JP2007508461A - Electroplating composition and electroplating method - Google Patents

Abstract

Disclosed is an electroplating composition and method for filling indented microstructures in a microelectronic workpiece during manufacturing of a semiconductor wafer or the like by metallization. The electroplating composition can include a mixture of copper and sulfuric acid, the ratio of copper concentration to sulfuric acid concentration being about 0.3 to about 0.8. Also, the disclosed electroplating composition provides a mixture of copper and sulfuric acid with a copper concentration near its solubility limit when the sulfuric acid concentration is about 65 to about 150 g / L (grams per liter of solution). Can be included. Such electroplating compositions can also include conventional additives such as accelerators, inhibitors, halides and / or smoothing agents. Disclosed is a method for electrochemically depositing a conductive material within a key point such as a groove and / or a contact hole formed in a semiconductor workpiece during manufacturing, and a plurality of anodic reactions using the disclosed electroplating solution Including methods suitable for the use of vessels.

Description

  This application claims priority to US patent application Ser. No. 10 / 688,420, filed Oct. 16, 2003, which is incorporated by reference in its entirety. TECHNICAL FIELD The present invention generally relates to an electroplating composition that deposits a conductive material in features such as grooves and / or contact holes formed in semiconductor workpieces. compositions and methods) and methods.

  In the manufacture of semiconductor integrated circuits and other microelectronic products from microelectronic workpieces such as semiconductor wafers or semiconductor wafer substrates, a metal layer is provided on the workpieces to electrically connect various elements on the integrated circuit. Interconnecting metallization, which interconnects, is often necessary. Electrical interconnects have traditionally been formed in semiconductor devices by first depositing a conductive layer on the surface of a semiconductor workpiece (eg, a wafer) by sputtering or similar techniques. Unnecessary portions of the conductive layer are removed by a chemical dry etching method using a pattern mask formed of a photoresist or the like. In previous devices, aluminum or an aluminum alloy was used to form the wiring circuit. However, in order to cope with an increasingly complicated semiconductor element, the wiring of the semiconductor element has to be made smaller and smaller. This, in other words, led to higher current densities and shorter lifetimes due to electromigration. In addition, thinning provides higher resistance that increases RC (resistance / capacitance) delay.

  In order to avoid excessive RC delay and device failure due to electromigration, metals such as copper having excellent conductivity and high electromigration resistance have been used to form the interconnects. However, it is difficult to dry etch copper or copper alloys deposited over the entire surface of the workpiece (as in the above-described process). For this reason, a new approach known as damascene processng has been adopted. First, a trench or canal is formed in a copper wiring according to a predetermined pattern on the workpiece surface for wiring. Also, in a double damascene pattern process, contact holes or vias are cut into the workpiece to connect a metal layer to its upper or lower metal layer. These grooves or contact holes are then filled with copper or a copper alloy. This method eliminates the need to remove unnecessary portions of the conductive layer by etching, and the workpiece surface needs to be polished to remove the excessive coating layer of the plated metal.

  However, the shape of the wiring groove and / or contact hole in the design of today's devices has a considerably large aspect ratio (ratio of depth to the width of the groove and / or contact hole) because the wiring width is narrower. . Small dimensions of key points such as device trenches and / or contact holes (for example, submicron of 1 μm, further submicron of 0.25 μm) are filled with a flat metal layer by a conventional sputtering method for depositing metal. Make it difficult to do. Chemical vapor deposition (CVD) has been employed to deposit various materials, but it is difficult to prepare a gas material suitable for copper or a copper alloy.

  Electrolytic plating by immersing the workpiece in a plating solution has subsequently been used to fill the grooves and / or contact holes with a material that requires electrical conductivity, typically copper or a copper alloy. . Electroplating methods typically require a thin, continuous, electrically conductive seed layer that is deposited on the workpiece prior to the plating process. The seed layer is generally formed from a conductive metal such as copper. Next, an electroplating of a desired metal is performed by applying an electric bias to the seed layer and exposing a workpiece such as a wafer substrate to an electroplating solution containing metal ions that applies plating to the entire seed layer in the presence of the electric bias. In general. An electroplating composition comprising copper (eg, copper sulfate) and an acid or conductive salt (eg, sulfuric acid) can be used. An acid such as sulfuric acid is added to the electroplating composition to impart high ionic conductivity to the plating composition necessary to achieve uniform electrodeposition. “Uniform electrodeposition” refers to the ability of a plating composition to deposit metal uniformly on a workpiece such as a wafer substrate. The acid does not participate in the electrode reaction, but reduces the resistivity in the electroplating composition, thus providing a conformal coverage of the plating material over the entire surface of the workpiece. When the copper concentration of the composition is low and the acid concentration is high, the throwing power of the composition is improved.

  A problem encountered with conventional plating solutions is that the deposition process in high aspect ratio grooves and / or contact holes is also affected by mass transfer, i.e. into the grooves and / or contact holes. This means that the diffusion of metal affects the reaction rate of the precipitation reaction in addition to the magnitude of the electric field (as is common to the larger critical elements). Thus, the rate at which the plating ions are supplied to the workpiece surface can limit the plating rate regardless of the voltage or current density applied to the plating surface. Highly conductive electroplating compositions that give good throwing power (e.g., high acid concentration compositions) do not provide good coverage and are within relatively small features on the device. That is, it does not fill the submicron size grooves and / or contact holes. This often leads to a reduction in the quality of the precipitate and leads to filling defects, typically voids. Voids often occur when the composition is used to fill relatively small grooves and / or contact holes. In order to obtain good quality precipitation, the mass transfer rate must be high in the precipitation process, and the decrease in the reactant concentration in the vicinity of or inside the grooves and / or contact holes must be small. However, typically in high acid concentration plating baths, the migration rate is limited by the relatively low metal ion concentration.

  The movement of plated metal ions is directly related to the concentration of plated metal ions in the electroplating composition. Higher metal ion concentrations result in faster metal migration into small points and higher metal ion concentrations in the depletion layer, i.e., in the boundary layer of the cathode surface, and therefore faster and more Good quality deposition can be achieved. However, in order to fill copper in the groove and / or contact hole of the substrate having a relatively large aspect ratio, when using a plating composition excellent in uniform electrodeposition and coating uniformity, as described above, Poor packing capacity. Before the trench and / or contact hole is filled, the entrance to the trench and / or contact hole is often blocked, which facilitates the formation of voids. Voids can also be caused by other forces such as non-uniform nucleation in the seed layer during plating, improper nucleation, and the generation of large particles in the plating. Unfortunately, typically when using low acids, plating compositions with high metal concentrations have poor throwing power and suppress the activity of the additive, resulting in areas that are not plated within the point.

  A significant number of voids and / or non-uniform deposition typically will severely reduce conductivity as well as poor electromigration resistance. In some cases, voids and / or non-uniformities may be large enough to cause open circuit and device failure. Briefly, as is known to those skilled in the art, when the copper concentration of the plating composition is low and the acid concentration is high, the plating composition has high conductivity and good polarizability, thereby providing uniform electrodeposition. Will be improved. On the other hand, it is known that when the copper concentration of the plating composition is high and the acid concentration is low, the metal ion migration of the composition is improved. In other words, there will be a sufficient metal ion concentration at the bottom of the high aspect ratio trench and / or contact hole to allow good point filling.

