US20040065540A1 - Liquid treatment using thin liquid layer - Google Patents
Liquid treatment using thin liquid layer Download PDFInfo
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- US20040065540A1 US20040065540A1 US10/609,518 US60951803A US2004065540A1 US 20040065540 A1 US20040065540 A1 US 20040065540A1 US 60951803 A US60951803 A US 60951803A US 2004065540 A1 US2004065540 A1 US 2004065540A1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3205—Deposition of non-insulating-, e.g. conductive- or resistive-, layers on insulating layers; After-treatment of these layers
- H01L21/321—After treatment
- H01L21/3213—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer
- H01L21/32133—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only
- H01L21/32134—Physical or chemical etching of the layers, e.g. to produce a patterned layer from a pre-deposited extensive layer by chemical means only by liquid etching only
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1619—Apparatus for electroless plating
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1655—Process features
- C23C18/1664—Process features with additional means during the plating process
- C23C18/1669—Agitation, e.g. air introduction
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/1601—Process or apparatus
- C23C18/1633—Process of electroless plating
- C23C18/1675—Process conditions
- C23C18/1676—Heating of the solution
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/001—Apparatus specially adapted for electrolytic coating of wafers, e.g. semiconductors or solar cells
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/0206—Cleaning during device manufacture during, before or after processing of insulating layers
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
- H01L21/02074—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a planarization of conductive layers
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- H—ELECTRICITY
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/28—Manufacture of electrodes on semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/268
- H01L21/283—Deposition of conductive or insulating materials for electrodes conducting electric current
- H01L21/288—Deposition of conductive or insulating materials for electrodes conducting electric current from a liquid, e.g. electrolytic deposition
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- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/67—Apparatus specially adapted for handling semiconductor or electric solid state devices during manufacture or treatment thereof; Apparatus specially adapted for handling wafers during manufacture or treatment of semiconductor or electric solid state devices or components ; Apparatus not specifically provided for elsewhere
- H01L21/67005—Apparatus not specifically provided for elsewhere
- H01L21/67011—Apparatus for manufacture or treatment
- H01L21/6715—Apparatus for applying a liquid, a resin, an ink or the like
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- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/70—Manufacture or treatment of devices consisting of a plurality of solid state components formed in or on a common substrate or of parts thereof; Manufacture of integrated circuit devices or of parts thereof
- H01L21/71—Manufacture of specific parts of devices defined in group H01L21/70
- H01L21/768—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics
- H01L21/76838—Applying interconnections to be used for carrying current between separate components within a device comprising conductors and dielectrics characterised by the formation and the after-treatment of the conductors
- H01L21/76841—Barrier, adhesion or liner layers
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Abstract
A treating head having a treating surface and a substrate treatment surface define a thin fluid gap that is filled with reactant liquid to form a thin liquid layer on the substrate for conducting a liquid chemical reaction treatment or other liquid treatment of the substrate. The thin liquid layer has a volume in a range of about from 50 ml to 500 ml. Preferably, the chemical composition, temperature, and other properties of liquid in the thin liquid layer are dynamically variable.
Description
- This application claims the benefit of U.S. Provisional Application Serial No. 60/392,203, filed Jun. 28, 2002.
- The invention is related to the field of integrated circuit fabrication, in particular to methods and apparatuses for the deposition, removal, and treatment of thin films using liquid chemical reactions.
- Electroless plating (or electroless deposition) of copper and other metals has received increasing interest in recent years. This interest is due in part because of the relatively low cost of electroless processes compared to other (e.g., vacuum) deposition techniques, and because of generally surface-controlled, selective, conformal deposition properties of electroless processes. Electroless deposition has a number of potential applications, such as repair of marginal seed layers for copper damascene electroplating, creation of seed layers and barrier layers directly on dielectrics that can be plated, and selective deposition of barrier and electromigration capping layers onto damascene metal (e.g., cobalt and cobalt alloys on copper).
- Conventional electroless metal deposition is conducted in a system containing one or multiple open baths containing plating solution. In a typical operation, a wafer holder immerses a substrate wafer face down in the plating solution during plating operations. The plating solution is exposed to ambient air, especially when the substrate wafer is being moved and the wafer holder does not cover the plating bath surface. Thus, an open bath system has disadvantages. For example, during the metal deposition step, ambient oxygen is readily dissolved in the solution, and the dissolved oxygen can interfere with the desired metal deposition (e.g., by slowing or preventing metal deposition). Electroless plating operations are typically performed at elevated temperatures in a range of 40° C. to 90° C., typically in a range of about 50° C. to 80° C. The plating solution components have a tendency to evaporate. The tendency of water and volatile components to evaporate is exacerbated by the need to ventilate the gaseous spaces over a plating bath, especially to remove explosive or toxic fumes inherent to the electroless solution (e.g., ammonia gas) or created by spontaneous decomposition of its components (e.g., dimethylamine, hydrogen). The heating load caused by evaporation substantially increases the size and costs of a heater required to maintain plating bath temperature. Condensation of evaporate bath constituents on plating-cell walls and on the wafer holder are a source of backside contamination. Maintaining bath concentration, therefore, requires complicated and expensive monitoring and control techniques. See, for example, U.S. Pat. No. 6,537,416, issued Mar. 25, 2003 to Mayer et al., and U.S. patent application Ser. No. 10/272,693, filed Oct. 15, 2002, which are hereby incorporated by reference. A conventional electroless plating bath typically can have a bath volume of 20 liters or more. Typical bath turnover rates required to avoid plate-out and composition drift are 6 hours to 10 hours. Assuming a processing rate of 20 wafers per hour, approximately 160 wafers can be processed with 20 liters.
- A problem of both face-down and face-up plating configurations is hydrogen-bubble entrapment on the plating surface and resulting defects. Hydrogen gas is created as a byproduct of almost all known electroless plating-solution reducing agents. A byproduct of most electroless plating oxidation half-reactions (i.e., the oxidation of the reducing agent) and of the self-degradation of the reducing agents is dissolved molecular hydrogen (H2). As these reactions continue (i.e., plating reactions and bath-aging), the amount of hydrogen increases until the solution becomes saturated and eventually supersaturated with dissolved hydrogen. When this occurs, the formation of hydrogen gas (bubbles) is spontaneous, and occurs most readily on solid interfaces (e.g., vessel walls, wafer surfaces). Areas in which bubbles are attached to the wafer are not plated, creating defects. Therefore, it is advantageous to utilize designs that minimize the propensity for hydrogen formation, or minimize the effective bath age.
- Solution pH influences the reaction rate of the electroless plating process. It is often useful to utilize an alkaline pH-adjuster, for example, lithium-, sodium-, or potassium-hydroxide, but preferably ammonium- or tetramethylammonium hydroxide (“TMAH”) to maintain or adjust the pH. Alkali metal pH-adjusters are inexpensive, but are often unsuitable for semiconductor applications because of their rapid diffusion into and poisoning of various device materials. Ammonium hydroxide is also inexpensive and does not generally degrade device performance, but it is volatile. Therefore, the maintenance of ammonium hydroxide concentration in a plating bath is problematic. TMAH and other analogous organic cation hydroxides do not suff er from either of these problems, but are significantly more expensive. The constituents of a semiconductor electroless plating solution, particularly the reducing agents and TMAH, can be expensive, leading to bath costs in a range of $25/liter to $100/liter. Therefore, one would like to use lower cost materials without the negative impacts. Also, the waste treatment of electroless plating solutions is complicated and expensive. A waste treatment process generally involves forced decomposition of the reducing agents, accompanied by hydrogen gas stripping and dilution. A small amount of dissolved reducing agent can spontaneously breakdown to create a large volume of hydrogen gas in a storage container (an explosive hazard), so the stripping of reducing agents must be driven to completion. A plating solution must also be stripped of metal. The cost of such plating solution post-processing (including capital equipment costs) is typically in a range of $5/liter to $10/liter. Inefficient use of the plating solution, therefore, increases the cost of plating operations significantly.
- Electroless plating solutions are also often inherently unstable. The instability manifests itself in auto-degradation of bath constituents and in the “plating-out” of bath metal as fine metallic particulate in the bulk solution and onto processing equipment walls, filters, and other system components. The presence of plate-out particles also increases the number of defects in the workpieces and diminishes process yield. Generally, the instability of plating solutions increases with reducing agent concentration and with temperature, and decreases with the addition of bath “stabilizers” (e.g., oxygen, chlorine, lead, tin, cadmium, selenium, tellurium). In opposition to this trend, the initiation of electroless plating of a particular metal onto a substrate and the plating deposition rate are also proportional to reducing agent concentration and temperature, and decrease with the addition of bath stabilizers. Thus, plating-solution instability and electroless plating rate and nucleation are inherently linked in a non-advantageous manner.
- Spray techniques have been suggested for electroless plating. See, for example, U.S. Pat. No. 6,065,424, issued May 23, 2000 to Shacham-Diamand et al. In such techniques, reacting plating solution is applied to a wafer surface as a spray or mist. Typically, the wafer is rotating under the spray or mist, and liquid solution is spun radially outwards. Under such conditions, it is difficult to maintain a sufficiently high and uniform reaction temperature because of the simultaneous cooling of the hot fluid by evaporation of the solvent (e.g., water). Alternatively, heating the backside of the wafer by a heated chuck is possible. Nevertheless, this requires a relatively massive element with sufficient heat capacity to maintain a globally uniform temperature over a standard 200 millimeter (mm) or 300 mm wafer. Also, the face-up base of the heating element/chuck is susceptible to chemical contamination and transfer of that contamination to the wafer backside. Furthermore, backside heating does not solve the problem of non-uniform evaporation and cooling of the bath solvent. On the other hand, a wafer chuck should be capable of spinning at high-revolutions per minute (rpm) to enable spin-drying. Splashing of liquid against apparatus walls and misting back onto the product surface can cause contamination of the apparatus and defects on the workpiece. Evaporation and misting of plating solution into the plating space results in substantial loss of the plating solution, and unwanted formation of volatile hazardous chemicals in the effluent.
- Wet processing of isolated conductive-metal circuits connected to transistor elements in the presence of light often encounters a number of processing challenges. One problem is the creation of a photo-induced power source when p-n junctions in the base-circuit transistors are exposed to light. Another problem is the completion of a corrosion circuit on the surface being processed between the exposed isolated metal lines and a processing electrolytic solution. The energy of the light photons is converted to electrical energy, creating a reverse bias potential and a corrosion circuit.
- Thus, liquid chemical reaction techniques, for example, immersion bath and spraying techniques, typically encounter problems such as: difficult or unsuitable control of reaction and process conditions; inability to vary rapidly or dynamically various operating conditions; inability to handle unstable reaction mixtures; accumulation of reaction byproducts; inefficient use of expensive liquid solutions; frequent wafer-handling between process steps; high capital cost of equipment for multi-step processes; and excessive use of valuable clean-room floor space.
- The invention helps to solve some of the problems mentioned above by providing systems and methods for liquid treatment of integrated circuit substrates using a thin liquid layer.
- A novel thin-liquid-layer processing module enables processing of integrated circuit wafers with high throughput and low cost of ownership. Embodiments of such a module are useful for, among others: electroless plating (e.g., deposition of seed layers or the modification of vacuum-deposited seed layers by electroless copper deposition); selective electroless deposition of cobalt and nickel (including combinations of Co, Ni, B, P, and W using electroless process solutions); metal etching (e.g., etching of copper, Ta, TiSN, Co, Ni, etc.); electroless (chemical) polishing (e.g., of copper); various surface treatments (e.g., copper surface reaction with benzotriazole or 3-mercapto-1-propane sulfonic acid); and cleaning and rinsing operations. In particular embodiments in accordance with the invention, a cobalt alloy is electrolessly plated onto copper material in an integrated circuit substrate. An example is a cobalt-capping layer for capping copper.
- The invention is described primarily with respect to its application to electroless plating, but the invention also includes embodiments useful for other liquid treatments, particularly chemical liquid reaction processes and related pretreatment and post-treatment operations. For example, removal of metal layers is also conducted in accordance with the current invention.
- Embodiments in accordance with the invention enable efficient use of small volumes of often unstable fluid reactants and other processing chemicals at elevated temperatures, with preferred embodiments having the ability to recycle these chemicals to reduce operating costs further. Embodiments in accordance with the invention also provide efficient use of surface-cleaning and particle-removing chemicals and the use of minimal water for rinsing operations. Electroless (or chemical) plating, polishing, etching, and rinsing operations are conducted in accordance with the invention with a high degree of global uniformity, using a minimal amount of fluid reactant.
