JP2009123886A - Forming method of multilayer wiring - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a forming method of a multilayer wiring having high adhesiveness and reliability in inter-wiring insulation while effective low inter-wiring capacity is maintained. <P>SOLUTION: The forming method of multilayer wiring includes a first process (Fig.1[1]) in which an inter-via layer insulating film 43 and an inter-wiring layer insulating film 44 containing siloxane structure are formed on a metal wiring 41a, a second process (Fig.1[2]-Fig.2 (not shown)) in which a dual damascene groove 48, being a recess reaching the metal wiring 41a, is formed at parts of the inter-via layer insulating film 43 and inter-wiring layer insulating film 44, and a third process (Fig.3[1]) in which the inter-via layer insulating film 43 and inter-wiring layer insulating film 44 as well as the metal wiring 41a exposed in the dual damascene groove 48 are applied with a hydrogen plasma treatment, so that a modified layer 49 is formed on the surfaces of the inter-via layer insulating film 43 and inter-wiring layer insulating film 44 while the surface of the metal wiring 41a is reduced. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for forming a multilayer wiring, for example, a method for forming a multilayer wiring used for forming a damascene wiring mainly composed of Cu.

  In an integrated circuit using silicon as a substrate (hereinafter referred to as “LSI (Large Scale Integrated circuit)”), Al (aluminum) or an Al alloy has been widely used as a conductive material. With the progress of miniaturization of LSI manufacturing methods, Cu (copper) has been used as a conductive material in order to reduce wiring resistance and increase reliability in wiring. However, Cu has a property of easily diffusing into the silicon oxide film. Therefore, in order to prevent diffusion of Cu, a conductive barrier metal film is used on the side surface and the bottom surface of the Cu wiring, and an insulating barrier film is used on the upper surface of the Cu wiring.

  With the progress of miniaturization of LSIs in recent years, the miniaturization of wiring dimensions has further progressed, and the increase in inter-wiring capacitance has become a problem, and the introduction of low dielectric constant films into the interlayer insulating film has been promoted. This is because not only miniaturization but also low dielectric constant of the interlayer insulating film is effective in order to connect at high speed and low power by using multi-layer wiring in the semiconductor element, and both of these are required to be compatible. Because it was.

  In order to reduce the effective capacitance between wirings, it has been necessary to lower the dielectric constant of an interlayer insulating film (in this case, a silicon oxide film (relative dielectric constant k = 4.2)). Examples of the low dielectric constant film include an HSQ (Hydrogen Silsesquioxane) film, a CDO (Carbon Doped Oxide), and an organic film. These low dielectric constant films are formed by a spin coating method or a vapor phase method.

Patent Document 1 describes a technique for improving the adhesion by forming a modified layer by performing NF ₃ plasma treatment on an organosiloxane film. Patent Document 2 describes a technique for forming a modified layer by reducing treatment on an organic siloxane film to protect the organic siloxane film. Patent Document 3 describes a technique for forming a porous insulating film using a cyclic organosiloxane raw material.

JP 2003-309173 A JP 2006-24641 A JP-T-2002-526916

  As an integration technique of the organic siloxane film, a method of forming a modified layer on the organic siloxane film and improving process resistance is used. However, since the modified layer is formed by desorption of carbon, there is a problem that the relative dielectric constant increases and the capacitance between the wirings increases. Therefore, when the modified layer is used, it has been desired to form the modified layer thinly while reducing the relative dielectric constant of the modified layer.

In the technique described in Patent Document 1, a technique is described in which a modified layer is formed by performing plasma treatment on the surface of an organic siloxane film, and in particular, NF ₃ plasma is used. Adhesion can be improved by treating the surface with NF ₃ plasma, but there is a problem that heat resistance deteriorates due to fluorine taken into the film. The formed modified layer needs to be stable.

  In the technique described in Patent Document 2, the modified layer is formed by plasma treatment of the organic siloxane film, but the modified layer is formed thick in the organic siloxane film having a relative dielectric constant of 2.5 or less. As a result, there has been a problem that the relative dielectric constant increases and the capacitance between the wirings increases.

  On the other hand, as a low dielectric constant film capable of realizing a relative dielectric constant of 2.5 or less as described above, a low dielectric constant insulating film is formed using a cyclic organosiloxane raw material as described in Patent Document 3. can do. However, when applied to a wiring interlayer insulating film in order to achieve a low wiring capacity, there has been a problem that a leakage current between wirings increases. That is, although the capacitance between the wirings can be reduced, the power consumption of the entire chip is increased due to the leakage current between the wirings, and the insulation reliability between the wirings is deteriorated. It was.

  As described above, there has been a demand for a multilayer wiring that can realize all of the low wiring capacitance, high adhesion, and high wiring reliability. Accordingly, the present invention provides a method for forming a multilayer wiring having high adhesion and high insulation reliability between wirings while maintaining effective low wiring capacity.

  The multilayer wiring forming method according to the present invention includes a first step of forming an insulating film containing a siloxane structure on a metal wiring, and a second step of forming a recess reaching the metal wiring in a part of the insulating film. And a third step of forming a modified layer on the surface of the insulating film and reducing the surface of the metal wiring by performing hydrogen plasma treatment on the insulating film and the metal wiring exposed in the recess It is characterized by including these.

  According to the present invention, the insulating film and the exposed metal wiring are subjected to hydrogen plasma treatment to form a modified layer on the surface of the insulating film and reduce the surface of the metal wiring, thereby reducing the dielectric constant of the insulating film. In addition, high reliability of insulation and high reliability of metal wiring connection are achieved at the same time, and by having high adhesion, the performance of wiring is improved, and high speed and low power consumption LSI is highly reliable. Can be formed.

