Manufacturing method of semiconductor device

CROSS-REFERENCE TO RELATED APPLICATIONS

0001This application is based upon and claims the benefit of priority from the prior Japanese Patent Application No. 2009-183147 filed on Aug. 6, 2009, the entire contents of which are incorporated herein by reference.

FIELD

0002The present disclosure generally relates to a manufacturing method of a semiconductor device.

BACKGROUND

0003Miniaturization of a semiconductor integrated circuit has been advanced according to scaling rules, and a wiring has been miniaturized along with elements of MOS transistors etc. A copper wiring with lower resistance has become a mainstream replacing an aluminum wiring. Patterning copper wiring with high accuracy is difficult. Thus, a damascene wiring is employed in which a recessed portion is formed in an insulating film to bury a wiring. Copper diffusion in an insulating film deteriorates insulating characteristics. Hence, a configuration is employed in which a copper wiring is wrapped, for example, by a barrier metal film or an insulating copper diffusion preventing film. In many cases, a copper wiring layer is formed by plating. A recessed portion for a wiring is formed over an interlayer dielectric film and a barrier metal film, a plating seed layer is formed by sputtering, and a copper layer is formed over the seed layer by electrolytic plating. The barrier metal film has a function to barrier against diffusion of copper atoms from the copper layer, and is formed, for example, with TiN, Ta, Ta/TaN or Ti. The seed layer functions as an electrode for electrolytic plating and as a seed for plating film formation, and formed with copper or a copper alloy. The barrier metal film and the seed layer formed by sputtering are formed over the interlayer dielectric film as well. The plating layer is formed over the seed layer. Unnecessary metal layers over the interlayer dielectric film are removed by chemical mechanical polishing (CMP) and a SiC or SiN insulating copper diffusion preventing film is deposited so as to cover the copper wiring and the interlayer dielectric film. In this manner, sides and a lower surface of the copper wiring formed as described above are covered by the seed layer and the barrier metal film, and the upper surface is covered by an insulating copper diffusion preventing film.

0004A melting point of copper is higher than that of aluminum. Thus, copper is an element in which migration is difficult to occur. However, electro migration (EM) may not be ignored in minute wirings (thin width wiring, narrow width wiring). Stress migration (SM) occurs in a large-width wiring (wide wiring). Suppressing migration, for example, by adding another element to copper to make a copper alloy has been studied.

0005According to Japanese Laid-open Patent No. H10-209156, when Cu—Ta, to which Ta of 0.5 wt. % is added, is heat-treated in an H reductive atmosphere, Ta is precipitated at the Cu grain boundary and suppresses the grain boundary diffusion. Accordingly, a void is hardly created, and the EM resistance is enhanced.

0006According to WO 2004/53971, an example is introduced in which a countermeasure for EM resistance and SM resistance is applied. In the example, additional elements in the copper alloy seed layer is diffused into a copper layer by heat treatment to form a copper alloy after forming a copper wiring film by using a copper alloy (Cu—Sn etc.) seed layer. When a copper alloy seed layer in which the additional elements that remain in crystal grains increases resistivity of a copper alloy wiring is formed by sputtering, the copper alloy seed layer deposited at a bottom of the wiring trench becomes thinner in a thin-width wiring compared with that in a large-width wiring. As a result, resistivity of the Cu wiring becomes low and resistivity of the Cu wirings varies depending on the wiring width. According to the embodiment, a method to suppress Cu migration is proposed. In the method, for example, additional elements such as Ti, Zn, Hf, Cr, Co, Al, Sn, Ni, Mg, and Ag are diffused from above the copper wiring film into the copper layer to Cu grain boundary and the vicinity that become SM and EM diffusion routes, thereby suppressing Cu migration. Oxidization of copper may be suppressed when stable metal oxide is formed by the additional elements even if the copper layer is exposed to oxidized species.

0007According to Japanese Laid-open Patent No. 2006-80234, a Cu alloy seed layer is formed such that the film thickness of sidewall portions and the film thickness of the bottom portions of the wiring trenches for a thin-width wiring and for a large-width wiring are substantially the same. A Cu layer is deposited over the seed layer by electroplating and annealed to form a wiring in which a ratio of an additional element decreases as the wiring trench becomes wider. The seed layer is formed, for example, by sputtering or CVD. However, the disclosure does not describe a specific film formation parameter that allows to control and adjust formation of a seed layer with substantially uniform film thickness. The additional element of the seed layer is assumed to be diffused typically in the copper layer. However, the disclosure does not describe how the additional element of the seed layer may be diffused typically in the copper layer.

0008In order to suppress a parasitic capacitance of a wiring, the interlayer dielectric film is preferably formed with materials with a low dielectric constant. For example, as a CVD low dielectric constant film, the following materials have been used. The materials include hydrogenated silicon oxycarbide (SiCOH) such as Aurora™ of ASM International NV, Black Diamond™ of Applied Materials, and CORAL™ of Novellus Systems and an organic coating film, SilK™, and a porous material such as porous silica. These materials have properties that easily permeate water content. When water content reaches a barrier metal film, oxidization etc. may be caused, thereby the barrier metal layer may be altered, and the barrier property may be lost.

0009According to M. Haneda et al., “Self-Restored Barrier using Cu—Mn alloy”, AMC 2007, pp.27-28 and H. Kudo et al., “Further Enhancement of Electro-migration Resistance by Combination of Self-aligned Barrier and Copper Wiring Encapsulation Techniques for 32-nm Nodes and Beyond”, IITC 2008, pp. 117-119, the inventors reported that a dual damascene structure in 45 nm generation is used to fabricate a semiconductor device to which a Cu—Mn alloy seed layer is applied over a Ta barrier metal film, and even when the barrier metal film is thin, the barrier property is self-restored by the additional element Mn of the alloy. Hence, reliability of the copper wiring is improved. According to M. Haneda and H. Kudo, an element mapping in the wiring of the self-restored barrier layer that is formed when heat treatment is applied to a sample of the wiring structure for 30 minutes at 350 degrees Celsius may be referred to.