- A thin liquid layer in accordance with the invention is a micro-sized reactor or treatment bath having a volume of the thin fluid gap between a wafer substrate and a treating head. In this specification, therefore, a thin liquid layer for performing a liquid treatment of a substrate surface is sometimes referred to as a “microcell”. The terms “microcell”, “microcell technology”, “microcell module”, and related terms are also used to refer to an apparatus or method in accordance with the invention comprising a treating head that defines a thin fluid gap with a substrate surface, which fluid gap is10 filled with liquid to form a thin liquid layer. A “supercell” and related terms generally mean a module or apparatus comprising microcell technology combined with the capability of conducting a plurality of pretreatment, cleaning, treatment, and post-treatment operations in a single module, usually without moving a wafer substrate from one station to another.
- In one aspect of the invention, the small volume of a thin liquid layer provides control of the degree or extent of the particular treatment operation. For example, by inserting an aliquot of liquid reactant at a certain concentration into a fluid gap and allowing it to remain in the fluid gap for a time sufficient for a known reaction to run to completion or to an equilibrium point, a controlled known amount of material is deposited on the substrate. For example, a layer having a thickness of 50 nanometers (nm) is deposited by including a known number of moles of reactants in the thin liquid layer sufficient to deposit 50 nm of material, and no more. Similarly, in an etching operation, a desired thickness of material is removed from a substrate surface by including a known number of moles of reactants in the thin liquid layer and allowing them to react to completion.
- In another aspect, such measured deposition, etching, or other treatment operations are conducted in a series of steps. For example, a partial etching is conducted, the substrate's treatment surface is examined, and then a further operation is conducted to complete the etching. In another aspect, a treatment is conducted in a series of steps because a single step operation is undesirable or impossible because of the production of reaction byproducts or for other reasons. For example, in the electroless plating of cobalt on copper, oxidation of the reducing agent generates hydrogen gas. In some embodiments, since the liquid in the thin liquid layer has a limited solubility of hydrogen gas, the liquid is flushed from the fluid gap and replaced with fresh reactants.
- Another advantage of an apparatus and a method in accordance with the invention is that the composition and flowrate of a treatment liquid into a fluid gap is controllable and dynamically variable during treatment operations. In one aspect, certain processes of a substrate treatment, such as nucleation, are conducted under quiescent conditions by injecting an aliquot of reactant liquid into a fluid gap and allowing it to sit. In contrast, certain other processes, such as in a growth phase of electroless cobalt plating, liquid reactant is continuously flowed into the fluid gap, generating convection in the thin liquid layer.
- A microcell is suitable for solving various problems related to electroless plating. In electroless plating techniques, some chemical reactant solutions are chemically unstable. In conventional plating technology, which usually relies on a bath, multiple liters of reactant liquids and other processing liquids are used. When they are unstable and they turn bad, they can no longer be used. In a microcell in accordance with the invention, very small amounts of liquid are used per wafer substrate treated. A conventional immersion bath typically holds a volume of 15 liters to 20 liters. In contrast, the volume of a thin liquid layer in accordance with the invention is in a range of about from 10 milliliters (ml) to 2000 ml, typically 25 ml to 500 ml, and usually 25 ml to 300 ml, depending on wafer size.
- Electroless plating involves a chemical oxidation redox reaction of dissolved metal ions in solution to achieve the desired metal deposition on a substrate. The chemical reaction is typically sensitive to temperature and to pH. A treating head positioned proximate to the substrate wafer forms a fluid gap having a small volume. The fluid gap is filled with liquid reactants or other liquid, depending on the phase of the process. The small volume of the resulting thin liquid layer allows temperature and pH, as well as other process variables, to be controlled and varied effectively. Among other functions, the treating head serves as a pre-heated “thermal mass”, or “heat capacitor”, that heats or cools the reactant fluid and maintains it at a desired temperature. By changing the temperature of a treating head, the temperature of the thin liquid layer is changed to a new temperature.
- Embodiments in accordance with the invention also enable electroless plating in a dark, light-free environment.
- In another aspect, pretreatment, liquid chemical treatment, and post-treatment operations are conducted in the same module, or “supercell”. In another related aspect, a supercell in accordance with the invention comprises a plurality of treating heads for performing multiple operations in a single microcell module.
- In one aspect, a single tube or a plurality of tubes function as liquid inlet tubes into the fluid gap. Typically, the inlet tubes define holes located about the central axis of a treating head so that fluid is injected proximate to the center of the fluid gap and of the treatment surface. Alternatively, the inlet hole or holes are located near a peripheral edge of a treating head creating a type of flow front that moves across a treatment surface of a substrate from one side to the other. This alternative is useful in avoiding the formation of a trapped air pocket or bubbles at the center of a thin liquid layer. In another aspect of the invention, a centrally located showerhead arrangement distributes liquid flow into a fluid gap so that flow is less concentrated at any particular point and so fluid convection is more uniform across a treatment surface. It is found that a showerhead also helps prevent the formation of a trapped bubble during filling.
- In one aspect, a microcell comprises a manifold and a fluid cavity integral with a treating head. In another aspect, to provide balanced distribution of liquid flowthrough the several inlet tubes, a thin piece of diffusion membrane material is placed above the inlet tubes. Flow across the diffusion membrane into the inlet tubes occurs only when there is sufficient pressure differential between the upper and lower side of the diffusion membrane. If there is insufficient pressure differential for flow, no flow occurs. When the pressure differential is achieved, flow occurs relatively evenly across the membrane and into the plurality of inlet tubes and generates a correspondingly balanced liquid flow pattern into and through the fluid gap. In still another aspect, a recirculation tube is in fluidic communication with a liquid source tube from a liquid source and with a liquid inlet tube that leads to a fluid gap. Preferably, a recirculation tube, a liquid source tube, and a liquid inlet tube are connected through a multi-way valve.
- In still another aspect, a manifold bypass tube leads from a manifold cavity and is in fluid communication either with a liquid source, or a drain, or both. A manifold bypass tube allows liquid from a manifold to be recirculated. A manifold bypass tube also functions to release pressure from the manifold cavity, or prevent pressure from forming in the manifold cavity. In another aspect, a manifold cavity typically includes a bubble removal tube for removing gas from the manifold cavity and for releasing pressure. In another aspect, liquid is filtered just priorto entering the fluid gap, usually with a 0.05 micron or 0.1 micron filter (FIG. 9).
- Cobalt and some other metals are ferromagnetic. In one aspect of the invention, magnetic force is used to attract magnetic particles of cobalt (or other metal) and thereby remove cobalt-containing particulate matter from a chemical reactant liquid, from a liquid layer, or from the surfaces of a microcell apparatus. In another aspect, a magnetic field is formed in a microcell to control and focus deposition of cobalt (or other metal) onto a treatment surface. Thus, an electromagnet in the treating head or the substrate holder is used to enhance nucleation, growth, and selectivity. In still another aspect, the magnetic field created by cobalt deposited on a treatment surface (or other magnetic material on a substrate) is measured to determine the amount of material deposited, the thickness of the layer, thickness uniformity, and topography. This allows efficient endpoint determination. In another aspect, continuous measurement of magnetic fields created by deposited cobalt or other magnetic material enables real-time feedback and quality control.
- In still another aspect, light is shown into the fluid gap and an optical sensor measures reflectivity, spectra, or other optical property to measure layer thickness, layer uniformity, and topography.
- In another aspect, a treating head comprises a peripheral edge corresponding substantially in shape to an outer edge of an integrated circuit wafer, and the peripheral edge forms a peripheral slit with the outer edge of the integrated circuit wafer when the wafer is in the substrate holder. The peripheral slit typically comprises a width in a range of about from 0.0 mm to 0.5 mm. A thin fluid gap in accordance with the invention typically comprises a width substantially in a range of about from 0.1 mm to 4 mm. Accordingly, a thin fluid gap typically comprises a volume in a range of about from 30 microliters per cm2 to 300 microliters per cm2 of substrate treatment surface.
- Other features, characteristics and advantages of embodiments in accordance with the invention will become apparent in the detailed description below.
- A more complete understanding of the invention may be obtained by reference to the drawings, in which:
- FIG. 1 depicts a microcell device in accordance with the invention in which a treating head in a lowered, operating position and a substrate wafer form a fluid gap filled by a thin liquid layer;
- FIG. 2 depicts a microcell device in accordance with the invention in which the treating head is in a raised position;
- FIGS.3A-3D schematically depict the stages of liquid flowing through an inlet tube to form a thin liquid layer in a fluid gap in accordance with the invention;
- FIG. 4 schematically depicts a treating head comprising a megasonic cleaner for removing undesired metal particles from a treatment surface;
- FIGS.5A-5C schematically depict a rotation of a plurality of treating heads for performing a plurality of surface treatments in the same microcell module in accordance with the invention;
- FIGS.6A-6C schematically depict the lowering of a megasonic treating head into an operating position in accordance with the invention;
- FIGS.7A-7E schematically depict a cross-sectional view of treating heads in which the head surface shape is selected to influence temperature or fluid-flow distribution in a thin liquid layer;
- FIGS.8A-8E schematically depict various designs of inlet-hole locations in the head surface of treating heads in accordance with the invention;
- FIG. 9 schematically depicts a microcell module in accordance with the invention comprising a treating head with a manifold cavity and a plurality of inlet tubes;
- FIG. 10 schematically depicts a microcell module in accordance with the invention in which liquid reactant is heated, and then flows into a fluid gap, or alternatively is cooled and recirculated to the liquid source;
- FIG. 11 schematically depicts a microcell module in accordance with the invention in which liquid flows into a manifold cavity, and then flows through inlet tubes into a fluid gap, or alternatively recirculates to a liquid source, or both;
- FIG. 12 schematically depicts an exhaust, or pressure differential, chuck in accordance with the invention for holding a substrate by means of a pressure differential;
- FIG. 13 contains a cross-sectional view of a treating head system in accordance with the invention;
- FIG. 14 contains a process flow diagram for a microcell apparatus suitable for unstable reaction mixtures; and
- FIG. 15 shows the results of electromigration (EM) tests comparing EM lifetime in wafers having Co-capped Cu lines with EM lifetime in baseline wafers having Cu lines with no Co-capping.
- The invention is described herein with reference to FIGS.1-15. It should be understood that the structures and systems depicted in schematic form in FIGS. 1-14 serve explanatory purposes and are not precise depictions of actual structures and systems in accordance with the invention. For example, the depiction of fluid inlet and outlet streams in the figures below is different from hardware in actual embodiments. Furthermore, the embodiments described herein are exemplary and are not intended to limit the scope of the invention, which is defined in the claims below.
- The terms “liquid treatment”, “treatment”, and related terms are used in a broad sense in this specification to designate any liquid-phase treatment of an integrated circuit substrate, including, for example, pre-treatment operations, cleaning techniques, liquid chemical reactions, rinsing, drying, and post-treatment operations. The term “liquid chemical reaction treatment” is also used in a narrower sense and refers to a treatment conducted at the treatment surface of an integrated circuit substrate involving chemical reaction; for example, deposition, etching, and polishing operations. Broad categories of chemical liquid reaction treatments include electroless metal plating, electroless etching, electrolytic plating, electrolytic etching, metal-oxide deposition, and liquid dielectric deposition.
- The term “dynamically variable” and related terms means that a variable or parameter of an apparatus, method, or composition is variable during a treatment process.
- FIG. 1 depicts a planar
cross-sectional view 100 of amicrocell apparatus 102 in accordance with the invention for conducting a liquid treatment, particularly a chemical liquid reaction treatment, using a thin liquid layer.Microcell apparatus 102 comprises a treatinghead 104, shown in FIG. 1 in a lowered, operating position. In a lowered, operating position,head surface 106 of treatinghead 104 forms afluid gap 108 with a face-up substrate wafer 110. Thus,fluid gap 108 is located betweenhead surface 106 andtreatment surface 112 ofsubstrate wafer 110. During liquid treatment oftreatment surface 112 in accordance with the invention,fluid gap 108 is filled by a thin liquid layer. - In this specification, terms of orientation, such as “face-up”, “above”, “below”, “up”, “down”, “top”, “bottom”, and “vertical” used to describe embodiments relate to the relative directions in FIGS.1-4, 7, and 9-14 in which a substrate wafer defines a substantially horizontal plane. It is understood, however, that the spatial orientation of substrates and apparatuses in embodiments in accordance with the invention are not confined to those depicted in the drawings.
- In a typical electroless process, overtime the plating metal tends to plate onto any available metal surface. The ease of initiation of the plating depends on a number of variables, including roughness, surface oxides, metal catalytic reactivity with the reducing agent, and metal ion reduction charge transfer resistances. Therefore, the presence of metal surfaces of a treating head is problematic. Nevertheless, it is generally desirable to use metal because metals process high thermal conductivity. Therefore, to avoid undesired plating of plating metal onto the metal surface of a treating head, in certain embodiments the exposed head surface is covered with a plastic film, typically having a thickness of about 1 mm or less to minimize interference with heat exchange between the treating head and the thin liquid layer.
