The present invention relates to a semiconductor device production method, more particularly a method for forming a capping (metal) layer.
Higher operating speed of devices for a semiconductor have been required to achieve higher degree of integration and higher performance, which has been promoting further miniaturization and layer multiplication of internal wiring of LSIs. The miniaturization and layer multiplication increase interconnect resistance and also inter-wiring capacitance, and affect signal transfer speed in the interconnects. The resulting signal transfer delay time limits operational speed of the device. Therefore, the operational speed has been improved by lowering dielectric constant of the interlayer dielectric film to control capacity between the interconnects, and decreasing resistance of the interconnect material to decrease interconnect resistance.
Consequently, attempts have been made to use copper having a low specific resistance of 1.7 μΩcm as an interconnect material and a porous, low-k material for the interlayer dielectric film. For forming copper interconnects, grooved interconnects formed by the dual damascene method have been attracting attention, because dry etching of copper is generally not easy. One of the methods for forming grooved interconnects provides grooves of desired shape beforehand in an interlayer dielectric film of silicon oxide, deposits an interconnect material in the grooves, and removes the surplus interconnect material by chemical mechanical polishing (hereinafter referred to as CMP).
Copper may react with, or diffuse into, the dielectric film 4. In order to secure interconnect reliability, therefore, it is necessary to provide the capping (metal) layer 8 or barrier film 3 between the copper interconnect 2 and dielectric film 4. The materials traditionally used for a copper diffusion barrier are metal nitrides, e.g., titanium, tantalum and tungsten nitride, and high-melting metals, e.g., tantalum, tungsten and alloy thereof, as the barrier film 3. On the other hand, the capping (metal) layer 8 to be provided on the copper interconnect 2 has been made of an electroconductive material, which can decrease its dielectric constant.
It is necessary for the capping (metal) layer 8 of an electroconductive material to be selectively deposited on the upper surface of the copper interconnect. Consequently, electroless plating has been studied to provide the capping (metal) layer 8.
U.S. Pat. No. 5,695,810 discloses formation of a cobalt-tungsten-phosphorus electroconductive film as a capping (metal) layer by electroless plating. Sodium hypophosphite is commonly used as a reducing agent for cobalt-tungsten-phosphorus electroless plating. It is known that the compound is unreactive with copper and cannot be directly plated on copper. Therefore, it is necessary to coat the copper interconnect with a seed layer of palladium or the like, before a cobalt-tungsten-phosphorus film is electrolessly plated thereon.
JP-A-2001-230220 discloses a substituted plating method for depositing palladium by dissolving copper. However, this method, which needs dissolution of copper as an interconnect material, may involve a problem of significant local corrosion of copper resulting from, e.g., excessive dissolution of the grain boundaries of the copper crystal to deteriorate connection reliability of the copper interconnect. Moreover, when a porous low-K dielectric film is used, a plating solution may penetrate into the pores to cause problems, e.g., separation of the plating nuclei there, which can prevent the sufficiently selective deposition. These problems may deteriorate insulation between the interconnects, which is required to form fine interconnects.
JP-A-2002-151518 discloses deposition of a cobalt-tungsten-boron film, which directly reacts with copper, by electroless plating while dispensing with palladium. This method, however, involves a problem that the capping (metal) layer is not deposited in places on the fine interconnect sections as the miniaturization proceeds. It involves another problem, when a capping (metal) layer is to be deposited on a semiconductor coated with a porous dielectric film, that the plating solution may penetrate into the porous film to deteriorate insulation between the interconnects, resulting from, e.g., deposition of the metal in the film (see
As discussed above, the conventional electroless plating methods for depositing a capping (metal) layer involve problems related to selective deposition, e.g., the film may not be deposited to totally cover copper, or may be deposited on a dielectric film in addition to the interconnect (see
The present invention is developed to solve the problems involved in the conventional techniques. More specifically, it is an object of the present invention to provide a semiconductor device of high reliability by taking a step for preventing a plating solution from penetrating into the dielectric film before an electroconductive capping (metal) layer is deposited by electroless plating, and by selectively depositing the capping (metal) layer on the copper interconnect. It is another object of the present invention to provide a method for producing the same.
The method of the present invention produces a semiconductor device provided with a capping (metal) layer to cover a copper interconnect formed in a dielectric film, wherein the capping (metal) layer is formed by electroless plating in two stages, one of which is an electroless plating reacting only on the copper surface in the first stage and another of which is an electroless plating reacting on the copper and/or capping (metal) layer surface in the second stage.
The method of the present invention also produces the semiconductor device, wherein the porous dielectric film surface is made water-repellent for the portion which may come into contact with a plating solution, before the capping (metal) layer is deposited by electroless plating.
The semiconductor device of the present invention is provided with a capping (metal) layer to cover a copper interconnect formed in a dielectric film, and also with a barrier film covering the sides and bottom of the copper interconnect, wherein the capping (metal) layer comprises at least two layers of an electroconductive material.
