TWI393186B - Processes and integrated systems for engineering a substrate surface for metal deposition - Google Patents

Description

Method for arranging the surface of a substrate for metal deposition and integrated system

The present invention relates to a method and an integrated system for arranging the surface of a substrate for metal deposition, in particular for producing an improved metal-to-metal interface or a germanium-to-metal interface for enhancing electromigration performance, providing low metal resistivity, And methods and integrated systems for improving metal-to-metal or germanium-to-metal interface adhesion to copper interconnects.

The integrated circuit uses conductive interconnects to wire individual devices to each other on a semiconductor substrate or to externally communicate with integrated circuits. Interconnect metallization of vias and trenches may comprise aluminum alloys and copper. Electro-migration (EM) is a well-known reliability problem for metal interconnects caused by electrons pushing and moving metal atoms in the direction of current at a rate determined by current density. Electromigration eventually leads to thinning of the metal line, which results in higher resistivity or the worst case, that is, the metal line collapses. Fortunately, not every interconnecting metal line on an integrated circuit (IC) has a current that moves in the same direction because it occurs primarily on the power and ground lines. However, as metal lines become narrower (ITRS, International Technology Roadmap for Semiconductors needs to shrink by about 0.7 times for each technology node), electromigration becomes a bigger problem.

In terms of aluminum wire, EM is a bulk phenomenon and good control can be obtained by a small amount of addition of a dopant such as copper. On the other hand, the EM on the copper wire is a surface phenomenon. It can occur anywhere where copper can move freely, typically at an interface with a weak adhesion between copper and another material. In today's dual damascene processing, this most often occurs at the top of the copper wire where it is typically bonded to the SiC diffusion barrier layer, but it can also occur on the copper/barrier layer interface. This problem will worsen for each transition to the next technology node and the resulting increase in current density.

The solution to the EM problem and the associated stress voids, another common reliability issue, has become the story of process integration: optimized deposition (ie reduction of barriers and thickness of the seed layer), Pre- and post-deposited wafer cleaning, surface treatment, etc., are fully directed to providing a uniform surface and good adhesion between these layers to minimize metal atom migration and hole transfer. In the dual damascene process, trenches (holes and vias) are etched in the dielectric layer and then, for example, tantalum (Ta), tantalum nitride (TaN), or a combination of the two. The barrier material is filled, followed by deposition of a copper seed layer, electroless copper plating, copper planarization using CMP, and deposition of a dielectric stack such as SiC/low-k/SiC. Since copper is easily formed on the copper when it is exposed to air, proper copper cleaning and copper oxide removal are required before copper is covered with SiC to ensure good adhesion between copper and SiC. For good EM performance and reduced metal resistivity, removal of copper oxide prior to SiC deposition is necessary.

In recent years, compared to SiC-coated copper, a cobalt alloy coating such as CoWP (cobalt-tungsten phosphide), CoWB (cobalt-tungsten boride), or CoWBP (cobalt-tungsten-boride) is used before the SiC dielectric barrier layer. Covering copper has been shown to significantly improve electromigration. 1 shows that cobalt alloy cap layers 20, 30 are deposited overlying copper layers 23, 33, respectively, and dielectrically overlying SiC layers 25, 35. The Ta and/or TaN barrier layers are shown as layers 24, 34. The cobalt alloy layers 20, 30 improve the adhesion between the copper layers 23, 33 and the SiC cap layers 25, 35. The cobalt alloy layers 20, 30 may also exhibit some degree of copper diffusion barrier properties. This cobalt alloy coating layer can be selectively deposited on copper by electroless deposition. However, electroless deposition is inhibited by thin copper oxide which can form when copper is exposed to air. Moreover, contaminants on the surface of the copper and dielectric layers can cause pattern-dependent plating effects, including: the pattern-dependent thickness of the Co alloy; and in part due to the "planning" period required to initiate the Co plating reaction. The pattern caused by the etching performed is dependent on the copper wire thickness loss. Therefore, it is important to control the processing environment to limit (or control) the growth of the original copper oxide, and to remove copper oxide and organic contaminants on the copper surface and to be in the dielectric immediately before depositing a metal coating such as a cobalt alloy. Organic and metallic contaminants on the surface of the layer are also important. Also, in order to reduce the variability of pattern dependent deposition, the surface of the dielectric layer must be controlled to normalize its effect on different pattern densities. For ensuring good interface adhesion and good EM performance, between coppers 23, 33, between copper and barrier layers (between 33 and 34, between 23 and 24), and for example, a cobalt alloy layer 20 The metal-to-metal interface of the adhesion promoting layer (or metal cladding layer) of 30 is critical. Moreover, since the metal lines become narrower, the physical vapor deposition (PVD) barrier and the seed crystal film form a larger portion of the metal lines, thereby increasing the effective resistivity and current density. Thin and conformal barriers and seed layers can alleviate this tendency by providing a stepped coverage of the positive shape and an acceptable resistance with an atomic layer deposition (ALD) barrier layer (TaN, Ru or hybrid combination). Barrier properties; while electroless Cu treatment provides a positive seed layer. However, to date, there has been no electroless Cu seed layer that can be attached to the produced ALD TaN barrier film.

In view of the above, there is a need to produce a metal-to-metal interface with improved electromigration performance, low surface resistance, and improved interface adhesion to copper interconnects.