  Attempts to address the problems brought about by using conventional plating compositions (ie compositions with low copper concentration and high acid concentration or visa versa) are not fully satisfactory. There wasn't. For example, various additives such as specific inhibitors, accelerators and / or levelers have been used at various concentrations. Other additives that may be used include halide ions such as chloride. The additive used is known to those skilled in the art, but depends on whether the plating composition has a high acid concentration and a low copper concentration, or the opposite. Certain additives reduce the deposition rate of metal atoms at a certain potential, thereby inhibiting the deposition process, while other additives increase the deposition rate of metal ions at a certain potential. Can accelerate the deposition rate. Unfortunately, available plating compositions have not fully solved the feature filling problem when processing relatively high aspect ratio key points where metal ion migration is somewhat limited.

  The electroplating composition and electroplating method of the present invention, as will be described in detail below, provide a surprisingly good filling capacity, from the bottom to the top of the high aspect ratio sub-micron size aspect. The filling capacity ensures better copper deposition and reduces or eliminates the presence of voids. Using the electroplating composition and method, the metal can be electroplated within the gist of the device, such as a trench and / or contact hole in a semiconductor device having a high aspect ratio of the semiconductor workpiece. The disclosed compositions and methods are applicable to a wide range of processes used to produce workpiece metal layers. To simplify the description, the compositions and methods are discussed primarily in the context of key metallization formed on semiconductor wafers that are processed to form integrated circuits or other microelectronic components. . The disclosed compositions and methods are not limited to the semiconductor wafer or point, but can be used in connection with any workpiece requiring metallization. The term "workpiece" is not limited to a semiconductor wafer, but rather refers to a relatively thin substrate having generally parallel planar first and second surfaces and a semiconductor wafer. In addition to ceramic wafers, microelectronic circuits or components, data storage elements or layers, and / or other substrates on which micromechanical elements are formed.

  The electroplating composition includes copper and acid that have previously avoided relative concentration. The electroplating composition provides a surprisingly good filling capacity, especially the ability to deposit copper from the bottom to the top for high aspect ratio key points of sub-micron dimensions (eg, 0.12 μm grooves). Reducing or substantially eliminating the presence of voids. Furthermore, the electroplating composition has less corrosion towards the seed layers and provides an excellent filling capacity as well. The electroplating composition can include an aqueous mixture of copper and sulfuric acid, wherein the ratio of copper concentration to sulfuric acid concentration (concentration is g / L) is from about 0.3 to about 0.8. The composition can also include an aqueous mixture of copper and sulfuric acid where the copper concentration is near its solubility limit when the sulfuric acid concentration is from about 65 to about 150 g / L. The composition may also contain conventional additives such as accelerators, inhibitors, halides and / or smoothing agents. The disclosed method utilizes an electroplating composition that deposits copper on a semiconductor workpiece. In addition, the method ensures excellent copper deposition with bottom-to-top filling capacity for high aspect ratio sub-micron sizes, reducing the presence of voids or substantially eliminating voids. To.

Do conventional electroplating compositions consisting of acids such as copper and sulfuric acid have a relatively low acid concentration whenever the copper concentration is relatively high to reduce the effects of heat and provide reasonable filling capacity? Alternatively, whenever the copper concentration is relatively low, it has a relatively high acid concentration so that the throwing power of the plating composition is good. The electroplating composition of the present invention does not follow such conventional wisdom. Indeed, the compositions of the present invention have an equivalent copper concentration that is closer to the acid concentration.
In a particular embodiment, the electroplating composition devised according to the present invention comprises an aqueous mixture of copper and sulfuric acid, the ratio of copper concentration to sulfuric acid concentration (all concentrations described as g / L being solution 1 Gram per liter) is from about 0.3 to about 0.8. In another specific embodiment, the electroplating composition comprises a mixture of copper and sulfuric acid, and the ratio of copper concentration to sulfuric acid concentration is from about 0.4 to about 0.7. In yet another embodiment, the electroplating composition comprises a mixture of copper and sulfuric acid and the ratio of copper concentration to sulfuric acid concentration is from about 0.5 to about 0.6.

In other embodiments, the electroplating composition comprises an aqueous mixture of copper and sulfuric acid, and the copper concentration in the composition is about 60, which is the solubility limit when the sulfuric acid concentration is about 65 to about 150 g / L. % To about 90%. In yet another embodiment, the electroplating composition comprises an aqueous mixture of copper and sulfuric acid, and the copper concentration in the composition is about its solubility limit when the sulfuric acid concentration is about 70 to about 120 g / L. It is in the range of 60% to about 90%. In another specific embodiment, the composition comprises an aqueous mixture of copper at a concentration of about 35 to about 60 g / L and sulfuric acid at a concentration of about 65 to about 150 g / L. In other embodiments, the composition comprises an aqueous mixture of copper at a concentration of about 45 to about 55 g / L and sulfuric acid at a concentration of about 75 to about 120 g / L.
Any electroplating composition having copper and sulfuric acid in the above ranges will provide excellent fillability, but a particularly useful electroplating composition is about 40 g / L copper and about 100 g / L sulfuric acid. Or an aqueous mixture of about 50 g / L copper and about 80 g / L sulfuric acid. Other exemplary embodiments include about 60 g / L copper and about 65 g / L sulfuric acid, or an aqueous mixture of about 47 g / L copper and about 70 g / L sulfuric acid.

Examples of the copper source used in the electroplating composition of the present invention include, for example, copper sulfate, copper fluoborate, copper gluconate, copper sulfamate, copper sulfonate, copper pyrophosphate, copper chloride, copper cyanide, and the like. A copper salt such as a combination of Although reference is primarily made herein to copper sulfate, it should be understood that copper available from any suitable source can be used in the disclosed compositions.
The electroplating composition can be used in combination with sulfuric acid or in place of sulfuric acid, other mineral acids such as fluorinated boric acid, organic acids such as methanesulfonic acid (MSA), amidosulfuric acid, aminoacetic acid, and combinations thereof. A combination of acids and organic acids may be included. The electroplating composition can further include additives such as inhibitors, accelerators, smoothing agents, etc. to assist in filling small points.

  The electroplating composition may contain additives such as halide ions such as chloride, bromide, iodide, and combinations thereof. In certain embodiments of the disclosed composition, the amount is sufficient to interact and suppress copper deposition at a constant voltage, or to increase the overvoltage to obtain a given current density applied. In amounts, chloride is added along with certain inhibitory additives (eg, polyethers). As is known to those skilled in the art, the halide concentration added is typically determined by the operating parameters selected for the particular hardware. In certain embodiments of the disclosed composition, the halogen concentration is from about 10 ppm to about 100 ppm. For example, about 50 ppm of HCl can be added to an electroplating composition comprising about 50 g / L copper and about 80 g / L sulfuric acid. In another embodiment, about 20 ppm of HCl can be added to an electroplating composition comprising about 40 g / L copper and about 100 g / L sulfuric acid. Other suitable additives (those known to those skilled in the art) may be added that are used to assist the inhibitor that reduces the deposition rate and / or to assist the accelerator that increases the deposition rate.