0000A self-restored response of the barrier by Mn occurs when heat of 200 to 400 degree Celsius is applied, and heat that is applied in a subsequent manufacturing process, for example, the temperature when forming a cap film by CVD after forming a conductive unit may be utilized. Accordingly, the self-restored barrier layer is easily formed without applying heat separately.

0010A. Isobayashi et al., “Thermally Robust Cu Interconnects with Cu—Ag Alloy for sub 45 nm Node”, IEEE IEDM 04, 2004, pp.953-956, describes forming a copper layer using a Cu—Ag alloy obtained by doping Ag to Cu which suppresses generation of voids due to stress migration and improves reliability.

SUMMARY

0011According to aspects of embodiments, a semiconductor device manufacturing method includes forming an interlayer dielectric film above a semiconductor substrate; forming a first wiring trench with a first width and a second wiring trench with a second width that is larger than the first width in the interlayer dielectric film; forming a first seed layer that includes a first additional element in the first wiring trench and the second wiring trench; forming a first copper layer over the first seed layer; removing the first copper layer and the first seed layer in the second wiring trench while leaving the first copper layer and the first seed layer in the first wiring trench; forming a second seed layer in the second wiring trench after removing the first copper layer and the first seed layer in the second wiring trench; and forming a second copper layer over the second seed layer.

0012The object and advantages of the invention will be realized and attained by means of the elements and combinations particularly pointed out in the claims.

0013It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are not restrictive of the invention, as claimed.

BRIEF DESCRIPTION OF DRAWINGS

0014<figref idref="DRAWINGS">FIGS. 1A to 1E</figref> are sectional views schematically illustrating processes for plating a damascene copper wiring layer in wiring trenches with different widths;

0015<figref idref="DRAWINGS">FIGS. 2A to 2B</figref> and <figref idref="DRAWINGS">FIGS. 2D to 2G</figref> are sectional views illustrating processes of a method to manufacture a semiconductor device according to an embodiment;

0016<figref idref="DRAWINGS">FIG. 2C</figref> is a graph illustrating change in thickness of a copper layer with time;

0017<figref idref="DRAWINGS">FIGS. 3A to 33</figref> are sectional views illustrating processes before forming a copper wiring in the method to manufacture the semiconductor device according to the embodiment;

0018<figref idref="DRAWINGS">FIGS. 4A to 4S</figref> are sectional views illustrating the processes to form the copper wiring in the method to manufacture the semiconductor device according to the embodiment; and

0019<figref idref="DRAWINGS">FIG. 5</figref> is a sectional view schematically illustrating an enlarged configuration of a dual damascene wiring in the method to manufacture the semiconductor device according to the embodiment.

DESCRIPTION OF EMBODIMENTS

0020Preferred embodiments will be explained with reference to accompanying drawings.

0021In creating a damascene wiring, a wiring trench is formed in an insulating film. A depth of the wiring trench is substantially constant regardless of a wiring width, and an area of a side wall per unit length of a long wiring is substantially constant regardless of a wiring width. A bottom area increases as a wiring width increases. Accordingly, regardless of whether an alloy seed layer is formed by sputtering with directivity process, or Chemical Vapor Deposition (CVD) process that is conformal, influence of a side wall is expected to be larger in a thin-width wiring compared with that of a large-width wiring.

0022An amount of the seed layer over the bottom is proportional to a wiring width when the seed layer is formed in a wiring trench with a substantially uniform thickness by the CVD that is conformal film formation. Amount of the seed layer over the side wall is substantially constant regardless of a wiring width. When an additional element in the seed layer over the side wall is redistributed to the entire wiring; a concentration of the additional element of the wiring in the thin-width wiring trench becomes higher than that in the large-width wiring trench.

0023Sputtering is a film formation method with directivity, and basically, a deposition amount over a flat surface per area may be substantially constant. When a barrier metal film and a seed layer are formed by sputtering, materials reaching a trench opening with a certain angular distribution deposit and distribute over sides and a bottom of the trench. The amount of materials reaching is considered to be proportional to an area of the opening (in other words, a wiring width). In the thin-width wiring trench, incidence angles to the sides and the bottom may be limited depending on the opening width. Accordingly, the seed layer formed in the thin-width wiring trench is thinner than the seed layer formed in the large-width wiring.

0024The inventors formed a copper wiring evaluation sample in the following manner. A Cu alloy seed layer is formed by sputtering, and a copper layer is formed thereover by electrolytic plating, heat treatment and polishing are applied, and a cap layer is formed. Resistivity of the sample is measured and a difference when no additional element is applied to the seed layer is reviewed. It is revealed that when a width of a wiring is larger, increase rate of resistance becomes higher.

0025It is assumed that a concentration of elements added to the seed layer is higher in the large-width wiring compared with that in the thin-width wiring. Based on the above described phenomenon, The phenomenon may not be understood considering that the additional elements simply diffuse over the entire wiring.

0026It is revealed that in a copper wiring obtained by forming a Ta barrier metal film in the wiring trench, a Cu—Mn alloy seed layer thereover and by plating the copper layer, even if the Ta barrier metal in the sides are oxidized by moisture content, the barrier function is recovered when the additional element Mn bonds to oxide. The above described consumption of the additional element occurs preferentially at a side where oxidization of the barrier film is likely to occur, in particular, a side with a minute wiring. Considering the additional element is consumed at the side wall, influence of the side wall is larger for the thinner-width wiring. Thus, when an amount of the element that enables an increase in EM resistivity in the thin-width wiring is added to the seed layer, thereby satisfying requirements of the thin-width wiring, resistivity increases because a consumption amount at the side walls are relatively small in the large-width wiring. Thus, it may be understood that the concentration of the additional element becomes high thereby increasing the resistivity.