In general, embodiments of the present invention meet this need by providing improved processes and systems that can produce improved metal-to-metal interfaces or germanium-to-metal interfaces to enhance electromigration performance and provide low metal Resistivity, and improved metal-to-metal or germanium-to-metal interface adhesion to copper interconnects. It will be apparent to those skilled in the art that the present invention can be implemented in many ways, including, for example, solutions, methods, processes, devices, or systems. Several embodiments of the invention are described below.

In one embodiment, a method of preparing a surface of a substrate is provided by selectively depositing a thin layer of a cobalt alloy material on a copper surface of a copper interconnect of the substrate in an integrated system to improve the copper mutual Wired electromigration performance, the method comprising: removing contaminants and metal oxides from the surface of the substrate in the integrated system; and re-using the reducing environment after removing contaminants and metal oxides in the integrated system The surface of the substrate. The method also includes selectively depositing a thin layer of the cobalt alloy material on the copper surface of the copper interconnect line in the integrated system after reconstructing the surface of the substrate.

In another embodiment, an integrated system for transporting and processing substrates in a controlled environment is provided that selectively deposits a thin layer of cobalt alloy on a copper surface of a copper interconnect to improve the copper interconnect The electromigration performance of the wire, the integrated system comprising: a laboratory environment transport chamber for feeding the substrate from a substrate carrier coupled to the laboratory environment transport chamber into the integrated system; and a substrate cleaning reaction And coupled to the laboratory environment transport chamber, wherein the substrate cleaning reactor cleans the surface of the substrate to remove metal-organic mis-contaminants on the surface of the substrate.

The system also includes: a vacuum transfer chamber operating at a vacuum pressure of less than 1 Torr; and a vacuum processing module for removing organic contaminants from the surface of the substrate, wherein at least one vacuum processing module is coupled to the vacuum transfer chamber And the vacuum processing module for removing organic contaminants is coupled to one of the at least one vacuum processing module of the vacuum transfer chamber and operates at a vacuum pressure of less than 1 Torr. The system further includes: a control environment transport chamber that is filled with an inert gas selected from the group of inert gases, and at least one control environmental processing module coupled to the control environment transport chamber. In addition, the system comprises: an electroless cobalt alloy material deposition processing module, wherein the surface of the substrate has been removed from metal contaminants and organic contaminants, and the copper surface has been removed from the copper oxide to deposit the cobalt alloy. a thin layer on the copper surface of the copper interconnect, the electroless cobalt alloy material deposition processing module is one of at least one control environment processing module coupled to the control environment transport chamber, and is selected from the group consisting of inert gases The group is filled with an inert gas and has a liquid delivery system in which the treatment liquid system is degassed.

In another embodiment, a method of preparing a substrate surface is provided by depositing a metal barrier layer along a copper interconnect structure of the substrate in an integrated system and depositing a thin copper seed layer thereon. The surface of the metal barrier layer is used to improve the electromigration performance of the copper interconnect. This method involves cleaning the exposed surface of the underlying metal in this integrated system to remove surface metal oxides. The underlying metal is the portion of the underlying interconnect that is electrically connected to the copper interconnect. The method also includes depositing the metal barrier layer along the copper interconnect structure in the integrated system. After depositing the metal barrier layer, the substrate is transported and processed in a controlled environment to prevent formation of the metal barrier oxide. The method further includes depositing the thin copper seed layer in the integrated system, and depositing a trench copper layer over the thin copper seed layer in the integrated system.

In another embodiment, a method of preparing a metal barrier surface of a substrate is provided by depositing a thin copper seed layer on a surface of a metal barrier layer of a copper interconnect structure in an integrated system, To improve the electromigration performance of this copper interconnect structure. The method comprises: reducing the surface of the metal barrier layer in the integrated system to cause a transition of the metal barrier oxide on the surface of the metal barrier layer, and leaving the surface of the metal barrier layer rich in metal. The method also includes depositing the thin copper seed layer in the integrated system and depositing a trench copper layer over the thin copper seed layer in the integrated system.

In another embodiment, an integrated system for processing a substrate in a controlled environment is provided that deposits a thin copper seed layer on the surface of a metal barrier layer of a copper interconnect. The integrated system includes a laboratory environment transport chamber that can feed the substrate into the integrated system from a substrate carrier coupled to the laboratory environment transport chamber. The integrated system also includes a vacuum transfer chamber that operates at a vacuum pressure of less than 1 Torr. The integrated system further includes a vacuum processing module for cleaning the metal oxide of the exposed surface of the underlying metal in the integrated system. At least one vacuum processing module is coupled to the vacuum transfer chamber. The underlying metal is the portion of the underlying interconnect that is electrically connected to the underlying interconnect. The vacuum processing module for cleaning is coupled to one of the at least one vacuum processing module of the vacuum transfer chamber and operates at a vacuum pressure of less than 1 Torr.

In addition, the integrated system includes a vacuum processing module for depositing the metal barrier layer. The vacuum processing module for depositing the metal barrier layer is coupled to one of the at least one vacuum processing module of the vacuum transfer chamber and operates at a vacuum pressure of less than 1 Torr. In addition, the integrated system includes a controlled environment transport chamber that is filled with an inert gas selected from the group of inert gases. At least one control environment processing module is coupled to the control environment transport chamber. The integrated system further includes an electroless copper deposition processing module for depositing a thin layer of the copper seed layer on the surface of the metal barrier layer. The electroless copper deposition processing module is one of the at least one control environment processing module coupled to the control environment transport chamber.