  In order to form a modified layer that maintains a low capacitance between wirings and is excellent in adhesion and insulation properties, it is necessary to form the modified layer as thin as possible. For that purpose, not only the approach of the modification treatment method but also the approach from the structure, composition and material of the organosiloxane film to be modified is necessary, and it is necessary to design the process flow in consideration of both.

  As a result of investigations on a method for forming a multilayer wiring using a cyclic organosiloxane raw material, the present inventors have found a suitable modified layer forming method that satisfies both the reliability of an insulating film and the reliability of copper wiring connection. .

  That is, it is an insulating film obtained by plasma vapor deposition by supplying at least a cyclic organosiloxane and an inert carrier gas to a reaction chamber, and the insulating film of at least one layer is made of at least silicon, oxygen, carbon, In the insulating film including the cyclic siloxane structure, a modified layer having a smaller amount of carbon atoms and a larger amount of oxygen atoms than the inside of the insulating film is formed by hydrogen plasma treatment in the insulating film portion including the cyclic siloxane structure in contact with the metal wiring. As a result, the leakage current between the wirings can be reduced while maintaining the low wiring capacity.

  Furthermore, by performing the modification process on the dual damascene trench, the reduction process of copper exposed at the via bottom and the modification of the insulating film surface can be performed simultaneously.

  The manufacturing method that satisfies both the improvement of the reliability of the insulating film and the reliability of the via Cu connection at the same time has an unexpected effect until a modified layer by the hydrogen plasma treatment according to the present invention is found. is there.

  That is, it is effective to perform the hydrogen plasma treatment according to the present invention in a state where the via hole bottom in the dual damascene trench is opened and copper is exposed at the via bottom. Furthermore, by performing the hydrogen plasma treatment according to the present invention, a modified layer having a smaller amount of carbon atoms and a larger amount of oxygen atoms than the inside of the insulating film is formed on the surface of the insulating film including the cyclic siloxane structure. The adhesion between the insulating film including the structure and the metal wiring can be improved.

  In particular, copper is used as the main component of the metal wiring, but the adhesion between the barrier metal covering the copper periphery and the insulating film including the cyclic siloxane structure is improved. In particular, when a refractory metal nitrogen compound such as TaN, TiN, WN, TiWN, or the like is used as the barrier metal, the adhesion is dramatically improved by reducing the amount of carbon on the surface of the insulating film including the cyclic siloxane structure. Improves.

  This is because a suitable reforming treatment is performed on an insulating film containing a suitable cyclic organosiloxane, whereby high-density siloxane units resulting from the cyclic structure are continuously bonded to form a high-density modified layer. This is because the present inventors have found that hydrogen plasma treatment is suitable for forming a layer in which the modified layer is excellent in adhesion and insulating properties.

  In other words, an insulating film containing a suitable siloxane structure is decarbonized by a suitable modification treatment to form a thin high-density modified layer so that the modification into the film does not proceed. This is a feature of the present invention.

  In particular, the modification of the lower surface of the groove is an indispensable element for maintaining the adhesion to the metal wiring. In this case, the hydrogen plasma treatment can be performed by applying a substrate bias to promote the modification of the lower surface of the groove as compared with the groove side wall, and can achieve both adhesion and low wiring capacity. It becomes like this.

  In an insulating film including a cyclic siloxane structure in which at least one layer of the insulating film is composed of at least silicon, oxygen, and carbon, a film composition having a larger number of carbon atoms than the number of silicon atoms is preferably light element carbon. In addition to the low dielectric constant of the insulating film itself due to the increase in the density, the densification reaction proceeds while suppressing rapid carbon extraction due to the reforming process, thus forming a high-density reformed layer with a nano-level thickness. This is because the inventors have found that they can do this.

  In particular, it is a film containing both an unsaturated hydrocarbon group and a hydrocarbon group having 3 or more carbon atoms, so that the decarbonization rate is reduced by the strong binding energy of the unsaturated hydrocarbon group, and the number of carbon atoms A large amount of hydrocarbon groups can keep a large amount of hydrocarbon components inside the film.

  In addition, compared with the random type siloxane structure, the cyclic siloxane structure has a low relative dielectric constant of the film, but a high-density modified layer can be formed because the cyclic structure having a smaller number of members is formed of O-Si-O. This is because the bonding angle is small and a high-density SiO structure is easily formed.

For example, the density of cocite (4-membered ring; 2.92 g / cm ³ ) is higher than that of quartz (6-membered ring; 2.65 g / cm ³ ). Therefore, the cyclic siloxane that is easy to form a high-density O—Si—O structure as a skeleton in advance is included in the film, so that oxygen substituted with carbon continuously binds the cyclic units and easily A high density and thin modified layer can be formed.

  Further, in order to form the modified layer so as to surround the metal wiring and the connection plug, all of the wiring interlayer insulating film, the hard mask film, and the via interlayer insulating film in contact with the metal wiring and the connection plug are at least silicon, The insulating film includes a siloxane structure composed of oxygen and carbon, and both have an insulating film structure formed from a raw material including both a side chain having 3 or more carbon atoms and a vinyl group.

  For example, by changing the raw material partial pressure during plasma excitation, a via interlayer insulating film is formed under a low partial pressure condition, a wiring interlayer insulating film is formed under a high partial pressure condition, and a relatively low pressure condition is achieved. A hard mask film and a via interlayer insulating film excellent in adhesion and film strength can be formed.

  Alternatively, the via interlayer insulating film has a C / Si ratio of about 1.4 by using two or more types of siloxane raw materials containing both a side chain having 3 or more carbon atoms and a vinyl group to change the ratio. SiOCH having a relative dielectric constant of 2.7, a wiring interlayer insulating film having a C / Si ratio of about 2.9 and a relative dielectric constant of 2.4, and a hard mask film having a C / Si ratio of 1.2 and a relative dielectric constant of 3.0 By forming each film, the modified layer according to the present invention can be formed on any insulating film. In this case, the modified layer is formed so as to surround the wiring except for the upper surface of the wiring, so that the adhesion can be further improved.