0027The above described phenomenon is considered to be unavoidable when trenches with different widths for a thin-width wiring and a large-width wiring are formed with common processes and a barrier metal film and a seed alloy layer are deposited to form a copper layer and unnecessary portions are removed to form a wiring. However, an increase in resistivity of the wiring needs to be avoided in anyway from a viewpoint of achieving the performance of the device. In the first place, electromigration that becomes a problem for a thin-width wiring is not a big problem in a large-width wiring. In the large-width wiring, stress migration may be a problem.

0028The above described problem may be solved if types and concentration of additional elements may be freely selected for the thin-width wiring and the large-width wiring. However, manufacturing the thin-width wiring and the large-width wiring in completely different processes increases the number of processes and may thereby reduce a yield. Countermeasures are reviewed in which at least, a recessed portion for burying a wiring is manufactured by common processes and additional processes cause less damage, thereby suppressing yield reduction. Copper electroplating liquid is obtained by adding additives to cupric sulfate solution, for example, chlorine ions, and three types of organic additives; an accelerator to promote plating, a suppressor to suppress copper deposition, and a leveler to suppress copper deposition and provide smoothness. By adding additives, deposition and growth of copper plating are controlled, thereby enabling the filling of a minute via or a wiring trench. In order to perform electroplating, a seed layer that becomes an electrode needs to be formed beforehand. <figref idref="DRAWINGS">FIGS. 1A to 1D</figref> are sectional views schematically illustrating processes for plating a copper wiring layer in wiring trenches.

0029As illustrated in <figref idref="DRAWINGS">FIG. 1A</figref>, a second insulating film <b>53</b> that functions as an interlayer dielectric film is laminated above a base substrate <b>51</b> that includes a first insulating film <b>52</b> functioning as an insulating copper diffusion preventing film or an etch stopper. Wiring trenches TR<b>1</b>, TR<b>2</b>, and TR<b>3</b> (at times, collectively called TR) are etched over the second insulating film <b>53</b> using a photoresist pattern etc. as an etching mask and the etching mask is removed. A ratio of a height to a width of the trench TR<b>1</b> (aspect ratio) is assumed to be 1, that of the trench TR<b>2</b> is assumed to be 0.5, and that of the trench TR<b>3</b> is assumed to be 0.25.

0030As illustrated in <figref idref="DRAWINGS">FIG. 1B</figref>, for example, a Ta barrier metal film <b>54</b> and a Cu—Mn alloy seed layer <b>55</b> are deposited by sputtering from above the trench so as to cover an inner surface of the trenches TR. The barrier metal film <b>54</b> and the seed layer <b>55</b> are formed over an upper surface of the second insulating film <b>53</b>. The barrier metal film <b>54</b> functions to reduce, if not prevent diffusion of copper and elements other than Ta. For example, the barrier metal film <b>54</b> is formed by a metal film of TaN, TiN, or Ti or by laminating the metal films. The seed layer <b>55</b> becomes an electrode for applying current when plating copper and is formed with copper or a copper alloy. In the case of the copper alloy, for example, an additional element of Mn may be selected from elements that have a function to suppress electromigration in copper wirings.

0031As illustrated in <figref idref="DRAWINGS">FIG. 1C</figref>, a copper layer <b>56</b> is plated over the seed layer <b>55</b> by electrolytic plating. At the beginning, a plating layer is (conformally) grown over the seed layer at the bottom of and the sides of the trench with a substantially uniform thickness. When an interval between plated copper layers <b>56</b> that are grown over opposing sidewalls in the trench become narrower than a certain width, a bottom-up growth in which a plating layer is rapidly grown from a bottom of the remaining narrow trench toward the upper part may be caused. In <figref idref="DRAWINGS">FIG. 1C</figref>, a bottom up growth occurs in the trench TR<b>1</b>.

0032As illustrated in <figref idref="DRAWINGS">FIG. 1D</figref>, when electroplating is further developed, the copper layer above the upper part of the wiring is further grown due to influence of the accelerator and thereby overplating occurs in which the film is relatively swollen. In the trench TR<b>2</b>, a width between plated copper layers over opposing side walls becomes narrower than a certain width before the trench is buried; thereby a bottom-up growth occurs. In the trench TR<b>3</b>, distances between plated copper layer over sidewalls are away from each other, thus conformal growth continues, and no bottom-up growth occurs until the trench is filled. The bottom-up growth and overplating are controlled by adjusting three types of additives to plating liquid.

0033As illustrated in <figref idref="DRAWINGS">FIG. 1E</figref>, a trench depth is assumed to be H, and a trench width is assumed to be W. When a thickness of a composite wiring layer that includes a barrier metal film, a seed layer, and a plated copper layer is substantially uniform d, in order for copper layers over both of the side walls to contact before the copper layer over the bottom fills the trench depth H ; the following expression may be satisfied: d<H and 2d=W, d=W/2. In other words, H>d=W/2 and the trench depth H is desired to be larger than a half of the trench width W. An aspect ratio of 0.5 may be a critical point whether a bottom-up growth occurs or not before the trench is filled.

0034Hence, a wiring with an aspect ratio of 0.5 or less is called a large-width wiring while a wiring with an aspect ratio of 0.5 or more is called a thin-width wiring.

0035<figref idref="DRAWINGS">FIGS. 2A to 2B</figref> and <figref idref="DRAWINGS">FIGS. 2D to 2G</figref> are sectional views illustrating major processes to manufacture a semiconductor device according to a basic embodiment. Two types of thin-width wirings and one type of a large-width wiring are illustrated.