Inhibitors generally increase cathode polarization and adsorb to the substrate surface, inhibiting or reducing copper deposition in the adsorbed region. Inhibitors added to the plating composition include, for example, inhibitors based on a two-component polyethylene glycol such as an inhibitor composed of a random / block copolymer of ethylene oxide and propylene oxide mixed in a wide range of ratios. Can be mentioned. For example, a copper CUBATH ViaForm inhibitor (DF75) commercially available from Enthone, Inc., West Haven, Connecticut, or Shipley, Marlborough, Massachusetts A commercially available Shipley C-3100 inhibitor may be used.
Electroplating composition embodiments can include any suitable type of inhibitor and concentration. For example, a copper / bath / viaform DF75 inhibitor can be used at a concentration of about 2 ml / L to about 30 ml / L, or about 2 ml / L to about 10 ml / L. As a further example, Shipley C-3100 inhibitors can be used at concentrations of about 5 ml / L to about 25 ml / L, or about 10 ml / L to about 20 ml / L. In certain embodiments, about 2 ml / L of CUBATH inhibitor is used in an electroplating composition comprising about 50 g / L copper and about 80 g / L sulfuric acid. In another example, a Shipley C-3100 inhibitor, commercially available from Shipley, Inc., of Marlborough, Mass., Is an electroplating containing about 40 g / L copper and about 100 g / L sulfuric acid at a concentration of about 17.5 ml / L. Used in the composition.

  The promoter competes with the inhibitor at the adsorption site that reduces cathode polarization and promotes copper growth in the adsorbed region. Examples of the accelerator used in the plating composition include sulfur-containing compounds such as disodium bissulfopropyl disulfide (SPS). Promoters with smaller molecular dimensions can diffuse faster than inhibitors. For example, a commercially available CUBATH ViaForm accelerator (DF74) or Shipley B-3100 accelerator (available from Shipley) from Enson may be used. Embodiments of the electroplating composition can include an accelerator such as, for example, CUBATH ViaForm DF74. Such accelerators can be used at any suitable concentration from about 2 ml / L to about 30 ml / L, or from about 2 ml / L to about 8 ml / L. For example, about 5 ml / L of accelerator can be used in an electroplating composition comprising about 50 g / L copper and about 80 g / L sulfuric acid. About 8 ml / L of the above accelerator can be used for a seed layer having excellent coverage such as CVD. For seed layers with poor bottom coverage (eg, bottom void), about 2 ml / L of DF74 or similar accelerator can be used. In another embodiment, about 10 ml / L of Shipley B-3-3 accelerator (commercially available from Shipley) is used in an electroplating composition comprising about 40 g / L copper and about 100 g / L sulfuric acid. .

Since the inhibitor and the promoter are densely present around the main point, and the inhibitor inhibits the copper growth, a small overhang of the seed layer can block the main point leading to the void in the main point. Thus, an electroplating composition in which the majority of the inhibitor is active at the top of the topographic point and the promoter is superior to the inhibitor in activity within the point to achieve growth from bottom to top. Is particularly useful.
The concentration of such components can be varied to be optimal for specific hardware and / or desired operating conditions. Suitable concentration ranges for additives (eg, halides, accelerators, inhibitors, optional smoothing agents) to the electroplating composition are known to those skilled in the art, but the specific treatment and / or means selected ( tool: For example, it can be changed depending on specific operating conditions relating to temperature, rotational speed, flow rate, current density).

  If the accelerating reaction continues after filling the point, excessive copper growth occurs on the point, creating a protrusion on the surface. Therefore, a smoothing agent such as CUBATH ViaForm smoothing agent DF79 or Shipley U-3100 smoothing agent (commercially available from Shipley Co., Ltd.) commercially available from Enson can be added to the electroplating composition disclosed herein. Other suitable smoothing agents can be used to weaken the current in the protrusion and form a smoothed surface. Specific embodiments of the electroplating composition include a smoothing agent concentration of about 0.5 ml / L to about 3 ml / L or about 1.0 to about 3.0 ml / L. For example, an electroplating composition comprising about 50 g / L copper and about 80 g / L sulfuric acid can use about 2.5 ml / L DF79 smoothing agent. In another example, an electroplating composition comprising about 40 g / L copper and about 100 g / L sulfuric acid can use about 2 ml / L Shipley U-3100 smoothing agent (commercially available from Shipley Company).

The operating temperature of the electroplating composition of the present invention can range from about 15 ° C to about 30 ° C or from about 22 ° C to about 27 ° C. For example, the operating temperature of an electroplating composition comprising about 50 g / L copper and about 80 g / L sulfuric acid has been found to be practical at about 25 ° C.
Methods of plating using the electroplating compositions of the present invention include, for example, Semitool, Inc., Kalispell, Montana, and Novellus Systems, San Jose, California. Inc.,), or a fountain plating reactor of the type currently marketed by Applied Materials, Inc. of Santa Clara, California. These instruments incorporate a plating reactor with an anode system that functions as a single anode, using either a single disk-like anode or a basket of anode particles.
However, a plating method carried out in a multi-anode reactor of the type described in US Pat. No. 6,497,801, US Pat. No. 6,569,297, US Pat. No. 6,565,729, and PCT Application Publication WO 00/61498. Are particularly suitable for use in the electroplating compositions described herein. US Pat. No. 6,497,801, US Pat. No. 6,569,297, US Pat. No. 6,565,729, and PCT application publication WO 00/61498 are incorporated herein by reference.

FIG. 7 (a) shows a partially schematic cross-sectional view of a typical plating station 110. The support member 140 includes a rotary motor 144 and a rotor 142 coupled thereto. Rotor 142 supports contact assembly 160. The rotor 142 can include a backing plate 145 and a seal 141. The backing plate 145 has a first position where it contacts the back side of the workpiece 101 (shown by a solid line in FIG. 7A) and a second position where the backing plate 145 is spaced from the back side of the workpiece 101 (FIG. 7 (a) (indicated by a broken line) and the workpiece 101 in the direction perpendicular to the workpiece 101 (arrow T).
The contact assembly 160 may include a holding member 162, a plurality of contacts 164 held by the holding member 162, and a plurality of shafts 166 extending between the holding member 162 and the rotor 142. Contact 164 may be a ring-type spring contact or other type of contact configured to lock to a portion of the seed layer on workpiece 101. Commercially available support members 140 and contact assemblies 160 can be used. Particularly suitable support members 140 and contact assemblies 160 are described in U.S. Patent 6,228,232, U.S. Patent 6,080,691, U.S. Patent Application 09 / 385,784, U.S. Patent Application 09 / 386,803, U.S. Patent Application 09 / 386,610, U.S. patent application 09 / 386,197, U.S. patent application 09 / 501,002, U.S. patent application 09 / 733,608, and U.S. patent application 09 / 804,696, all of which are incorporated herein by reference. Is done.

The plating station 110 includes a reaction vessel 130 having an external housing or chamber 131 and an internal chamber 132 (both chambers are schematically shown in FIG. 7A) disposed in the chamber 131. The internal chamber 132 holds at least one electrode (not shown in FIG. 7A), and guides the flow of a processing liquid such as an electroplating composition in the embodiment of the present invention to the workpiece 101. . The processing liquid overflows the weir (as indicated by arrow F) and flows into an external chamber 131 that captures the processing liquid for recirculation, reuse, or disposal.
At the time of operation, the support member 140 grips the workpiece 101 at a workpiece processing site (such as a plane of the workpiece) of the reaction vessel 130 and immerses at least the plating surface of the workpiece 101 into the processing liquid. A potential is applied between the plating surface of the workpiece 101 and one or more electrodes (described in more detail below with reference to FIG. 7 (b)) located in the inner container 132, in the treatment liquid. Create an electric field. For example, in one process, the contact assembly 160 is biased to a negative potential with respect to the electrodes in the inner vessel 132 to plate the conductive material onto the workpiece 101. Also, in one aspect of this process, one electrode (a “thieving” electrode) is biased to a negative potential with respect to the other electrode to control the application uniformity of the material to the workpiece 101.