  In general, when the amount of carbon in the insulating film is large, the adhesion to the metal wiring tends to decrease. However, by using the insulating film in the present invention and further using the hydrogen plasma treatment, the dielectric constant of the insulating film is reduced and the leakage is reduced. A reduction in current and an improvement in adhesion can be achieved.

  The siloxane structure is characterized in that the number of carbon atoms per unit volume inside the insulating film is larger than the number of oxygen atoms. In addition, the bonded state of carbon atoms includes both a hydrocarbon group having at least 3 carbon atoms and an unsaturated hydrocarbon group.

The siloxane structure preferably includes a cyclic siloxane structure composed of oxygen atoms and silicon atoms. The cyclic siloxane has a three-membered ring structure, and the density of the insulating film including the cyclic siloxane structure is 1.2 g / cm ³ or less.

  As a suitable modified layer formed from such an insulating film, in the multilayer wiring in which at least one of the insulating films is an insulating film including a siloxane structure composed of at least silicon, oxygen, and carbon, the annular layer A modified layer having a smaller amount of carbon atoms and a larger amount of oxygen atoms than the inside of the insulating film including a cyclic siloxane structure is formed at least at a part of the interface between the insulating film including the siloxane structure and the metal wiring. .

The interface portion is an interface with a metal wiring. The modified layer has more oxygen atoms than carbon atoms. The modified layer is characterized in that the sum of the number of oxygen atoms and the number of nitrogen atoms is larger than the number of carbon atoms. The modified layer has a thickness of 20 nm or less. The modified layer has a density of 2.0 g / cm ³ or more.

  In the multilayer wiring, the insulating film is composed of a hard mask film in a wiring part, a wiring interlayer insulating film in a wiring part, and a via interlayer insulating film in a via plug part, the hard mask film, the wiring interlayer insulating film, Each of the via interlayer insulating films is an insulating film including a siloxane structure made of silicon, oxygen, and carbon, and the number of carbon atoms is larger than that in the insulating film. The wiring interlayer insulating film> via interlayer insulating film> hard In the multilayer wiring in the order of the mask film, the modified layer is formed at the interface with the metal in any of the hard mask film, the wiring interlayer insulating film, and the interlayer via insulating film, The composition is characterized in that the number of carbon atoms per unit volume and the number of oxygen atoms are larger than in the corresponding insulating films.

  As a suitable modified layer forming method, there are a step of forming a hard mask film on the insulating film, a step of applying a photoresist on the hard mask film and patterning a groove, and using the resist as a mask. Forming a groove in the hard mask film by dry etching; removing the photoresist by first oxygen ashing; and forming a groove in the insulating film by dry etching using the hard mask film as a mask. And a step of forming a modified layer by performing a modification treatment on the groove.

The reforming treatment is a decarbonization treatment. The decarbonization treatment is hydrogen plasma. The hydrogen plasma for performing the reforming treatment is a mixed gas of hydrogen and Ar or hydrogen and He. The plasma for performing the modification treatment is performed by applying a substrate bias. The treatment is performed in a hydrogen atmosphere. The modification treatment is performed by hydrogen annealing. An etching gas for the dry etching is a mixed gas of at least Ar, O ₂ , and CF ₄ .

  Before describing the present invention in detail, the meaning of terms in the present application will be described.

The low dielectric constant insulating film is, for example, a film (interlayer insulating film) that insulates and separates wiring materials, and a silicon oxide film (relative dielectric constant 4.2) in order to reduce capacitance between multilayer wirings that connect semiconductor elements. Refers to a material having a lower relative dielectric constant. In particular, as the porous insulating film, for example, a silicon oxide film is made porous to reduce the relative dielectric constant, an HSQ (Hydrogen Silsesquioxane) film, or SiOCH, SiOC (for example, Black) (Diamond ^™ , CORAL ^™ , Aurora ^™ ) or the like is made porous to reduce the relative dielectric constant. In order to further reduce the dielectric constant of these films, a film forming technique using a cyclic siloxane raw material is being studied.

When the cyclic siloxane is a cyclic unit in which Si—O is counted as one unit, for example, the three-membered ring means a hexagonal molecular structure composed of (SiO) ₃ . A 4-membered ring means an octagonal molecular structure composed of (SiO) ₄ . The cyclic organic siloxane means a molecular structure having a hydrocarbon group in the side chain of the cyclic siloxane structure. Examples of the hydrocarbon group include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a vinyl group. Such a cyclic siloxane raw material is effective for forming a porous insulating film, but is not necessarily limited to a porous film in the present invention. Note that the composition of the insulating film is a ratio of the number of atoms contained per unit volume.

  In the plasma vapor deposition method, for example, a gaseous raw material is continuously supplied to a reaction chamber under reduced pressure, molecules are excited by plasma energy, and the substrate is subjected to a gas phase reaction or a substrate surface reaction. This is a technique for forming a continuous film. The case where the reactivity of the monomer is improved by introducing a highly reactive side chain such as a vinyl group into the raw material molecule in advance is sometimes called a plasma polymerization method.

  Damascene wiring refers to a buried wiring formed by embedding a metal wiring in a groove of a previously formed interlayer insulating film and removing excess metal other than in the groove by, for example, CMP (Chemical Mechanical Polishing). . When forming damascene wiring with Cu, a wiring structure is generally used in which the side and outer periphery of the Cu wiring are covered with a barrier metal, and the upper surface of the Cu wiring is covered with an insulating barrier film. For damascene wiring, there is a “single damascene wiring method” in which a metal contact plug is formed in a connection hole and then a wiring groove is formed, and a “dual damascene wiring method” in which metal is embedded at a time after forming a connection hole and a wiring groove. There is.