In another embodiment, an integrated system for processing a substrate in a controlled environment is provided that deposits a thin copper seed layer on the surface of a metal barrier layer of a copper interconnect. The system includes a laboratory environment transport chamber that can feed the substrate from the substrate carrier coupled to the laboratory environment transport chamber into the integrated system. The integrated system also includes a vacuum transfer chamber that operates at a vacuum pressure of less than 1 Torr. At least one vacuum processing module is coupled to the vacuum transfer chamber.

The integrated system further includes a vacuum processing module for reducing the metal barrier layer. The vacuum processing module for reducing the metal barrier layer is coupled to one of the at least one vacuum processing module of the vacuum transfer chamber and operates at a vacuum pressure of less than 1 Torr. In addition, the integrated system includes a controlled environment transport chamber that is filled with an inert gas selected from the group of inert gases. At least one control environment processing module is coupled to the control environment transport chamber. In addition, the integrated system includes an electroless copper deposition processing module for depositing a thin layer of the copper seed layer on the surface of the metal barrier layer. The electroless copper deposition processing module is one of the at least one control environment processing module coupled to the control environment transport chamber.

In another embodiment, a method of preparing a surface of a substrate is provided by selectively depositing a metal layer on the surface of the substrate or polysilicon of the substrate in an integrated system to form a metal deuterated layer. The method includes: removing organic contaminants from the surface of the substrate in the integrated system; and, after removing the organic contaminants, reducing the surface of the germanium or polysilicon in the integrated system to place germanium on the surface of the germanium or polysilicon The oxide is converted into helium. After the surface of the tantalum or polysilicon is reduced, the substrate is transported and processed in a controlled environment to prevent the formation of the tantalum oxide, reducing the surface of the tantalum or polysilicon to increase the selectivity of the metal on the surface of the tantalum. The method also includes selectively depositing the metal layer on the surface of the germanium or polysilicon of the substrate after the surface of the germanium or polysilicon is reduced.

In another embodiment, an integrated system for processing a substrate in a controlled environment is provided that selectively deposits a metal layer on the surface of the substrate to form a metal deuterated layer. The system includes a laboratory environment transport chamber that can feed the substrate from the substrate carrier coupled to the laboratory environment transport chamber into the integrated system. The integrated system also includes a vacuum transfer chamber that operates at a vacuum pressure of less than 1 Torr. The integrated system further includes a vacuum processing module for removing organic contaminants from the surface of the substrate. At least one processing vacuum module is coupled to the vacuum transfer chamber. The vacuum processing module for removing organic contaminants is coupled to one of the at least one vacuum processing module of the vacuum transfer chamber and operates at a vacuum pressure of less than 1 Torr.

In addition, the integrated system includes a vacuum processing module for restoring the surface of the crucible. At least one vacuum processing module for reducing the surface of the crucible is coupled to the vacuum transfer chamber and operates at a vacuum pressure of less than 1 Torr. Additionally, the integrated system includes a control environment transport chamber that is filled with an inert gas selected from the group of inert gases, and at least one control environment processing module is coupled to the control environment transport chamber. The integrated system further includes an electroless metal deposition processing module for selectively depositing a thin layer of the metal on the surface of the crucible after the surface of the crucible has been restored, the electroless metal deposition processing module being coupled to the control environment At least one of the transport chambers controls one of the environmental processing modules.

Other embodiments and advantages of the present invention will be apparent from the description and appended claims.

The present invention provides several exemplary embodiments of improved metal integration techniques that modify the interface of the metal by removing the interface metal oxide to improve the electromigration metal resistivity and interface adhesion. It will be understood by those skilled in the art that the present invention can be implemented in many ways, including a program, method, apparatus, or system. Several embodiments of the invention are described below. It will be apparent to those skilled in the art that the present invention may be practiced without some or all of the specific details mentioned herein.

2A shows an exemplary cross-section of an interconnect structure after patterning using a dual damascene engraving process. The interconnect structure is on the substrate 50 and has a dielectric layer 100 that is previously fabricated to form metallized wires 101 therein. The metallized wire is typically formed by etching a trench into the dielectric layer 100 and then filling it with a conductive material such as copper.

In this trench, a barrier layer 120 is present to prevent diffusion of the copper material 122 into the dielectric layer 100. The barrier layer 120 may be composed of PVD tantalum nitride (TaN), PVD tantalum (Ta), ALD TaN, or a combination of these films. We can also use other barrier materials. The barrier layer 102 is deposited over the planarized copper material 122 to protect the copper material 122 from premature oxidation when the vias 114 are etched through the insulating dielectric material 104, 106 to the barrier layer 102. The barrier layer 102 also functions as a selective etch stop layer and a copper diffusion barrier layer. An exemplary material of the barrier layer 102 comprises tantalum nitride (SiN) or tantalum carbide (SiC).

