof include H ₃ AsO ₄ (arsenic acid), HN ₃ (hydrogen azide), H ₂ CO ₃ (carbonic acid), H ₃ BO ₃ (boric acid), and the like.

  Next, a method for cleaning the wafer 1 using the cleaning solution 107 made of an orthoperiodic acid aqueous solution or an aqueous solution in which the above-mentioned various acids are mixed will be described with reference to FIGS.

  First, the wafer 1 on which the Ru film 23 is deposited is carried into the processing chamber 101 of the cleaning apparatus 100, and the wafer 1 is floated by supplying nitrogen gas from the gas supply unit 105 to the upper surface of the stage 102 (FIG. 14). Next, the wafer 1 is held horizontally by pressing the pins 103 against the side surface of the wafer 1 (FIGS. 12 and 13).

  Subsequently, the cleaning liquid 107 in the cleaning tank 108 is supplied to the upper surface (back surface) of the wafer 1 through the nozzle 109 while rotating the stage 102, and the back surface and side surfaces of the wafer 1 are cleaned. Further, the outer edge portion of the lower surface (device surface) of the wafer 1 is also cleaned as necessary. For example, a mixed aqueous solution of orthoperiodic acid (concentration 30 wt%) and nitric acid (concentration 30 wt%) heated to 60 ° C. is used as the cleaning liquid 107.

  During cleaning, the pins 103 in contact with the wafer 1 are rotated in a horizontal plane. As a result, the wafer 1 is rotated by the frictional force with the pins 103 and the position of the side surface in contact with the pins 103 is changed, so that the entire side surface of the wafer 1 can be cleaned. The cleaning apparatus 100 used here is described in detail in Japanese Patent Application No. 11-117690 by the present inventors.

  The back surface and side surface cleaning of the wafer 1 using the cleaning liquid 107 of this embodiment can also be performed using an apparatus other than the cleaning apparatus 100 such as a known Bernoulli chuck spin etching apparatus. Further, prior to the cleaning of this embodiment, the back surface of the wafer 1 may be brush cleaned.

The etching rate of the Ru film 23 using the above orthoperiodic acid + nitric acid mixed aqueous solution (60 ° C.) was 2.244 × 10 ⁻³ g / min in terms of weight. On the other hand, in the case of the above-mentioned Japanese Patent Application Laid-Open No. 7-155782, the etching rate of Ru when using a solution (100 ° C.) of 33% HIO ₃ : 20% ICl = 1: 1 is 1.567 × 10 ^{− In} the case of JP-A-7-224333, the Ru etching rate when using 37% HI + 0.01 mol / l I ₂ solution (70 ° C.) is 0.9625 × 10 ⁻⁶ g / Both the minute and the minute are extremely small, and it can be said that qualitatively they are not substantially dissolved. That is, according to the method of the present invention, it is possible to dissolve Ru at an etching rate that is 1000 times higher than these conventional techniques. In addition, the method of the present invention has the advantage that Ru can be dissolved at a lower temperature than the prior art solution.

  Next, a method for forming a lower electrode using the Ru film 23 as an electrode material will be described. First, the wafer 1 that has been subjected to the above-described cleaning process is carried into the common inspection apparatus shown in FIG. 10, and after checking the degree of contamination on the back surface and side surfaces, using a common annealing (heat treatment) apparatus, the temperature is about 700 ° C. The stress of the Ru film 23 is relaxed by annealing (heat treatment) the wafer 1 in a nitrogen atmosphere.

  Next, the wafer 1 is transferred to a CVD apparatus (not shown), and a silicon oxide film 24 is deposited on the Ru film 23 as shown in FIG. Since oxygen-based gas is used for dry etching of the Ru film 23, an oxidation-resistant material such as the silicon oxide film 24 is used for the etching mask.

  Next, a lithography process is performed on the wafer 1 using the shared apparatus shown in FIG. That is, as shown in FIG. 23, a hard mask for dry etching the Ru film 23 is formed by dry etching the silicon oxide film 24 using the photoresist film 25 deposited on the silicon oxide film 24 as a mask. To do.

