US20020027261A1 - Selective Deposition Process For Passivating Top Interface Of Damascene-Type Cu Interconnect Lines - Google Patents

Abstract

The reliability, electromigration resistance, adhesion, and electrical contact resistance of planarized, in-laid metallization patterns, e.g., of copper, are enhanced by a process comprising selectively depositing on the planarized, upper surfaces of the metallization features at least one thin layer comprising at least one passivant element for the metal of the features, reacting the at least one passivant element to chemically reduce any deleterious oxide layer present at the upper surfaces of the metallization features, and diffusing the at least one passivant element for a distance below the upper surface to form a passivated top interface. The passivated top interfaces advantageously exhibit reduced electromigration and improved adhesion to overlying metallization with lower ohmic contact resistance. Planarization, as by CMP, may be performed subsequent to reaction/diffusion to remove any elevated, reacted and/or unreacted portions of the at least one thin layer. The invention finds particular utility in “back-end” metallization processing of high-density integrated circuit semiconductor devices having sub-micron dimensioned metallization features.

Description

CROSS-REFERENCE TO RELATED APPLICATIONS
• This application contains subject matter related to subject matter disclosed in co-pending U.S. patent application Ser. No. 09/132,282, filed on Aug. 11, 1998 and Ser. No. 09/225,546, filed on Jan. 5, 1999.[0001]
FIELD OF THE INVENTION
• The present invention relates to electrical devices, e.g., semiconductor integrated circuit devices, having in-laid ( “damascene”-type) metallization patterns, e.g., interconnection lines, etc., and to a method for minimizing, or substantially preventing, deleterious electromigration of the metallic element(s) of the metallization pattern. More specifically, the present invention relates to semiconductor devices comprising copper (Cu) interconnection patterns and is applicable to manufacture of high speed integrated circuits having sub-micron dimensioned design features and high electrical conductivity interconnect structures.[0002]
BACKGROUND OF THE INVENTION
• The present invention relates to a method for forming metal films as part of metallization processing of particular utility in the manufacture of electrical and electronic devices, e.g., circuit boards and semiconductor integrated circuits, and is especially adapted for use in processing employing “in-laid” or “damascene”-type technology.[0003]
• The escalating requirements for high density and performance associated with ultra-large scale integration (ULSI) semiconductor device wiring are difficult to satisfy in terms of providing sub-micron-sized (e.g., 0.18 μm and under), low resistance-capacitance (RC) time constant metallization patterns, particularly wherein the sub-micron-sized metallization features, such as vias, contact areas, lines, etc. require grooves, trenches, and other shaped openings or recesses having very high aspect (i.e., depth-to-width) ratios due to microminiaturization.[0004]
• Semiconductor devices of the type contemplated herein typically comprise a semiconductor wafer substrate, usually of doped monocrystalline silicon (Si) or, in some instances, gallium arsenide (GaAs), and a plurality of sequentially formed interlayer dielectrics and electrically conductive patterns formed therein and/or therebetween. An integrated circuit is formed therefrom containing a plurality of patterns of conductive lines separated by inter-wiring spacings, and a plurality of interconnect lines, such as bus lines, bit lines, word lines, and logic interconnect lines. Typically, the conductive patterns of vertically spaced-apart metallization layers or strata are electrically interconnected by a vertically oriented conductive plug filling a via hole formed in the inter-layer dielectric layer separating the layers or strata, while another conductive plug filling a contact area hole establishes electrical contact with an active device region, such as a source/drain region of a transistor, formed in or on the semiconductor substrate. Conductive lines formed in groove- or trench-like openings in overlying inter-layer dielectrics extend substantially parallel to the semiconductor substrate. Semiconductor devices of such type fabricated according to current technology may comprise five or more layers or strata of such metallization in order to satisfy device geometry and microminiaturization requirements.[0005]
• Electrically conductive films or layers of the type contemplated for use in e.g., “back-end” semiconductor manufacturing technology for fabricating devices having multi-level metallization patterns such as described supra, typically comprise a metal such as titanium (Ti), tantalum (Ta), tungsten (W), aluminum (Al), chromium (Cr), nickel (Ni), cobalt (Co), silver (Ag), gold (Au), copper (Cu) and their alloys. In use, each of the enumerated metals presents advantages as well as drawbacks. For example, Al is relatively inexpensive, exhibits low resistivity, and is relatively easy to etch. However, in addition to being difficult to deposit by lower cost, lower temperature, more rapid “wet” type technology such as electrodeposition, step coverage with Al is poor when the metallization features are scale down to sub-micron size, resulting in decreased reliability of interconnections, high current densities at certain locations, and increased electro-migration. In addition, certain low dielectric constant materials, e.g., polyimides, when employed as dielectric inter-layers, create moisture/bias reliability problems when in contact with Al.[0006]