-
Reactor head 104 comprises a significant mass of a highly conducting material with a heat capacity substantially greater than that of the substrate. Generally, the total (not specific) heat capacity of the head is designed to be more than 10 times greater than that of the substrate, and the thermal conductivity of the heating mass in the head is designed to be as large as possible, generally greater than 0.2 Watt cm−1 K−1. Examples of suitable head materials are metals such as copper (Cu), aluminum (Al), titanium, and iron, particularly aluminum and copper. Because the material for the heating mass of the head may not be compatible with the reacting fluids (e.g., some electroless solutions have a tendency to plate onto a head metal), the bottom surface of the head is typically covered or coated with a thin film of a compatible material (not shown), such as a polyvinylidene difluoride (PVDF), polyethylene (PE), polypropylene (PP), or polytetrafluorethylene (PTFE) coating. The film is sufficiently thick (about 1 mm) to be continuous and to protect the head from spurious reaction and also to resist breaking under handling and typical operation. However, the thin protective film is also sufficiently thin so that it does not substantially reduce the heat-transferring ability of the head to treatment surface 112 (via the thin liquid layer of reactants in the fluid gap between the head and the substrate wafer). Preferably, the flow path of injected liquid through the head is thermally insulated to avoid premature thermal decomposition. Aliquid inlet tube 114 made of a suitable material (e.g., plastic) carries liquid tohead surface 106 of the head and intofluid gap 108 betweenhead surface 106 andtreatment surface 112 ofwafer 110. In a preferred embodiment, the liquid is directed to a number of fluid inlet holes (e.g., a “shower head” or distribution outlet) whose location and density are selected to improve and optimize the uniformity of the chemical reaction treatment. -
Microcell apparatus 102 includes areactor containment vessel 120 having anouter wall 122 and acontainment vessel bottom 124.Containment vessel 120 is made from material suitable for withstanding the temperatures and corrosive conditions of plating and etching operations. Examples of suitable materials include polyvinyl chloride (PVC), PVDF, PTFE and various copolymers, PE and PP.Microcell reactor 102 comprises awafer chuck 130 for supportingsubstrate wafer 110 havingsubstrate treatment surface 112, which is chemically treated in accordance with the invention.Wafer chuck 130 includes arotary shaft 132 connected to a motor (not shown) located belowcontainment vessel bottom 124.Wafer chuck 130 also includes three or more support pins 134 for holdingwafer 110 abovechuck arms 136. Alignment pins 138 are useful for centeringwafer 110 during its insertion intomicrocell module 102 via a wafer-handling robot arm, and are typically tapered to facilitate this operation. Alignment pins 138 also serve to containwafer 110 from spinning out during operations occurring with rotation (pre-wetting, thin film plating or etching, rinsing, and high speed drying). Designs and uses of a chuck have been described with reference to copper edge bevel removal (EBR) operations, for example, in U.S. Pat. No. 6,537,416, issued Mar. 25, 2003 to Mayer et al., which is incorporated by reference. - An
exit drain 140 is located atbottom 124 ofcontainment vessel 120. Rinse waste and reactant chemical material not otherwise diverted for recyclingexit containment vessel 120 throughdrain 140. Theinside bottom 142 ofcontainment vesse 120 is preferably sloped towardsexit drain 140 to facilitate draining. In a preferred embodiment,microcell reactor 102 contains a reactantrecycling diversion system 150.Diversion system 150 comprises one ormore troughs 152 located radially outward fromwafer 110.Troughs 152 preferably are movable up or down for alignment substantially with the horizontal plane ofwafer 110 to collect fluid 154 emanating fromwafer treatment surface 112 in a radial direction (which is induced in large measure by the rotation of the wafer surface). Connected to each of these troughs is aseparate drain hole 156. Atrough 152 is preferably designed such that fluid is directed downward and into adrain hole 156, typically by locatingdrain hole 156 at the lowest location of the trough. Drain holes 156 lead to aprimary drain tube 158. In a preferred embodiment,primary drain tube 158 fits inside asecondary drain tube 159 with a slightly larger diameter. Thus, aprimary drain tube 158 is movable up or down insecondary drain tube 159 and is designed with enough travel to stay always insidesecondary tube 159 over its normal length of operational travel. In certain embodiments, asecondary tube 159 is in fluid communication with a treatment liquid source (not shown) for recycling collected treatment liquid to the source. In one aspect, one or more collection troughs are activated for movement up or down, allowing a trough to be positioned relative to a substrate to capture liquid exiting from the thin liquid layer. Alternatively, the fluid gap may be moved with respect to a collection trough by moving a substrate together with the treating head up or down. Preferably, drains associated with each collection trough are separate, thereby allowing liquid collected in one drain to be processed differently from a liquid collected in another drain. For example, cleaning or rinsing liquid is typically discarded, whereas expensive plating liquid is collected and recirculated in certain embodiments. Electroless plating solutions may require expensive waste treatments, so separating concentrated plating waste from more dilute rinses is desirable. The path or trajectory of liquid exiting from a thin fluid gap depends strongly on the rotational speed of the substrate and is used to direct fluid into various troughs. If a substrate is spinning very quickly, liquid exits nearly horizontally. If spinning slowly or not at all (0 rpm to 10 rpm) during some period of the process, then the liquid tends to drip off the side of the wafer and it is collected in appropriately positioned collection troughs or at the bottom of a containment chamber in an exit drain. - FIG. 2 depicts a planar
cross-sectional view 160 ofmicrocell apparatus 102 in which treatinghead 104 is in a raised position.Microcell apparatus 102 optionally includes one or several rinsenozzles 161 or similar applicators for dispensing a thin film of deionized water (DI) or other solution onto substrate surfaces. Preferably,nozzle 161 is located at the periphery ofcontainment vessel 120 to spray liquid inward ontotreatment surface 112. For example, DI water or a solution containing a surfactant is useful for pre-wetting awafer 110, for removing air and entrapped bubbles from the wafer, and for rinsing chemical left after deposition or material-removal operations from awafer treatment surface 112. Optionally, heated DI is used to improve the efficiency of a liquid reaction treatment by minimizing heating times when hot reactant fluids are used subsequent to DI treatment. An optional rinse nozzle (not shown) directed at backside 162 of awafer 110 is useful for removing incidental presence of processing fluids from backside 162. Heating awafer 110 from both the top and bottom with hot DI is useful for preparing awafer 110 for heated processing, in some cases improving throughput. In some embodiments, after pre-wetting liquid is applied to awafer 110, a substantial fraction of the total pre-wetting liquid (which may contain DI water, surfactants, dilute acid, or reducing agents), is removed by spinning and is routed to exitdrain 140. - FIG. 2 depicts a magnetic source in the form of a
magnetic induction coil 180 embedded in treatinghead 104. In one aspect of the invention,magnet 180 generates a magnetic force to attract magnetic particles of cobalt (or other metal) and thereby remove metal-containing particulate matter from a chemical reactant liquid, from a liquid layer, or from the surfaces of a microcell apparatus. In another aspect,magnet 180 generates a magnetic field to control and focus deposition of cobalt (or other metal) onto a treatment surface. Thus, an electromagnet in the treating head or the substrate holder is used to enhance nucleation, growth, and selectivity. In still another aspect,magnet 180 generates a magnetic field, and amagnetic field sensor 182 proximate tosubstrate 110 measures the amount of ferromagnetic material deposited, the thickness of the layer, thickness uniformity, and topography. This allows efficient endpoint determination. In another aspect, continuous measurement of magnetic fields created by deposited cobalt or other magnetic material enables realtime feedback and quality control. - FIG. 2 depicts a
light source 184 and optical sensor 186.Light source 184 directs light at asubstrate 110, and optical sensor 186 measures reflectivity, transmittance, a spectrum, or other optical property to determine layer thickness, layer uniformity, and topography. - FIGS.3A-3D schematically depict stages of liquid flowing through an inlet tube to form a thin liquid layer in a fluid gap in accordance with the invention. Treating
head 204 withhead surface 206 is moved downwards (FIG. 3A) and formsfluid gap 208 betweenhead surface 206 and substrate wafer 210 (FIG. 3B). Reactant liquid 211 flows throughliquid inlet tube 214, and makes contact withwafer treatment surface 212 at wafer center 213 (FIG. 3B). The time at which the fluid is turned on, the drop rate of the head to the wafer, and the relative velocity between the head and the rotating (or stationary) wafer are controlled to develop a uniform wetting front emanating fromwafer center 213 and growing radially outwards (FIG. 3C). Eventually,gap 208 is filled with liquid, which formsthin liquid layer 220, and drops 222 emanate from peripheral slit opening 224 at a rate equal to the reactant feed rate (FIG. 3D). A particular wetting and filling operation depends on fluid temperature, viscosity, and surface tension, and on the approach velocity and relative rotation rates of treatinghead 204 andsubstrate wafer 210. - The term “flowing liquid into a thin fluid gap” and related terms in this specification are used broadly to refer to several different types of liquid flowing operations. In one sense, flowing liquid into a thin fluid gap means simply flooding the gap or filling it with the liquid to form a thin liquid layer in accordance with the invention. Then, after a thin liquid layer has been formed, the flow of liquid into the thin fluid gap ceases or continues at a same flow rate or continues at a different flow rate. In a second sense, therefore, flowing liquid into a thin fluid gap means continuously flowing liquid, either at steady-state or at an unsteady state, into a thin fluid gap and out of the gap at a corresponding flow rate. It is a feature of some embodiments in accordance with the invention that a liquid treatment can be conducted by filling a thin fluid gap with liquid to form a thin liquid layer, and then cease flow for a period of time, thereby conducting essentially a batch operation. On the other hand, continuous flow operations are conducted in some embodiments.
- The terms “upstream” and “downstream” are used in this specification in their usual sense with reference to directions of process flow streams and relative locations in a process.
- In another aspect, a treating head is heated and maintained at an elevated temperature by one or a plurality of means. In another aspect, an
electrical heating element 170 is attached to the top of (FIGS. 1, 2), or embedded into, a treating head. The temperature is controlled by a regulator that senses the head's temperature via thermocouple, thermistor, or similar device embedded in the bulk of the head. Alternatively, a heat exchange manifold with a high-surface-area fluid path interfaces with flow of an externally temperature-controlled head-exchange fluid. - A treating head rotates with the wafer, opposite to the wafer, or is stationary. Rotation enables modification and control of the hydrodynamics and mass transfer of reactants in the thin liquid layer to the treatment surface.
Fluid gap - In one aspect, pre-wetting and cleaning of the treatment surface is conducted before plating or other chemical liquid reaction treatment. For example, exposing the treatment surface with an activator solution prior to nucleation is conducted using a thin liquid layer in the fluid gap, or alternatively by spraying or otherwise rinsing the treatment surface.
- In another aspect, post-treatment scrubbing of a treatment surface is conducted using megasonic technology. A megasonic transducer is disposed proximate to the substrate treatment surface. In some embodiments, a liquid film is disposed on a substrate treatment surface and then a quartz rod or similar device with a transducer is extended over the treatment surface. The quartz rod vibrates at a very high frequency. The resulting pressure waves in the liquid provide sufficient mechanical energy to clean the treatment surface. For example, a commercially available megasonic device, sold under model name “Goldfinger”, operating at 830 kHz and 125 watts with approximately 50/1000 inch spacing between the unit and the treatment surface provides good cleaning of the substrate. A number of treatments are useful in combination with megasonic agitation in various locations of a microcell reactor for highly efficient cleaning and rinsing of apparatus surfaces. These cleaning treatments typically utilize commercially available proprietary solutions designed to complex with various metal ions, to alter the solution zeta potential, and to modify the surfaces' point of zero surface, thereby freeing the surface of particles.