  The metal wiring mainly contains Cu, for example. In order to improve the reliability of the metal wiring, a metal element other than Cu may be included in the member made of Cu, or a metal element other than Cu may be formed on the upper surface or side surface of Cu.

  The CMP method is a method of flattening the unevenness of the wafer surface that occurs during the multilayer wiring formation process by polishing the wafer by bringing it into contact with a polishing pad that is rotated while flowing a polishing liquid over the wafer surface. In the wiring formation by the damascene method, in particular, after a metal is buried in the wiring groove or via hole, it is used for removing a surplus metal portion and obtaining a flat wiring surface.

  The barrier metal refers to a conductive film having a barrier property that covers the side and bottom surfaces of the wiring in order to prevent the metal elements constituting the wiring from diffusing into the interlayer insulating film or the lower layer. For example, when the wiring is made of a metal element containing Cu as a main component, high wiring such as tantalum (Ta), tantalum nitride (TaN), titanium nitride (TiN), titan (WTi), tungsten carbonitride (WCN) A melting point metal, a nitride thereof, or a laminated film thereof is used.

  The insulating barrier film is formed on the upper surface of the Cu wiring and has a function of preventing Cu oxidation and Cu diffusion into the insulating film and a role as an etching stop layer during processing. For example, a SiC film, a SiCN film, a SiN film, or the like is used.

  A semiconductor substrate is a substrate on which a semiconductor device is configured. In particular, not only a substrate made on a single crystal silicon substrate but also an SOI (Silicon on Insulator) substrate, a TFT (Thin film transistor) liquid crystal manufacturing substrate, etc. Also includes a substrate.

  A hard mask refers to an insulating film that serves as a protective layer to be laminated on an interlayer insulating film when it is difficult to perform direct CMP due to a decrease in strength due to the lower dielectric constant of the interlayer insulating film.

  The passivation film is formed in the uppermost layer of the semiconductor element and has a role of protecting the semiconductor element from moisture from the outside. In the present invention, a silicon oxynitride film (SiON) formed by a plasma CVD method, a polyimide film, or the like is used.

  The PVD method may be a normal sputtering method. However, in order to improve the embedding characteristics, the film quality, and the uniformity of the film thickness within the wafer surface, for example, the long throw sputtering method, the collimated sputtering method, the ionized sputtering, etc. A sputtering method with high directivity such as a method can also be used. When sputtering an alloy, a metal film other than the main component is previously contained in the metal target at a solid solubility limit or less, so that the formed metal film can be used as an alloy film. In the present invention, it can be used mainly when forming a Cu seed layer or a barrier metal film when forming a damascene Cu wiring.

  The TDDB (Time Dependent Dielectric Breakdown) life is a technique for predicting the time until dielectric breakdown by an accelerated test. For example, when measuring the TDDB life between wirings, a comb-shaped TEG (Test Element Group) is used, and the wiring is relatively high at about 1 to 4 MV / cm between the wirings under a measurement condition of a predetermined temperature (for example, 125 ° C.). An electric field is applied and the leakage current flowing between the wirings is monitored. By measuring the time from the electric field application start time to the dielectric breakdown, the superiority and inferiority of the TDDB life can be compared.

  In the m-ELT (modified Edge Liftoff Test) test, an epoxy layer is applied to a sample, and after curing at about 120 ° C., the sample is cooled. A peeling force is applied to the end face of each layer of the sample by the residual stress of the epoxy layer generated by cooling, and the peeled portion is detected by image processing and the temperature at that time is recorded. Since the residual stress value of the epoxy layer can be determined from the temperature at the time of peeling, the stress intensity (peeling strength) applied to the test thin film is calculated assuming that the energy released during peeling is approximately equal to the elastic energy stored in the epoxy layer. It is a technique to do. It can be judged that the larger the value, the better the adhesion.

(First embodiment)
In the present invention, a low dielectric constant insulating film suitable as an interlayer insulating film is provided for an insulating film having a cyclic siloxane structure in which at least a cyclic organosiloxane raw material is supplied to a reaction chamber and an insulating film is formed by plasma vapor deposition. Thus, by forming a suitable modified layer, it is possible to achieve both a reduction in inter-wiring capacitance and ensuring insulation reliability. As a wiring structure formed according to the present invention, a wiring structure when used for multilayer wiring on a semiconductor substrate on which a semiconductor element is formed will be described in detail.

  The outline of the multilayer wiring forming method of the present embodiment is the first step of forming the via interlayer insulating film 43 and the wiring interlayer insulating film 44 each including a siloxane structure on the metal wiring 41a (FIG. 1 [1]). And a second step of forming a dual damascene groove 48 as a recess reaching the metal wiring 41a in part of the via interlayer insulating film 43 and the wiring interlayer insulating film 44 (FIG. 1 [2] to FIG. 2 [2]). Then, by performing hydrogen plasma treatment on the via interlayer insulating film 43 and the wiring interlayer insulating film 44 and the metal wiring 41a exposed in the dual damascene trench 48, the surface of the via interlayer insulating film 43 and the wiring interlayer insulating film 44 is modified. And a third step (FIG. 3 [1]) for reducing the surface of the metal wiring 41 a while forming the quality layer 49. Below, each process is demonstrated in detail.

  As shown in FIG. 1 [1], a barrier metal film 40 a, a metal wiring 41 a, and an insulating barrier film 42 are laminated on a semiconductor substrate 50 on which a semiconductor element is formed. A wiring interlayer insulating film 44 and hard mask films 45a and 45b are formed. The (first) insulating film according to claim 1 is a wiring interlayer insulating film 44, and the (second) insulating film is a via interlayer insulating film 43. Here, although the via interlayer insulating film 43 and the wiring interlayer insulating film 44 are shown separately, they may be made of the same material.