• Copper (Cu) and Cu-based alloys are particularly attractive for use in large scale integration (LSI), very large-scale integration (VLSI), and ultra-large scale (ULSI) semiconductor devices requiring multi-level metallization systems for “back-end” processing of the semiconductor wafers on which the devices are based. Cu- and Cu alloy-based metallization systems have very low resistivities, i.e., significantly lower than that of W and even lower than those of previously preferred systems utilizing Al and its alloys, as well as a higher (but not complete) resistance to electromigration. Moreover, Cu and its alloys enjoy a considerable cost advantage over a number of the above-enumerated metals, notably Ag and Au. Also, in contrast to Al and the refractory-type metals (e.g., Ti, Ta, and W), Cu and its alloys can be readily deposited at low temperatures in good quality, bright layer form by well-known “wet” plating techniques, such as electroless and electroplating techniques, at deposition rates fully compatible with the requirements of device manufacturing throughput.[0007]
• Electroless plating of Cu generally involves the controlled auto-catalytic deposition of a continuous film of Cu or an alloy thereof on a catalytic surface by the interaction of at least a Cu-containing salt and a chemical reducing agent contained in a suitable solution, whereas electroplating comprises employing electrons supplied to an electrode (comprising the surface(s) to be plated) from an external source (i.e., a power supply) for reducing Cu ions in solution and depositing reduced Cu metal atoms on the plating surface(s). In either case, a nucleation/seed layer is required for catalysis and/or deposition on the types of substrates contemplated herein. Finally, while electroplating requires a continuous nucleation/seed layer, very thin and discontinuous islands of a catalytic metal may be employed with electroless plating.[0008]
• As indicated above, a commonly employed method for forming “in-laid” metallization patterns as are required for “back-end” metallization processing of semiconductor wafers employs “damascene”-type technology. Generally, in such processing methodology, a recess (i.e., an opening) for forming, e.g., a via hole in a dielectric layer for electrically connecting vertically separated metallization layers, or a groove or trench for a metallization line, is created in the dielectric layer by conventional photolithographic and etching techniques, and filled with a selected metal. Any excess metal overfilling the recess and/or extending over the surface of the dielectric layer is then removed by, e.g., chemical-mechanical polishing (CMP), wherein a moving pad is biased against the surface to be polished/planarized, with the interposition of a slurry containing abrasive particles (and other ingredients) therebetween.[0009]
• A variant of the above-described technique, termed “dual damascene” processing, involves the formation of an opening comprising a lower contact or via hole section in communication with an upper groove or trench section, which opening is filled with a conductive material, typically a metal, to simultaneously form a conductive via plug in electrical contact with a conductive line.[0010]
• Referring now to FIG. 1, schematically shown therein in simplified cross-sectional view, is a conventional damascene-type processing sequence employing relatively low cost, high manufacturing throughput plating and CMP techniques for forming recessed “back-end” metallization patterns (illustratively of Cu-based metallurgy but not limited thereto) in a semiconductor device formed in or on a[0011]semiconductor wafer substrate1. In a first step, the desired arrangement of conductors is defined as a pattern ofrecesses2 such as via holes, grooves, trenches, etc. formed (as by conventional photolithographic and etching techniques) in thesurface4 of a dielectric layer3 (e.g., a silicon oxide and/or nitride or an organic polymeric material) deposited or otherwise formed over thesemiconductor substrate1. In a second step, a layer of Cu or Cu-basedalloy5 is deposited by conventional plating techniques, e.g., electroless or electroplating techniques, to fill therecesses2. In order to ensure complete filling of the recesses, the Cu-containinglayer5 is deposited as a blanket (or “overburden”) layer of excess thickness t so as to overfill therecesses2 and cover theupper surface4 of thedielectric layer3. Next, the entire excess thickness t of the metaloverburden layer5 over the surface of thedielectric layer3 is removed by a CMP process utilizing an alumina (Al₂O₃)-based slurry, leavingmetal portions5′ in therecesses2 with their exposedupper surfaces6 substantially co-planar with thesurface4 of thedielectric layer3.
• The above-described conventional damascene-type process forms in-[0012]laid conductors5′ in thedielectric layer3 while avoiding problems associated with other types of metallization patterning processing, e.g., blanket metal layer deposition, followed by photolithographic masking/etching and dielectric gap filling. In addition, such single or dual damascene-type processing can be performed with a variety of other types of substrates, e.g., printed circuit boards, with and/or without intervening dielectric layers, and with a plurality of metallization levels, i.e., five or more levels.
• A drawback associated with Cu-based “back-end” metallization is the possibility of Cu diffusion into adjacent structures, e.g., an underlying semiconductor substrate (typically Si) or a dielectric layer, resulting in degradation of semiconductive or insulative properties, as well as poor adhesion of the deposited Cu or Cu alloy layer to various materials employed as dielectric inter-layers, etc. As a consequence of these phenomena associated with Cu-based metallurgy, it is generally necessary to provide an adhesion promoting and/or diffusion barrier layer intermediate the semiconductor substrate and the overlying Cu-based metallization layer. Suitable materials for such adhesion/barrier layers include, e.g., Ti, W, Cr, Ta, and TaN.[0013]
• Another drawback associated with the use of Cu or Cu-based metallurgy for “back-end” metallization processing of semiconductor devices, results from the undesirable formation of copper oxide(s), e.g., Cu[0014]₂O, CuO, CuO₂, etc., on the planarized Cu or Cu-based alloy surfaces of the in-laid metallization features as a result of oxidation, etc., due to the strong chemical oxidizing agents conventionally included in CMP slurries for enhancing Cu dissolution/removal rates or as a result of exposure of the freshly abraded Cu-based surfaces to an oxidizing atmosphere, e.g., air or oxygen. The thickness of the copper oxide layer can vary depending upon the particular CMP processing conditions, e.g., stronger oxidizing agents contained in the CMP slurry result in thicker oxide layers, as does increased duration of exposure of freshly abraded, post CMP Cu surfaces to oxidizing atmospheres, e.g., air.