The via dielectric layer 104 is deposited over the barrier layer 102. The via dielectric layer 104 may be composed of an organo-silicate glass (OSG) or other type of dielectric material preferably having a low dielectric constant. Exemplary cerium oxide may include: plasma enhanced chemical vapor deposition (PECVD), undoped tetraethoxysilane (TEOS), PECVD fluorine-doped bismuth glass (FSG) , fluorinated silica glass), high density plasma (HDP) FSG, organo-silicate glass (OSG), porous OSG, and the like. We can also use commercially available dielectric materials including: Black Diamond (I) and Black Diamond (II) sold by California, Santa Clara, Applied Materials; Coral sold by San Jose, Novellus Systems; Arizona, Phoenix, ASM Aurora sold by America Inc. The trench dielectric layer 106 overlies the via dielectric layer 104. The trench dielectric layer 106 can be a low dielectric constant (low k) dielectric material such as a carbon doped oxide (C-oxide). The low k dielectric material may have a dielectric constant of about 3.0 or less. In one embodiment, the via and trench dielectric layers are simultaneously composed of the same material and are deposited simultaneously to form a continuous film. Subsequent to deposition of trench dielectric layer 106, substrate 50 containing these structures is subjected to patterning and etching processes to form vias 114 and trenches 116 via known techniques.

2B shows that after the via holes 114 and the trenches 116 are formed, the barrier layer 130 and the copper layer 132 are deposited along the via holes 114 and the trenches 116 and fill the via holes and trenches. The barrier layer 130 may be composed of tantalum nitride (TaN), tantalum (Ta), ruthenium (Ru), or a mixed combination of these films. Although these are generally considered materials, we can also use other barrier materials. A copper film 132 is then deposited to fill the vias 114 and trenches 116.

As shown in FIG. 2C, after the copper film 132 fills the via hole 114 and the trench 116, the substrate 50 is planarized by chemical-mechanical polishing (CMP) to remove the surface of the dielectric layer 106. The copper material (or copper overlying layer) and the barrier layer (or barrier overlying layer). As shown in FIG. 2D, the next step covers the copper surface 140 with a copper/SiC interface adhesion promoting layer 135 such as a cobalt alloy. Examples of cobalt alloys include: CoWP, CoWB, or CoWBP, which can be selectively deposited over copper by electroless treatment. The thickness of the adhesion promoting layer may be as thin as a single molecular layer, which is only a few angstroms, for example 5 angstroms; and for a thicker layer, it may be, for example, 200 angstroms to 300 angstroms, which may also serve as a diffusion barrier for Cu. Layer, so no dielectric coverage is required.

Chemical mechanical polishing (CMP) of copper often uses benzotrizole (BTA) as a copper corrosion inhibitor. Copper forms a Cu-BTA complex with BTA. The substrate that has been treated by Cu CMP and post-CMP cleaning will contain a copper residue in the form of a Cu-BTA complex, as shown by the hollow circles in Figure 3, on both the Cu line and the adjacent dielectric layer. We must remove the Cu-BTA complex on the dielectric layer to prevent leakage current and metal short circuit increase. Further, in addition to the various organic contaminants shown by the solid circles in Fig. 3, there is a small amount of residue of Ta or other barrier material as shown by the hollow triangle of Fig. 3. In addition to these contaminants, there are also various metal oxides, mainly CuO and CuO ₂ , as shown by the solid triangle in FIG. Cu-BTA complexes, metal oxides, and organic contaminants are three major surface contaminants that must be removed from the substrate surface. The preparation of dielectric layer surfaces and metal surface systems that are free of organic contaminants and metal compound-free contaminants are challenging and require multiple surface preparation steps that can include both dry and wet processing.

The following coefficients provide an exemplary process and system for surface preparation of the underlying metal that allows the overlying metal layer to be deposited on top of the top with good adhesion between the two metal layers. These metal layers deposited by the exemplary process flow and system will exhibit improved EM performance and thus overall lower metal resistivity.

1. Arranging the copper surface for cobalt alloy deposition Case I: When metal CMP stops on the dielectric layer

4A shows an embodiment of a process flow for electroless deposition of a cobalt alloy over the back CMP copper surface 140 of the dual damascene via-trench structure shown in FIG. 2C. The substrate used in the process flow 400 of FIG. 4A has just completed the metal CMP process to remove overlying layers of copper and barrier layers, such as Ta and/or TaN. As described above with respect to Figure 3, various different metals and organic contaminants are present on the surface of the substrate.

The process begins in step 401 where metal-organic miscellaneous contaminants (or mismatched metal-organic contaminants) such as Cu-BTA complexes, as well as metal oxides, are removed from the surface of the substrate. Although metal contaminants will be removed from both the copper and dielectric surface, the purpose of this step is to increase selectivity and improve the Co film by eliminating potential metal sources that can later serve as nucleation sites for subsequent Co alloy deposition. Shape. During this step, I -BTA copper complexes may be removed from the substrate surface, the copper oxide (CuO _x), and, for example, tantalum oxide (TaO _y) of the other metal oxides. The amount of copper oxide to be removed depends on the extent of contamination and the depth of the metal oxide on the surface. The metal complex and the metal oxide can be removed by O ₂ /Ar sputtering treatment, or a one-stage wet chemical removal treatment or a continuous two-stage wet chemical treatment. The preferred embodiment uses a wet process to remove the miscible metal and metal oxide. This wet chemical removal treatment may use: an organic acid such as DeerClean supplied by Japan, Kanto Chemical Co., Inc.; or a semi-aqueous solvent such as ESC supplied by Delaware, Wilmington, DuPont. 5800; an organic base, such as tetramethylammonium hydroxide (TMAH); a miscamine such as ethylene diamine, diethylene triamine; or a patented chemical, such as by Connecticut, West Haven, Enthone, Inc. provides ELD clean and Cap Clean 61. Removal of Cu-BTA from the surface of the dielectric layer ensures that copper from the Cu-BTA complex does not oxidize to copper oxide and subsequently reduces to copper during other surface preparation steps; does not reduce selectivity and is dielectric A nucleation point on which the Co alloy can be grown is provided on the surface of the layer; no short circuit is caused and leakage current is increased. Therefore, the Cu-BTA removal process can also reduce the yield loss due to metal short circuit or leakage current.