  The wiring interlayer insulating film 44 uses a raw material of a cyclic organosiloxane structure composed of a three-membered ring or a four-membered ring, and supplies it to the reaction chamber using an inert carrier gas composed of He, Ar, Ne, Xe, Rn, etc. Film formation can be performed by applying high-frequency power.

  For example, the via interlayer insulating film 43 and the wiring interlayer insulating film 44 are low dielectric constant insulating films formed by a method according to the present invention using a cyclic organosiloxane raw material composed of at least silicon, oxygen, carbon, and hydrogen. As such a raw material, for example, a cyclic organosiloxane represented by [Chemical Formula 3] or [Chemical Formula 4] is preferable. Since these raw materials contain an unsaturated hydrocarbon group in the structure, desorption of the side chain carbon of carbon in the deposition plasma can be suppressed, and a large amount of carbon can be taken into the insulating film.

  Their film thickness is preferably about 50 to 200 nm. A layer having excellent adhesion may be inserted by changing the raw material partial pressure during plasma excitation.

  The via interlayer insulating film 43 may be a SiOCH layer having a carbon component smaller than that of the wiring interlayer insulating film 44 by adding or replacing film forming conditions and mixed gas materials. The hard mask film 45a may be a SiOCH layer having a carbon component less than that of the wiring interlayer insulating film 44 by changing the film formation conditions of the wiring interlayer insulating film 44, adding a mixed gas material, or replacing them. .

  For example, as the wiring interlayer insulating film 44, an insulating film containing cyclic siloxane formed by vaporizing a raw material made of [Chemical Formula 3] and using a plasma vapor deposition method is used, and a via interlayer insulating film 43 and a hard mask film 45a are used. As an alternative, it is possible to vaporize the raw material consisting of [Chemical Formula 5], select an insulating film containing siloxane formed by plasma vapor deposition, and continuously grow these.

  By using an insulating film formed using such an unsaturated hydrocarbon and a raw material having an alkyl group having a carbon molecular weight of 3 or more, a modified layer suitable for the interface between the insulating film and the metal is formed by hydrogen plasma treatment. It becomes easy.

  The hard mask film 45b is a silicon oxide film. The hard mask 45b may be deleted as necessary.

  The metal wiring 41a is mainly composed of Cu, and in order to improve the reliability of the metal wiring, a metal element other than Cu may be included in the member made of Cu. It may be formed. The metal wiring 41a can be formed by a sputtering method using a Cu target, a CVD method, or an electrolytic plating method using a Cu film formed by these methods as an electrode. It is also effective to select and add at least one of aluminum, tin, titanium, tungsten, silver, zirconium, indium, and magnesium as the metal element other than the main component. It is also effective to insert a metal other than Cu, for example, a compound such as tungsten (W) or CoWP as an adhesion layer or between the Cu wiring and the insulating barrier film.

  The barrier metal film 40a can be formed using a sputtering method, a CVD method, an ALCVD (Atomic Layer Chemical Vapor Deposition) method, or the like. For example, refractory metals such as tantalum (Ta), tantalum nitride (TaN), titanium nitride (TiN), titan (WTi), titan nitride (WTiN), tungsten carbonitride (WCN), nitrides thereof, or the like The laminated film is used. In particular, it is preferable to use a laminated film of Ta / TaN (= upper layer / lower layer).

  The insulating barrier film 42 is made of SiN, SiCN, SiC film, etc., and has a film thickness of 20 to 50 nm, and is formed by a plasma CVD method.

Hard mask layer 45a, 45b is, SiO _2, SiON, can be used SiC, SiCN, or the like, the film thickness is preferably about 50 to 200 nm.

  Here, a wiring interlayer insulating film 44 formed using three-membered cyclic organosiloxane [Chemical Formula 3] will be described as an example. The step of forming the via interlayer insulating film 43 and the wiring interlayer insulating film 44 corresponds to the first step in the claims.

  Subsequently, as shown in FIG. 1 [2], a via hole 46 is formed by patterning using a photoresist and dry etching. Then, an organic film 51, a low-temperature oxide film 52, an ARC (Antireflective Coatings) 53, and a photoresist 54 are sequentially laminated thereon, and the photoresist 54 is patterned.

Subsequently, as shown in FIG. 2 [1], by performing dry etching using the photoresist 54 as a mask, a hard mask groove 47 as a wiring groove is transferred and formed in the hard masks 45a and 45b. At this time, the photoresist 54 can be efficiently and completely removed using O ₂ plasma ashing for the ashing process of the photoresist 54. At that time, since the wiring interlayer insulating film 44 is hardly etched, the side wall of the wiring groove to be formed later is not exposed to O ₂ plasma.

  Subsequently, as shown in FIG. 2 [2], by performing dry etching using the hard mask films 45 a and 45 b as a mask, a dual damascene groove 48, which is a wiring groove, is formed in the wiring interlayer insulating film 44.

The dry etching method of the wiring interlayer insulating film 44 at this time will be described in detail. For example, a mixture of tetrafluorocarbon (CF ₄ ), argon (Ar), and nitrogen (N ₂ ) in an arbitrary ratio can be used as an etching gas, and etching can be performed using a parallel plate type dry etching apparatus. .

Specifically, using a parallel plate type 8 inch etching apparatus, with a gas flow rate ratio Ar / N ₂ / CF ₄ / O ₂ = 300/100/25/6 sccm, the distance between substrates (GAP) = 35 mm, It can be performed at a pressure of 50 mTorr (6.65 Pa), an upper electrode frequency of 60 MHz, an upper electrode power of 1000 W, a lower electrode frequency of 13.56 MHz, and a lower electrode power of 100 W.