• Such copper oxide-containing layer(s) disadvantageously increase contact resistance and reduce or prevent adhesion of layers thereto, e.g., silicon nitride-based capping layers. Moreover, the copper oxide layers are brittle, increasing the likelihood of circuit disconnect or reduced conductivity due to separation, as by peeling, of the copper oxide layer from conductor layers in contact therewith. Yet another significant disadvantage attributable to the presence of copper oxide at the interface between adjacent electrical conductors results from the rapid diffusion of Cu atoms and/or ions along the oxide layer. The latter characteristic of copper oxide layers disadvantageously results in enhanced material transport during electrical current flow and thus increases the electromigration rate of Cu atoms and/or ions along Cu-based conductor lines.[0015]
• Electromigration occurs in extended runs or lengths of metal conductor lines carrying significant currents. According to a conventional theory for explaining the mechanism of electromigration, the current flow within the conductor line can be sufficient to result in movement of metal (Cu) atoms and/or ions along the line via momentum transfer engendered by collision of the metal (Cu) atoms and/or ions with energetic, flowing electrons. The current flow also creates a thermal gradient along the conductor length which increases the mobility of the metal ions and/or atoms. As a consequence of the momentum transfer and the thermally enhanced mobility, metal (Cu) atoms and/or ions diffuse in the direction of the current flow, and metal loss at the source end of the conductor eventually results in thinning of the conductor line. The electromigration effect can continue until the conductor line becomes so thin that it separates from the current input or forms an open circuit, resulting in circuit (i.e., semiconductor chip) failure. As this usually occurs over an extended period of operation, the failure is often seen by the end-user.[0016]
• As design rules for high integration density, high speed semiconductor devices extend deeper into the sub-micron range, e.g., about 0.18 μm and under, e.g., about 0.15 μm and below, and the number of metallization levels increases, the reliability of the “back-end” interconnection patterns and systems become particularly critical for the obtainment of desired operating characteristics and performance.[0017]
• Thus, there exists a need for metallization process methodology which avoids the above-mentioned drawbacks associated with oxide layer formation, electromigration, etc., and which enables formation of metallization members, e.g., interconnect and routing lines, particularly of Cu or Cu-based alloys, having high reliability, high product yield, improved electromigration resistance, and high performance. In particular, there exists a need for eliminating the problems associated with electromigration and oxide layer formation resulting from CMP processing to form “in-laid”, “damascene-type” Cu-based metallization patterns. Moreover, there exists a need for improved metallization processing technology which is fully compatible with conventional process flow, methodology, and throughput requirements in the manufacture of integrated circuit semiconductor devices and other devices requiring “in-laid” metallization patterns.[0018]
DISCLOSURE OF THE INVENTION
• An advantage of the present invention is a method of manufacturing an electrical or electronic device having highly reliable, electromigration-resistant metallization patterns.[0019]
• Another advantage of the present invention is a method of manufacturing a semiconductor integrated circuit device having highly reliable, electromigration-resistant Cu-based metallization patterns.[0020]
• Yet another advantage of the present invention is a method of manufacturing “in-laid”, “damascene”-type Cu-based metallization patterns having improved reliability, high conductivity, and improved electromigration resistance.[0021]
• Still another advantage of the present invention is an improved method of forming high-density, “in-laid” metallization patterns by a “damascene”-type, CMP-based process which is fully compatible with existing process methodology for forming integrated circuit semiconductor devices and printed circuit boards.[0022]
• Additional advantages and other features of the present invention will be set forth in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or will be learned from the practice of the invention. The advantages of the present invention may be realized and obtained as particularly pointed out in the appended claims.[0023]
• According to one aspect of the present invention, the foregoing and other advantages are achieved in part by a method of manufacturing an electrical device, the method comprising the sequential steps of:[0024]
• (a) providing a substrate including at least one damascene-type, metal feature in-laid in the upper, exposed surface of a layer of dielectric material overlying at least a portion of the substrate, the at least one metal feature including an upper, exposed surface substantially co-planar with the upper surface of the layer of dielectric material;[0025]
• (b) selectively depositing on the exposed upper surface of the at least one metal feature at least one layer comprising at least one metallic passivant element for passivating the upper surface of the at least one metal feature; and[0026]
• (c) effecting reaction between at least a portion of the at least one layer comprising at least one metallic passivant element and the upper surface of the at least one metal feature to form a passivating layer thereat, whereby electromigration of the metal of the at least one metal feature is minimized or substantially prevented.[0027]
• According to embodiments of the present invention, the method further comprises the step of:[0028]