FIG. 7 (b) is a schematic diagram of an embodiment of a reaction vessel 130 having multiple electrodes including a thief electrode. The reaction vessel 130 includes a spiral drainage channel 134 between the inner chamber 132 and the outer chamber 131. The drainage channel 134 receives the processing liquid such as the electroplating composition in the embodiment of the present invention that overflows the internal chamber 132, and guides the processing liquid toward the liquid outlet 135. The liquid flows into the internal chamber 132 through the primary inlet 136a and the secondary inlet 136b. The primary inlet 136 a is connected to a primary flow path 137 that guides a part of the processing liquid in the internal chamber 132 to the primary outflow guide 170. The primary outlet guide 170 has a hole 171 that guides the flow toward the central axis 139 of the inner chamber 132. As a result, the flow proceeds upward from the primary spill guide 170 toward the point of the workpiece to be filled.
The secondary inlet 136b can be connected to a dispensing device 189 that guides a secondary liquid, such as an electroplating composition, for example, the same or different from the embodiment of the present invention to a plurality of electrodes. The internal chamber 132 includes four concentric electrodes 180. Controller 183 is operatively connected to electrodes 180a-d to individually control the current flowing through each electrode and thus control the corresponding conductive path between the electrode and the workpiece point.

The electrode 180 is housed in a field shaping unit 176 having a plurality of corresponding electrode compartments 177 (shown as compartments 177a-177d) separated by a partition 178. The distributor 189 guides the secondary liquid to each compartment 177 via a plurality of corresponding distributor channels 179 (shown as distributor channels 179a-179d). Thus, the secondary liquid passes through the distributor 189, passes by the electrode 180, and travels upward toward the point of the workpiece. The effect of the field forming unit 176 on the electric field formed by the electrode 180 is as if the electrode 180 is located at the exit of each compartment 177, as indicated by the imaginary line electrode positions 181a-181d.
The primary outflow guide 170 forms an inwardly facing container wall 138 (shown in dotted lines in FIG. 7 (b)) that extends upward and outward from the primary fluid inlet 136a. A shield 184 having a hole 182 is located between the electrode 180 and the point of the workpiece 101 and can control the interaction of the point of the workpiece, the fluid flow and the electric field in the reaction vessel 130.

  In the reaction vessel 130 shown in FIG. 7B, each compartment 177 has one or more holes (eg, holes and / or slots) 174 through which liquid and bubbles pass. Accordingly, bubbles trapped in each compartment 177 travel radially outward through the holes 174 in each compartment until they flow out of the internal chamber 132. Each compartment 177 may include an interface member 175. The interface member 175 may include a filter or other element configured to trap air bubbles and other particles while allowing the secondary liquid to pass toward the point of the workpiece. it can. In another embodiment, the interface member 175 prevents or substantially prevents secondary fluid from passing toward the point, but allows the ions to pass toward the workpiece. including. Indeed, the secondary fluid flows out of the internal chamber 132 through the hole 174 and via the spiral drainage channel 134. The first fluid can be collected in a separated drainage (not shown). In another embodiment, the ionic membrane allows passage of fluid as well as ions.

One or more of the aforementioned reactor assemblies can be easily integrated into processing equipment that can perform multiple methods on a workpiece, such as a semiconductor microelectronic workpiece. One such processing device is an electroplating device commercially available from Semitool, Inc., located in Kalispell, Montana. 9A and 9B show examples of such integration.
The apparatus of FIG. 9A includes a plurality of processing stations 210. These processing stations comprise one or more cleaning / drying stations and one or more electroplating stations (other suitable immersion-chemical processing equipment can use electroplating compositions). The apparatus comprises a heat treatment station, such as 215, which includes at least one thermal reactor suitable for rapid heat treatment (RTP).
The workpiece is transferred between the processing station 210 and the RTP station 215 using one or more robot transfer mechanisms 220 arranged for linear movement along a central route 225. One or more stations 210 may also incorporate structures suitable for performing on-site cleaning. All processing stations, not just the robotic transfer mechanism, are placed in a storage box that is supplied with filtered air at a positive pressure, thereby floating in the air, which can reduce the processing efficiency of microelectronic workpieces. You can limit the amount of impurities.

  FIG. 9 (b) shows another representative processing apparatus that can use the electroplating composition of the present invention. The processing equipment shown in FIG. 9 (b) includes an RTP station 235 located in a portion 230 containing at least one thermal reactor, and can be integrated into the equipment set. Unlike the processing equipment of FIG. 9 (a), at least one thermal reactor is enabled by a dedicated robotic mechanism 240. The dedicated robot mechanism 240 receives the workpiece transferred to the robot mechanism by the robot transfer mechanism 220. Transfer can take place via an intermediate staging door / area 245. As such, it enables the reactor portion 230 of the processing equipment to be hygienically separated from other equipment portions. Furthermore, such a configuration allows an annealing station to be introduced as a separate module that is attached to enhance the performance of existing equipment sets.

The electroplating composition of the present invention can be used in any of a myriad of workpiece metallization processes that form interconnects and vias in the workpiece. For example, FIGS. 8 (a) -8 (d) show a flow chart of some possible electrochemical deposition metallization processes, using the disclosed electroplating composition, interconnects, vias or Other key points can be formed.
A typical damascene pattern processing flow is shown in FIG. In the damask pattern processing, the workpiece is first provided with a metal seed layer and a barrier / adhesion layer that is disposed on the insulating layer in which the grooves (or other key points of the device) are formed. The seed layer is used to pass current during the next metal electroplating process. Typically, the seed layer is a very thin layer of metal that can be applied using one of several methods. For example, a metal seed layer can be deposited by physical vapor deposition or chemical vapor deposition to produce a layer on the order of about 500 mm thick. Also, the seed layer can be formed from copper, gold, nickel, palladium, and most or all other metals. The seed layer is formed on an intricate surface due to the presence of grooves recessed in the insulating substrate or other key points of the device.

  In some methods, an electrochemical (electrode or electrolysis) repair or enhancement step of the seed layer is performed (not shown in FIG. 8 (a)) prior to using the electroplating composition of the present invention. . Specifically, the seed layer needs to be suitable for subsequent metal deposition, or an additional deposition step that provides an “enhanced” seed layer, with additional layers on the already existing seed layer. If a metal needs to be deposited and augmented, a seed layer such as a very thin seed layer can be repaired. The enhanced seed layer is typically nominally located at all points on the sidewalls of substantially all recessed points distributed within the workpiece, with the thickness located outside the workpiece surface. About 10% or more of the seed layer. For example, the seed layer enhancement process is performed as disclosed in US Pat. No. 6,290,833 and US Pat. No. 6,565,729, which are incorporated herein by reference. Once the seed layer enhancement process is performed, the process can proceed to a cleaning process.

With continued reference to FIG. 8 (a), a copper layer is electroplated in the form of a coating layer on the seed layer. The covering layer is plated to the extent that an upper layer is formed, and a copper layer is provided that fills a groove (or other element point) used to form the interconnect wiring. The copper layer can then optionally be washed, typically with DI (deionized) water, and the copper layer can (optionally) be dried. Washing / drying, if done, can be done in the chamber where the electrochemical plating occurs, or in another chamber depending on the plating equipment used.
Subsequently, the workpiece is transferred to a stripping unit where excess copper is removed, for example by bevel-etch. In some methods using the electroplating compositions disclosed herein, excess copper may be removed from the workpiece, for example, by methods such as those disclosed in US patents incorporated herein. It is selectively removed from the back side and / or the peripheral edge on the processing side of the workpiece. Thereafter, the workpiece that has been etched at an oblique angle and whose back side is cleaned can be cleaned. Backside cleaning and initial DI water wash can be performed simultaneously.