Cu-BTA complexes and other metal oxide contaminants are two major metal contaminants to be removed during this step, which can be accomplished in a controlled or uncontrolled ambient (environment). For example, Cu-BTA can be removed by a wet cleaning process comprising: a cleaning solution comprising tetramethylammonium hydroxide (TMAH); a miscamine such as ethylenediamine, Ethylene triamine; or a patented cleaning chemical such as ELD clean and Cap Clean 61 supplied by Enthone, Inc. of Connecticut, West Haven. Metal oxides, especially copper oxides, can be removed using weak organic acids such as citric acid, or other organic or inorganic acids that can be used. In addition, we can also use acids containing very thin (i.e., <0.1%) peroxides, such as sulfuric-peroxide mixtures. This wet cleaning process also removes other metal or metal oxide residues.

The presence of BTA on copper lines of different patterns or different feature types (such as small, dense, small, individually independent or wide copper wires) is the result of the protection of these lines, to some extent occurring in these characteristics. The extent of the galvanic effect on the ministry is related. This can result in the formation of a protective layer that is dependent on the pattern. This dependence further affects the deposition characteristics of the Co alloy, resulting in pattern dependent deposition characteristics, sometimes referred to as an incubation effect or an initiation effect. The removal of BTA from the Cu wire can help eliminate the pattern-dependent deposition effects of this cobalt alloy (to be deposited in a subsequent step) and provide uniform cobalt alloy deposition in tight and individual independent features.

We can remove organic contaminants by, for example, an oxidizing plasma treated with an oxygen-containing plasma of step 403. The oxygen (O ₂ ) plasma treatment is preferably carried out at a relatively low temperature of less than 120 ° C. High temperature O ₂ plasma treatment will oxidize copper to a thicker layer, which will be more difficult to reduce later. Therefore, it is preferred to treat the low temperature O ₂ plasma. In one embodiment, the O ₂ plasma treatment can be a downstream plasma treatment. Alternatively, we can also use O ₂ /Ar sputtering to physically remove organic contaminants while removing organic residues (or contaminants). O ₂ plasma treatment and O ₂ /Ar sputtering treatment are typically operated at pressures below 1 Torr.

Once the substrate surface is free of contaminants such as Cu-BTA, metal oxides, and other organic contaminants, the substrate should be exposed to an oxygen-free environment to protect the copper surface from oxidation. Copper oxidation is not a self-limiting process. The amount and duration of exposure of the copper surface to oxygen should be limited (or controlled) to minimize copper oxide formation. Although the copper oxide will be reduced in a later step, the thicker copper oxide layer may not be completely reduced. Therefore, it is important to limit the exposure of copper to the oxygen system in cases where organic contaminants must be removed. In order to achieve control of oxygen and limited exposure, the substrate should be transported or disposed of in a controlled environment, such as an environment under vacuum or an environment filled with an inert gas.

To ensure that the copper surface is free of copper oxide, in step 405 we rebuild the substrate surface in a reducing environment to convert any residual copper oxide to copper. Any prior metal cleaning steps have removed any metal from the dielectric layer, so metal reduction is only done on the copper wire. The reduction of the copper surface can be achieved by treatment with a hydrogen-containing plasma to convert the copper oxide to copper (or substantially copper). Exemplary reactive gases that can be used to produce hydrogen-containing plasma include hydrogen (H ₂ ), ammonia (NH ₃ ), and carbon monoxide (CO). For example, a hydrogen-containing plasma produced by hydrogen (H ₂ ), ammonia (NH ₃ ), or a combination of two gases, and the substrate is at an elevated temperature between 20 ° C and 300 ° C. Lower, while reducing the surface of the substrate. In one embodiment, the hydrogen plasma treatment is a downstream plasma treatment. Once the substrate has been subjected to hydrogen reduction treatment, the substrate is ready for cobalt alloy deposition. The copper surface must be carefully protected to ensure that no copper oxide is formed. As described above, the electroless deposition of the cobalt alloy is suppressed by the presence of the copper oxide. Therefore, it is important to control the handling and transport environment to minimize oxygen exposure to the copper surface.

In the next processing step 407, a cobalt alloy such as CoWP, CoWB or CoWBP is electrolessly deposited on top of the copper surface. The electroless deposition of the cobalt alloy is a wet process and is deposited only on the catalytic surface, such as a copper surface. The cobalt alloy is only selectively deposited on the copper surface.