• (d) selectively removing any remaining reacted and/or unreacted portion(s) of the at least one layer comprising at least one metallic passivant element which extend(s) above the upper surface of the layer of dielectric material, thereby making the upper surface of the at least one in-laid metal feature substantially co-planar with the upper surface of the layer of dielectric material.[0029]
• In accordance with embodiments of the present invention, the electrical device comprises a semiconductor integrated circuit device, and step (a) comprises providing as the substrate a semiconductor wafer of monocrystalline silicon (Si) or gallium arsenide (GaAs) having a major surface, the dielectric layer is formed over at least a portion of the major surface, the at least one damascene-type, in-laid metal feature comprises a plurality of features of different widths and/or depths for providing vias, inter-level metallization, and/or interconnection lines of at least one active device region or component formed on or within the semiconductor wafer, and the metal of the at least one in-laid metal feature is unalloyed copper (Cu); and step (b) comprises selectively depositing, as by electroless deposition or chemical vapor deposition (CVD), at least one layer comprising at least one metallic passivant element capable of chemically reducing any copper oxide present on the upper surface of the at least one Cu metal feature, the at least one metallic passivant element being selected from the group consisting of: magnesium (Mg), titanium (Ti), tantalum (Ta), cobalt (Co), nickel (Ni), palladium (Pd) and chromium (Cr).[0030]
• In embodiments according to the present invention, step (c) is performed substantially simultaneously with step (b), e.g., at ambient temperatures; whereas according to other embodiments of the present invention, step (c) is performed after step (b), as by annealing in an inert atmosphere; and step (d) comprises selectively removing, as by etching or chemical-mechanical polishing (CMP), any remaining elevated, reacted and/or unreacted portion(s) of the layer comprising at least one metallic passivant element which extend(s) above the upper surface of the layer of dielectric material, thereby making the upper surface of the at least one in-laid metal feature substantially co-planar with the upper surface of the dielectric layer.[0031]
• According to further embodiments of the present invention, step (a) for providing the substrate including at least one damascene-type, in-laid metal feature comprises the preliminary steps of:[0032]
• i. forming a dielectric layer on a surface of a substrate, the dielectric layer having an exposed, upper surface;[0033]
• ii. forming at least one recess in the exposed, upper surface of the dielectric layer;[0034]
• iii. depositing a metal layer filling the at least one recess and extending over the upper surface of the dielectric layer;[0035]
• iv. removing the portion(s) of the metal layer extending over the upper surface of the dielectric layer; and[0036]
• v. removing (e.g., by CMP) any excess thickness portion(s) of the metal layer filling the at least one recess which extend(s) above the upper surface of the dielectric layer, thereby making the upper, exposed, upper surface of the at least one in-laid metal feature substantially co-planar with the exposed, upper surface of the dielectric layer.[0037]
• According to another aspect of the present invention, a method of manufacturing a semiconductor integrated circuit device comprises the sequential steps of:[0038]
• (a) providing a substrate comprising a semiconductor wafer of monocrystalline Si or GaAs and having a major surface, a dielectric layer formed on at least a portion of the major surface and having an exposed, upper surface, at least one damascene-type, unalloyed Cu metal feature in-laid in the exposed, upper surface of the dielectric layer, the at least one Cu metal feature including an exposed, upper surface substantially co-planar with the exposed, upper surface of the dielectric layer;[0039]
• (b) selectively depositing at least one layer comprising at least one metallic passivant element for the Cu metal feature on the upper surface of the at least one Cu metal feature, the at least one metallic passivant element being capable of chemically reducing any copper oxide present on the upper surface of the at least one metal feature and selected from the group consisting of: magnesium (Mg), titanium (Ti), tantalum (Ta), cobalt (Co), nickel (Ni), palladium (Pd), and chromium (Cr); and[0040]
• (c) effecting reaction between at least a portion of the at least one layer comprising at least one metallic passivant element and the upper surface of the at least one Cu metal feature to form a passivating layer thereat, whereby electromigration of Cu atoms and/or ions from the at least one Cu metal feature is minimized or substantially prevented.[0041]
• According to embodiments of the present invention:[0042]
• step (a) comprises providing a semiconductor wafer having a dielectric layer on a major surface thereof which comprises a plurality of in-laid, unalloyed Cu metal features of different widths and/or depths for providing vias, inter-level metallization, and/or interconnection lines of at least one active device region or component formed on or within the semiconductor wafer;[0043]
• step (b) comprises selectively depositing the at least one layer comprising at least one metallic passivant element by electroless deposition or chemical vapor deposition (CVD); and[0044]
• step (c) is performed substantially simultaneously with step (b) at ambient temperature or subsequent to step (b) by annealing at an elevated temperature in an inert atmosphere.[0045]
• According to still further embodiments of the present invention, the method comprises the further step of:[0046]
• (d) selectively removing any elevated, remaining reacted and/or unreacted portion(s) of the at least one layer comprising at least one metallic passivating element which extend(s) above the upper surface of the layer of dielectric material, thereby making the upper surface of the at least one in-laid, Cu metal feature substantially co-planar with the upper surface of the dielectric layer.[0047]