- Thus, a reactor module in accordance with the invention is useful in combination with a number of other important devices and techniques. FIG. 4 schematically depicts a planar cross-sectional view300 of an apparatus 302 that contains an
alternative treating head 304 comprising amegasonic cleaner 305 for removing undesired metal particles from wafer 310 includingtreatment surface 312. A vibratingelement 316 typically is a rod, plate, or wedge. Vibratingelement 316 is connected to avibration transducer 318, which in turn is connected to a mounting plate or similar aligning fixture 319. The megasonic cleaner is a stand-alone element (as in FIG. 4) or it is integrated into head surface 306 of a treating head. In some embodiments, an apparatus in accordance with the invention comprises a polishing pad and head (not shown). In another aspect, treatinghead 305 or a polishing pad is moved in close proximity to substrate treatment surface 312 (preferably while it is rotating). - FIGS.5A-5C schematically depict a
head array 404 comprising a plurality of treating heads for performing a plurality of surface treatments in the same microcell in accordance with the invention. FIGS.5A-5C show the inherent flexibility of a treating head device combined with a face-up rotating wafer module. In FIG. 5A, amicrocell reactor head 406 for forming a thin liquid layer in a fluid gap is disposed in a raised position overcontainment vessel 408. Above the reactor treating head, attached to a rotarymain shaft 410 are amicrowave cleaning head 412 and treatingheads 415, 416. Examples of useful functional types of treating heads have been described above, but embodiments in accordance with the invention are not limited to those particular functions. In one aspect, a plurality of different reactor heads provide different operating conditions to effect different liquid chemical reaction treatments or other liquid treatments. A further example is a treating head that is specifically designed for rinsing the surface; for example, a plastic, unheated head that rotates with the wafer and has outlet holes for cleaning liquid. This is particularly useful when treating a surface that is hydrophobic in nature or has hydrophobic areas. A thin-gap-creating head over a hydrophobic surface makes it possible to maintain complete wetting using very little rinse water to clean surfaces. FIG. 5B shows partial rotation around rotarymain shaft 410. FIG. 5C shows completed rotation of cleaninghead 412 into a raised position abovecontainment vessel 408. FIGS. 6A-6C schematically depict the lowering ofmegasonic treating head 412 into an operating position in accordance with the invention. In FIG. 6A,head 412 is in a raised position abovecontainment vessel 404. FIG. 6B shows a partially loweredarray 404, and FIG. 6C showsarray 404 in a lowered position in which megasonic treatinghead 412 is disposed near to a treatment surface of a substrate wafer. - As depicted in FIGS. 1 and 2, treating
head 104 is characterized by ahead surface 106 having a shape that is substantially flat and horizontal. In other embodiments, a treating head has a head surface that has been shaped to control or improve process conditions; for example, to effect a more uniform temperature distribution or a desired fluid-flow distribution in a thin liquid layer. FIG. 7A schematically depicts a cross-sectional view of a treatinghead 450 with ahead surface 452 that is upwardly conical, typically forming an angle to the horizontal plane ofsubstrate 454 in a range of about from 1 degree to 30 degrees. A head surface shape as in FIG. 7A forms anarrow slit 456 at itsperipheral edge 457 withouter edge 458 ofsubstrate wafer 454, while the upward conical surface increases the volume offluid gap 459 compared to the volume formed by a flat head surface. FIG. 7B schematically depicts a cross-sectional view of a treatinghead 460 with acentral head surface 461 that is upwardly conical and with an outer head surface 462 that is substantially flat and horizontal. A head surface shape as in FIG. 7B forms anarrow fluid gap 464 withsubstrate 466 at its outer head surface 462, while upwardconical surface 461 increases the volume of the fluid gap compared to the volume formed by a flat head surface. FIG. 7C schematically depicts a cross-sectional view of a treatinghead 470 having acentral head surface 472 that is substantially flat and horizontal, and having anouter head surface 473 that is substantially flat and horizontal. Whenouter head surface 473 is positioned very near a substrate surface, it forms a narrowperipheral slit 474, but the width offluid gap 475 corresponding tocentral head surface 472 is wider and provides a larger volume. FIG. 7D schematically depicts a cross-sectional view of a treatinghead 480 having ahead surface 482 that is substantially convex relative to a face-upsubstrate treatment surface 484. FIG. 7E schematically depicts a cross-sectional view of a treatinghead 490 having acentral head surface 492 that is downwardly conical, and having anouter head surface 494 that is substantially flat and horizontal relative tosubstrate 496. A treatinghead 490 forms afluid gap 497 that is thin at the center of awafer 496, and is relatively thick at the edges of the wafer. - FIGS.8A-8E schematically depicts bottom views of treating heads showing various designs of inlet-hole locations in the head surface of treating heads in accordance with the invention. FIG. 8A depicts treating
head 510 havinghead surface 512 with a centrally locatedinlet hole 514. FIG. 8B depicts treatinghead 520 havinghead surface 522 with a centrally located showerhead arrangement of inlet holes 524 that distributes liquid flow into a fluid gap so that it is less concentrated at any particular point and so fluid convection is more uniform across a treatment surface. FIG. 8C depicts treatinghead 530 havinghead surface 532 with a plurality of inlet holes 534 extending fromcenter 536 on a radial path outwards to edge 538. FIG. 8D depicts treatinghead 540 havinghead surface 542 with a plurality of inlet holes 544 in a substantially straight line through the center of 546. FIG. 8E depicts treatinghead 550 havinghead surface 552 with aninlet hole 554 located near a peripheral edge, creating a type of flow front that moves across a treatment surface of a substrate from one side to the other. This alternative is useful in avoiding the formation of a trapped air pocket or bubbles at the center of a thin liquid layer. - FIG. 9 schematically depicts a
cross section 600 of amicrocell module 602 in accordance with the invention.Microcell module 602 comprises a microcell-reactor treating head 604 and a chuck 606 for holding asubstrate wafer 608. When asubstrate wafer 608 is present in substrate holder 606, treatinghead 604 andsubstrate 608 define athin fluid gap 612 that is located betweenhead surface 614 of treatinghead 604 andtreatment surface 616 ofsubstrate 608. Treatinghead 604 comprises amanifold cavity 618 and a plurality ofinlet tubes 620 that provide passage of fluid frommanifold cavity 618 through inlet holes 622 into afluid gap 612. Thus, treatinghead 604 serves as a showerhead-type inlet manifold for liquid and gaseous fluids intothin fluid gap 612.Microcell 602 further comprises amanifold inlet 624 through which fluid flows intomanifold cavity 618. In liquid treatment methods in accordance with the invention, liquid influid gap 612 forms athin liquid layer 626. Typically, the combination of treatinghead 604 and substrate-holding chuck 606 are contained within acontainment chamber 630 when treatinghead 604 is in a lowered position, as depicted in FIG. 9, proximate tosubstrate wafer 608 to formthin fluid gap 612.Containment chamber 630 comprises anexit drain 631. In certain preferred embodiments, treatinghead 604 comprises zonedheaters 632 controlled by conventional means. In another aspect, as depicted in FIG. 9, a substrate-holder chuck 606 comprisesbackside dispensing tubes 634 for directing heating fluid, deionized water, cleaning liquids orother liquids 635 atbackside 636 of asubstrate 608. In certain embodiments, chuck 606 includesbackside zone heaters 638 forheating substrate 608. A multizoned heater generates and controls a nonuniform heating profile in treatinghead 604 or in a substrate holder 606, and thereby enhances temperature control in athin liquid layer 626. Time-varying control of a heater allows dynamic variation of temperatures during the treatment process. -
Microcell apparatus 602 further includes a first source tube 640 and asecond source tube 642 from firstliquid source 644 and secondliquid source 646, respectively. In certain preferred embodiments in accordance with the invention, a plurality of liquid streams are mixed at or near the fluid gap, allowing an unstable chemical mixture to be formed at or near the point of use and thereby avoid premature reaction or decomposition. Accordingly, as depicted in FIG. 9,microcell apparatus 602 includes point of use mixer 648. First, and second liquid streams in first andsecond source tubes 640, 642, respectively, flow into mixer 648 where they are mixed. The mixed liquid stream exits mixer 648 and flows throughmanifold inlet 624 intomanifold cavity 618. - Treating
head 604 functions as a showerhead-type injection manifold and thereby provides distributed flow of liquid intofluid gap 612. In another aspect, adiffusion membrane 650 located inmanifold cavity 618 balances liquid flow frommanifold cavity 618 throughinlet tubes 620 intofluid 612. Typically, adiffusion membrane 650 rests onmanifold cavity bottom 652 and coversinlet tubes 620. In another aspect, ahydrophilic membrane 650 maintains bubble-free wetting of asubstrate treatment surface 616. Preferably, adiffusion membrane 650 is selected so that flow across the diffusion membrane into the inlet tubes occurs only when there is sufficient pressure differential between the upper and lower side of the diffusion membrane. If there is insufficient pressure differential for flow, no flow occurs. When the pressure differential is achieved, flow occurs relatively evenly across the membrane and into the plurality of inlet tubes and generates a correspondingly balanced liquid flow pattern into and through the fluid gap. - In still another aspect,
microcell apparatus 602 comprises amanifold bypass tube 660 that leads frommanifold cavity 618 and is in fluidic communication either with a liquid source, or a drain, or both.Manifold bypass tube 660 allows liquid from a manifold to be diverted and recirculated.Manifold bypass tube 660 also functions to release pressure from the manifold cavity, or prevent pressure from forming in the manifold cavity. By appropriate control ofmanifold bypass valve 662, liquid flow throughmanifold cavity 618 intothin fluid gap 612 is controlled. Althoughmanifold bypass 660 is depicted in FIG. 9 at the side of treatinghead 604, in practicemanifold bypass tube 660 is preferably located at thecenter 664 of treatinghead 604 to allow rotation of treatinghead 604. Chuck 606 is connected torotary shaft 666, which provides rotation ofsubstrate 608. - FIG. 10 schematically depicts a
cross-section 700 of a microcell module 702 in accordance with the invention. Microcell module 702 comprises a microcell-reactor treating head 704 and achuck 706 for holding asubstrate wafer 708. Treatinghead 704 and chuck 706 are disposed withincontainment chamber 710, which has anexit drain 711. When asubstrate wafer 708 is present insubstrate holder 706, treatinghead 704 andsubstrate 708 define athin fluid gap 712 that is located betweenhead surface 714 of treatinghead 704 and treatment surface 716 ofsubstrate 708. - A
liquid inlet tube 720 passes through treatinghead 704 andinlet hole 722 intofluid gap 712. During operation,fluid gap 712 is filled with liquid to form athin liquid layer 715 in accordance with the invention. Aliquid source tube 724 is in fluidic communication withliquid inlet tube 720 andrecirculation tube 726 through 3-way source valve 728. Liquid reactant is present inliquid source 730.Liquid source tube 724 is in fluidic communication withsource exit 732 ofliquid source 730. In certain preferred embodiments, microcell module 702 comprisesliquid heater 734, which heats liquid fromliquid source 730 as it flows intoliquid source tube 724. In more preferred embodiments, microcell module 702 comprises aliquid cooler 736 for cooling a heated recirculated liquid flowing inrecirculation tube 726 back intoliquid source 730.Valve 728 is controlled to control the portion of heated liquid inliquid source tube 724 that flows throughliquid inlet tube 720 intothin fluid gap 712.Valve 728 is controllable so that all, or none, or just a portion of liquid flowing inliquid source tube 724 flows intoliquid inlet tube 720. Preferably,valve 728 is dynamically controllable so that the amounts of liquid inliquid inlet tube 720 andrecirculation tube 726 are dynamically variable during treatment operations. In certain embodiments, microcell apparatus 702 includes aliquid recycle tube 740 with dynamicallycontrollable recycle valve 744 for recycling collectedliquid reactant 742 from the bottom of containment chamber 710 (or from adiversion system 150, as described with reference to FIG. 1) back toliquid source 730. - Reactant
liquid source 730 optionally includes a heat exchanger for cooling (to stop autocatalytic reactions) or heating (preparing the chemical for reaction and subsequent recycling). The choice of heating, cooling, recirculating, and recycling operations within microcell 702 in methods in accordance with the invention is determined by the properties of the particular materials/chemicals being used, their stability, and processing temperature. Chemicals and mixtures that are highly unstable are kept cool and then heated only right before application to the wafer. For example, in certain embodiments, cool fluid is pumped from aliquid source 730, heated in-line inheater 734, and/or heated in the intricacies of any feed lines imbedded in a heated treating head, and then introduced into the thin fluid gap beneath treating head. While the fluid is in the gap, it is also optionally being heated by aheated head 704. After use, the hot liquid is ejected fromgap 712 and recycled back to a cooled containment vessel via arecycling tube 740 or a reactantrecycling diversion apparatus 150, as described with reference to FIG. 1. Alternatively, collected liquid exits throughdrain 711 for waste disposal. More stable chemistries are maintained inliquid source 730 at or near an operating temperature desired in athin liquid layer 715. Commonly, a “bleed and feed” of the fluid in the reactant vessel is employed to avoid substantial changes to bath properties due to consumption of reactants in the process, dilution due to rinse water introduction to the bath, and auto-decomposition. Determination of the optimum liquid-source size and turnover rate is made according to reactant solution stability measurements consistent with the liquid-source turnover time (i.e., removal rate (liter/hr)/source volume (liter)). Removal rate calculations include considerations of evaporation, consumption, decomposition, rinse-water introduction, and efficiency of reactant-collection in a recycling diversion apparatus. - In another aspect, treating
head 704 typically comprises agas injection tube 746 for injecting inert gas intofluid gap 712 to ejectthin liquid layer 715.Gas injection tube 746 is also useful for removing gas bubbles fromthin liquid layer 715 influid gap 712 and for releasing pressure fromthin liquid layer 715. - Preferably, chuck706 includes
multizone heaters 747 for heating substrate wafer 716. - In another aspect, liquid is filtered just prior to entering the fluid gap, usually with a 0.05 micron or 0.1
micron filter 748 located inliquid inlet tube 720. - In another aspect, microcell702 preferably includes a plurality of
inert gas nozzles 752 located for creating an inert-gas blanket (e.g., nitrogen) around the outer edge of the wafer to inhibit or prevent air oxidation of the wafer surface andthin liquid layer 715. -
Chuck 706 is connected torotary shaft 766, which provides rotation ofsubstrate 708. - A thin liquid layer typically completely covers the treatment surface of a wafer substrate, even very hydrophobic surfaces, due to the proximity of the head surface to the substrate and to the combined properties of liquid viscosity and surface tension. The liquid in a thin fluid gap in accordance with the invention typically does not exit the surface of the wafer unless some external force is applied to it. Under typical process conditions, liquid does not begin to exit from the open edge of a thin liquid layer in a fluid gap having a peripheral-slit width of 1 mm to 2 mm until the substrate wafer is rotated about 50 rpm or greater. In some embodiments, gas is injected into the fluid gap to expel liquid from the fluid gap, thereby removing the surface tension and any associated suction between the treating head and a substrate wafer.