  At this time, by etching using the hard mask 45b as a mask, there is an advantage that the line / edge / roughness of the groove can be improved as compared with the case where the photoresist 54 is processed using the mask. The process of FIG. 1 [2]-FIG. 2 [2] above corresponds to the second process in the claims.

  Subsequently, as shown in FIG. 3 [1], a modified layer 49 is formed by performing a modification process on the side wall after etching. At this point, since the photoresist 54 for groove patterning has already been completely removed, the modification process can be performed under conditions preferable for modification.

At this time, it is preferable to perform H ₂ plasma treatment as a preferable modification treatment condition. The treatment time depends on the plasma conditions, but is preferably about 5 to 30 seconds. Excessive plasma treatment is not preferable because it promotes decarburization of the groove sidewall and groove bottom.

Specifically, the H ₂ plasma irradiation uses a parallel plate type in-situ etching apparatus, a distance between substrates (GAP) = 30 mm, a pressure of 10 mTorr (1.33 Pa), an upper electrode frequency of 60 MHz, an upper electrode power of 600 W, The treatment can be performed with only hydrogen gas at a lower electrode frequency of 13.56 MHz and a lower electrode power of 100 W for 5 seconds.

At this time, a mixed gas such as H ₂ / Ar, H ₂ / He may be used as a gas system for performing the H ₂ plasma irradiation.

Specifically, the plasma irradiation uses a parallel plate type in-situ ashing apparatus, the gas flow rate ratio is H ₂ / He = 200/300 sccm, the distance between substrates (GAP) = 40 mm, and the pressure is 20 mTorr (2.66 Pa). The treatment can be performed at an upper electrode frequency of 60 MHz, an upper electrode power of 500 W, a lower electrode frequency of 13.56 MHz, and a lower electrode power of 100 W.

Note that the apparatus for performing the H ₂ plasma treatment is not limited to the in-situ etching apparatus, but can be performed in a chamber provided in addition to a sputtering chamber for forming a barrier metal film.

  At this time, as a typical example, the modified layer 49 is formed on the side wall of the wiring interlayer insulating film 44 and the lower surface of the groove. However, the modified layer may be formed on other portions. For example, the modified layer 49 may also be formed on the via interlayer insulating film 43 at the bottom of the trench, the sidewall of the via hole 46, and the like.

  For example, when an insulating film containing cyclic siloxane is used for the via interlayer insulating film 43 and the wiring interlayer insulating film 44, the modified layer 49 of the groove sidewall, the groove lower surface, and the via sidewall has a high density of 20 nm or less. It is formed. On the other hand, when another SiOCH insulating film is used for the via interlayer insulating film 43, a modified layer 49 of 30 to 50 nm may be formed on the via sidewall and the groove lower surface.

  In this way, by forming the modified layer 49 at the connection interface with the metal wiring 41b, the adhesion between the metal wiring 41b and the wiring interlayer insulating film 44 or the via interlayer insulating film 43 can be improved. It becomes like this. This is because the adhesion of the barrier metal to the modified layer is improved compared to the structure without the modified layer. This is because in the composition of the modified layer, the number of oxygens is larger than the number of carbons, so that the adhesion with the barrier metal is improved.

  At this time, since the reforming process is performed in a state where the Cu under the via is exposed, the reduction of Cu oxide under the via and the insulating film surface (the groove side wall, the groove lower surface, the via side surface) are performed by performing the hydrogen plasma process. The reforming by decarbonization can be performed at the same time. The process shown in FIG. 3 [1] corresponds to the third process in the claims.

  Finally, as shown in FIG. 3 [2], the barrier metal film 40b and the metal wiring 41b are embedded in the dual damascene trench 48, and the surplus wiring is removed by CMP to form dual damascene wiring.

  The leakage current between wirings of the multilayer wiring thus produced, that is, the leakage current between wirings at room temperature in a TEG having a line / space = 100 nm / 100 nm and a facing length of 5 cm, was compared with that without a modified layer. It was confirmed that the leakage current between the wirings was reduced by about 3 digits.

  That is, in the cyclic SiOCH film having more carbon atoms than the oxygen number, it is essential to reduce the leakage current, and by forming a suitable modified layer according to the present invention, insulation reliability is ensured while maintaining wiring performance. become able to.

  As a result of performing composition analysis between the wirings of the multilayer wiring thus produced by TEM-EELS, when the modified layer is formed by hydrogen plasma treatment, the insulating film surface (groove side wall, groove lower surface, via side surface) It was confirmed that a modified layer of 15 nm or less was formed. It can be seen that the composition of the modified layer is more oxygen than carbon.

When a wiring interlayer insulating film is formed on a silicon substrate, a pseudo hydrogen plasma treatment is performed, and the modified layer formed on the surface is evaluated using XRR, the density of the modified layer is 2.0 g / It was confirmed that it was cm ³ or more.

  At this time, the inside of the wiring interlayer insulating film is an insulating film including a cyclic siloxane structure composed of at least silicon, oxygen, and carbon. From the result of TEM-EELS, the carbon atom weight of the insulating film is more than twice the oxygen atom weight. I know that there is. It is a feature of the present invention that the carbon content and the oxygen content are reversed in the modified layer of 15 nm or less.

  Therefore, by using the manufacturing method according to the present invention, a low dielectric constant and a high insulation reliability of the interlayer insulating film can be achieved at the same time, and by having high adhesion, the wiring performance can be improved and high speed can be achieved. In addition, a low power consumption LSI can be formed with high reliability.

(Second embodiment)
As shown in FIG. 4, MOSFET 10 is formed as a semiconductor element on semiconductor substrate 11, silicon oxide film 12 a is formed through TiN film 32, and tungsten 33 is formed as a connection plug. Furthermore, as in the first embodiment, Ta / TaN films 31a to 31e as barrier metal films, CuAl films 30a to 30e as metal wirings, SiCN films 28a to 28e as insulating barrier films, and wiring interlayer insulating films Annular SiOCH films 29a to 29e, modified layers 49a to 49e, and the like are formed to form a multilayer wiring structure. Further thereon, Ta / TaN film 31f, CuAl film 30f, SiCN films 28f and 28g, silicon oxide films 12b and 13, silicon oxynitride film 34, Ti / TiN films 35a and 35b, AlCu film 36, and the like are formed. ing.