0036In <figref idref="DRAWINGS">FIG. 2A</figref>, the first insulating film <b>52</b> and the second insulating film <b>53</b> are laminated over the base substrate <b>51</b> and the wiring trenches TR<b>1</b>, TR<b>2</b>, and TR<b>3</b> are formed over the second insulating film <b>53</b>. The trenches TR<b>1</b> and TR<b>2</b> are assumed to be thin-width trenches while the trench TR<b>3</b> is assumed to be a large-width trench. The barrier metal film <b>54</b> and the seed layer <b>55</b> are formed by covering an inner surface of the trench TR. The copper layer <b>56</b> is plated over the seed layer <b>55</b>. In the state of <figref idref="DRAWINGS">FIG. 2A</figref>, filling the thin-width trenches TR<b>1</b> and TR<b>2</b> is completed. Overplating occurs in which the film is relatively swollen after filling the trenches because the copper layer of the upper part of the wiring is further grown due to influence of the plating accelerator. A conformal growth continues in the large width trench TR<b>3</b>. The seed layer <b>55</b> is a copper or copper alloy layer. Thus, the seed layer <b>55</b> and the copper layer <b>56</b> are collectively called a copper layer <b>57</b>.

0037<figref idref="DRAWINGS">FIG. 2B</figref> illustrates a state in which overplating is further developed. A thickness of the copper layer <b>57</b> above the second insulating layer <b>53</b> is assumed to be T<b>1</b>, while a thickness of the copper layer <b>57</b> in the large-width trench is assumed to be T<b>2</b> and substantially minimum and maximum values are indicated by subscripts, min and max. A thickness of the copper layer <b>57</b> over the trench TR<b>1</b> is T<b>1</b> max while a thickness of the copper layer <b>57</b> over the trench TR<b>2</b> is assumed to be T<b>1</b> min, and a thickness of the copper layer from the bottom in the large-width trench TR<b>3</b> is assumed to be T<b>2</b> max.

0038<figref idref="DRAWINGS">FIG. 2C</figref> is a graph illustrating change in thickness of the copper layer with time. The horizontal axis indicates time t, while the vertical axis indicates a thickness of the copper layer from the bottom of the trench. The solid line indicates a thickness of the copper layer <b>57</b> in the thin-width wiring, while the dashed line indicates a thickness of the copper layer in the large-width wiring trench. The trench depth H is indicated by the dashed line. When the thickness of the copper layer reaches the trench depth H, filling the trench is completed. The thickness of the copper layer <b>57</b> in the thin-width trench higher than the trench depth H indicates a thickness of the copper layer formed relatively swollen due to influence of overplating. A substantially minimum thickness T<b>1</b> min of the copper layer <b>57</b> over the thin-width trench and a substantially maximum thickness T<b>2</b> max of the copper layer <b>57</b> in the large-width trench will be described. After completing filling the thin-width trench, swelling due to influence of overplating occurs and the substantially minimum swelling thickness T<b>1</b> min increases as well, thereby the T<b>1</b> min exceeds T<b>2</b> max. The plating completes at a state of T<b>1</b> min−T<b>2</b> max>=0. Hereinafter, the seed layer <b>55</b> is called a first seed layer and the copper layer <b>56</b> is called a first copper layer.

0039As illustrated in <figref idref="DRAWINGS">FIG. 2D</figref>, the substrate is immersed in etching liquid to etch the copper layer <b>57</b>. The etching progresses substantially uniformly. The copper layer <b>57</b> (the first copper layer <b>56</b> and the first seed layer <b>55</b>) in the large-width trench is substantially completely removed (etched for the amount of T<b>2</b> max). In this state, even if the thickness of the copper layer <b>57</b> over the thin-width trench decreases for the amount of T<b>2</b>max, T<b>1</b> min−T<b>2</b> max>=0. Thus, the surface is substantially equal to or higher than the trench and a state in which the trench is filled is maintained.

0040<figref idref="DRAWINGS">FIG. 2E</figref> illustrates a state in which the thin-width trench is filled with the copper layer <b>57</b>, and the copper layer <b>57</b> (in other words, the first copper layer <b>56</b> and the first seed layer <b>55</b>) in the large-width trench is completely removed. The barrier metal layer <b>54</b> remains.

0041As illustrated in <figref idref="DRAWINGS">FIG. 2F</figref>, a copper alloy second seed layer <b>58</b> is newly deposited with the barrier metal layer <b>54</b> being exposed in the large-width trench, and a second copper layer <b>59</b> is plated thereover. The second seed layer <b>58</b> is a layer different from the first seed layer <b>55</b> and the composition may be freely selected. A copper alloy to which an appropriate amount of elements suitable for the large-width wiring is added or pure copper may be used for the second seed layer <b>58</b>. The second seed layer <b>58</b> and the second copper layer <b>59</b> are collectively called a copper layer <b>60</b>.

0042As illustrated in <figref idref="DRAWINGS">FIG. 2G</figref>, after completing plating by filling the large-width trench with the second copper layer <b>59</b>, heat treatment is applied for crystal stabilization and unnecessary metal layers over the interlayer dielectric film <b>53</b> are removed by chemical mechanical polishing (CMP). A conventional method may be used for heat treatment for crystal stabilization. In the large-width wiring trench TR<b>3</b>, the seed layer <b>58</b> the composition of which is different from the compositions in the thin-width wiring trenches TR<b>1</b> and TR<b>2</b> is filled. The additional element sufficiently diffuses in the copper layer when heat of 300 degree Celsius or more is applied to the additional element in the seed layer at a later process, thereby the copper layer <b>57</b> of the thin-width wiring and the copper layer <b>60</b> of the large-width wiring have different compositions. Accordingly, the copper wirings with different additional elements may be formed in the thin-width wiring and the large-width wiring.