- FIG. 11 schematically depicts a cross-section800 of a
microcell module 802 in accordance with the invention.Microcell module 802 comprises a microcell-reactor treating head 804 and achuck 806 for holding asubstrate wafer 808. When asubstrate wafer 808 is present insubstrate holder 806, treatinghead 804 andsubstrate 808 define athin fluid gap 812 that is located betweenhead surface 814 of treatinghead 804 andtreatment surface 816 ofsubstrate 808. Treatinghead 804 comprises amanifold cavity 818 and a plurality ofinlet tubes 820 that provide passage of fluid frommanifold cavity 818 through inlet holes 822 into afluid gap 812. Thus, treatinghead 804 serves as a showerhead-type inlet manifold for liquid and gaseous fluids intothin fluid gap 812.Microcell 802 further comprises amanifold inlet 824 through which fluid flows intomanifold cavity 818. In chemical liquid reaction treatment or other liquid treatment methods in accordance with the invention, liquid influid gap 812 forms athin liquid layer 826. Typically, the combination of treatinghead 804 and substrate-holdingchuck 806 are contained within acontainment chamber 830 when treatinghead 804 is in a lowered position, as depicted in FIG. 11, proximate tosubstrate wafer 808 to formthin fluid gap 812.Containment chamber 830 comprises anexit drain 831. In certain preferred embodiments, treatinghead 804 comprises zonedheaters 832. In another aspect, as depicted in FIG. 11, a substrate-holder chuck 806 comprisesbackside dispensing tubes 834 for directing heating fluid, deionized water, cleaning liquids, orother liquids 835 atbackside 836 of asubstrate 808. In certain embodiments,chuck 806 includesbackside zone heaters 838 forheating substrate 808. A multizoned heater generates and controls a nonuniform heating profile in treatinghead 804 or in a substrate-holder 806, and thereby enhances temperature control in athin liquid layer 826. Time-varying control of a heater allows dynamic variation of temperatures during the treatment process. -
Microcell apparatus 802 further includes aliquid source tube 840 from liquid source 844.Liquid source tube 840 is in fluidic communication throughmanifold inlet 824 withmanifold cavity 818. - Treating
head 804 functions as a showerhead-type injection manifold and thereby provides distributed flow of liquid intofluid gap 812. In another aspect, adiffusion membrane 850 located inmanifold cavity 818 balances liquid flow frommanifold cavity 818 throughinlet tubes 820 intofluid 812. Typically, adiffusion membrane 850 rests onmanifold cavity bottom 852 and coversinlet tubes 820. In another aspect, ahydrophilic membrane 850 maintains bubble-free wetting of asubstrate treatment surface 816. Preferably, adiffusion membrane 850 is selected so that flow across the diffusion membrane into the inlet tubes occurs only when there is sufficient pressure differential between the upper and lower side of the diffusion membrane. If there is insufficient pressure differential for flow, no flow occurs. When the pressure differential is achieved, flow occurs relatively evenly across the membrane and into the plurality of inlet tubes and generates a correspondingly balanced liquid flow pattern into and throughfluid gap 812. - In still another aspect,
microcell apparatus 802 comprises a manifold bypass tube. 860 that leads frommanifold cavity 818 and is in fluidic communication throughbypass valve 862 with recirculation to 864.Manifold bypass tube 860 allows liquid from a manifold to be diverted and recirculated.Manifold bypass tube 860 also functions to release pressure from the manifold cavity, or prevent pressure from forming in the manifold cavity. By appropriate control ofmanifold bypass valve 862, liquid flow throughmanifold cavity 818 intothin fluid gap 812 is controlled. Althoughmanifold bypass 860 is depicted in FIG. 11 at the side of treatinghead 804, in practicemanifold bypass tube 860 is located at thecenter 864 of treatinghead 804 to allow rotation of treatinghead 804.Chuck 806 is connected torotary shaft 866, which provides rotation ofsubstrate 808. - In another aspect,
apparatus 802 typically comprises agas injection tube 868 located in treatinghead 804 for injecting inert gas intofluid gap 812 to eject thin liquid layer 815.Gas injection tube 868 is also useful for removing gas bubbles from thin liquid layer 815 influid gap 812 and for releasing pressure from thin liquid layer 815. - Thus, in one aspect of the invention, a liquid layer in a fluid gap is expelled by injecting gas into the fluid gap using sufficient pressure. Alternatively or additionally, the chemicals in the gap are flushed by flowing water through
manifold cavity 818 andinlet tubes 820. This flushing is typically followed with expulsion of the rinse water from the gap by injecting gas intofluid gap 812. When injected proximate to the center of the fluid gap, the gas displaces the liquid radially outwards. The trajectory of the injected liquid depends to a large degree on the pressure and flowrate of gas into the fluid gap and on the rotational speed of the substrate. Using corresponding collection troughs and exit drains as described above, ejected fluid is recycled, processed to recover components, processed to expel undesired byproducts, and recycled or discarded. In this manner, an expensive plating solution is used again. In a rinse phase, the treating head is still down. An objective of the rinse phase is to clean the wafer of residual chemicals, as well as clean the head. The treating head is rinsed to avoid evaporation of plating solution and resultant drying and plating of chemicals on the treating surface of the head. Typically, deionized rinsing water is injected through the treating head into the fluid gap and the substrate is spun at a relatively high rotation rate. Multiple rinses can be beneficial. In another aspect, the rotation rate is thereafter slowed down and the treating head is lifted. Preferably, the treating head is further cleaned in its upper position with a spray stream of deionized water or other cleaning liquid. - In an exemplary embodiment of the invention, a fluid gap is filled (flooded) to form a thin liquid layer on a 200 mm substrate wafer by spinning the substrate at a speed in a range of about from 10 rpm to 50 rpm, preferably about 25 rpm, and flowing liquid at a flowrate of about from 100 ml per minute to 500 ml per minute into the center of the fluid gap. Alternatively, a thin liquid layer is formed by flowing liquid from either a single hole or manifold with essentially the same rotation rate and flowrate, but flowing the liquid from an edge. During a plating operation, the rotation rate is typically in a range of from 0 rpm to about 100 rpm, and the liquid flowrate is anywhere from 0 ml per minute to 500 ml per minute.
- Certain embodiments in accordance with the invention include a substrate holder that comprises an exhaust chuck, in which a substrate is held in the chuck by means of a pressure differential. FIG. 12 depicts schematically a cross-sectional view870 of an
exhaust chuck system 872 located in containment chamber 874. As depicted with its essential elements in FIG. 12,exhaust chuck system 872 includessubstrate supporter 876 that supports asubstrate wafer 878. Anexhaust tube 880 is located inlower containment chamber 882. Typically, air or other gas is drawn from the bottom of containment chamber 874 throughexhaust tube 880. Anannular collar 884 in containment chamber 874 is located proximate tosubstrate 878, usually just below it, restricting gas flow from upper containment chamber 885 above the substrate tolower containment chamber 882 below the substrate.Annular collar 884 forms anarrow flow passage 886 between its inside collar edge 888 and outer wafer edge 890 ofsubstrate wafer 878. Anannular seal 892 creates a seal between anouter collar lip 893 and achamber wall lip 894 whenchuck system 872 is in a closed, chucking position, as depicted in FIG. 12.Narrow flow passage 886 typically has a width in a range of about from 1 mm to 7 mm. The constriction of flow causes a pressure differential, the pressure abovesubstrate 878 being greater than the pressure below it. The pressure differential creates a chucking action that holdssubstrate 878 onsubstrate support 876. This is an alternative to a conventional vacuum chuck, which pulls on the wafer and requires a rotary union inside to maintain the vacuum. The exhaust flow throughexhaust tube 880 is relatively uniform and thereby pulls the substrate uniformly down on supportingchuck base 876. With a 4-mm-flow-passage 886, about 1 meter per second of air flowing throughnarrow flow passage 886 produces about 20 pounds of force on a 200 mm wafer substrate. In another aspect,annular collar 884 is moved down (or up, depending on the particular configuration) for wafer handling using a collar-moving mechanism onupper chamber wall 895, which includesrotatable wheel 896. An example of a moving mechanism of a chuck is described in U.S. Pat. No. 6,126,382, issued Oct. 3, 2000 to Scales et al., which is hereby incorporated by reference. Asannular collar 884 is moved down,narrow flow passage 886 is opened, and the pressure differential is thereby removed. On the other hand, the exhaust flow throughexhaust tube 880 is typically maintained. An advantage of an exhaust chuck is that it eliminates clamps, pins, and other structural clamping and aligning structures that cause defects and interfere with maintaining and removing a thin liquid layer (not shown) onsubstrate 878. Preferably,annular collar 884 includes drain holes 897 for liquid drainage. - FIG. 13 contains a
cross-sectional view 900 of a preferred treating head system 902 in accordance with the invention. System 902 includes a treatinghead 904, asubstrate holder 906 for holding a substrate wafer 908, and a dam or fluid-bearing ring 910. Fluid-bearing ring 910 is connected to treatinghead 904 and forms a peripheral edge of treatinghead 904. Typically, fluid=bearing ring 910 is an integral part of treatinghead 904. During operation, with treatinghead 904 in a lowered position, fluid-bearing ring 910 andtreatment surface 911 of wafer 908 define a peripheral slit 912 nearouter edge 913 of substrate wafer 908. Fluid-bearing ring 910 typically comprises a radial thickness of about 1 mm. Fluid-bearing ring 910 is typically disposed in a range of about from 0.25 mm to 3 mm radially inwards fromouter edge 913 of wafer substrate 908. Fluid-bearing ring 910 typically protrudes about 0.1 mm to 1.5 mm below the plane ofhead surface 914 of treatinghead 904. Fluid-bearing ring 910 substantially encloses a fluid gap 915 defined byhead surface 914 of treatinghead 904 andtreatment surface 911 of substrate wafer 908. Fluid-bearing ring 910 constricts or prevents the flow of liquid from a thin liquid film out of fluid gap 915. Peripheral slit 912 comprises a width (vertical dimension in FIG. 13) between fluid-bearing ring 910 andtreatment surface 911 in a range of about 0.0 mm to 0.3 mm. In some embodiments, when treatinghead 904 and substrate wafer 908 are stationary or are rotated in the same direction at the same rotation rate, peripheral slit 912 is virtually zero. In other embodiments, when treatinghead 904 and substrate wafer 908 are not rotated together, peripheral slit 912 has a width greater than zero, even though infinitesimal. Practically, a positive pressure differential between a thin liquid layer present in a filled-fluid gap 915 and the region radially exterior to fluid-bearing ring 910 causes the width of peripheral slit 912 to be greater than zero. In preferred embodiments, as depicted in FIG. 13, treatinghead 904 comprises anupper region 916 having an increased diameter 917 compared to outside diameter 918 of fluid-bearing ring 910. Increased diameter 917 results in an increase in the thermal mass of treatinghead 904, which is useful for maintaining a desired temperature of a thin liquid film in fluid gap 915. A fluid-bearing ring 910 is useful for several reasons. A fluid-bearing ring 910 makes control of the width of thin fluid gap 915 easier. Also, the tendency for liquid in fluid gap 915 to drain is reduced, particularly when using a chuck or other apparatus that makes contact with the wafer edge and creates a “channel” for liquid to drain out of fluid gap 915. Specifically, fluid-bearing ring 910 allows fluid to drain out of the region external of the ring, but prevents or inhibits fluid from flowing from fluid gap 915 through peripheral slit 912. Also, a fluid-bearing ring 910 confines fluid in fluid gap 915 under conditions of high wafer and/or head rotation. A high rotation rate enables a significant increase in convection of mass and heat without liquid in fluid gap 915 being ejected from the gap because a peripheral slit between ring 910 at the peripheral edge of treatinghead 904 and the substrate below is very narrow or even closed. Furthermore, flushing of chemicals and rinse water is greatly improved. In a preferred embodiment, gas is introduced into the center of fluid gap 915 to expel a thin liquid layer or other liquid, and a gas bubble is thereby created. The presence of a fluid-bearing ring 910 allows slow expansion of the bubble and controlled expulsion of liquid from fluid gap 915 through slit 912. In preferred embodiments, wafer substrate 908 and treatinghead 904 are both spinning at the same rate, preferably in a range of about 300 rpm to 800 rpm, in the same direction. A pressurized gas bubble is introduced into the center of the water and is slowly allowed to force fluid out of slit 912 created by fluid-bearing ring 910. The centripetal forces on the fluid entrained on the wafer and head allow these surfaces to be rapidly drained of excess fluid, and thereby reduces the likelihood of fluid dripping back down from treatinghead 904 onto wafer 908. In a case in which wafer 908 has both a hydrophobic area (e.g., low-k Coral™ dielectric) and a hydrophilic surface area (e.g., copper metal), an apparatus having a treating head system 902 and a high rpm process for expelling liquid from fluid gap 915 is particularly useful for reducing the incidence of chemical defects and water-spot defects (e.g., streaks, stains, contamination). - The pH often tends to drift during cobalt plating. For example, in some embodiments, the liquid plating solution contains an ammonium ion and the solution is heated to an elevated temperature. In aqueous solutions, the ammonium ion is in equilibrium with the amount of dissolved ammonia gas by the chemical equilibrium:
- NH4 ++OH−⇄NH3(dissolved gas)+H2O.