  Next, after removing the photoresist film 25 by ashing, as shown in FIG. 24, the Ru film 23 is dry-etched using the silicon oxide film 24 as a mask, so that the lower electrode 23A of the information storage capacitive element is formed. Form. For etching the Ru film 23, for example, a mixed gas of oxygen gas and chlorine gas is used. Etching equipment uses inductively coupled plasma etching equipment, ECR (Electron Cyclotron Resonance) plasma etching equipment, ICP (Inductively Coupled Plasma) etching equipment, magnetron RIE (Reactive Ion Etching) plasma etching equipment, helicon wave plasma etching equipment, etc. . Etching of the Ru film 23 is performed using the lower TiN film 19 as an etching stopper while monitoring light having a wavelength of 406 nm, which is a Ti emission peak, for example.

  Next, in order to remove the etching residue of the Ru film 23, the wafer 1 is cleaned using the cleaning apparatus shown in FIGS. At this time, by using the above-described orthoperiodic acid + nitric acid mixed aqueous solution as the cleaning liquid, it is possible to sufficiently remove the Ru residue attached to the side surface and the back surface of the wafer 1.

Next, as shown in FIG. 25, the TiN film 19 is dry etched using the silicon oxide film 24 as a mask. For the etching of the TiN film 19, for example, a mixed gas of boron trichloride (BCl ₃ ) and chlorine is used. As an etching apparatus, for example, an ECR plasma etching apparatus is used.

  Next, after the silicon oxide film 24 is removed by dry etching, as shown in FIG. 26, a BST film 26, which is a capacitive insulating film material, is deposited on the lower electrode 23A by a CVD method. Subsequently, by cleaning the wafer 1 using the cleaning apparatus shown in FIGS. 12 to 14, the BST film 26 deposited on the side surface and the back surface of the wafer 1 is removed. As the cleaning liquid at this time, for example, hydrofluoric acid is used.

As the capacitor insulating film material, in addition to the BST film 26, a high dielectric material such as Ta ₂ O ₅ (tantalum oxide), or a perovskite type such as PZT, PLT, PLZT, SBT, PbTiO ₃ , SrTiO ₃ , or BaTiO _{3 is used.} Ferroelectric materials containing a crystal structure can also be used. Also in this case, the unnecessary high / ferroelectric film deposited on the side surface and the back surface of the wafer 1 is removed by cleaning the wafer 1 using the cleaning apparatus shown in FIGS. For example, high-concentration hydrofluoric acid is used as a cleaning liquid for these materials.

Next, in order to remove crystal defects in the BST film 26, the wafer 1 is annealed (heat treatment) in an oxygen atmosphere at about 700.degree. In addition, when using a high dielectric material such as Ta ₂ O ₅ or a ferroelectric material including a perovskite crystal structure such as PZT, PLT, PLZT, SBT, PbTiO ₃ , SrTiO ₃ , or BaTiO ₃ , In order to remove defects, the wafer 1 is annealed (heat treatment) in an oxygen atmosphere.

  Next, as shown in FIG. 27, a Ru film 27, which is an upper electrode material, is deposited on the BST film 26 by a CVD method. Also in this case, the wafer 1 is cleaned using the cleaning apparatus shown in FIGS. 12 to 14 after the Ru film 27 is formed. At this time, by using the above-described orthoperiodic acid + nitric acid mixed aqueous solution as the cleaning liquid, the Ru film 27 attached to the side surface and the back surface of the wafer 1 can be sufficiently removed.

  As a result, the information storage capacitive element C constituted by the lower electrode 23A made of the Ru film 23, the capacitive insulating film made of the BST film 26, and the upper electrode 29 made of the Ru film 27 is completed. Further, through the steps so far, a DRAM memory cell composed of the memory cell selection MISFET Qs and the information storage capacitor element C connected in series with the MISFET Qs is completed.

  Thereafter, as shown in FIG. 28, a silicon oxide film 28, a silicon nitride film 29, and a silicon oxide film 30 are sequentially deposited on the information storage capacitor element C by a CVD method, and then the silicon nitride film 29 is used as an etching stopper. A wiring groove 31 is formed in the silicon oxide film 30 by dry etching, and then a buried Cu wiring 33 is formed inside the wiring groove 31 via a barrier metal film 32.

  In order to form the embedded Cu wiring 33, for example, a barrier metal film 32 made of a TiN film, a TaN film, or the like is deposited by sputtering (or CVD) on the inside of the wiring groove 31 and on the silicon oxide film 30, and subsequently. A Cu film (33) is deposited on the barrier metal film 32 by sputtering.