The plating, cleaning and etching steps may be performed in the same chamber or in separate chambers. The etched workpiece is subsequently annealed. Prior to annealing, the workpiece may be washed with, for example, DI water. The workpiece can be annealed by any suitable method. For example, the workpiece may be annealed by a conventional method using a heating furnace, or 100 ° C. or less by a method such as the method disclosed in US Pat. No. 6,508,920 incorporated herein. Or even at ambient room temperature. The workpiece can then be chemically mechanically polished to remove, for example, copper that has been deposited in excess of that desired for the device gist.
As shown in FIG. 8 (b), an alternative process that utilizes the electroplating composition of the present invention may be cleaned before copper deposition to limit surface defects and remove unwanted material therefrom. A pre-wetting step can be included. As shown in FIG. 8 (b), all of the pre-cleaning or wetting steps, copper plating, backside cleaning and / or bevel etching, and DI water cleaning steps can be performed with plating equipment. Good. Thereafter, an annealing process and a CMP process outside the plating apparatus are continued.

In another possible treatment suitable for use with the electroplating composition of the present invention, a seed layer repair or augmentation step can be performed prior to copper deposition (FIG. 8 (c)). The seed layer repair process may include electrochemical deposition of the second seed layer and then proceed to DI water cleaning. For example, the second seed layer can be deposited by any suitable means as described above. As shown in FIG. 8 (c), all of the steps of seed repair, copper plating, backside cleaning and / or oblique etching, and DI water cleaning may be performed with plating equipment. Thereafter, an annealing process and a CMP process outside the plating apparatus are continued.
In another alternative process utilizing the electroplating composition of the present invention, as shown in FIG. 8 (d), all of the steps of copper plating, backside cleaning / bevel etching, DI water cleaning, and annealing treatment May be performed with a plating apparatus. Thereafter, CMP can be performed outside the plating equipment.

  As described above, the electroplating composition of the present invention can be used in a large number of electroplating devices by any kind of metallization method for workpieces. In addition, a number of processing parameters can be used for the metallization process using the electroplating compositions disclosed herein. The processing parameters utilized will depend on the point being filled, the equipment used, and other such variables known to those skilled in the art. Although only an exemplary embodiment, one possible process is shown below.

  An acidic electroplating composition during the electrochemical deposition of copper within the point of the device, such as workpiece interconnects and / or vias (by one or all other suitable methods described above). A thin seed layer can be eroded (etched) that leads to void formation. Accordingly, a workpiece load bias of, for example, about 0.1 V to about 1.0 V can be applied to the plating surface of the workpiece while the workpiece is immersed in the electroplating composition of the disclosed embodiment. For example, it has been found that a load bias of 0.4 V or higher for a 200 nm workpiece results in filling of the void-free point. In order to further increase the plating efficiency, for example, for plating in which copper having a thickness of 1.0 μm is deposited on a 200 nm wafer, the wafer can be rotated at about 40 rpm to about 200 rpm while being immersed in the electroplating composition. During plating, the wafer is rotated at about 10 rpm to about 150 rpm. In an exemplary embodiment of the plating method, the wafer is immersed and rotated at about 75 rpm, and during plating, about 1.0 rpm is used for about 5 seconds and about 1.0 rpm for about 25 seconds at 1.0 A. Spin at 40 rpm and about 40 rpm for the remaining time required to deposit to the desired thickness at 4.5A. As is known to those skilled in the art, rotation speed, bias, and usage time depend on the plating equipment used and the element to be formed.

In order to further increase the plating efficiency, for example, for plating where 0.85 μm thick copper is deposited on a 200 nm wafer, the wafer was rotated at about 40 rpm to about 200 rpm while immersed in the electroplating composition. During plating, the wafer is rotated at about 10 rpm to about 150 rpm. In an exemplary embodiment of the plating method, the wafer is immersed and rotated at about 75 rpm, and during plating, about 75 rpm at 1.0 A for about 5 seconds, and about 40 rpm at about 1.0 A for about 5 seconds, Rotate at about 40 rpm for about 39 seconds at 2.0 A and about 60 rpm until the desired thickness is reached at 8.22 A.
Alternatively, and to further illustrate a possible method of setting the current density to increase plating efficiency, 1 μm of copper can be deposited on a 200 nm wafer having a copper seed layer of about 400 kg. The wafer can be rotated at about 150 rpm. The current density can be about ² mA / cm ² to about 70 mA / cm ² . Alternatively, it may be about 3mA / cm ^{2 ~} about 25mA / cm ² current density until the time to reach the desired thickness. Of course, the current density employed can be varied during the plating process, but typically it does not necessarily start at a low current density and end at a high current density.

Example 1 and Comparative Data Table 1 shows typical examples of the electroplating composition of the present invention.
Table 1
Component concentration (g / L)
Copper 50
Sulfuric acid 80
Accelerator (DF74) 5.0
Inhibitor (DF75) 2.0
Smoothing agent (DF79) 2.5
Hydrogen chloride 50 ^*
* Halogen concentration is ppm
At a suitable current density (eg, as described above), as in the results shown in FIGS. 2 (e), 3 (d), 4 (d)-(f), and 5 (b). Void-free filling was achieved using the electrochemical composition of this example.

  For comparison, a prior art electroplating composition was subjected to testing under the same conditions using the same additive at the same concentration. As can be seen in FIGS. 4 (a)-(c), some key points of voids were obtained. Specifically, prior art electroplating compositions containing a combination of conventional high copper and low acid (ie, 50 g / L copper and about 10 g / L sulfuric acid) resulted in vias with visible voids. . From a comparison of the results shown in FIGS. 4 (a)-(c) versus FIGS. 4 (d)-(f), the prior art high copper / low acid electroplating compositions (FIGS. 4 (a)-(c )) Demonstrates that the formation of interconnects with significant voids that appear as dark spots in the photograph in the lower region of the interconnects has occurred. Interconnect filling using an electroplating composition of one embodiment of the present invention as shown in FIG. 4 (d) causes the interconnect grooves to appear as can be seen in the photograph of FIG. 4 (d). Although stopped before full filling, a visible void-free interconnect was formed, which was a significant improvement over the results of conventional electroplating compositions. Furthermore, although the interconnect formed using the example electroplating composition as shown in FIG. 4 (f) shows some voiding, the number and size of voids in the interconnect is As can be seen in the photograph of 4 (c), significantly less compared to the voiding that occurs in the interconnects formed using the prior art high copper / low acid electroplating compositions, and It is getting smaller.

  For further comparison, another prior art electroplating composition (ie, conventional low copper / high acid composition) using the same additives (at the same concentration) under the same conditions As a result of the test, a groove having a void with a seam was formed as shown in FIG. Specifically, prior art electroplating compositions containing 20 g / L copper and 180 g / L sulfuric acid produced voids with seams in the metallized grooves. In comparison, an electrochemical plating composition of an embodiment of the present invention, specifically, a composition comprising 80 g / L sulfuric acid and 50 g / L copper (as shown in FIG. 5 (b)). B) A void-free point was produced in a groove of the same size.