  On the cyclic SiOCH films 29a to 29e in contact with the CuAl films 30a to 30e, modified layers 49a to 49e having a smaller amount of carbon atoms and a larger amount of oxygen atoms than the cyclic SiOCH films 29a to 29e are formed. The thickness of the modified layers 49a to 49e is controlled to about 10 to 20 nm.

  Here, the metal wiring material is mainly composed of Cu, and in order to improve the reliability of the metal wiring material, a metal element other than Cu may be included in the member made of Cu, and the metal element other than Cu may be Cu. It may be formed on the upper surface, side surface, or the like. Cu was formed by electrolytic plating using a Cu layer having a thickness of 40 nm formed by PVD as a seed layer. The Cu layer formed by the PVD method contains 1.2 atm% or less of Al inside. The SiCN films 28a to 28g as the insulating barrier films have a film thickness of 30 nm and are formed by a plasma CVD method.

  The cyclic SiOCH films 29a to 29e as the wiring interlayer insulating films are formed by the plasma vapor deposition method using the cyclic organosiloxane raw material [Chemical Formula 3], and have a relative dielectric constant of 2.4 and a thickness of Is 250 nm including the via layer portion. CuAl films 30a-30e as metal wirings and Ta / TaN films 31a-31e as barrier metal films are embedded in dual damascene trenches composed of annular SiOCH films 29a-29e as interlayer insulating films. ing. As the Ta / TaN films 31a to 31f, Ta (15 nm) / TaN (5 nm) (= upper layer / lower layer) laminated films formed by the PVD method were used.

  As the metal wiring material, a seed layer was formed by a PVD method using a Cu target containing 1.2 atm% Al, and then Cu was formed by a plating method. The height of each wiring layer was set to 170 nm for the CuAl films 30a to 30e and 300 nm for the CuAl film 30f. In addition, a hard mask film or the like may be inserted in order to protect the surface of the wiring interlayer insulating film during Cu-CMP. The hard mask film is a silicon oxide film, a silicon carbide film, a silicon carbon nitrogen film, or the like, and preferably has a higher relative dielectric constant and higher mechanical strength than the wiring interlayer insulating film. Therefore, a SiOCH film having a relative dielectric constant of about 3.0 may be used.

  Al was used for the upper layer wiring, and Ti / TiN35a, Al-Cu36, and Ti / TiN35b were formed by the PVD method. The thickness of each metal film was about 0.3 μm for Ti / TiN35a, 1.5 μm for Al—Cu36, and 0.3 μm for Ti / TiN35b. At this time, a metal was continuously embedded in the grooved via hole. The upper layer was covered with a silicon oxynitride film 34 as a passivation film.

  When the above wiring structure is used, the introduction of the modified layer makes it possible to achieve both capacitance between wirings and insulation reliability. Moreover, when a TDDB test between wirings was performed using a comb-shaped TEG with a wiring spacing of 70 nm, when an electric field of 2.5 MV / cm was applied at 125 ° C., the insulation life was 120 hours or more, and sufficient TDDB resistance was obtained. Confirmed to have.

  In addition, after forming such a device, the wafer was diced, a chip was cut out, and then mounted on a ceramic package and sealed with a resin. When the chip size was 25 mm □ and the temperature cycle test from −65 ° C. to 150 ° C. was performed up to 1000 cycles, the modified layer according to the present invention improved the adhesion, and no peeling was observed in 50 chips. On the other hand, it was confirmed that under the conditions where the modified layer was not formed, two samples were generated in which some peeling occurred from the corners of the chip because of poor adhesion.

  Although this embodiment has been described in detail with respect to the dual damascene structure, it can be similarly applied to single damascene wiring. In addition, the present invention relates to a multilayer wiring structure and a method of manufacturing the multilayer wiring that require both improved capacitance between the wiring and high insulation reliability by forming the modified layer, and any manufacturing method thereof. The present invention can be applied to a thing, and the use possibility is not limited at all. Further, while the present invention has been described in connection with some preferred embodiments, these embodiments are merely illustrative of the invention and are not meant to be limiting. I can understand.

  For example, the semiconductor manufacturing apparatus technology having a CMOS circuit, which is a field of use as the background of the invention made by the present inventor, has been described in detail. However, the present invention is not limited thereto, for example, DRAM (Dynamic Random Access Memory) ), SRAM (Static Random Access Memory), flash memory, FRAM (Ferro Electric Random Access Memory), MRAM (Magnetic Random Access Memory), semiconductor products having memory circuits such as resistance change memory, logic such as microprocessors The present invention can also be applied to a semiconductor product having a circuit, or a mixed-type semiconductor product in which they are listed simultaneously. The present invention can also be applied to a semiconductor device, an electronic circuit device, an optical circuit device, a quantum circuit device, a micromachine, or the like having an embedded alloy wiring structure at least partially.

  In addition, the formation of the modified layer according to the present invention can also be confirmed from the completion. Specifically, for the wiring interlayer film, the composition of the modified layer can be confirmed by analyzing the wiring interlayer insulating film around the metal wiring by TEM-EELS measurement. This can be confirmed by analyzing the interface between the via interlayer insulating film and the wiring interlayer insulating film.

  The formation of the modified layer according to the present invention can also be confirmed by confirming a microcomputer control program stored in the semiconductor manufacturing apparatus. For example, identification is performed based on whether or not a program configured to include a hydrogen plasma processing sequence in addition to the resist ashing sequence is included in the etching of the annular SiOCH film, or whether the program is stored. Can do. Alternatively, in the wiring formation process flow, it is possible to specify whether or not the process to be modified after the groove processing by etching is described in the process flow.