• Additional advantages of the present invention will readily become apparent to those skilled in the art from the following detailed description, wherein only the preferred embodiment of the present invention is shown and described, simply by way of illustration of the best mode contemplated for carrying out the method of the present invention. As will be understood, the present invention is capable of other and different embodiments, and its several details are capable of modification in various obvious respects, all without departing from the present invention. Accordingly, the drawing and description are to be regarded as illustrative in nature, and not as limitative.[0048]
BRIEF DESCRIPTION OF THE DRAWINGS
• The following detailed description of an embodiment of the present invention can best be understood when read in conjunction with the following drawings, in which like reference numerals are employed throughout to designate similar features, wherein:[0049]
• FIG. 1 illustrates, in simplified, cross-sectional schematic form, a sequence of processing steps for forming a pattern of damascene-type, in-laid Cu metallization features according to conventional practices for manufacture of semiconductor integrated circuit devices; and[0050]
• FIG. 2 illustrates, in simplified cross-sectional schematic form, a sequence of processing steps for selectively passivating the upper surfaces, i.e., the top interfaces of the pattern of Cu in-laid metallization features of FIG. 1 according to the inventive methodology.[0051]
DESCRIPTION OF THE INVENTION
• The present invention addresses and solves problems arising from manufacturing electrical devices comprising in-laid metallization patterns, e.g., semiconductor integrated circuit devices, wherein, as part of the fabrication methodology, a plurality of recesses formed in the surface of a dielectric layer overlying a semiconductor substrate comprising at least one active device region or component are filled with a metal, illustratively unalloyed Cu, which is subject to electromigration when the device is in use. More specifically, the present invention enables the formation of in-laid metallization patterns, e.g., of Cu-based metallurgy, in which the tendency for electromigration of the principal metallic element or component is minimized or substantially prevented, and which provide improved adhesion to, and low contact resistance with, adjacent (e.g., overlying) metallization patterns and/or levels in contact therewith.[0052]
• The present invention enables the formation of in-laid metallization patterns having passivated upper surfaces (top interfaces) which have little or substantially no tendency for promoting electromigration of atoms and/or ions of the principal underlying metal component and provide improved adhesion with overlying metallization by means of techniques which are fully compatible with the requirements of automated manufacturing technology and product throughput. Briefly stated, according to the present invention, conventional damascene-type methodology (such as illustrated in FIG. 1) is employed for forming an in-laid metallization pattern in a dielectric layer overlying a suitable substrate, e.g., a semiconductor wafer comprising at least one active device region or component, by which processing a metal material, e.g., unalloyed Cu, is utilized for filling the pattern of recesses in the dielectric layer. Subsequent to planarization processing, as by chemical-mechanical polishing (CMP), at least one thin layer comprising at least one passivant element for the metal material, e.g., Cu, is selectively deposited on the exposed, upper surface(s) of the feature(s) of the metallization pattern, and reaction between the at least one passivant element and the upper surface(s) of the metal of the in-laid metallization feature(s) is effected for selectively forming a passivating layer thereat, the passivation reaction including reduction of any deleterious oxide of the metal of the metallization feature(s) present at the upper surface(s) thereof. The passivation reaction may occur simultaneously with the selective deposition of the at least one thin layer comprising at least one passivant element, i.e., at ambient temperature, or alternatively, may occur subsequent to the selective deposition, as by annealing at an elevated temperature in an inert atmosphere. Any elevated, remaining reacted and/or unreacted portion(s) of the at least one thin layer comprising at least one passivant element remaining after reaction/passivation of the upper surface(s), or top interface(s), of the metallization feature(s) is (are) selectively removed, as by CMP, thereby making the exposed, passivated upper surface(s), or top interface(s) of the metallization pattern substantially co-planar with the exposed, upper surface of the dielectric layer. By way of example, but not limitation, a thin layer comprising magnesium (Mg) as passivant element can readily reduce CuO[0053]₂typically present on the upper surfaces of unalloyed Cu metallization features. In such instance, the remaining reacted and/or unreacted portions of the passivant layer removed by CMP comprise Mg and MgO.
• An embodiment of the present invention will now be described with reference to FIG. 2, which shows, in simplified, cross-sectional, schematic fashion, an illustrative, but not limitative, embodiment of the present invention comprising a sequence of processing steps performed on a semiconductor wafer substrate-based workpiece produced according to the process sequence illustrated in FIG. 1, wherein similar reference numerals are used throughout to denote similar features. As will be apparent to one of ordinary skill in the art, the inventive process is readily adapted for use in the manufacture of a variety of electrical and electronic devices utilizing in-laid metallization patterns, e.g., printed circuit boards and integrated circuit semiconductor devices. It should also be recognized that the process steps and structures described below do not necessarily form a complete process flow for manufacturing such devices. However, the present invention can be used in conjunction with conventional technology currently employed