After electroless deposition of the cobalt alloy, the process flow can proceed to process step 409 where deposition cleaning can be selected. Post-deposition cleaning can be accomplished using a brush cleaning process with a chemical solution, such as a solution comprising CP72B supplied by Pennsylvania, Allentown, Air Products and Chemicals, Inc. I may also use other substrate surface cleaning process, for example, Lam, C3 ^TM or P3 ^TM cleaning technology. Other post-cleaning chemicals may include hydroxylamine-based chemicals to remove any metal-based contaminants that may remain on the surface of the dielectric layer after electroless plating.

As noted above, for the preparation of copper surfaces for cobalt alloy deposition, especially after hydrogen plasma reduction on copper surfaces, environmental control of processing and wafer transport is very important. 4B shows an overview of an exemplary integrated system 450 that minimizes exposure of the substrate surface to oxygen in a critical step after surface treatment. Moreover, since this is an integrated system, the substrate is immediately transported from one processing station to the next, which limits the exposure of the prepared copper surface to oxygen. The integration system 450 can be used to process the substrate through the entire process of the process 400 of FIG. 4A.

As noted above, surface treatment, electroless deposition of cobalt alloys, and selected post-cobalt alloy deposition processes include mixed dry and wet processes. Wet processing typically operates at near atmospheric pressure, while dry O ₂ plasma, hydrogen plasma, and O ₂ /Ar sputtering are operated at pressures less than 1 Torr. Therefore, this integrated system must be capable of operating a mix of dry and wet processes. The integration system 450 has three substrate transport modules (or chambers) 460, 470, and 480. Shipping chambers 460, 470, and 480 can be equipped with automatic controls to move substrate 455 from one processing region to another. This processing area can be a substrate carrier, a reactor, or a loadlock. The substrate transport module 460 operates in a laboratory environment with respect to room temperature, atmospheric pressure, and exposure to a high efficiency Particulate Air Filter (HEPA) or ultra high efficiency filtration. Laboratory (or plant) environment for air filtered by ULPA (Ultra Low Penetration Air Filter). Module 460 employs a substrate loader (or substrate carrier) 461 as an interface to bring substrate 455 into the integrated system, or to return the substrate to carrier 461 to continue processing external to system 450.

As described above in process flow 400, as shown in FIG. 2C, after the substrate has been planarized by metal CMP to remove excess metal from the surface of the substrate, and only the metal in the metal trench is left, substrate 455 It is brought to an integrated system 450 for cobalt alloy deposition such as CoWB, CoWP, or CoWBP. As described in step 401 of process 400, surface contaminants such as Cu-BTA complexes, as well as other metal oxide residues, must be removed from the surface of the substrate. Cu-BTA and metal oxides may be removed by a wet cleaning process comprising a cleaning solution, which may be, for example, a solution comprising TMAH, or a fault comprising, for example, but not limited to, ethylenediamine or diethylenetriamine. A solution of the amine. After removal of the BTA-metal complex, the metal oxide remaining on the surface of the copper and dielectric layers can be removed using a wet cleaning process comprising a cleaning solution, such as a solution containing citric acid, Or a solution of other organic acids that may or may not selectively remove copper oxide from copper. Metal oxides, especially copper oxides, can be removed using weak organic acids such as citric acid, or other organic or inorganic acids that can be used. In addition, an acid containing a very thin (i.e., <0.1%) peroxide, such as a sulfuric acid-peroxide mixture, can also be used. This wet cleaning process also removes other metal or metal oxide residues.

We can integrate the wet cleaning reactor 463 with the laboratory environment transport module 460, which operates under laboratory environmental conditions. Wet cleaning reactor 463 can be used to perform a one-stage or two-stage cleaning as described in step 401 of Figure 4A above. Alternatively, an additional wet cleaning reactor 463' can be integrated with the laboratory environment transport module 460 to provide a first stage of the two-stage cleaning process to be performed in the reactor 463, while in the reactor 463' The second stage to be carried out is provided. For example, a cleaning solution containing, for example, a chemical to clean the TMAH of Cu-BTA is located in the reactor 463, and a cleaning liquid containing a weak organic acid such as citric acid for cleaning metal oxides is located in the reactor. 463'.

Laboratory environmental conditions refer to environments that are under atmospheric pressure and open. Although the wet cleaning reactor 463 can be integrated with the laboratory environment transport module 460 during the process flow 400, this processing step can also be performed immediately after the metal CMP and before the substrate is brought to the integrated system for cobalt alloy deposition. . Alternatively, the wet cleaning process can be performed in a controlled ambient processing environment where the control environment is maintained during and after the wet cleaning step.

Organic residues (or contaminants) that have not been removed by previous wet cleaning can be removed by removing Cu-BTA and metal oxides, for example, by oxygen plasma, O ₂ /Ar sputtering, or Ar The dry oxidation plasma treatment of the sputtering method is removed. As noted above, most plasma or sputtering processes operate at pressures below 1 Torr, so it is desirable to couple such systems (or devices, or chambers, or modules) to A transport module that operates at a vacuum pressure of, for example, 1 Torr. If the transport module integrated with the plasma processing is under vacuum, since it is not necessary to evacuate the transport module for a long time, the substrate transport is more efficient and the processing module can be maintained under vacuum. In addition, since the transport module is under vacuum, the substrate after cleaning via plasma treatment is only exposed to very low concentrations of oxygen. The O ₂ plasma processing reactor 471 can be coupled to the vacuum transport module 470 assuming an O ₂ plasma treatment to clean the organic residue.