0043Diffusion of the additional elements in the seed layers <b>55</b> and <b>58</b> may be performed by utilizing heat at a later process or by adding a separate heat treatment process. For example, utilizing heat application in the later process may include a temperature when forming an insulating copper diffusion preventing film (an upper cap layer, or an etch stopper film ES<b>2</b> described later in <figref idref="DRAWINGS">FIG. 43</figref>), for example, of 400 degree Celsius.

0044In diffusion of additional elements in the seed layers <b>55</b> and <b>58</b>, for example, an additional element such as Mn reacts, for instance, at an interface of an oxidized barrier metal layer <b>54</b> and an interface of an oxidized upper cap film to form a new chemical compounds layer with a diffusion prevention function, the thin-width wiring copper layer <b>57</b> and the large-width wiring copper layer <b>60</b> have different barrier film compositions respectively. Accordingly, copper wirings that include barrier film composition layers with different metal elements or compositions for the thin-width wiring and the large-width wiring may be formed.

0045Controlling diffusion of the additional elements of the seed layers <b>55</b> and <b>58</b> typically to the copper layer by using the additional elements that react with the oxidized barrier metal film within a certain performance allowable range (for example, wiring resistance and reliability) determined by a user may be achieved by the following manner. That is forming the barrier metal layer <b>54</b> with a film thickness so as not to be lost by oxidization from the insulating film <b>53</b> or by using an insulating film <b>53</b> that is less likely to cause oxidization of the barrier metal layer.

0046Controlling diffusion of the additional elements of the seed layers <b>55</b> and <b>58</b> to the interface of the barrier metal layer <b>54</b> and the copper layer <b>57</b> (or barrier metal layer <b>54</b> and a copper layer <b>60</b>) may be achieved by the following manner. That is to increase an amount of the additional elements by increasing a target concentration or forming the barrier metal layer <b>54</b> with a thin film, or using an insulating film <b>53</b> that easily cause oxidization of the barrier metal layer <b>54</b>.

0047Hereinafter, a method to manufacture a semiconductor device according to a more specific embodiment will be described.

0048As illustrated in <figref idref="DRAWINGS">FIG. 3A</figref>, for example, a hard mask layer obtained by laminating an oxide film and a nitride film is deposited over a surface of a silicon substrate Sub by CVD and a photo resist mask PR<b>1</b> that defines a trench for isolating an element is formed over the surface of the hard mask layer. A hard mask HM is formed by etching the hard mask layer using the photoresist mask PR<b>1</b> as a mask. The photoresist mask PR<b>1</b> is removed as required and the silicon substrate Sub is etched using the hard mask HM as an etching mask to form an element isolation trench.

0049As illustrated in <figref idref="DRAWINGS">FIG. 3B</figref>, after thermally oxidizing a surface of the formed trench, a silicon oxide film IL is deposited by high density plasma (HDP) CVD. The silicon oxide film IL fills the element isolation trench.

0050As illustrated in <figref idref="DRAWINGS">FIG. 3C</figref>, the oxide silicon layer IL above the hard mask HM is removed by chemical mechanical polishing (CMP). After that, the hard mask HM is removed as well. Accordingly, a shallow trench isolation type element isolation region STI is formed. The element isolation region STI defines an active region. A through oxide film is formed over a surface of the active region and a p-type well PW and an n-type well NW are formed by dividing a transistor region into an n channel (NMOS) transistor region and a p-channel (PMOS) transistor region by a resist mask and by applying ion implantation. After that, the through oxide film is removed. As an example, an nMOS transistor that operates at 1.2 V will be described below.

0051As illustrated in <figref idref="DRAWINGS">FIG. 3D</figref>, the surface of the active region is thermally oxidized to form a gate oxide film Gox with a thickness of 1.3 mm. A non-doped polycrystalline silicon layer PS is deposited over the gate oxide film Gox with a thickness of about 100 nm CVD.

0052As illustrated in <figref idref="DRAWINGS">FIG. 3E</figref>, a photoresist pattern PR<b>2</b> is formed over the polycrystalline silicon layer PS, and the polycrystalline silicon layer PS is patterned by anisotropic dry-etching of reactive ion etching. A gate electrode G is formed over each of the active regions. The photoresist pattern PR<b>2</b> is removed.

0053As illustrated in <figref idref="DRAWINGS">FIG. 3F</figref>, ion implantation for forming an extension region is carried out using the gate electrode G as a mask. An n-MOS transistor region and a p-MOS transistor region are separated by a resist mask, and for example, ion implantation of As+ to the n-MOS region and B+ to the p-MOS region are carried out. Extension regions Ex are formed at both sides of the gate electrode G.

0054As illustrated in <figref idref="DRAWINGS">FIG. 3G</figref>, an oxide silicon film with a thickness of <b>10</b> nm is deposited over a whole surface of the substrate by CVD, the oxide silicon film over a flat surface is removed by anisotropic dry etching, and sidewall spacers SW are left over side walls of the gate electrode. A low resistance source drain diffusion layer Dif is ion implanted using the gate electrode G and sidewall spacers SW as masks. The nMOS transistor region and the pMOS transistor region are separated by the resist mask. For example, ion implantation of P+ to the n-MOS region, and B+ to the p-MOS region are carried out. The ion implanted impurities are activated, for example, by applying rapid thermal annealing.

0055As illustrated in <figref idref="DRAWINGS">FIG. 3H</figref>, a lower interlayer insulating film LIL is formed by depositing an oxide silicon film with a thickness of 180 nm as a lower insulating film LDL and a SiC film with a thickness of 30 nm as a cap layer CL by CVD over the silicon substrate by covering the gate electrode G. A contact hole CH is etched over the lower interlayer insulating film LIL using the photoresist mask PR<b>3</b> as an etching mask. A low resistance source drain diffusion layer Dif is exposed at a bottom of the contact hole CH. The photoresist mask PR<b>3</b> is removed.