- Since warm dissolved ammonia gas has a relatively high partial vapor pressure, it tends to evaporate very quickly into any air above the bath. Continual or continuous adjustment of pH and other liquid properties is done with a multiple chemistry flow capability by which chemical constituents of a reactant solution are contained in a plurality of reactant liquid sources, and the flow rate from one or a plurality of liquid sources into the fluid gap is dynamically variable.
- In another aspect, a post-treatment anneal of a substrate wafer is conducted in an apparatus in accordance with the invention, either at low temperature up to about 400° C., or up to about 1000° C. using a very rapid thermal process (RTP) heater.
- In another aspect, the chemical composition of a plating solution is varied during plating operations so that the chemical composition of the deposited metal layer varies spatially within the layer. Such a structure may alternatively be viewed as a multilayer structure. For example, phosphor, tungsten, or boron are known to improve the barrier properties of cobalt. In accordance with certain aspects of the invention, a particular cobalt alloy is deposited at the bottom of a capping layer, a different cobalt alloy is formed for the bulk of the capping layer, and a third cobalt alloy provides the top of a capping layer.
- A process flow diagram for a microcell apparatus920 suitable for unstable reaction mixtures is depicted in FIG. 14. A liquid reaction mixture is formed by mixing liquid streams from two separate liquid sources. A first liquid source 924 contains components of the reaction mixture that are inherently stable at an elevated temperature. For example, in the case of an electroless plating solution, liquid source 924 contains metal ions, buffers, complexing agents, surfactants, etc. A second
liquid source 926 contains unstable or destabilizing components of the reaction mixture that cause the bath to react and potentially to decompose prematurely. For example, in the case of electroless plating, second liquid source contains reducing agents. Acontainment vessel 928 encloses treatinghead 922 andwafer chuck 930 supporting awafer substrate 932. In a closed position, treatinghead 922 forms athin fluid gap 934 withsubstrate 932. In some embodiments, the material in liquid source 924 is heated by a heater 935 to a temperature slightly higher than the desired operating temperature in microcellthin film layer 936 located influid gap 934. The higher temperature value in liquid source 924 is controlled such that when liquid from source 924 is mixed with an appropriate amount of cooler liquid (e.g., reducing agents) fromliquid source 926, the temperature of the reaction mixture after mixing is substantially the same as the desired temperature in thin liquid layer 936 (which is typically the same as the temperature of treating head 922). In process 920, a first liquid stream is pumped from first liquid source 924 infirst source tube 938 bypump 940 throughfilter 942 for continuous filtration, and then through a flow meter/controller 944 into three-way recirculation valve 946.Recirculation vale 946 is dynamically controllable so that all or a portion of firstliquid stream 938 is diverted into recirculation stream inrecirculation tube 948. Undiverted firstliquid stream 950 continues towardsmicrocell fluid gap 934. Downstream from three-way valve 946, atee 952 intoline 950 allows the introduction of either DI water or pressured gas (e.g., N2) for forcing the removal of fluid frommicrocell gap 934. Further downstream, atee 954 allows injection of a second liquid stream insecond source tube 956 from secondliquid source 926 intomixture line 958. For example, in electroless plating, secondliquid stream 956 comprises a relatively small volume of concentrated reducing agents. Methods of introducing pressurized reducing agent throughtee 954 intomixture line 958 include the use of a gear orsyringe pump 960. By controlling the concentrations inliquid sources 924, 926 and the flow rates inliquid streams mixture line 958 are accurately controlled. In some cases, it is useful to introduce an inline mixing chamber downstream oftee 954 to properly mix the reaction mixture upstream ofmicrocell inlet tube 962. - In still another aspect, modules comprising microcell (thin liquid layer) devices in accordance with the invention are stacked substantially vertically. This enables higher throughput of substrates per unit surface area of manufacturing floor space. Since many pre-treating, rinsing, and post-treating operations are performed in a single microcell in accordance with the invention, utilization of production space improves.
- Although embodiments in accordance with the invention are described herein mainly with respect to electroless plating techniques, it is clear that an apparatus and a method in accordance with the invention-are useful for many types of wet substrate treatments. Various substrate treatments include liquid chemical reactions as well as non-reactive treatments (e.g., pretreatment cleaning and rinsing). In an important aspect of the invention, a plurality of substrate treatments of a substrate are conducted sequentially in one module or supercell. An example of a liquid chemical reaction treatment is the uniform etching of a substrate surface. Another example is the stripping of an oxide from a substrate surface. For example, a protective oxide layer or an oxide layer that simply formed in an oxidizing environment is stripped off before electroless plating operations begin. In another aspect, metal particles and other contaminants are cleaned from a treating head, containment chamber walls, and other surfaces prior to liquid chemical reaction treatment.
- Electroless plating is an autocatalytic plating technique, the process physics enabling selective deposition of a metallic coating by a controlled chemical reduction that is catalyzed on metal or alloy being deposited. Electroless plating depends on the action of a chemical reducing agent in solution to reduce metallic ions to the metal. Unlike a homogeneous chemical reduction, the plating reaction takes place only on “catalytic” surfaces rather than throughout the plating solution. The process occurs by the simultaneous reduction of metal and the oxidation of a “reducing agent” on the metal surface. These two processes do not have to occur at exactly the same place on the metal surface, but there must be an electrical path between the location of the reducing agent's oxidation (generating excess electrons) and the location of metal deposition (combining the generated electrons with metal ions). Electroless plating has been used for depositing a large number of materials, including Cu, Ni, Co, Fe, Pd, Pt, Ru, Rh, Au, Ag, Sn, Pb, as well as alloys containing these metals, plus Mn, Mg, W, P and/or B. Various metals are deposited electrolessly onto an electronic component, including, for example, copper, nickel, cobalt, gold, silver, palladium, platinum, rhodium, cobalt, tungsten phosphorous, and combinations thereof. Electroless polymerization is performed by an analogous electroless process for some conductive polymers (e.g., polyanaline). Typical chemical reducing agents include ammonium hypophosphite ((NH4)H2PO2), formaldehyde (CH2O), hydrazine, borohydride, dimethylamine borane-(DMAB), glyoxylic acid, redox-pairs (e.g., Fe(II)/Fe(III)) and derivatives of these. A chemical reducing agent in plating solution is a source of electrons for the reduction of a metal ion to a deposited metal atom on the surface:
- M n+ ne=M 0
- where Mn+ represents a reducible metal ion in the solvent (typically water). Complexing agents (e.g., acetate, succinate, malate, malonate, citrate, etc.) are often used in plating solutions to enhance solubility at pH values where the metal ion would otherwise be insoluble. Complexation of the metal is also useful for shifting the potential of deposition to obtain desirable conditions for deposition.
- In some cases, a particularly strong and catalytically-active reducing agent is important at the beginning of an electroless plating process in order to initiate plating of the metal onto the substrate surface. This is even more important in cases where the initiation of the plating process is on a foreign metal surface (e.g., initiation of cobalt electroless deposition onto a copper surface).
- Accordingly, preferred embodiments in accordance with the invention involving electroless plating on a foreign substrate (e.g., cobalt on copper) typically comprise a two-phase process including a nucleation phase and a growth phase. In the nucleation phase, a desired depositing metal (e.g., cobalt) is caused to deposit on a foreign metal substrate surface (e.g., copper). Afterwards, in the growth phase, the desired metal (e.g., cobalt) grows on a film of similar metal (e.g., cobalt). Typically, optimum or idealized process conditions for the nucleation phase are different from those of the growth phase. For example, for electroless plating of cobalt on copper, the optimal set of conditions for the nucleation reaction to occur is very different from that of the growth reaction. Nucleation of cobalt onto a copper substrate involves the generation of excess reduced cobalt-metal atoms at the copper surface at a sufficient concentration for formation of a nucleation layer of cobalt. To create this concentration of surface cobalt atoms, a reducing agent of sufficient strength (i.e., an agent having suitable free-energy driving-force and kinetics) to reduce sufficient metal ions at a sufficiently rapid rate is required. One example of such a reducing agent is mopholine borane. Because the process of cobalt-ion reduction is likely stepwise, the creation of partially-reduced surface-absorbed metal ions presents a problem. The partially-reduced ions can diffuse away into the electrolyte and not aid in the nucleation process. To minimize this possibility, initiation of the electroless plating operation during a nucleation phase is typically performed under stagnant conditions. If the wafer were spinning quickly, rapid vigorous fluid flow would prevent the partially-reduced cobalt ions from accumulating, and nucleation would slow or not occur. On the other hand, once nucleation has occurred, the kinetics of the reducing-agent oxidation and cobalt reduction are quite different. It is believed that cobalt grows on copper in a more rapid, virtually single-step reduction reaction, and fluid convection caused by a high rotational speed enhances mass transfer and deposition rates. Furthermore, the kinetics of the reducing agent (e.g., morpholine borane) are substantially slower on the cobalt surface than on copper. Therefore, during the cobalt growth phase, a different set of chemical (composition and concentration of reducing agents) and physical (e.g., temperature, rotation rate) conditions are desirable.
- Thus, in one aspect of the invention, a method for electroless plating of a cobalt alloy on copper comprises two distinct process phases, nucleation and growth, which are conducted separately under different process conditions, usually with different process chemistry. Typically, a third phase, activation, precedes nucleation.
- The term “activation”, as used broadly herein, means pretreatment to facilitate nucleation. For example, copper typically has a contaminant on it, or a natural oxide, or some chemical that was left there intentionally, such as benzotrizol, which is a copper corrosion inhibitor. A common technique of stripping such materials before nucleation is to expose the surface to a reducing agent, such as dimethylamine borane (DMAB), or to a dilute acid, such as sulfuric acid. Activation includes one or a plurality of operations, depending on the particular pre-conditions and the particular substrate. In a narrow sense, the term “activation” designates a process that makes a surface chemically active for nucleation chemistry. The term “pretreatment” refers generally to processes that prepare a substrate surface for chemical reaction treatment using a thin liquid layer in accordance with the invention. Some pretreatment processes are conducted using thin-liquid-layer techniques in accordance with the invention, while others, for example, spraying, do not use a thin liquid layer. An activation process preceding nucleation is an example of a pretreatment.
- An example of an activation process is removal of a surface contaminant, a natural oxide, or BTA to activate the surface. A typical activation sequence comprises pre-wetting the treatment surface, and then adding a dilute, 1% to 5% sulphuric solution onto the surface. A dilute acid solution reduces the oxide and also tends to corrode it slightly. In addition or alternatively, activation is conducted using a reducing agent, such as DMAB. Other exemplary activating reducing agents are the hypophosphite and glyoxylate ions. Activation is conducted using a thin liquid layer in accordance with one aspect of the invention. Alternatively, activation is conducted using a spray technique or a conventional bath.
- The next phase is nucleation. An exemplary liquid mixture for conducting nucleation of cobalt onto copper comprises: 0.03 mol/l CoCl2.6H2O, 0.06 mol/l citric acid, 0.015 mol/l DMAB. At 60° C. and pH 8.5, the nucleation time is as short as about 2 seconds to 3 seconds. Preferably, nucleation is conducted under quiescent conditions, that is, with minimal or no fluid convection. This is achieved in accordance with the invention by flowing the liquid nucleation mixture into a thin fluid gap to fill the gap, and then decreasing or stopping the flow of solution into the gap.