Since the laboratory environment transport module 460 is operated under atmospheric pressure and the vacuum transport module 470 is operated under vacuum (<1 Torr), the load compartment 465 is disposed between the two modules to The substrate 455 can be transported between two modules 460 and 470 that operate at different pressures. The carrier chamber 465 is for operation at a vacuum pressure of less than 1 Torr, or in a laboratory environment, or to be filled with an inert gas selected from a group of inert gases.

For example, after the substrate 455 is finished with an oxidative plasma treatment of O ₂ , the substrate 455 is moved into a hydrogen-containing reduction plasma reduction chamber (or module) 473. Hydrogen-containing plasma reduction is typically treated at low pressures, which are less than 1 Torr; therefore, it can be coupled to vacuum delivery module 470. Once the substrate 455 is reduced with a hydrogen-containing plasma, the copper surface is clean and free of copper oxide. In the preferred embodiment, this is completed without removing the substrate from the chamber after the O ₂ plasma processing the substrate 455 can simultaneously H ₂ or H ₂ / NH ₃ plasma reduction step. In either case, the substrate is ready for cobalt alloy deposition after the reduction process is completed.

As described above, after the substrate is reconstituted by the hydrogen-reducing plasma, it is important to control the processing and transport environment to minimize the exposure of the copper surface to oxygen. Substrate 455 should be treated under controlled conditions where the environment is vacuum or filled with more than one inert gas to limit the exposure of substrate 455 to oxygen. The dashed line 490 encloses the boundary contour of a portion of the integrated system 450 of Figure 4B, which shows the processing system and transport module whose environment is controlled. Transport and handling under control environment 490 can limit the exposure of the substrate to oxygen.

Electroless deposition of a cobalt alloy is a wet treatment comprising reducing a cobalt species in a solution by a reducing agent, which may be a phosphorus group (eg, hypophosphorous acid), a boron group (eg, dimethylamine borane), or two A combination of a phosphorus group and a boron group. CoWP can be deposited using a solution of a phosphorus-based reducing agent. CoWB can be deposited using a solution of a boron-based reducing agent. CoWBP can be deposited using a solution of a phosphorus-based and boron-based reducing agent. In one embodiment, the cobalt alloy electroless deposition solution is a base. Alternatively, the cobalt alloy electroless deposition solution may also be acidic. Since the wet processing is typically carried out under atmospheric pressure, the transport module 480 coupled to the electroless deposition reactor should be operated at near atmospheric pressure. In order to ensure that the environment is controlled to be in an anaerobic state, the control environment transport module 480 can be filled with an inert gas. In addition, all of the liquid used in this treatment needs to be degassed, i.e., the dissolved oxygen is removed by a commercially available degassing system. Exemplary inert gases include: nitrogen (N ₂ ), helium (He), neon (Ne), argon (Ar), krypton (Kr), and xenon (Xe).

In one embodiment, a wet cobalt alloy electroless deposition reactor (or apparatus, or system, or module) is coupled to a rinsing and drying system (or apparatus, or module) to cause the substrate to be fed in a dry state. The electroless deposition system 481 is discharged and the system 481 (dry in/out) is sent out in a dry state. This dry in/out requirement integrates the electroless deposition system 481 with the control environment transport module 480 and avoids the need for a wet automated control transport step for the separate flush drying module. The environment of the electroless deposition system 481 must also be controlled to provide low (or limited) concentrations of oxygen and humidity (water vapor). We can also fill this system with an inert gas to ensure that there is only a low concentration of oxygen in this treatment environment.

Alternatively, the electroless deposition of the cobalt alloy can be carried out in a dry/dry manner similar to the recently disclosed electroless copper. For the electroless deposition of copper, dry/dry copper-free treatment has been developed. This process uses a proximity processing head to limit the contact of the electroless treatment fluid with the substrate surface over the confinement region. The surface of the substrate other than the one below the processing head is dried. The details of such a process and system are known from the following U.S. Patent Application Serial No. 10/607,611, entitled "Apparatus And Method For Depositing And Planarizing Thin Films On Semiconductor Wafers", filed on June 27, 2003; No. 10/879,263, entitled "Method and Apparatus For Plating Semiconductor Wafers", filed on June 28, 2004, the contents of which are incorporated herein. Electroless plating of cobalt alloys can use similar proximity processing heads to facilitate the initiation of dry/dry processing.

After the cobalt alloy is deposited in system 481, substrate 455 can be sent to an optional post deposition cleaning reactor. I can use the following methods for this cleanup: for example, cleaning chemicals, mechanical assistance chemical or hydroxylamine of CP72B of (e.g. brushing); or using other methods, such as immersion cleaning, spin washed clean, or C3 ^TM proximity technology. The rinsing and drying system must also be integrated with the scrubbing system to allow the substrate 455 to dry in/out of the wet cleaning system 483. I use inert gas to fill system 483 to ensure that limited (or low) oxygen is present in the system. As described above with respect to Figure 4A, since post deposition cleaning is optional, system 483 is constructed in dots to indicate that it is optional. Since the post deposition cleaning step is the final processing to be operated by the integration system 450, the substrate 455 must be brought back into the carrier 461 after processing. Thus, as shown in FIG. 4B, the cleaning system 483 can alternatively be coupled to the laboratory environment transport module 460. If the cleaning system 483 is coupled to the laboratory environment transport module 460, the cleaning system 483 will not operate in a controlled environment and the inert gas does not need to be filled with the system.