  Next, in order to remove the Cu film adhering to the side surface and the back surface of the wafer 1, the wafer 1 is cleaned by using the cleaning apparatus shown in FIGS. For example, nitric acid or concentrated sulfuric acid is used as the cleaning liquid. By performing this cleaning, it is possible to prevent Cu contamination of the wafer 1 in the lower layer process group (initial element forming process and wiring process before forming the gate insulating film).

  Next, the Cu film (33) is annealed (heat treatment) to sufficiently embed the Cu film (33) in the wiring groove 31, and then the unnecessary Cu film (33) outside the wiring groove 31 is subjected to chemical mechanical polishing. The embedded Cu wiring 33 is formed by a so-called damascene method which is removed by the method. The method for forming the buried Cu wiring 33 is described in detail in Japanese Patent Application No. 11-117690 (Tanabe).

  As mentioned above, the invention made by the present inventor has been specifically described based on the embodiment. However, the present invention is not limited to the embodiment, and various modifications can be made without departing from the scope of the invention. Needless to say.

  In the above-described embodiment, the case where an aqueous solution using water as a solvent that does not cause a problem with reaction with a solute or contamination of the wafer is used as the cleaning liquid. However, the present invention is not limited to this. Other inorganic solvents may be used.

  In the above embodiment, the case where the capacitor electrode is made of Ru has been described. However, in the wafer cleaning method of the present invention, the capacitor electrode is made of a white metal other than Ru, such as Pt (platinum), Ir (iridium), The present invention can also be applied to a case where Rh (rhodium), Pd (palladium), Os (osmium), or the like is used. Orthoperiodic acid or the like is used for the cleaning liquid when the electrode is made of Ir. In addition, aqua regia is used as the Pt cleaning liquid, and aqua regia or concentrated nitric acid is used as the Pd cleaning liquid.

The present invention is applicable not only to DRAM using a transition metal-containing film as a capacitor material but also to a CMIS integrated circuit in which a gate insulating film of a MISFET is made of a high dielectric material such as Ta ₂ O ₅ (tantalum oxide). Can be applied.

  The present invention can be applied to a semiconductor manufacturing process in which a wafer on which a film containing a transition metal such as ruthenium (Ru) is deposited is continuously processed in large quantities.

It is principal part sectional drawing of the semiconductor substrate which shows the mass production method of the semiconductor integrated circuit device which is one embodiment of this invention. It is principal part sectional drawing of the semiconductor substrate which shows the mass production method of the semiconductor integrated circuit device which is one embodiment of this invention. It is principal part sectional drawing of the semiconductor substrate which shows the mass production method of the semiconductor integrated circuit device which is one embodiment of this invention. It is principal part sectional drawing of the semiconductor substrate which shows the mass production method of the semiconductor integrated circuit device which is one embodiment of this invention. It is principal part sectional drawing of the semiconductor substrate which shows the mass production method of the semiconductor integrated circuit device which is one embodiment of this invention. It is principal part sectional drawing of the semiconductor substrate which shows the mass production method of the semiconductor integrated circuit device which is one embodiment of this invention. It is principal part sectional drawing of the semiconductor substrate which shows the mass production method of the semiconductor integrated circuit device which is one embodiment of this invention. It is principal part sectional drawing of the semiconductor substrate which shows the mass production method of the semiconductor integrated circuit device which is one embodiment of this invention. It is principal part sectional drawing of the semiconductor substrate which shows the mass production method of the semiconductor integrated circuit device which is one embodiment of this invention. It is a figure explaining the shared concept of the lithography process in the mass production process of a semiconductor integrated circuit device. It is sectional drawing which shows the peripheral part of the wafer in which the Ru film | membrane was deposited. It is a schematic sectional drawing which shows an example of the washing | cleaning apparatus used by one embodiment of this invention. It is a top view which shows the stage of the washing | cleaning apparatus shown in FIG. It is a schematic sectional drawing which shows the wafer holding method of the washing | cleaning apparatus shown in FIG. It is a figure which shows the etching rate of Ru by the various washing | cleaning liquid used in the semiconductor manufacturing process. It is a figure which shows the etching rate of Ru in various oxidizing agents. It is a graph which shows the relationship between the orthoperiodic acid aqueous solution of various density | concentrations, and the etching rate of Ru. It is a graph which shows the relationship between nitric acid concentration and an etching rate when Ru is etched using the aqueous solution which added nitric acid to the orthoperiodic acid aqueous solution. (A)-(d) is a graph which shows the relationship between nitric acid mixing ratio and an etching rate when Ru is etched using the solution which added nitric acid aqueous solution to orthoperiodic acid aqueous solution. It is the graph which displayed the etching rate of Ru in the solution which added the nitric acid aqueous solution to the orthoperiodic acid aqueous solution with the contour line. It is a figure which shows the change of the etching rate of Ru at the time of adding various commercially available acids to orthoperiodic acid aqueous solution. It is principal part sectional drawing of the semiconductor substrate which shows the mass production method of the semiconductor integrated circuit device which is one embodiment of this invention. It is principal part sectional drawing of the semiconductor substrate which shows the mass production method of the semiconductor integrated circuit device which is one embodiment of this invention. It is principal part sectional drawing of the semiconductor substrate which shows the mass production method of the semiconductor integrated circuit device which is one embodiment of this invention. It is principal part sectional drawing of the semiconductor substrate which shows the mass production method of the semiconductor integrated circuit device which is one embodiment of this invention. It is principal part sectional drawing of the semiconductor substrate which shows the mass production method of the semiconductor integrated circuit device which is one embodiment of this invention. It is principal part sectional drawing of the semiconductor substrate which shows the mass production method of the semiconductor integrated circuit device which is one embodiment of this invention. It is principal part sectional drawing of the semiconductor substrate which shows the mass production method of the semiconductor integrated circuit device which is one embodiment of this invention.