0056As illustrated in <figref idref="DRAWINGS">FIG. 31</figref>, a TiN layer with a thickness of 3 nm is formed by atomic layer deposition (ALD) and a W layer with a thickness of 180 nm is deposited by CVD to fill the contact hole CH. Unnecessary metal layers over the lower interlayer insulating film LIL are removed by CMP and a conductive plug PL is left in the contact hole CH.

0057<figref idref="DRAWINGS">FIG. 3J</figref> illustrates a lower structure US formed as described above. The processes described above are known and may be replaced with other known processes and structures. In the description below, the lower structure US is simplified.

0058An embodiment to form a damascene wiring over a lower structure will be described below. A single damascene first copper line is formed over a W plug and a dual damascene second copper wiring is formed thereover. Both the first copper wiring and the second copper wiring include a thin-width wiring and a large-width wiring respectively.

0059As illustrated in <figref idref="DRAWINGS">FIG. 4A</figref>, an insulating film DL<b>1</b> is formed over a lower structure US that includes a cap layer CL. For example, a SiOC film with a thickness of 220 nm is deposited by CVD. As an insulating film, a SiO film made of tetraethoxysilane (TEOS) or silane gas and formed by plasma-promoted (PE) CVD or thermal CVD may be used. In order to reduce a parasitic capacitance of a wiring, it is desirable to use an insulating film with dielectric constant lower than that of the oxide silicon. As an inorganic film with a low dielectric constant, for example, a SiOC film made of organosilane-base material, a film made of organosiloxane-base material, a film made of hydrogenerated siloxane-base material, and a nano-clustering silica film made of a porous silica base material may be used. An etch stopper layer ES<b>1</b> is formed over the insulating film DL<b>1</b>. For example, a SiC film with a thickness of 30 nm is deposited at temperature of 300 to 450 degree Celsius, for example, 400 degree Celsius by plasma-enhanced chemical vapor deposition (PECVD) using tetramethylsilane as a material. As an etch stopper layer, for example, a SiC film and a SiN film deposited by PECVD may be used.

0060A first inter-layer dielectric film ILD<b>1</b> is made up of a lamination of the insulating film DL<b>1</b> and the etch stopper layer ES<b>1</b>. The highest layer in the lower structure is a SiC cap layer CL and a W plug locally penetrates. As an insulating film with low dielectric constant, for example, an organic coating film of SiLK or a porous silica film may be used instead of the SiOC film.

0061As illustrated in <figref idref="DRAWINGS">FIG. 4B</figref>, a wiring trench is etched over the first inter-layer dielectric film ILD<b>1</b> (ES<b>1</b>+DL<b>1</b>) using a photoresist mask PR<b>4</b> as an etching mask. A conductive plug is exposed at a bottom of the wiring trench. The left wiring trench is a thin-width trench. The center and right wiring trenches are large-width trenches. The width of the wiring trench is for example, 50 nm to 30,000 nm. The photoresist mask PR<b>4</b> is removed.

0062As illustrated in <figref idref="DRAWINGS">FIG. 4C</figref>, a Ta film with a thickness of 5 nm is formed, for example, by sputtering (PVD, physical vapor deposition) as a barrier metal film <b>11</b> so as to cover an inner wall of the wiring trench. For example, the film is formed by sputtering using a Ta target and discharge gas, Ar or N₂by applying power of 160 mW/mm²to 640 mW/mm²to the target. Instead of the Ta film, a laminated layer of Ta/TaN or a Ti film may be used. The film thickness may be 1 nm to 15 nm. ALD may be used instead of PVD.

0063A Cu—Mn alloy film as a seed layer <b>12</b> for plating is formed over the barrier metal film <b>11</b>, for example, by a thickness of 35 nm PVD. For example, sputtering is performed by using a Cu—Mn alloy target and by applying power of DC 10 kW in 10⁻¹Pa Ar atmosphere. The additional element Mn of the copper alloy film is for suppressing electromigration in the thin-width wiring. Besides the Cu—Mn alloy, a Cu alloy obtained by mixing Cu with one of Al, Ti, or Sn, or by mixing Cu with two or more of Mn, Al, Ti, and Sn may be used.

0064As illustrated in <figref idref="DRAWINGS">FIG. 4D</figref>, a copper layer <b>13</b> is plated over the seed layer <b>12</b> by electrolytic plating. For example, a set of copper sulfate basic bath and additives of VIA FORM (™) NEXT available from Enthone Inc. may be used. Electroplating is applied at current density of 13.5 mA/cm2 for 2.5 seconds and at current density of 8.3 mA/cm2 for 20 seconds, using plating liquid that includes an accelerator of 6 mL/L to 12 mL/L, for example, 10 mL/L, a suppressor of 1 mL/L to 5 mL/L, for example, 2 mL/L, and a leveler of 1 mL/L to 5 mL/L, for example, 3 mL/L. The L means liter. A plating thickness in blanket film conversion is about 75 nm.

0065A film thickness T<b>1</b> min above the first inter-layer dielectric film ILD<b>1</b> in the thin-width wiring trench is about 180 nm, and a film thickness T<b>2</b> max of the copper layer from the bottom of the large width wiring trench is about 110 nm. In the large-width wiring trench, more than a half of the trench depth 250 nm is not filled and the film thickness T<b>2</b> max of the copper layer from the bottom of the large width wiring trench is smaller than the film thickness T<b>1</b> min of the copper layer above the inter layer insulating film in the thin-width wiring trench.

0066As plating liquid, other general-purpose copper plating liquid may be used. For example, VIA FORM (™) of Enthone Inc., Via Form series of VIA FORM EXTREME(™), and ULTRAFILL (™) series of Rohm and Haas company may be used.