- An exemplary liquid mixture for conducting the growth phase of electroless plating of cobalt onto copper comprises: 0.03 mol/l CoCl2.6H2O, 0.06 mol/l citric acid, 0.015 mol/l DMAB, 0.03 mol/l ammonium hypophosphite. Addition of hypophosphite ion enhances the subsequent growth rate. Ammonium ion improves the stability of the plating solution, slowing the process and preventing homogeneous reaction. Temperature is typically in a range of from 45° C. to 70° C., preferably about 60° C. The pH is maintained in a range of from 8 to 10, preferably about 9.75.
- The relative amounts of cobalt, boron, and phosphorus in the deposited cobalt alloy is varied by varying the relative concentrations of CoCl2.6H2O, DMAB, and ammonium hypophosphite in the plating-reaction growth-phase solution.
- In one aspect, the process operations of the nucleation and growth phases are conducted separately in accordance with the invention. Preferably, the substantially distinct nucleation and growth phases are conducted in a fluid gap of a microcell device that forms thin liquid layers in accordance with the invention. Nevertheless, it is clear that nucleation-phase processes can be conducted separately from growth-phase processes in accordance with the invention using conventional techniques, such as immersion bath and spraying techniques.
- An advantage of using a microcell or supercell apparatus in accordance with the invention is that the process conditions are closely controlled and dynamically variable. Similarly, the composition of the liquid plating solution is dynamically variable. Another advantage is that many or all of the pretreatment, rinsing, drying and other process operations are conducted in a supercell in accordance with the invention.
- A microcell apparatus and a method using a thin liquid layer in accordance with the invention were utilized to deposit selectively a cobalt-capping layer on top of copper lines, resulting in improved electromigration performance of an integrated circuit. Preparation and processing of the integrated circuit wafers was conducted using four major categories of processes: 1) copper recess and precleaning; 2) cobalt electroless plating; 3) post-cleaning; and 4) rinsing and drying.
- Each wafer was transported to a wafer chuck of a microcell apparatus after CMP copper planarization and barrier (e.g., Ta, TaN) removal, which yielded a surface having a large number of electrically isolated, exposed copper features, such as lines, vias, and pads. The wafer (200 mm diameter) was first wetted with DI water by spraying the water onto the treatment surface while the treating head was in an open, up position away from the surface. Next, the treating head having a substantially flat horizontal treatment surface was lowered to form a thin fluid gap having a width (in the vertical dimension) of about 1.5 mm between the head surface and wafer treatment surface. The wafer was rotated at about 25 rpm, and an etchant was introduced into the thin fluid gap at a rate of about 1 liter per minute until the fluid gap was completely filled (about 10 seconds). Alternatively, the etchant could have been sprayed onto the surface in a continuous fashion at a flow rate of about 1 liter per minute with the wafer rotating at 250 rpm (this alternative uses more chemical). We have found that it was desirable to recess the exposed copper structures on each of the wafers approximately 100 Å to 300 Å below the plane of the dielectric to improve the overall performance of the resulting circuit structures. It is believed that by performing this controlled recess: 1) damaged surface copper left over from the CMP process was removed, thereby improving the activity of the copper for nucleation of cobalt onto the surface; and 2) by plating into a recessed structure, lateral growth of the capping layer was prevented (by the confinement of the trench wall), thereby reducing or eliminating the encroachment of adjacent conductive lines. Generally, the copper was recessed with an ambient-temperature reactive etching mixture of hydrogen peroxide (from 1% to 5%) and glycine (from 0.2% to 2%). The pH of the solution was changed to a slightly alkaline pH (about 8 to 10) by the addition of an alkaline agent, such as tetramethylammonium hydroxide (TMAH), for optimum rate control and reproducibility. This mixture resulted in a conformal recessing process (i.e., relatively flat etch profile) and a slow, controllable etching rate (50 Å/min to 300 Å/min), independent of the size of the feature. Target amount of metal recess was in a range of about 100 Å to 300 Å. After the desired amount of time (etched thickness), the etchant was removed from the fluid gap area by flushing the inlet line and fluid gap with DI water.
- Generally, after these etching and rinsing operations, the wafer was megasonically cleaned with a dilute solution containing a copper complexing agent (e.g., citric acid, EDTA). A slow rotation rate (10 rpm to 25 rpm) combined with about 125 Watts of megasonic energy at about 0.85 MHz was found to be suitable. This cleaning helped to remove spurious particles and extract copper (and other) metal ions that might have been ion-exchanged with the surface dielectric layers during the formation of metal ions in the etching step. After this clean, the wafer was again rinsed and was ready for selective electroless cobalt plating.
- The selective electroless cobalt plating is described here with reference to FIG. 14. About 3 liters of cobalt plating solution stored in a heated tank924 was continuously circulated and filtered 942 at 1 liter per minute. Generally, the plating solution contained a mixture of 30 g/L COCl2*6H2O, 54 g/L NH4Cl, 57 g/l citric acid monohydrate, and about 625 g/L of 25%/w TMAH. The solution was heated to 72° C., and the solution pH was 9.75 at that temperature. An in-
line flow meter 944 measured flow rate upstream from a three-way valve 946 that was used either to direct plating solution back (recirculation stream 948) to-heated storage tank 924, or to direct the plating solution (undiverted stream 950) tomicrocell reactor head 922. To feed the plating solution to the microcell'sthin fluid gap 934, three-way valve 946 was opened and fluid passed intoline 950 at 1 liter/minute past atee 952 used for other purposes (e.g., later flushing of chemicals). Atee 954 served as an injection point for the introduction of reducing agent from a secondliquid source 926. The reducing agent solution (80 g/L DMAB, 15 g/L ammonium hypophosphite, and 25 ml/L 25%/w TMAH) was introduced intoline 958 at a rate of 85 ml/min at the same time as the reactant from the heated storage tank. Downstream oftee 954,inline mixer 960 provided mixing of the two liquid solutions to form a reaction mixture ininlet line 962. - To insure complete gap filling, the wafer was rotated at 75 rpm while the liquid reaction mixture was injected for about 7 seconds (200 mm wafer, 1.5 mm gap). Treating head922 (containing imbedded flow lines and fittings to incoming fluid lines) was made of titanium, had a circular diameter of approximately 200 mm, and had a vertical thickness of approximately 1 inch. This head was attached to a thermal mass and temperature control block (made of highly conductive aluminum) using thermal contact paste. The block was about 65 mm thick and 220 mm in diameter. An electric heating coil was attached to the top of this heater block. A thermocouple temperature probe was embedded in
titanium treating head 922 and was used with a feedback controller to maintain the head temperature at 70° C. The treating head comprised a showerhead-type outlet for flowing liquid into the thin fluid gap. The outlet comprised about 50 outlet holes arranged in a 2-inch diameter circle, each of the holes having a diameter of about 0.8 mm. The lower head surface oftitanium treating head 922 adjacent tofluid gap 934 was coated with a PTFE film (spray coated, about 0.1 mm thick). - After the liquid reaction mixture filled the fluid gap without any entrapped bubbles, the liquid flow into the fluid gap and the rotation of the wafer were completely stopped (i.e., no flow, 0 rpm) for a period of 20 seconds. During this time, the solution was quiescent, a desirable condition for nucleation during initiation of the plating process at the copper surface. After this nucleation period, the wafer was generally rotated at a very slow rate (2 rpm to 10 rpm) until completion of the plating growth phase (to the desired thickness). This slow rotation rate was found to improve azmuthal uniformity of the plating process. The film growth rate during the growth phase was approximately 250 Å/min (actual value depended strongly on exact pH and temperature).
- At the end of plating, DI water was injected into
tee 952. The preliminary rinsing of the wafer and head was accomplished by rotating the wafer at 150 rpm with a DI flow rate of 1 liter/m for about one minute. - The post-plating cleaning processes involved the injection of a treatment chemistry suitable for removing spurious cobalt particles from the surface and metal ions from the dielectric (ion exchange removal). The solution combined a buffered pH and strong complexing agents with a weak etching character. A suitable solution for cobalt-cap-layer treatment was a 10-1 dilution of the proprietary cleaning solution ESC-784 (ESC Incorporated, Bethlehem, Pa.). This solution was combined with a simultaneous megasonic treatment (125 W, 0.85 MHz, 12 RPM, 1 liter/min flow, 1 minute treatment), and was followed by a DI rinse of the liquid tubing lines, treating head, fluid gap, and wafer (150 rpm, 1 l/min). The rinse water was ejected from the gap by introducing pressurized nitrogen (flow
rate 700 cc/min STP) into the gap and increasing the rotation rate to about 300 rpm. With the wafer still rotating, the head was lifted away from the wafer and DI rinse water was sprayed onto the wafer's surfaces. The treating head was then tilted to allow excess water to drain from it, and the treating head was allowed to dry. - TEM imaging of the wafers showed that the film thickness of the cobalt film on top of the copper was generally about 300 Å, and was confined within the trenches in the dielectric material of the wafer. Cobalt films of 100 Å thickness were also deposited on copper. The cobalt films were conformal, covering the copper lines. SEM was conducted of a copper damascence comb test, patterned and capped with cobalt. Results of SEM showed that the underlying copper lines were completely and selectively coated with cobalt, without spurious material created between the lines.
- Various performance data show good electronic properties on integrated circuit wafers fabricated in accordance with the invention. A line leakage comparison for conductive copper lines capped with cobalt showed no significant difference in the performance of the recessed and capped features compared to the controls. In contrast, non-recessed features showed considerably higher leakage currents, presumably because of the average closer distance between the edge of the cobalt-capped areas and the edge of the lines (encroachment). FIG. 15 shows the results of electromigration (EM) tests comparing EM lifetime of Co-capped Cu with the EM lifetime in baseline wafers having Cu lines without Co-capping. Control baseline wafers did not have a Co-capping layer, but were otherwise processed in the same manner as the cobalt-processed wafers. The average EM lifetime of control wafers is about 50 hours. In contrast, wafers plated electrolessly with Co in accordance with the invention showed significant improvement of EM lifetime (at least 10× increase). In the case of wafers having Co-capping of 100 Å thickness, there was no failure during 500 hours of the EM test time. There was one failure out of 16 samples that had 300 Å thick Co-capping. These results show that electroless capping with cobalt in accordance with the invention is very effective in improving EM lifetime of narrow Cu-interconnects.
- The particular systems, designs, methods and compositions described herein are intended to illustrate the functionality and versatility of the invention, but should not be construed to be limited to those particular embodiments. Systems and methods in accordance with the invention are useful in a wide variety of circumstances and applications to conduct a liquid chemical reaction treatment and other liquid-phase treatments performed on an integrated circuit substrate. It is evident that those skilled in the art may now make numerous uses and modifications of the specific embodiments described, without departing from the inventive concepts. It is also evident that the steps recited may, in some instances, be performed in a different order; or equivalent structures and processes may be substituted for the structures and processes described. Since certain changes may be made in the above systems and methods without departing from the scope of the invention, it is intended that all subject matter contained in the above description or shown in the accompanying drawings be interpreted as illustrative and not in a limiting sense. Consequently, the invention is to be construed as embracing each and every novel feature and novel combination of features present in or inherently possessed by the systems, methods and compositions described in the claims below and by their equivalents.
Claims (90)
1. An apparatus for thin-liquid-layer treatment of a surface of an integrated circuit substrate, comprising:
a substrate holder;
a treating head proximate to the substrate holder, the treating head including a head surface that forms a thin fluid gap between the head surface and a substrate treatment surface when a substrate is present in the substrate holder; and
a liquid inlet tube for flowing liquid into a thin fluid gap.
2. An apparatus as in claim 1 wherein the thin-liquid-layer treatment comprises a treatment selected from a group consisting of a chemical liquid reaction treatment and a cleaning treatment.
3. An apparatus as in claim 1 wherein the thin-liquid-layer treatment comprises a chemical liquid reaction treatment selected from a group consisting of electroless metal plating, etching, electrolytic plating, electrolytic etching, metal-oxide deposition, and liquid dielectric deposition.
4. An apparatus as in claim 1 wherein the treating head comprises a peripheral edge corresponding substantially in shape to an outer edge of an integrated circuit wafer, and wherein the peripheral edge forms a peripheral slit with the outer edge of the integrated circuit wafer when the wafer is in the substrate holder.
5. An apparatus as in claim 4 wherein the peripheral slit comprises a width in a range of about from 0.0 mm to 0.5 mm.
6. An apparatus as in claim 1 wherein a thin fluid gap comprises a width substantially in a range of about from 0.1 mm to 4 mm.
7. An apparatus as in claim 1 wherein a thin fluid gap comprises a volume in a range of about from 30 microliters per cm2 to 300 microliters per cm2 of substrate treatment surface.
8. An apparatus as in claim 1 wherein the substrate holder further comprises a plurality of support pins for supporting a substrate in the substrate holder.
9. An apparatus as in claim 1 , further comprising a rotary head shaft connected to the treating head for rotating the treating head.