in the art, e.g., integrated circuit fabrication methodology, and, consequently, only so much of the commonly practiced process steps are included here as are necessary for an understanding of the present invention. As employed throughout the present disclosure and claims, the terms “substrate” and/or “semiconductor wafer substrate” include, e.g., a semiconductor substrate per se or an epitaxial layer formed on a suitable semiconductor substrate. The expressions “passivant” and “passivating element”, as employed herein, refer to elements which are capable of reaction with at least the surface of a metal of an in-laid metallization feature and any oxide(s) of the metal present thereat, as to form a top surface or top interface “passivation layer”, which according to the context of the present invention, refers to an uppermost layer or strata of the metallization feature which effectively reduces electromigration of atoms and/or ions of the principal metallic component of the feature and provides good adhesion and low ohmic electrical resistance with an overlying metallization layer in contact therewith. Finally, the drawing figures representing cross-sections of portions of a semiconductor device during fabrication processing are not drawn to scale, but instead are drawn as to best illustrate the features of the present invention.[0054]
• Referring now to the first view shown in FIG. 2, in a preliminary step according to the present invention, a semiconductor wafer substrate-based workpiece similar to that shown in the third view of FIG. 1 is provided, having a desired in-laid metallization pattern, comprising a[0055]semiconductor wafer substrate1, adielectric layer3overlying substrate1 and having a pattern ofrecesses2 of different widths and/or depths formed in the exposed,upper surface4 thereof, and alayer5 of a metal subject to electro-migration, illustratively Cu, filling therecesses2, the exposed,upper surfaces6 of themetal layer5 being substantially co-planar with the exposed,upper surface4 of thedielectric layer3.
• In the illustrated structure,[0056]semiconductor substrate1 typically comprises a wafer of monocrystalline Si or GaAs,layer3 comprises an insulative material typically utilized as an inter-layer dielectric (“ILD”), i.e., an inorganic material such as a silicon oxide, nitride, or oxynitride, or an organic-based or derived material, such as parylene, benzocyclobutene (BCB), etc.Recesses2 formed in the upper, exposedsurface4 ofdielectric layer3 are utilized for forming vias, inter-level metallization, and/or interconnection routing of at least one active device region or component formed on or withinsemiconductor wafer substrate1 and typically include openings having high aspect (i.e., depth-to-width) ratios greater than one, with sub-micron or micron-sized dimensions, i.e., widths of from about 0.08 to about 3.0 μm and depths of from about 0.4 to about 2.0 μm.
• Referring now to the second view shown in FIG. 2, in a first step according to the inventive methodology, at least one[0057]thin layer7 comprising at least one passivant element (e.g., Ni) for the metal5 (e.g., unalloyed Cu) of the in-laid metal feature(s) of the metallization pattern is selectively deposited on the exposed,upper surface6 thereof, as by a selective electroless deposition or chemical vapor deposition (CVD) technique. Selectivity of the deposition towards themetal5 of the metal features may be obtained by use of suitable deposition bath composition in the case of electroless deposition and by appropriate selection of organo-metallic precursor gas(es) in the case of CVD. For example, selective electroless deposition of alayer7 comprising at least one passivant element, for reducing deleterious oxides and electromigration tendency of unalloyed Cu, e.g., chosen from the group consisting of magnesium (Mg), titanium (Ti), tantalum (Ta), cobalt (Co), nickel (Ni), palladium (Pd), and chromium (Cr), may be obtained by appropriate use of an electroless deposition solution comprising a boride, phosphide, or boride/palladium compound of the metal to be selectively plated on the metal feature(s), whereas selective CVD of the above-enumerated passivant elements may be obtained by use of appropriate organo-metallic precursor gas(es). By way of illustration, but not limitation, Ni be selectively electrolessly plated on unalloyed Cu metal features from deposition solutions comprising NiB, NiP or NiBPd, or selectively CVD deposited on unalloyed Cu metal features by use of a Ni-based organo-metallic precursor gas. Given the present disclosure and objectives of the invention, suitable electroless deposition bath compositions and/or organo-metallic precursor gases for use with the other enumerated passivant elements can be determined for use in a particular application.
• According to an essential feature of the present invention, the at least one passivant element contained in the at least one[0058]thin layer7 must be capable of chemically reducing any oxide(s) of themetal5 of the metallization feature(s) which are disadvantageously present at the upper surface(s)6 thereof, e.g., as a result of oxidation by oxidants present in the abrasive slurry employed for the CMP planarization processing, or as a result of exposure to air of the freshly abraded surfaces produced during the CMP. By way of illustration, but not limitation, in the illustrated case where unalloyed Cu (e.g., electroplated)metal5 is utilized for forming the metallization pattern, such deleterious copper oxides include Cu₂O, CuO, and CuO₂. As a consequence of the above requirement, the at least onethin layer7 comprising the at least one passivant element (e.g., Ni or Mg) must be of sufficient thickness to provide substantially complete reduction of the oxide layer as well as diffusion of the at least one passivant element into themetal5 of the metallization feature to a predetermined minimum distance d_min.belowsurface6, thereby establishing thereat a passivatedsurface layer8, as shown in the third view of FIG. 2. Passivated top surface (or top interface)layer8, according to the invention, forms a new top surface or top interface for subsequent adherent, low ohmic resistance contact with an overlying metallization level, while providing minimal, or substantially no tendency for electromigration of the principal metal5 (e.g., Cu) of the metallization feature. Given the present disclosure and objectives of the invention, appropriate thicknesses for the at least onealloying element layer7, as well as minimum diffusion depth d_min., can be determined and optimized for use in a particular application.