0067As illustrated in <figref idref="DRAWINGS">FIG. 4E</figref>, a plated copper layer <b>13</b> in the large-width wiring trench and a seed layer <b>12</b> under the plated copper layer <b>13</b> are removed by etching. For example, Cu and the Cu alloy are selectively removed for a thickness of 110 nm for 3.5 seconds using dilute solution of H₂SO₄:H₂O₂:pure water=2:15:125 (volume ratio). Wet etching may be applied for 2 seconds using dilute solution of HF:H2O₂:pure water=1:1:200 (volume ratio). The plated copper layer and the copper alloy seed layer under the plated copper layer in the large-width wiring trench are removed. The copper layer in the thin-width wiring trench region is wet-etched; however, the thin-width wiring trench is not exposed.

0068As illustrated in <figref idref="DRAWINGS">FIG. 4F</figref>, a second seed layer <b>14</b> is deposited. The second seed layer <b>14</b> is, for example, a Cu—Al alloy film with a thickness of 35 nm, and formed by sputtering using a Cu—Al target by applying power of DC 10 kW in 10⁻¹Pa Ar atmosphere. The second seed layer <b>14</b> is a seed layer for plating a copper wiring in the large-width wiring trench and preferably formed by pure copper or a copper alloy with a function to suppress an increase in wiring resistance while suppressing stress migration. Additional elements for the copper alloy may be one or two or more of Ti, Al, Ag, Sn, or Mn and the additional elements that are different from the additional elements of the first seed layer may be selected. Elements that may satisfy performance desired for the thin-width wiring and the large-width wiring may be added independently from each other with appropriate concentrations. The same elements with different concentrations may be added to the thin-width wiring and the large-width wiring.

0069As illustrated in <figref idref="DRAWINGS">FIG. 4G</figref>, copper plating for forming a large-width wiring is applied over the semiconductor substrate where the thin-width wiring trench is filled to form a second copper layer <b>15</b>. For example, a copper layer with a thickness of 250 nm to 10,000 nm is electroplated at current density of 3 mA/cm²to 55 mA/cm², using copper sulfide base solution that includes an accelerator of 3 mL/L to 15 mL/L, for example, 6 mL/L, a suppressor of 1 mL/L to 10 mL/L, for example, 2 mL/L, and a leveler of 1 mL/L to 10 mL/L, for example, 2.5 mL/L. Bottom-up growth and overplating are not required and concentrations of additives are different from those of the plating liquid for the first copper layer <b>13</b>. In the example, concentration of the accelerator and leveler for the second copper plating are selected to be lower than those for the first copper plating.

0070As illustrated in <figref idref="DRAWINGS">FIG. 4H</figref>, heat treatment is applied for crystal stabilization of the formed copper layer. A method substantially the same as a conventional method may be used for the heat treatment. For example, heat treatment may be applied for 90 seconds at 25 degree Celsius in N₂/H₂atmosphere.

0071As illustrated in <figref idref="DRAWINGS">FIG. 41</figref>, CMP is applied to remove unnecessary metal layers over the interlayer dielectric film. A first copper wiring that is typically buried in the wiring trench is formed.

0072Sufficient heat application over 300 degree Celsius at a subsequent process diffuses the additional element of the first seed layer <b>12</b>, for example, Mn and the additional element of the second seed layer, for example, Al toward an interface of the barrier metal or the copper wiring. As described above, diffusion of additional elements of the seed layers may be performed by applying heat treatment separately.

0073As illustrated in <figref idref="DRAWINGS">FIG. 43</figref>, a second etch stopper layer ES<b>2</b>, a second low dielectric constant film DL<b>2</b>, and a third etch stopper layer ES<b>3</b> are formed over the first etch stopper layer ES<b>1</b> by covering the first copper wiring. The second etch stopper layer ES<b>2</b> functions as an insulating copper diffusion preventing film (cap layer) for the first copper wiring. For example, a SiC film with a thickness of 30 nm is deposited at 400 degree Celsius, for example, by plasma CVD. Over the SiC film, a SiOC film with a thickness of 300 nm is deposited at the substrate temperature of 400 degree Celsius, for example, by CVD. Moreover, a SiC film with a thickness of 30 nm is deposited.

0074As an insulating copper diffusion preventing film, SiC film, SiOC film, SiCN film, SiON film and SiN film that are made of organosilane-base material and silane gas may be used. A thickness of a low dielectric constant film may be in a range of 100 nm to 500 nm. Film formation temperature may be in a range of 350 to 400 degree Celcius.

0075As illustrated in <figref idref="DRAWINGS">FIG. 4K</figref>, the third etch stopper layer ES<b>3</b>, the second low dielectric constant film DL<b>2</b>, and the second etch stopper layer ES<b>2</b> are etched to form a via hole using a photoresist mask PR<b>5</b> as an etching mask. A diameter of the via hole is, for example, 70 nm. The photoresist mask PR<b>5</b> is removed.

0076As illustrated in <figref idref="DRAWINGS">FIG. 4L</figref>, the via hole is filled and a photoresist film PR<b>6</b> is applied over the third etch stopper layer ES<b>3</b>. A pattern for forming wiring trenches is exposed over the photoresist film PR<b>6</b> and is developed. The photoresist film is left in a deep via hole.

0077As illustrated in <figref idref="DRAWINGS">FIG. 4M</figref>, the third etch stopper layer ES<b>3</b> and the second low dielectric constant insulating film DL<b>2</b> are etched for 150 nm to form a thin-width wiring trench and a large-width wiring trench with a certain width and a height. The photoresist mask PR<b>6</b> is removed. Here, a via-first in which a wiring trench is formed after forming a via hole is described. However, a via-last in which a via hole is formed after forming a wiring trench may be used.