Example 2 and Comparative Data Table 2 shows another example of the electroplating composition of the present invention.
Table 2
Component concentration (g / L)
Copper 40
Sulfuric acid 100
Accelerator (B-3100) 10.0
Inhibitor (C-3100) 17.5
Smoothing agent (U-3100) 3.0
Hydrogen chloride 20 ^*
* Halogen concentration is ppm
For example, at a suitable current density as described above, as shown in FIG. 6B, filling of vias without voids was achieved using the electroplating composition of this example in the present invention.
For comparison, a prior art electroplating composition was tested under the same conditions (in the same concentration) using the same additives as in Example 2. As can be seen in FIG. 6 (a), filling of voided vias was obtained with the prior art electroplating composition. Specifically, the comparative electroplating composition of the prior art consists of a conventional high acid and low copper combination (ie 20 g / L copper and 180 g / L sulfuric acid), as shown in FIG. As shown, the result was a via with a visible void, while the electroplating composition of the examples of the present invention showed surprisingly good results, as shown in FIG. Without via filling was achieved.

Example 3
As shown in FIGS. 2 (a)-(e), copper semiconductor interconnect trenches that are 1/2 the height of the interconnect and about 0.12 to about 0.15 .mu.m wide have various implementations. Filled using the example electroplating compositions, these compositions were varied in copper concentration with an acid concentration of about 80 g / L and compared to various prior art compositions. Specifically, as shown in FIGS. 2 (a) and 2 (c), using a prior art electroplating composition containing 20 g / L copper and 80 g / L acid, The groove was filled. As can be seen in the photographs of these drawings, the prior art low copper / high acid composition yields devices with visible voids. However, relatively, as shown in FIGS. 2 (b) and 2 (d), the electroplating composition of the present invention having a copper concentration and an acid concentration close to the limit of the solubility of copper is formed by voids formed. A device having a relatively small number of was obtained. Specifically, as shown in FIGS. 2 (b) and 2 (d), an interconnecting groove was filled using an electroplating composition containing 35 g / L copper and 80 g / L sulfuric acid. However, it gave excellent results.

Example 4
As the results summarized in the diagram of FIG. 2 (f) show a number of examples, electroplating compositions with increasing copper concentrations and relatively low acid concentrations were subjected to testing. This increase in copper concentration for low acid concentrations (contrary to conventional wisdom) again gave surprisingly good results.
Specifically, the additive concentration and the halide concentration were kept constant while changing the acid concentration and the copper concentration to 10 g / L to 150 g / L and 20 g / L to 50 g / L, respectively. After plating, the plated wafer was cut in the transverse direction to inspect for the presence of voids. Regarding the electroplating composition of each example subjected to the test, five points filled in each of three kinds of sizes (0.12, 0.15, 0.20 μm) were examined. The number of main points filled out of 5 was counted for each size. The perfect score is 5 for each size. This data is then input into a statistical analysis software tool (ie, JMP statistical analysis software program), which produced a graphical leverage plot shown in FIG. 2 (f). . As can be seen from FIG. 2 (f), an electroplating composition having a relatively high copper concentration and a relatively low acid concentration (that is, the electroplating of the embodiment of the present invention in which the copper concentration is close to the solubility limit). The composition) has a statistically significant improvement in the filling capacity from the bottom to the top of the point.

Example 5 and Comparative Data As shown in FIGS. 3 (a)-(d), using the following electroplating composition, the width of the interconnect is ½ and the width is about 0.15 μm. The copper semiconductor interconnect trench was filled. In the composition, the sulfuric acid concentration was changed by setting the copper concentration to 20 g / L or 50 g / L (in FIGS. 3A and 3B, 20 g / L copper and 80 g / L respectively). 150 g / L acid, in FIGS. 3 (c) and (d), 50 g / L copper and 10 g / L acid and 80 g / L acid, respectively). As shown in FIG. 3 (a), an electroplating composition containing 20 g / L copper and 80 g / L acid was used to fill the interconnect grooves.
For comparison, an electroplating composition similar to a conventional typical high acid / low copper composition containing 20 g / L copper and 150 g / L sulfuric acid as shown in FIG. Used to fill the interconnect grooves. With such a composition, again poor results were obtained.
For further comparison, as shown in FIG. 3 (c), an electroplating composition containing 50 g / L copper and 10 g / L sulfuric acid was used to fill the interconnect grooves. The results are shown in FIG. 3 (c) (note that the results shown in FIG. 3 (d) are excellent when the electroplating composition of the present invention is used as described in Example 1). Shows that

Example 6
As the results summarized in the diagram of FIG. 3 (f) further show, increasing the acid concentration while increasing the copper concentration to or near the solubility limit results in a statistically significant improvement in the filling of key points. The Numerous examples of electroplating compositions have been tested, and these compositions have stepped up acid concentrations and kept the copper concentration relatively high near the solubility limit at a particular acid concentration. .
Specifically, the additive concentration and the halide concentration were kept constant while changing the acid concentration and the copper concentration to 10 g / L to 150 g / L and 20 g / L to 50 g / L, respectively. After plating, the plated wafer was cut in the transverse direction to inspect for the presence of voids. Regarding the electroplating composition of each example subjected to the test, five points filled in each of three kinds of sizes (0.12, 0.15, 0.20 μm) were examined. The number of main points filled out of 5 was counted for each size. The perfect score is 5 for each size. This data was then entered into a statistical analysis software tool (ie, JMP statistical analysis software program), which produced the graphical leverage plot shown in FIG. 3 (f). As can be seen from FIG. 3 (f), when the copper concentration is at or near the limit of solubility, the filling ability from the bottom to the top of the point is improved statistically significantly.

  Although the electroplating composition and method of the present invention have been described with reference to a plurality of embodiments and examples, it is understood that the present invention is not limited to the above embodiments and examples. Let's go. On the contrary, the invention is intended to cover all modifications, alternatives, and equivalents falling within the spirit and scope of the invention as defined by the appended claims.