10. An apparatus as in claim 1 wherein the fluid gap is dynamically variable.
11. An apparatus as in claim 1 , further comprising a head heater for heating the treating head.
12. An apparatus as in claim 1 , further comprising a multizone head heater.
13. An apparatus as in claim 1 wherein the liquid inlet tube is integral with the treating head.
14. An apparatus as in claim 1 , further comprising:
a manifold cavity disposed in the treating head;
a manifold inlet for providing fluidic communication between a liquid source and the manifold cavity; and
a plurality of liquid inlet tubes integral with the treating head for flowing liquid from the manifold cavity into a fluid gap when a substrate is present in the substrate holder.
15. An apparatus as in claim 14 , further comprising a manifold recirculation tube between the manifold cavity and the liquid source.
16. An apparatus as in claim 14 , further comprising a bubble removal tube in fluidic communication with the manifold cavity.
17. An apparatus as in claim 1 , further comprising:
a treating liquid source;
a containment chamber containing the substrate holder and having an outlet drain; and
a recycling tube between the outlet drain and the treating liquid source.
18. An apparatus as in claim 1 , further comprising:
a containment chamber containing the substrate holder; and
a liquid diversion system wherein the liquid diversion system includes a collection trough, and the collection trough is disposed in a containment chamber substantially radially outwards from the substrate holder.
19. An apparatus as in claim 1 , further comprising a substrate heater integral with the substrate holder for heating a substrate from the backside of the substrate.
20. An apparatus as in claim 1 wherein the substrate holder is a differential pressure chuck comprising an annular collar disposed in the containment vessel, the annular collar including an inside collar edge, the inside collar edge forming a narrow flow passage between the inside collar edge and the outer edge of a substrate wafer when a wafer is present in the wafer holder.
21. An apparatus as in claim 20 wherein the narrow passage has a width in a range of about from 0.2 mm to 7 mm.
22. An apparatus as in claim 1 , further comprising a liquid heater for heating liquid from a treating liquid source, the liquid heater being disposed upstream from the liquid inlet tube.
23. An apparatus as in claim 22 , further comprising:
a liquid source tube from a treating liquid source;
a recirculation tube for recirculating treating liquid from a liquid source tube back to the treating liquid source; and
a liquid cooler for cooling recirculating treating liquid.
24. An apparatus as in claim 1 , further comprising a plurality of gas injection ports proximate to the wafer holder for injecting inert gas proximate to a wafer edge when a substrate wafer is present in the substrate holder.
25. An apparatus as in claim 1 , further comprising:
a plurality of treating liquid sources including a first treating liquid source and a second treating liquid source; and
a liquid mixer, the mixer being located proximate to the treating head, for mixing a first treating liquid from the first treating liquid source and a second treating liquid from the second treating liquid source.
26. An apparatus as in claim 23 wherein a first liquid source comprises an activation liquid source, and a second liquid source comprises a plating solution source.
27. An apparatus as in claim 1 , further comprising a head array, the head array including a plurality of treating heads.
28. An apparatus as in claim 1 wherein the head surface has a shape that is substantially flat.
29. An apparatus as in claim 1 , further comprising a magnetic source located in the treating head for creating a magnetic field in a thin fluid gap to clean a liquid in the gap.
30. An apparatus as in claim 1 further comprising:
a magnetic source for creating a magnetic field in a thin fluid gap; and
a magnetic sensor for detecting an amount of metal present on a substrate present in the substrate holder.
31. An apparatus as in claim 1 wherein said treating head comprises a megasonic cleaning head.
32. An apparatus as in claim 1 , further comprising a gas inlet tube for injecting wafer release gas into a space selected from a group consisting of a manifold cavity and a thin fluid gap.
33. An apparatus as in claim 1 wherein the liquid inlet tube is suitable for injecting wafer release gas into a thin fluid gap.
34. An apparatus as in claim 1 , further comprising a gas release tube in fluidic communication with the liquid inlet tube to release gas located in a thin fluid gap.
35. An apparatus as in claim 1 , further comprising:
a light source; and
an optical sensor for measuring an optical property related to an amount of material deposited on a substrate treatment surface.
36. An apparatus as in claim-35 wherein said optical property is selected from a group consisting of optical reflectivity, optical transmittance, and optical spectrum.
37. A method of liquid treatment of a surface of an integrated circuit substrate, comprising:
placing an integrated circuit substrate having a treatment surface in a substrate holder;
disposing a treating head having a head surface proximate to the treatment surface, the head surface and the treatment surface thereby defining a thin fluid gap; and
flowing liquid into the thin fluid gap to form a thin liquid layer.
38. A method as in claim 37 wherein flowing liquid into the thin fluid gap comprises dynamically varying a property of the liquid.
39. A method as in claim 37 wherein disposing the treating head proximate to the treatment surface comprises forming a peripheral slit between a peripheral edge of the treating head and an outer edge of the substrate.
40. A method as in claim 39 wherein forming a peripheral slit comprises forming a slit having a width in a range of about from 0.0 mm to 0.5 mm.
41. A method as in claim 39 , further comprising dynamically varying the peripheral slit.
42. A method as in claim 37 wherein disposing the treating head proximate to the treatment surface comprises defining a thin fluid gap having a volume in a range of about from 30 microliters per cm2 to 300 microliters per cm2 of substrate treatment surface.
43. A method as in claim 42 , further comprising dynamically varying the volume of the thin fluid gap.
44. A method as in claim 37 wherein the liquid treatment comprises a treatment selected from a group consisting of: electroless metal plating, electroless chemical etching, electrolytic plating, electrolytic etching, metal-oxide deposition, and liquid dielectric deposition.
45. A method as in claim 37 , further comprising rotating the substrate.
46. A method as in claim 45 , further comprising dynamically varying a rotational speed of the substrate.
47. A method as in claim 37 , further comprising rotating the treating head.
48. A method as in claim 47 , further comprising dynamically varying a rotational speed of the treating head.
49. A method as in claim 37 , further comprising heating the treating head.
50. A method as in claim 49 , further comprising dynamically varying the heating of the treating head.
51. A method as in claim 49 wherein heating the treating head comprises creating a nonuniform temperature profile in the treating head.
52. A method as in claim 37 wherein flowing liquid into the fluid gap comprises:
flowing liquid into the fluid gap during a first period of time; and then substantially ceasing flowing liquid into the fluid gap during a second period of time.
53. A method as in claim 37 wherein flowing liquid into the fluid gap comprises flowing liquid into the fluid gap at a flowrate in a range of about from 0 ml/min. to 2000 ml/min.
54. A method as in claim 37 wherein flowing liquid into the fluid gap comprises dynamically varying a flow rate of liquid into the fluid gap.
55. A method as in claim 37 wherein flowing liquid into the fluid gap comprises dynamically varying a composition of the liquid.
56. A method as in claim 37 , further comprising:
flowing a first treating liquid into a mixer;
flowing a second treating liquid into the mixer to form a mixed liquid with the first treating liquid; and
then flowing the mixed liquid into the fluid gap.
57. A method as in claim 56 , further comprising:
varying a property of the mixed liquid upstream of the fluid gap to form a second mixed liquid; and
then flowing the second mixed liquid into the fluid gap.
58. A method as in claim 37 wherein flowing liquid into the fluid gap comprises flowing liquid through a showerhead-type manifold.
59. A method as in claim 37 , further comprising recycling liquid from a containment space to a treating liquid source.
60. A method as in claim 37 , further comprising diverting treatment liquid from a containment space using a liquid diversion system.
61. A method as in claim 60 wherein diverting treatment liquid comprises collecting liquid in a collection trough disposed substantially radially outwards from the substrate.
62. A method as in claim 37 , further comprising recirculating a portion of liquid to a liquid source instead of flowing the portion of liquid into the fluid gap.
63. A method as in claim 37 , further comprising heating the liquid before flowing the liquid into the fluid gap.
64. A method as in claim 37 , further comprising:
heating treatment liquid upstream of the fluid gap;
diverting a recirculation-portion of the treatment liquid instead of flowing the recirculation-portion into the fluid gap;
cooling the recirculation-portion of treatment liquid; and
then flowing the recirculation-portion of treatment liquid to a treatment liquid source.
65. A method as in claim 37 wherein flowing liquid into the fluid gap comprises flowing a pre-wetting liquid into the thin fluid gap.
66. A method as in claim 37 wherein flowing liquid into the fluid gap comprises flowing a rinsing liquid into the thin fluid gap.
67. A method as in claim 37 , further comprising injecting wafer release gas into the thin fluid gap.
68. A method as in claim 67 wherein injecting wafer release gas comprises injecting gas through a tube selected from a group consisting of a liquid inlet tube and a gas inlet tube.
69. A method as in claim 37 wherein flowing liquid into the fluid gap comprises flowing liquid from a liquid source into a manifold cavity located in the treating head.
70. A method as in claim 37 , further comprising diverting a recirculation-portion of liquid from the manifold cavity back to the liquid source.
71. A method as in claim 37 , further comprising heating the substrate from the backside of the substrate.
72. A method as in claim 71 , further comprising dynamically varying the heating.
73. A method as in claim 37 , further comprising creating a pressure differential between an upper containment chamber above the substrate and a lower containment chamber below the substrate, wherein the pressure in the upper containment chamber is greater than in the lower containment chamber.
74. A method as in claim 73 wherein creating a pressure differential comprises drawing a partial vacuum in the lower containment chamber, thereby drawing gas from the upper containment chamber around the outer edge of the substrate through a narrow passage between the inside collar edge of an annular collar and the outer edge of the substrate.
75. A method as in claim 74 wherein the narrow passage has a width in a range of about from 1 mm to 7 mm.
76. A method as in claim 37 wherein flowing liquid into the fluid gap comprises flowing an electroless plating solution into the fluid gap.
77. A method as in claim 76 wherein flowing an electroless plating solution into the fluid gap comprises:
flowing a nucleation solution into the fluid gap; and
then flowing a growth solution into the fluid gap.
78. A method as in claim 77 , further comprising flowing an activator solution into the fluid gap before flowing the nucleation solution.
79. A method as in claim 37 wherein flowing liquid into the fluid gap comprises flowing an etching solution.
80. A method of depositing a foreign-metal layer onto a base-metal material on a treatment surface of an integrated circuit substrate using a thin liquid layer, comprising:
treating the treatment surface with a nucleation-phase reactant liquid containing foreign-metal atoms under nucleation-phase reaction conditions; and
thereafter treating the treatment surface by forming a thin liquid layer of a growth-phase reactant liquid containing foreign-metal atoms under growth-phase reaction conditions, the nucleation-phase liquid chemical reaction conditions being different from the growth-phase liquid chemical reaction conditions.
81. A method as in claim 80 wherein treating the treatment surface with a nucleation-phase reactant liquid comprises a process selected from the group consisting of: forming a thin liquid layer of the nucleation-phase reacting liquid on the treatment surface, and spraying the treatment surface with nucleation-phase reactant liquid.
82. A method as in claim 80 , further comprising activating the base-metal material using an activator liquid prior to treating with the nucleation reactant liquid.
83. A method as in claim 82 wherein activating the base-metal material comprises forming a thin liquid layer of activator liquid on the treatment surface.
84. A method as in claim 83 wherein activating the base-metal material comprises forming a thin liquid layer comprising DMAB.
85. A method as in claim 80 wherein the foreign-metal atoms comprise cobalt.
86. A method as in claim 80 wherein the base-metal material comprises substantially copper.
87. A method of depositing a foreign-metal layer onto a base-metal material on a treatment surface of an integrated circuit substrate, comprising:
treating the treatment surface with a nucleation-phase reactant liquid containing foreign-metal atoms under nucleation-phase reaction conditions; and
thereafter treating the treatment surface with a growth-phase reactant liquid containing foreign-metal atoms under growth-phase reaction conditions, the nucleation-phase liquid chemical reaction conditions being different from the growth-phase liquid chemical reaction conditions.
88. A method as in claim 87 , further comprising activating the base-metal material using an activator liquid prior to treating with the nucleation reactant liquid.
89. A method as in claim 87 wherein the foreign-metal atoms comprise cobalt.
90. A method as in claim 87 wherein the base-metal material comprises substantially copper.
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US11/200,338 US7690324B1 (en) | 2002-06-28 | 2005-08-09 | Small-volume electroless plating cell |
US11/201,709 US8257781B1 (en) | 2002-06-28 | 2005-08-11 | Electroless plating-liquid system |
US11/213,190 US7686935B2 (en) | 1998-10-26 | 2005-08-26 | Pad-assisted electropolishing |
US11/731,706 US8147660B1 (en) | 2002-04-04 | 2007-03-30 | Semiconductive counter electrode for electrolytic current distribution control |
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US11/213,190 Continuation-In-Part US7686935B2 (en) | 1998-10-26 | 2005-08-26 | Pad-assisted electropolishing |
US11/731,706 Continuation-In-Part US8147660B1 (en) | 2002-04-04 | 2007-03-30 | Semiconductive counter electrode for electrolytic current distribution control |
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