• [0059]Layer7 can, depending, inter alia, upon theparticular metal5 of the metallization pattern and choice and number of passivant element(s), comprise a single layer including one passivant element or two or more elements. Alternatively,layer7 can comprise two or more overlying layers, each including one passivant element. The latter alternative may be preferred when co-deposition of multiple passivant elements in single layer form is impractical or results in poor control of the relative amounts of each passivant element.
• According to another feature of the present invention, reaction between the at least one passivant element contained in the at least one[0060]thin layer7 to chemically reduce any oxide(s) present at theupper surface6 of the metal feature(s) can, depending upon the chemical reactivity between the particular passivant element(s) and the particular oxides, occur substantially simultaneously with the deposition oflayer7, i.e., at the ambient temperature during deposition, or alternatively, subsequently thereto at an elevated temperature, e.g., by annealing in an inert atmosphere. By way of illustration, but not limitation, in the case of alayer7 of Ni as passivant element and unalloyed Cu asmetal5 of the metallization feature(s), copper oxide reduction may be achieved substantially simultaneously with Ni deposition at ambient temperatures of from about 20 to about 300° C., whereas with alayer7 of a less reactive passivant element, such as Co, annealing (in an inert atmosphere) at a temperature of from about 200 to about 450° C. for from about 30 sec. to about 60 min. is necessary to effect copper oxide reduction. In the former case of reaction at ambient temperature, however, a subsequent annealing treatment, as indicated in the third view of FIG. 2, may be required for formation of diffusedlayer8, whereas, in the latter case, where reaction requires elevated temperature, reduction of the copper oxides and formation of diffusedlayer8 can occur substantially simultaneously with diffusion of the passivant element.
• Referring now to the final view illustrated in FIG. 2,[0061]elevated layer portions7′ which extend above the level ofupper surface4 ofdielectric layer3, and composed of reacted and/or unreacted portions of layer(s)7 (e.g., comprising Mg and/or MgO) may remain on or overpassivating surface layer8 at the upper surface(s) of the metal features after completion of the reaction and diffusion treatment(s). In the next step according to the inventive methodology, any such remaining layer portion(s)7′ is (are) selectively removed, e.g., by etching using an etchant selective against the material of thedielectric layer3 or by chemical-mechanical planarization (CMP), thereby re-establishing co-planarity of theupper surface6 of the in-laid metal feature(s) and theupper surface4 of thedielectric layer3. The thus-produced, planarized, in-laid metallization pattern havingpassivating layer8 at the upper surfaces (top interfaces)6 thereof for minimizing or substantially preventing electromigration therefrom and therealong may then be subjected to further “back-end” metallization processing, as by damascene-type techniques, for forming adherent, low ohmic resistance electrical contact with at least one additional overlying layer of metallization.
• The present invention thus provides a simple, convenient, and reliable method for reducing, or substantially preventing, deleterious electromigration of metal from in-laid metallization patterns as well as improved adhesion and lower resistance electrical contact thereto, by selectively depositing at least one thin layer comprising at least one passivant element for the metal of the metallization pattern, which at least one passivant element (1) chemically reduces any deleterious oxide layer present at the upper-surfaces of the metallization feature and (2) diffuses into the upper surface thereof to form a passivated top interface. The present invention enables the formation of extremely reliable interconnect members and patterns, illustratively of Cu, but not limited thereto, by providing a method for reliably reducing, or substantially preventing deleterious electromigration, particularly suitable for use in semiconductor “back-end” damascene-type processing, and equally applicable to “dual-damascene”-type processing.[0062]
• The inventive methodology enjoys particular utility in the manufacture of semiconductor devices having sub-micron dimensioned metallization features and high aspect ratio openings. Moreover, the inventive method can be practiced at manufacturing rates consistent with the requirements for economic competitiveness, and is fully compatible with conventional process flow for automated manufacture of high-density integration semiconductor devices. In addition, the invention is particularly well suited to the manufacture of circuit boards and other types of electrical and electronic devices and/or components.[0063]
• In the previous description, numerous specific details are set forth, such as specific materials, structures, reactants, processes, etc. in order to provide a better understanding of the present invention. However, the present invention can be practiced without resorting to the details specifically set forth. In other instances, well known processing materials and techniques have not been described in detail in order not to unnecessarily obscure the present invention.[0064]
• Only the preferred embodiment of the present invention and but a few examples of its versatility are shown and described in the present disclosure. It is to be understood that the present invention is capable of use in various other combinations and environments and is susceptible of changes or modifications within the scope of the inventive concept as expressed herein.[0065]