  After reading this specification, it will be apparent to persons skilled in the art that many changes and substitutions by equivalent components and techniques may be readily made, and such changes and substitutions are It is clear that it falls within the true scope and spirit. Although the present invention has been described with reference to the above embodiments, the present invention is not limited to the above embodiments. Various changes that can be understood by those skilled in the art can be made to the configuration and details of the present invention. Further, the present invention includes a combination of some or all of the configurations of the above-described embodiments as appropriate.

  The present invention can also be expressed as follows. (1) A wiring groove and a via hole are formed in an insulating film on a semiconductor substrate, and a plurality of wirings and connection plugs in which the wiring groove and the via hole are filled with metal are stacked, and at least a part of the insulating film is a first In the multilayer wiring composed of the insulating film, at least one layer of the first insulating film is an insulating film including a siloxane structure made of silicon, oxygen, and carbon, and the siloxane structure inside the first insulating film Is a modified layer having a larger number of carbon atoms than the number of silicon atoms, and a smaller number of carbon atoms and a larger number of oxygen atoms at the interface between the first insulating film and the metal than in the first insulating film In the method of forming a semiconductor device, a step of forming a hard mask film over the insulating film including the siloxane structure, and applying a photoresist over the hard mask film. A groove patterning step, a step of forming a groove in the hard mask film by dry etching using the photoresist as a mask, a step of removing the photoresist film by oxygen ashing, and a step of drying using the hard mask film as a mask. A method for forming a multilayer wiring, comprising: a step of forming a groove in an insulating film containing the siloxane structure by etching; and a step of performing a modification treatment by hydrogen plasma treatment of the groove. (2) The method for forming a multilayer wiring according to (1), wherein the hydrogen plasma treatment is a plasma treatment using a mixed gas of hydrogen and helium. (3) The method for forming a multilayer wiring according to (1), wherein the hydrogen plasma treatment is a plasma treatment using a mixed gas of hydrogen and argon. (4) The method for forming a multilayer wiring according to (1) to (3), wherein the hydrogen plasma treatment is performed by applying a substrate bias. (5) The insulating film containing the siloxane structure is formed by a plasma polymerization method using at least the raw material of [Chemical Formula 3] or [Chemical Formula 4], as described in (1) to (4) above Formation method of multilayer wiring.

It is sectional drawing (the 1) which shows 1st embodiment of this invention. It is sectional drawing (the 2) which shows 1st embodiment of this invention. It is sectional drawing (the 3) which shows 1st embodiment of this invention. It is sectional drawing which shows 2nd embodiment of this invention.

Explanation of symbols

10 MOSFET
11, 50 Semiconductor substrate 12a, 12b, 13 Silicon oxide film 28a, 28b, 28c, 28d, 28e, 28f, 28g SiCN film 29a, 29b, 29c, 29d, 29e Annular SiOCH film (insulating film)
30a, 30b, 30c, 30d, 30e, 30f CuAl film (metal wiring)
31a, 31b, 31c, 31d, 31e, 31f Ta / TaN film 32 TiN film 33 Tungsten 34 Silicon oxynitride film 35a, 35b Ti / TiN film 36 AlCu film 40a, 40b Barrier metal film 41a, 41b Metal wiring 42 Insulating barrier Film 43 Via interlayer insulating film (insulating film)
44 Wiring interlayer insulating film (insulating film)
45a, 45b Hard mask film 46 Via hole 47 Hard mask groove 48 Dual damascene groove 49, 49a, 49b, 49c, 49d, 49e Modified layer 51 Organic film 52 Low temperature oxide film 53 ARC
54 photoresist

Claims (8)

A first step of forming an insulating film containing a siloxane structure on the metal wiring;
A second step of forming a recess reaching the metal wiring in a part of the insulating film;
A third step of forming a modified layer on the surface of the insulating film and reducing the surface of the metal wiring by performing a hydrogen plasma treatment on the insulating film and the metal wiring exposed in the recess;
A method for forming a multilayer wiring, comprising: The second step includes
Forming a hard mask film on the insulating film;
Applying a photoresist on the hard mask film and forming a groove pattern in the photoresist;
Forming a groove in the hard mask film by dry etching using the photoresist as a mask;
Removing the photoresist by oxygen ashing after the dry etching;
Forming a groove as the recess in the insulating film by dry etching using the hard mask film as a mask after removing the photoresist.
The method of forming a multilayer wiring according to claim 1. In the third step, a mixed gas of hydrogen and helium is used for the hydrogen plasma treatment.
The method for forming a multilayer wiring according to claim 1 or 2, wherein: In the third step, a mixed gas of hydrogen and argon is used for the hydrogen plasma treatment.
The method for forming a multilayer wiring according to claim 1 or 2, wherein: In the third step, a bias voltage is applied to the substrate on which the insulating film and the metal wiring are formed, and the hydrogen plasma treatment is performed.
The method for forming a multilayer wiring according to any one of claims 1 to 4, wherein: In the first step,
By plasma polymerization using at least one of the raw materials represented by the following [Chemical Formula 1] and [Chemical Formula 2],

Forming the insulating film;
The method for forming a multilayer wiring according to any one of claims 1 to 5, wherein: The metal wiring is made of copper or copper alloy,
The method for forming a multilayer wiring according to any one of claims 1 to 6. The siloxane structure consists of silicon, oxygen and carbon,
The siloxane structure in the insulating film has more carbon atoms than silicon atoms,
The modified layer has fewer carbon atoms and more oxygen atoms than the insulating film,
The method for forming a multilayer wiring according to any one of claims 1 to 7, wherein:

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