It is a graph explaining the solubility of copper sulfate in sulfuric acid at about 25 ° C. Copper having a width of about 0.12 μm to about 0.15 μm at half the height of the interconnect formed by the example of the electroplating composition with an acid concentration of about 80 g / L and varying the copper concentration 2 is a scanning electron microscope (SEM) photograph of semiconductor interconnects. Copper having a width of about 0.12 μm to about 0.15 μm at half the height of the interconnect formed by the example of the electroplating composition with an acid concentration of about 80 g / L and varying the copper concentration 3 is an SEM photograph of semiconductor interconnections. Copper having a width of about 0.12 μm to about 0.15 μm at half the height of the interconnect formed by the example of the electroplating composition with an acid concentration of about 80 g / L and varying the copper concentration 3 is an SEM photograph of semiconductor interconnections. Copper having a width of about 0.12 μm to about 0.15 μm at half the height of the interconnect formed by the example of the electroplating composition with an acid concentration of about 80 g / L and varying the copper concentration 3 is an SEM photograph of semiconductor interconnections. Copper having a width of about 0.12 μm to about 0.15 μm at half the height of the interconnect formed by the example of the electroplating composition with an acid concentration of about 80 g / L and varying the copper concentration 3 is an SEM photograph of semiconductor interconnections. It is an illustrative plot which shows the filling result to the main point when changing the ratio of acid / copper in the electroplating composition which raised the copper concentration of the sample continuously. An interconnection of a copper semiconductor having a height of about 0.15 μm at half the height of the interconnect formed by the embodiment of the electroplating composition with a copper concentration of about 20 g / L and varying the acid concentration. It is a SEM photograph. An interconnection of a copper semiconductor having a height of about 0.15 μm at half the height of the interconnect formed by the embodiment of the electroplating composition with a copper concentration of about 20 g / L and varying the acid concentration. It is a SEM photograph. An interconnection of a copper semiconductor having a height of about 0.15 μm and a half of the height of the interconnection formed by the embodiment of the electroplating composition with a copper concentration of about 50 g / L and varying the acid concentration. It is a SEM photograph. An interconnection of a copper semiconductor having a height of about 0.15 μm and a half of the height of the interconnection formed by the embodiment of the electroplating composition with a copper concentration of about 50 g / L and varying the acid concentration. It is a SEM photograph. It is a SEM photograph of an interconnection groove having a width of about 0.023 μm and a half of the height of the interconnection groove before electroplating. It is a graphical plot which shows the filling result to the main point when changing the acid / copper ratio in the electroplating composition which raised the acid concentration of the sample continuously. A copper semiconductor having an acid concentration of about 10 g / L and a copper concentration of about 50 g / L, which is half the height of an interconnect formed by a prior art electroplating composition and a width of about 0.25 μm. It is a SEM photograph of interconnection. A copper semiconductor having an acid concentration of about 10 g / L and a copper concentration of about 50 g / L, which is half the height of an interconnect formed by a prior art electroplating composition and a width of about 0.25 μm. It is a SEM photograph of interconnection. A copper semiconductor having an acid concentration of about 10 g / L and a copper concentration of about 50 g / L, which is half the height of an interconnect formed by a prior art electroplating composition and a width of about 0.25 μm. It is a SEM photograph of interconnection. The height of the interconnect formed by an embodiment of the electroplating composition of the present invention with an acid concentration of about 80 g / L and a copper concentration of about 50 g / L, and a width of about 0.25 μm. 4 is an SEM photograph of copper semiconductor interconnects. The height of the interconnect formed by an embodiment of the electroplating composition of the present invention with an acid concentration of about 80 g / L and a copper concentration of about 50 g / L, and a width of about 0.25 μm. 4 is an SEM photograph of copper semiconductor interconnects. The height of the interconnect formed by an embodiment of the electroplating composition of the present invention with an acid concentration of about 80 g / L and a copper concentration of about 50 g / L, and a width of about 0.25 μm. 4 is an SEM photograph of copper semiconductor interconnects. A copper semiconductor having an acid concentration of about 180 g / L and a copper concentration of about 20 g / L, which is half the height of an interconnect formed by a prior art electroplating composition and a width of about 0.2 μm. It is a SEM photograph of interconnection. Half the height of the interconnect formed by the embodiment of the electroplating composition of the present invention with an acid concentration of about 80 g / L and a copper concentration of about 50 g / L, and a width of about 0.2 μm. 4 is an SEM photograph of copper semiconductor interconnects. Via of a copper semiconductor having a width of about 0.16 μm and half the height of a via formed by a conventional electroplating composition having an acid concentration of about 180 g / L and a copper concentration of about 20 g / L It is a SEM photograph of. The height of the via formed by the example of the electroplating composition in the embodiment of the present invention in which the acid concentration is about 100 g / L and the copper concentration is about 40 g / L, and the width is about 0. It is a SEM photograph of a via of a copper semiconductor which is 16 μm. 1 is a cross-sectional view of a representative electrical processing station with a processing chamber or reactor for processing equipment that utilizes an electrochemical composition. 1 is a partial cross-sectional view of a typical processing chamber or reactor that can utilize an electrochemical composition. FIG. 2 is a representative process flow chart illustrating one of many possible methods for performing metallization of a semiconductor workpiece utilizing the electrochemical compositions and methods of the present invention. 2 is a representative process flow chart illustrating one of many possible methods for performing metallization of a semiconductor workpiece utilizing the electrochemical compositions and methods of the present invention. 2 is a representative process flow chart illustrating one of many possible methods for performing metallization of a semiconductor workpiece utilizing the electrochemical compositions and methods of the present invention. 2 is a representative process flow chart illustrating one of many possible methods for performing metallization of a semiconductor workpiece utilizing the electrochemical compositions and methods of the present invention. 1 shows representative processing equipment that can utilize an electroplating composition. 1 shows representative processing equipment that can utilize an electroplating composition.

Claims (69)