The present invention adopts electroless plating to deposit an electroconductive capping (metal) layer on a copper interconnect, wherein the protective film is selectively deposited on the copper interconnect while preventing penetration of a plating solution into the dielectric film in which the copper interconnect is provided, to prevent deterioration of copper interconnect and device reliability.
Other objects, features and advantages of the invention will become apparent from the following description of the embodiments of the invention taken in conjunction with the accompanying drawings.
The preferred embodiments of the semiconductor device and semiconductor device production method of the present invention are described by referring to the drawings.
Steps (A) to (I) are repeated in a required number of cycles, to form a laminated interconnect layer (
The dielectric film 4 may be inorganic or organic. The inorganic dielectric film is preferably of a compound having the siloxane bond, e.g., SiO2, methyl siloxane, silsesquioxane hydride or methyl siloxane hydride. It can be formed by spraying or plasma-aided CVD. The organic dielectric film is of a hydrocarbon-based, low-k insulating material containing an aromatic ring. The commercial products useful for the film include Dow Chemical's “SILK” and “BCB”, Allied Signal's “FLARE”, and Schumacher's “VELOX”. These insulating materials are more preferably made porous, because decreased dielectric constant can be expected. The copper interconnect 2 can be formed electrical or electroless copper plating.
The barrier film 3 may be of a high-melting metal, e.g., titanium, tantalum, tungsten or alloy thereof, nitride, e.g., titanium, tantalum or tungsten nitride, or cobalt alloy, the film of which is produced by electroless plating.
The capping (metal) layer 1 is selectively deposited on the copper interconnect, as illustrated by the figures. The selective deposition is achieved by electroless plating. The method for producing the capping (metal) layer 1 is described.
In the porous dielectric film for the semiconductor device, the dielectric film surface is subjected to a hydrophobic treatment to form a hydrophobic surface 24. Next, the capping (metal) layer 101 is uniformly deposited on the surface 24 by electroless plating with a plating solution catalytically active on the copper surface and less active on the deposited metal (the solution is hereinafter referred to as the catalytic electroplating solution for undercoating) and then the capping (metal) layer 102 is deposited to a desired thickness by electroless plating with a plating solution active on the deposited metal (the solution is hereinafter referred to as the electroplating solution for thick film).
The dielectric film may be treated to have a hydrophobic surface with a known agent. The preferable agents include an alkyl silane coupling agent and surface treatment agent having a perfluoroalkyl group. The preferable catalytic electroplating solutions for undercoating include those containing an aldehyde, e.g., formaldehyde or glyoxylic acid, ascorbic acid, or borane complex, e.g., morpholine borane, as a reducing agent. The electroplating solution for thick film may be a known one having a gas barrier capacity. The one capable of forming a cobalt-tungsten-boron alloy is particularly preferable.
The capping (metal) layer 1 grows isotropically from the copper interconnect 2, by which is meant that it grows not only in the direction from the copper interconnect 2 upwards at a right angle but also in the direction from the copper interconnect 2 edge to the upper side of the barrier film 3 or further to the upper side of the dielectric film 4 by the distance same as thickness of the capping (metal) layer 1. It grows to the upper side of the barrier film 3 when the capping (metal) layer 1 is thinner than the barrier film 3, or to the upper side of the dielectric film 4 beyond the barrier film 3 when the capping (metal) layer 1 is thicker than the barrier film 3. Moreover, when the plating reaction on the surface of the barrier film 3 formed in Step (C) is active, the capping (metal) layer 1 extends isotropically from the barrier film 3 edge to the upper side of the dielectric film 4, as shown in
The semiconductor device illustrated in
In this embodiment, the dielectric layer serving as the etch stop layer is provided between the layers where no capping (metal) layer is provided. However, it may be provided only on the interconnect layer.
EXAMPLE 1 is described by referring to
Next, the coated substrate was treated by chemical mechanical polishing using a chemical mechanical polisher (IPEC's 472 type) with alumina-dispersed abrasive containing hydrogen peroxide at 1 to 2% and a pad (IC-1000 available from Rodel Corp.) at a polishing pressure of 190 G/cm2. It was polished up to the barrier film 3, to form the copper interconnect 2 after removing an interconnect conductor (
Then, the dielectric film surface was treated to be hydrophobic, where it was immersed in a 3% by weight solution of octadecyltrimethoxy silane/ethanol for 5 minutes, dried at 120° C., and then washed in isopropyl alcohol for 1 minute.