Claims (20)

What is claimed is:

1. A method of manufacturing an electrical device, which method comprises the sequential steps of:

(a) providing a substrate including at least one damascene-type, metal feature in-laid in the exposed, upper surface of a layer of dielectric material overlying at least a portion of said substrate, the at least one metal feature including an upper, exposed surface substantially co-planar with said upper surface of said layer of dielectric material;

(b) selectively depositing on said exposed upper surface of said at least one metal feature at least one layer comprising at least one metallic passivant element for passivating said upper surface of said at least one metal feature; and

(c) effecting reaction between at least a portion of said at least one layer comprising at least one metallic passivant element and said upper surface of said at least one metal feature to form a passivating layer thereat, whereby electromigration of the metal of said at least one metal feature is minimized or substantially prevented.

2. The method as inclaim 1, further comprising the step of:

(d) selectively removing any elevated, remaining reacted and/or unreacted portion(s) of said at least one layer comprising at least one metallic passivant element which extend(s) above said upper surface of said layer of dielectric material, thereby making said upper surface of said at least one metal feature substantially co-planar with said upper surface of said dielectric layer.

3. The method as inclaim 1, wherein said electrical device comprises a semiconductor integrated circuit device, and:

step (a) comprises providing as said substrate a semiconductor wafer of monocrystalline silicon (Si) or gallium arsenide (GaAs) having a major surface, said dielectric layer is formed over at least a portion of said major surface, and said at least one damascene-type, in-laid metal feature comprises a plurality of features of different widths and/or depths for providing vias, interlevel metallization, and/or interconnection lines of at least one active device region or component formed on or within said semiconductor wafer.

4. The method as inclaim 3, wherein:

said metal of said at least one in-laid metal feature is unalloyed copper (Cu).

5. The method as inclaim 4, wherein:

step (b) comprises selectively depositing at least one layer comprising at least one metallic passivant element capable of chemically reducing any copper oxide present on said upper surface of said at least one Cu metal feature.

6. The method as inclaim 5, wherein:

step (b) comprises selectively depositing at least one layer comprising at least one metallic passivant element selected from the group consisting of: magnesium (Mg), titanium (Ti), tantalum (Ta), cobalt (Co), nickel (Ni), palladium (Pd), and chromium (Cr).

7. The method as inclaim 6, wherein:

said at least one metallic passivant element is Mg.

8. The method as inclaim 5, wherein:

step (b) comprises selectively depositing said at least one layer comprising said at least one metallic passivant element by electroless deposition or chemical vapor deposition (CVD).

9. The method as inclaim 5, comprising:

performing step (c) substantially simultaneously with step (b).

10. The method as inclaim 9, comprising:

performing step (c) at ambient temperature.

11. The method as inclaim 5, comprising:

performing step (c) after step (b) by annealing at an elevated temperature in an inert atmosphere.

12. The method as inclaim 3, further comprising the step of:

(d) selectively removing any elevated, remaining reacted and/or unreacted portion(s) of said at least one layer comprising at least one metallic passivant element which extend(s) above said upper surface of said layer of dielectric material, thereby making said upper surface of said at least one metal feature substantially co-planar with said upper surface of said dielectric layer.

13. The method as inclaim 12, wherein:

step (d) comprises selectively removing by etching.

14. The method as inclaim 12, wherein:

step (d) comprises selectively removing by chemical-mechanical polishing (CMP).

15. The method as inclaim 1, wherein:

step (a) for providing said substrate including at least one damascene-type, in-laid metal feature comprises the preliminary steps of:

i. forming a dielectric layer on a surface of a substrate, said dielectric layer having an exposed, upper surface;

ii. forming at least one recess in said exposed, upper surface of said dielectric layer;

iii. depositing a metal layer filling the at least one recess and extending over said upper surface of said dielectric layer;

iv. removing the portion(s) of the metal layer extending over said upper surface of said dielectric layer; and

v. removing any excess thickness portion(s) of the metal layer filling the at least one recess which extend(s) above said upper surface of said dielectric layer, thereby making the upper, exposed surface of said at least one in-laid metal feature substantially co-planar with said upper surface of said dielectric layer.

16. The method as inclaim 15, wherein:

preliminary step v. comprises planarizing by chemical-mechanical polishing (CMP).

17. A method of manufacturing a semiconductor integrated circuit device, which method comprises the sequential steps of:

(a) providing a substrate comprising a semiconductor wafer of monocrystalline Si or GaAs and having a major surface, a dielectric layer formed on at least a portion of said major surface and having an exposed, upper surface, at least one damascene-type, unalloyed Cu metal feature in-laid in said exposed, upper surface of said dielectric layer, the at least one Cu metal feature including an exposed, upper surface substantially co-planar with said exposed, upper surface of said dielectric layer;

(b) selectively depositing at least one layer comprising at least one metallic passivant element for said Cu metal feature on said upper surface of said at least one Cu metal feature, said at least one metallic passivant element being capable of chemically reducing any copper oxide present on said upper surface of said at least one metal feature and selected from the group consisting of: magnesium (Mg), titanium (Ti), tantalum (Ta), cobalt (Co), nickel (Ni), palladium (Pd), and chromium (Cr); and

(c) effecting reaction between at least a portion of said at least one layer comprising at least one metallic passivant element and said upper surface of said at least one Cu metal feature to form a passivating layer thereat, whereby electromigration of Cu atoms from said at least one Cu metal feature is minimized or substantially prevented.

18. The method as inclaim 17, wherein:

step (b) comprises selectively depositing said at least one layer comprising at least one metallic passivant element by electroless deposition or chemical vapor deposition (CVD); and

step (c) is performed substantially simultaneously with step (b) at ambient temperature or subsequent to step (b) by annealing at an elevated temperature in an inert atmosphere.

19. The method as inclaim 17, farther comprising the step of:

(d) selectively removing any elevated, remaining reacted and/or unreacted portion(s) of said at least one layer comprising at least one metallic passivant element which extend(s) above said upper surface of said layer of dielectric material, thereby making said upper surface of said at least one Cu metal feature substantially co-planar with said upper surface of said dielectric layer.

20. The method as inclaim 17, wherein:

step (a) comprises providing a semiconductor wafer having a dielectric layer on a major surface thereof which comprises a plurality of in-laid, unalloyed Cu metal features of different widths and/or depths for providing vias, inter-level metallization, and/or interconnection lines of at least one active device region or component formed on or within said semiconductor wafer.

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