Explanation of symbols

1 Semiconductor substrate (wafer)
2 element isolation trench 3 p-type well 4 silicon oxide film 5 gate oxide film 6 gate electrode 7 n-type semiconductor region 8, 9 silicon nitride film 10 silicon oxide film 11, 12 contact hole 13 plug 14 n-type semiconductor region (source, drain) )
15 Silicon oxide film 16 Through hole 17 Plug 18 Silicon oxide film 19 TiN film 20 Through hole 21 Plug 22 Barrier metal 23 Ru film 23A Lower electrode 24 Silicon oxide film 25 Photoresist film 26 BST film 27 Ru film 28 Silicon oxide film 29 Nitride Silicon film 30 Silicon oxide film 31 Wiring groove 32 Barrier metal 33 Embedded Cu wiring 100 Cleaning device 101 Processing chamber 102 Stage 103 Pin 104 Driving section 105 Gas supply section 106 Pipe 107 Cleaning liquid 108 Cleaning tank 109 Nozzle BL Bit line C Information storage capacity Element Qs MISFET for memory cell selection
WL Word line

Claims (5)

(A) a step of preparing a semiconductor wafer;
(B) depositing a desired film containing a transition metal element on the semiconductor wafer;
(C) removing the film deposited on the back surface of the semiconductor wafer or the outer edge of the main surface of the semiconductor wafer from the semiconductor wafer on which the film is deposited;
(D) performing a desired process on the semiconductor wafer from which the film on the outer surface of the back surface or the main surface has been removed;
Including
In the removing step in the step (c),
(C1) A predetermined interval is provided between the main surface of the semiconductor wafer and the stage so that the main surface of the semiconductor wafer and the stage are not in contact with each other, and the semiconductor is provided by a plurality of pins arranged on the stage. Supporting the side of the wafer;
(C2) supplying the cleaning liquid to the back surface of the semiconductor wafer while rotating the semiconductor wafer integrally with the stage and supplying an inert gas from the stage side toward the periphery of the main surface of the semiconductor wafer. ;
A method for manufacturing a semiconductor integrated circuit device including:   2. The method of manufacturing a semiconductor integrated circuit device according to claim 1, wherein in the step (c2), the flow of the cleaning liquid to the outer edge portion of the main surface of the semiconductor wafer is controlled by controlling the rotational speed of the stage. A method of manufacturing a semiconductor integrated circuit device.   2. The method of manufacturing a semiconductor integrated circuit device according to claim 1, wherein the film containing the transition metal element is a film containing a white metal element.   4. The method of manufacturing a semiconductor integrated circuit device according to claim 3, wherein the film containing the white metal element is a ruthenium film.   2. The method of manufacturing a semiconductor integrated circuit device according to claim 1, wherein the film containing the transition metal element is a ruthenium film.

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