0078As illustrated in <figref idref="DRAWINGS">FIG. 4N</figref>, a Ta film with a thickness of 5 nm is formed over the interlayer dielectric film in which the wiring trench and the via hole are formed. For example, the Ta film is formed by sputtering a Ta target. A Cu—Mn alloy film with a thickness of 35 nm is formed over the Ta film as a seed layer <b>22</b> by sputtering. The processes are substantially the same as the processes illustrated in <figref idref="DRAWINGS">FIG. 4C</figref>. The seed layer <b>22</b> is a copper alloy to which elements that may suppress electromigration in the thin-width wiring are added.

0079As illustrated in <figref idref="DRAWINGS">FIG. 4O</figref>, a copper layer <b>23</b> is electrolytically plated over the seed layer <b>22</b>. The process is, as in the electrolytic plating in <figref idref="DRAWINGS">FIG. 4D</figref>, performed under a condition in which a bottom-up growth and overplating are likely to occur in the thin-width wiring trench. The via hole is a thin-width trench with an aspect ratio far above 0.5. Bottom-up growth occurs in the via hole and a via conductor is formed. Plating processes in the wiring trench is performed in substantially the same manner as that of the single damascene process illustrated in <figref idref="DRAWINGS">FIG. 4D</figref>. The electrolytic plating is completed when a thickness T<b>1</b> min of a copper layer above the interlayer dielectric film in the thin-width wiring trench becomes thicker than a thickness T<b>2</b> max of the copper layer from the bottom of the large-width wiring trench.

0080As illustrated in <figref idref="DRAWINGS">FIG. 4P</figref>, the copper layer <b>23</b> and the seed layer <b>22</b> in the large-width wiring trench are removed by etching the copper layer <b>23</b>. Accordingly, a state remains in which the copper wiring is buried in the thin-width wiring trench. The process is substantially the same as the process illustrated in <figref idref="DRAWINGS">FIG. 4E</figref>. However, even for the large-width wiring trench, the copper layer <b>23</b>, and the seed layer <b>22</b> are left in the lower via hole.

0081As illustrated in <figref idref="DRAWINGS">FIG. 4Q</figref>, a new seed layer <b>24</b> is formed and a new copper plated layer <b>25</b> is formed. The processes are substantially the same as the processes illustrated in <figref idref="DRAWINGS">FIGS. 4F and 4G</figref>. The new seed layer is pure copper or a copper alloy that includes an appropriate amount of additives that suppresses an increase in wiring resistance while suppressing stress migration.

0082As illustrated in <figref idref="DRAWINGS">FIG. 4R</figref>, heat treatment is applied for stabilizing the copper alloy. The process is substantially the same as the process illustrated in <figref idref="DRAWINGS">FIG. 4H</figref>.

0083As illustrated in <figref idref="DRAWINGS">FIG. 4S</figref>, unnecessary metal layers over a surface of the interlayer insulating film are removed by CMP. A second copper wiring layer is formed. Sufficient heat application over 300 degree Celsius at subsequent processes diffuses the additional element of the seed layer <b>22</b>, for example, Mn and the additional element (if any) of the seed layer <b>24</b> toward an interface of the barrier metal or a copper wiring. As described above, diffusion of additional elements of the seed layers may be performed by a separate heat treatment process. A SiC layer with a thickness of 30 nm is deposited over a planarized surface in which a copper wiring is exposed as an insulating cap film CL that reduces, if not prevent copper diffusion or an etch stopper layer by CVD at 400 degree Celsius. A multilayer wiring is formed by repeating the copper wiring formation processes as required.

0084<figref idref="DRAWINGS">FIG. 5</figref> is a sectional view schematically illustrating a configuration of a dual damascene wiring according to the above described embodiment. The left side indicates a thin-width wiring, while the right side indicates a large-width wiring. A recessed portion for a dual damascene wiring includes a via hole and a wiring trench which is continuous from the upper part of the via hole.

0085A barrier metal film <b>21</b> is formed by covering a whole surface of the recessed portion, and the first seed layer <b>22</b> and the first copper layer <b>23</b> are formed over the barrier metal film <b>21</b>. The first copper layer <b>23</b> in the large-width wiring trench and the seed layer <b>22</b> under the first copper layer <b>23</b> are removed. In the via hole, the first seed layer <b>22</b> over the barrier metal film <b>21</b> and the first copper layer <b>23</b> above the first seed layer <b>22</b> remain. The second seed layer <b>24</b> is formed over the barrier metal film <b>21</b> in the large-width wiring trench and the second seed layer <b>24</b> is formed over the first copper layer <b>23</b> that fills the via hole. The second copper layer <b>25</b> is formed over the second seed layer <b>24</b>. In other words, a large-width dual damascene wiring has a configuration as if single damascene wirings are stacked because of the manufacturing processes. However, no barrier metal film exists over the copper wiring that fills the via hole.

0086According to the embodiment described above, etching is used for removing copper layers in the large-width wiring as illustrated in <figref idref="DRAWINGS">FIGS. 4E and 4P</figref>. Reverse plating may be used instead of etching. In other words, a polarity of applied voltage is reversed by immersing the substrate in the electrolytic plating liquid and copper in the plated layer is dissolved into the plating liquid thereby reducing a thickness of the copper layer.

0087Moreover, plating is used for forming a copper layer for wiring. Instead of the plating, physical vapor deposition (PVD) such as sputtering or Chemical Vapor Deposition (CVD) may be used.

0088All examples and conditional language recited herein are intended for pedagogical purposes to aid the reader in understanding the invention and the concepts contributed by the inventor to furthering the art, and are to be construed as being without limitation to such specifically recited examples and conditions, nor does the organization of such examples in the specification relate to a showing of the superiority and inferiority of the invention. Although the embodiment(s) of the present inventions have been described in detail, it should be understood that various changes, substitutions, and alterations could be made hereto without departing from the spirit and scope of the invention.