Next, the coated substrate was further coated with the first capping (metal) layer 101, where it was immersed in the plating solution described below and treated under the conditions also described below for cobalt-based electroless plating (
Next, the coated substrate was further coated with a second capping (metal) layer 102, where it was treated under the conditions described below for cobalt-based electroless plating and washed with pure water (
The semiconductor device thus prepared was processed by focused ion beams (FIB) to observe its cross-section including the wiring grooves 7 and connection holes 10 by a scanning electron microscope (hereinafter referred to as SEM). It was found that the copper interconnect 2 was coated with cobalt and cobalt-tungsten-boron alloy, uniformly deposited to form a 3 nm thick and 40 nm thick layer, respectively. Neither cobalt nor cobalt-tungsten-boron alloy were observed on the dielectric film surface or in the porous part in the dielectric film 4. The short-circuit test was carried out by applying a voltage between the interconnects. No short circuit was observed. The SEM analysis was conducted from the surface. No interconnect was found to have undeposited cobalt-tungsten-boron alloy. It was thus confirmed that the plating procedure adopted in EXAMPLE 1 provided the capping (metal) layers 1 selectively on the copper interconnect 2, causing no undeposition of the metals or deposition of the metals on any part other than the interconnect surface, like the one shown in
The cobalt alloy formed an electrolessly plated film, composed of 79% of cobalt, 20% of tungsten and 1% of boron, all percentages by atom, as confirmed by Auger electron spectroscopy.
As discussed above, by the plating procedure adopted in EXAMPLE 1, cobalt and cobalt-tungsten-boron alloy are selectively formed as the capping (metal) layers 1 on the copper interconnect 2. These capping (metal) layers 1 prevented oxidation of the copper interconnect 2 and diffusion of copper from the copper interconnect 2 to the dielectric film 4 to control increase of the copper interconnect 2 resistance, making the semiconductor highly reliable.
In EXAMPLES 2 to 6, the dielectric substrate described in Table 1 was coated with the layers, where the combination of the plating pretreatment steps was changed to evaluate the selective deposition. The semiconductor was prepared in each of EXAMPLES following the procedure similar to that for EXAMPLE 1. The dielectric film 4 prepared in each of EXAMPLES 4 to 6 and COMPARATIVE EXAMPLE 1 was not porous. Selectivity was evaluated by SEM analysis and elementary analysis based on energy dispersion X-ray (EDX) spectroscopy according to the following patterns. Evaluation of undeposited part
In COMPARATIVE EXAMPLES 1 and 2, the respective porous substrate and SiO2 dielectric substrate, also described in Table 1, were coated with the capping (metal) layer without having been pretreated for plating.
These results indicate that hydrophobicizing the dielectric film surface as a plating pretreatment step can control penetration of the plating solution into the porous body and resulting abnormal deposition of the metals therein, and the abnormal deposition on the dielectric film surface. Moreover, plating with a catalytic electroplating solution for undercoating prevents undeposition on the cupper interconnect surface. Therefore, these results have confirmed the effect of the present invention of producing a copper interconnect and device of high reliability.
In EXAMPLE 7, the capping (metal) layer 1 was prepared in a manner similar to that for EXAMPLE 1, and evaluated by a life test. The semiconductor prepared in EXAMPLE 7 was provided with a 4-layered capping (metal) layer, as illustrated in
Interconnect resistance increased by 2% after 600 hours and 5% after 1200 hours. No dielectric breakdown was observed after 1200 hours.
It was thus demonstrated that the semiconductor of this embodiment was stable over a long period of time. The reliability test with a voltage applied to the semiconductor also has confirmed the effect of the present invention of producing a copper interconnect and device of high reliability.
The semiconductor was prepared in EXAMPLE 8 in the same manner as in EXAMPLE 1, except that the dielectric film 26 was provided on the capping (metal) layer 1. The dielectric film 26 was of SiO2, which was not porous. It was subjected to the life test, conducted in the same manner as in EXAMPLE 7.
Interconnect resistance increased by 2% after 600 hours and 4% after 1200 hours. No dielectric breakdown was observed after 1200 hours.
It was thus demonstrated that the semiconductor of this embodiment was stable over a long period of time. The reliability test with a voltage applied to the semiconductor also has confirmed the effect of the present invention of producing a copper interconnect and device of high reliability.
It should be further understood by those skilled in the art that although the foregoing description has been made on embodiments of the invention, the invention is not limited thereto and various changes and modifications may be made without departing from the spirit of the invention and the scope of the appended claims.
The semiconductor production method of the present invention deposits a capping (metal) layer on a copper interconnect in a semiconductor, wherein the capping (metal) layer is deposited by electroless plating in 2 stages, with a plating solution active on the copper interconnect surface to form the first capping (metal) layer and then with another plating solution active on the copper and/or capping (metal) layer surface to form the second capping (metal) layer, to prevent undeposition of the capping (metal) layer thereby producing the copper interconnect and device of high reliability free of problems, e.g., oxidation of the copper interconnect resulting from the undeposition. The method of the present invention also treats the porous dielectric film to have a water-repellent surface for the portion which may come into contact with a plating solution to prevent penetration of the solution into the porous dielectric film and resulting abnormal deposition of the metals thereon, and also the abnormal deposition on the dielectric film between the interconnects before depositing the capping (metal) layer by electroless plating, in order to prevent short circuit between the interconnects and thereby to secure reliability of the copper interconnect and device.
Further, combining the above pretreatments enables the capping (metal) layer to be selectively formed only on the copper interconnect to provide a semiconductor device composed of highly reliable copper interconnect and device.
Number | Date | Country | Kind |
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2003-206653 | Aug 2003 | JP | national |