  An aqueous-based electroplating composition comprising about 35 to about 60 g / L copper, about 65 to about 150 g / L sulfuric acid, and a glycol-based inhibitor.   The composition of claim 1, wherein the glycol-based inhibitor is present at a concentration of about 2 to about 30 ml / L.   The composition of claim 1 further comprising a copper deposition promoter present at a concentration of about 2 to about 30 ml / L.   The composition of claim 1, further comprising about 10 to about 100 ppm of halide ions.   The composition of claim 4 further comprising from about 30 to about 60 ppm hydrogen chloride.   An electroplating composition comprising about 35 to about 60 g / L copper, about 65 to about 150 g / L sulfuric acid, and about 2 to about 30 ml / L copper precipitation inhibitor, the balance being water A composition.   The composition of claim 6 further comprising a copper deposition accelerator at a concentration of about 2 to about 30 ml / L.   The composition according to claim 6, wherein the copper precipitation inhibitor is a random or block copolymer.   The composition according to claim 6, wherein the copper deposition inhibitor is a copper, bath, viaform inhibitor or Shipley C-3100 inhibitor.   The composition of claim 6 wherein the copper precipitation inhibitor is based on glycol.   The composition according to claim 6, further comprising a copper precipitation accelerator.   The composition of claim 11, wherein the copper deposition accelerator is a copper, bath, viaform accelerator or Shipley B-3100 accelerator.   The composition according to claim 11, wherein the copper deposition accelerator is SPS.   The composition of claim 6 further comprising from about 10 to about 100 ppm hydrogen chloride.   An aqueous electroplating composition comprising about 35 to about 60 g / L copper, about 65 to about 150 g / L sulfuric acid, about 2 to about 30 ml / L copper deposition accelerator, and about 2 to about 30 ml / L copper deposition inhibitor and about 40 to about 60 ppm hydrogen chloride.   The composition of claim 15, wherein the copper precipitation inhibitor is based on glycol.   The composition according to claim 15, wherein the copper deposition accelerator is a sulfur-containing compound.   The composition of claim 1 further comprising about 50 ppm hydrogen chloride.   An electroplating composition comprising about 45 to about 55 g / L of copper, about 75 to about 120 g / L of sulfuric acid, a copper deposition inhibitor, and a copper deposition accelerator.   20. The composition of claim 19, wherein the glycol based inhibitor has a concentration of about 2 to about 10 ml / L.   20. The composition of claim 19, further comprising a copper deposition promoter present at a concentration of about 2 to about 8 ml / L.   21. The composition of claim 19, further comprising about 10 to about 100 ppm halide ions.   20. The composition of claim 19, further comprising about 30 to about 60 ppm hydrogen chloride.   The composition according to claim 21, wherein the copper deposition accelerator is a sulfur-containing compound.   The composition of claim 19 further comprising a smoothing agent.   An electroplating composition comprising an aqueous mixture of copper and sulfuric acid having a copper / acid solution having a g / L ratio of about 0.4 to about 0.8, a copper deposition inhibitor, and a copper deposition accelerator. A composition comprising.   27. The composition of claim 26, wherein the copper precipitation inhibitor is a random or block copolymer.   27. The composition of claim 26, wherein the copper deposition inhibitor is a copper, bath, viaform inhibitor or Shipley C-3100 inhibitor.   27. The composition of claim 26, wherein the copper precipitation inhibitor is based on glycol.   27. The composition of claim 26, further comprising a copper deposition promoter present at a concentration of about 2 to about 30 ml / L.   27. The composition of claim 26, wherein the copper deposition accelerator is a copper, BATH ViaForm accelerator or Shipley B-3100 accelerator.   27. The composition of claim 26, wherein the copper deposition accelerator is SPS.   27. The composition of claim 26, further comprising about 10 to about 100 ppm hydrogen chloride.   An electroplating composition, an aqueous based mixture of copper and sulfuric acid having a copper / acid solution g / L ratio of about 0.3 to about 0.8, a copper deposition inhibitor, and a copper deposition accelerator Only an electroplating composition comprising a mixture of copper and sulfuric acid having a g / L ratio of copper to acid of about 0.3 to about 0.8 is used to deposit copper on the workpiece. Plating composition.   An electroplating composition, wherein when the sulfuric acid concentration is about 65 to about 150 g / L, the copper concentration in the composition is in the range of about 60% to about 90% of its solubility limit. A composition comprising an aqueous mixture, a copper deposition inhibitor, and a copper deposition accelerator.   36. The composition of claim 35, wherein the copper precipitation inhibitor is present at a concentration of about 2 to about 30 ml / L.   36. The composition of claim 35, further comprising a copper deposition promoter present at a concentration of about 2 to about 30 ml / L.   37. The composition of claim 36, further comprising about 10 to about 100 ppm halide ions.   37. The composition of claim 36, further comprising about 30 to about 60 ppm hydrogen chloride.   37. The composition of claim 36, wherein the copper precipitation inhibitor has a concentration of about 2 to about 10 ml / L.   37. The composition of claim 36, further comprising a copper deposition promoter present at a concentration of about 2 to about 8 ml / L.   The composition according to claim 36, wherein the copper deposition accelerator is a sulfur-containing compound.   37. The composition of claim 36, wherein the copper precipitation inhibitor is based on glycol.   An electroplating composition comprising about 40 g / L copper, about 100 g / L sulfuric acid, a copper deposition inhibitor, and a copper deposition accelerator.   45. The composition of claim 44, wherein the copper precipitation inhibitor is present at a concentration of about 2 to about 30 ml / L.   45. The composition of claim 44, further comprising a copper deposition promoter present at a concentration of about 2 to about 30 ml / L.   45. The composition of claim 44, further comprising about 10 to about 100 ppm halide ions.   45. The composition of claim 44, further comprising about 30 to about 60 ppm hydrogen chloride.   45. The composition of claim 44, wherein the copper precipitation inhibitor has a concentration of about 2 to about 10 ml / L.   45. The composition of claim 44, further comprising a copper deposition promoter present at a concentration of about 2 to about 8 ml / L.   45. The composition of claim 44, wherein the copper deposition accelerator is a sulfur-containing compound.   45. The composition of claim 44, wherein the copper precipitation inhibitor is based on glycol.   An aqueous electroplating composition comprising about 50 g / L copper, about 80 g / L sulfuric acid, about 2 to about 10 ml / L copper deposition inhibitor, and about 2 to about 8 ml / L copper deposition accelerator. A composition comprising an agent.   54. The composition of claim 53, further comprising about 10 to about 100 ppm halide ions. A method of plating a workpiece,
Supplying a workpiece having a plurality of key points of the element including the seed layer, and metallizing the key points of the element;
Using an electroplating composition comprising about 35 to about 60 g / L copper, about 65 to about 150 g / L sulfuric acid, and an inhibitor based on glycol, copper is deposited within the key points of the device. And a step comprising:   56. The method of claim 55, further comprising a seed enhancement treatment step.   56. The method of claim 55, further comprising cleaning and drying the workpiece, wherein the cleaning and / or drying is performed in a chamber in which copper is deposited.   56. The method of claim 55, further comprising selectively etching copper deposited on the workpiece.   56. The method of claim 55, further comprising the step of cleaning a back side of the workpiece after copper has deposited on the workpiece.   The method of claim 55, further comprising annealing the workpiece at a temperature of about 100 ° C. or less.   56. The method of claim 55, further comprising a pre-treatment step of cleaning the workpiece prior to depositing copper, wherein the pre-treatment step of cleaning the workpiece is performed in the same plating equipment that performs the precipitation. Method.   56. The method of claim 55, wherein the electroplating composition comprises about 35 to about 60 g / L copper, about 65 to about 150 g / L sulfuric acid, and about 2 to about 30 ml / L copper deposition inhibitor. A method of plating a workpiece,
Supplying a workpiece having a plurality of key points of the element including the seed layer, and metallizing the key points of the element;
About 35 to about 60 g / L copper, about 65 to about 150 g / L sulfuric acid, about 2 to about 30 ml / L copper deposition accelerator, about 2 to about 30 ml / L copper precipitation inhibitor, and about 40 to Depositing copper within a plurality of key points of the device using an electroplating composition comprising about 60 ppm hydrogen chloride.   The electroplating composition includes a mixture of copper and sulfuric acid having a copper / acid g / L ratio of about 0.4 to about 0.8, a copper deposition inhibitor, and a copper deposition accelerator. 63. The method according to 63.   The electroplating composition includes a mixture of copper and sulfuric acid having a copper / acid g / L ratio of about 0.3 to about 0.8, a copper deposition inhibitor, and a copper deposition accelerator, 64. Only an electroplating composition comprising a mixture of copper and sulfuric acid having an acid g / L ratio of about 0.3 to about 0.8 is used to deposit copper on the workpiece. Method. A processing method applying a metallized interconnect structure, comprising:
Supplying a workpiece having a metal seed layer formed by an initial deposition process;
A deposition process involving the supply of electroplating power to a plurality of concentric anodes located at different locations within the main fluid chamber of the reactor relative to the work piece, on the seed layer within the main fluid chamber of the reactor. Repairing the seed layer by electrochemically depositing additional metal to prepare an enhanced seed layer;
An electroplating composition comprising an inhibitor based on about 35 to about 60 g / L copper, about 65 to about 150 g / L sulfuric acid, and glycol is used to deposit metal on the enhanced seed layer. And a process for analyzing.   68. The treatment method of claim 66, wherein the electroplating composition comprises about 35 to about 60 g / L copper, about 65 to about 150 g / L sulfuric acid, and about 2 to about 30 ml / L copper deposition inhibitor. . A processing method applying a metallized interconnect structure, comprising:
Supplying a workpiece on which a metal seed layer is formed;
The seed layer is repaired by electrochemically depositing additional metal on the seed layer in the main fluid chamber by a deposition process that includes the supply of electroplating power to multiple electrodes in the main fluid chamber of the reactor. Providing an enhanced seed layer;
Individually controlling the supply of power to at least two electrodes during repair of the seed layer;
Using the electroplating composition comprising a mixture of copper and sulfuric acid having a copper / acid g / L ratio of about 0.4 to about 0.8, a copper deposition inhibitor, and a copper deposition accelerator, the seed layer Depositing copper on the enhanced seed layer under conditions where the deposition rate of the electrolytic deposition process is substantially faster than the deposition rate of the process used to repair the Method.   69. The treatment method of claim 68, wherein the electroplating composition comprises a mixture of copper and sulfuric acid having a copper / acid g / L ratio of about 0.3 to about 0.8.