As described above, the removal process of Cu-BTA and metal oxide can also be performed immediately after the metal CMP and before the substrate is brought to the integrated system for cobalt alloy deposition.

Case II: When metal CMP stops on the barrier layer

Figures 5A-5C show cross-sections of interconnect structures at various different processing stages. The copper layer on the substrate of Figure 5A has been planarized by CMP. The barrier layer 130 has not been removed but remains on the surface of the substrate. Figure 6A shows an embodiment of a process flow for the preparation of a surface for electroless deposition of a cobalt alloy over copper in a dual damascene metal trench. The substrate used in the process flow 600 of Figure 6A has just completed the copper CMP process to remove copper. As shown in Figure 5A, the barrier layer remains on the surface of the substrate. The difference between Case II and Case I is that in Case II, the surface of the dielectric layer 106 is not exposed to Cu-BTA complex or other copper compound residue. Compared to Case I, the dielectric layer surface in Case II has a higher quality (or less metal contaminant). Thus, the processing step for removing the copper oxide on the dielectric layer, which is formed after the O ₂ plasma to remove the organic contaminants, can be omitted.

This process begins in step 601 where metal contaminants such as Cu-BTA or metal oxide are removed from the surface of the substrate. As noted above, Cu-BTA complexes and metal oxides are two key surface metal contaminants to be removed. The treatment for removing metal contaminants such as Cu-BTA and metal oxides from the surface of the substrate has been described above. For example, Cu-BTA and a metal oxide comprising a copper oxide can be removed by a wet cleaning process comprising a cleaning solution, for example comprising tetramethylammonium hydroxide (TMAH), or for example ethylenediamine. Or a misamine of diethylenetriamine. The removal of Cu-BTA eliminates the pattern-dependent deposition effect of the cobalt alloy (to be deposited in the final step), thus providing uniform cobalt alloy deposition in tight and independent features.

Metal oxides, especially copper oxides, can be removed using weak organic acids such as citric acid, or other organic or inorganic acids that can be used. In addition, an acid containing a very thin (i.e., <0.1%) peroxide, such as a sulfuric acid-peroxide mixture, can also be used. This wet cleaning process also removes other metal or metal oxide residues.

At step 602, the organic contaminants comprising the remaining BTA on the surface of Cu and the barrier layer are removed. We can remove organic contaminants by, for example, dry oxygen (O ₂ ) plasma treatment or treatment with other oxidative plasma treatments such as H ₂ O, ozone, or hydrogen peroxide vapor. As mentioned above, the oxygen-containing plasma treatment is preferably carried out at a relatively low temperature of 50 ° C or less, preferably 120 ° C or less. Oxygenated plasma treatment can be processed downstream. Alternatively, we can also use O ₂ /Ar sputtering to physically remove organic contaminants while removing organic residues (or contaminants). As noted above, the O ₂ plasma treatment and the O ₂ /Ar sputtering process are typically operated at pressures less than 1 Torr.

Once the substrate surface is free of contaminants such as Cu-BTA, metal oxides, and organic contaminants, the substrate should be exposed to an oxygen-free environment to protect the copper surface from further oxidation. As shown in FIG. 5B, after the surface contaminants are removed, in step 603, a barrier layer such as Ta, TaN, Ru, or a combination of these materials is removed from the surface of the substrate. The barrier layer can be removed by, for example, CF ₄ plasma, O ₂ /Ar sputtering, CMP treatment, or by wet chemical etching. Both CF ₄ plasma etching and O ₂ /Ar sputtering are operated at pressures less than 1 Torr.

The copper oxide present on the copper surface 140 of FIG. 5A and produced during the plasma oxidation step can be completely removed during the barrier metal removal step 603. Therefore, the treatment using H-containing plasma to reduce the copper surface becomes optional. However, to ensure that the copper surface is free of copper oxide, the surface of the substrate can be (optionally) reduced in step 605 to convert any residual copper oxide to copper. Copper surface reduction can be achieved by treatment with hydrogen-containing plasma to convert copper oxide to copper. The processing gas and processing conditions used in the hydrogen-containing plasma treatment have been described in the above case I. Once the substrate has been subjected to hydrogen reduction treatment, the substrate is ready for cobalt alloy deposition. The copper surface must be carefully protected from oxygen to ensure that no copper oxide is formed. As described above, the electroless deposition of the cobalt alloy is suppressed by the presence of the copper oxide. Therefore, it is important to control the handling and transport environment to minimize or eliminate oxygen exposure to the copper surface.

At the next processing step 607, a cobalt alloy such as CoWP, CoWB or CoWBP is electrolessly deposited on top of the reduced copper surface 140'. The cobalt alloy shows layer 135 as shown in Figure 5C. Electroless deposition of cobalt alloys is selective deposition and is a wet process. The cobalt alloy is only deposited on the copper surface.

As in the case I above, after the electroless deposition of the cobalt alloy, the process flow can proceed to a process step 609 of selective deposition followed by a deposition process. Post-deposition cleaning can be carried out using a scrubbing treatment with a chemical solution such as a solution containing CP72B supplied by Air Products and Chemicals, Inc. of Airentown, Pennsylvania, or a hydroxylamine based chemical to remove Any metal contaminants that are present on the surface of the dielectric layer due to electroless deposition processing. We can also use other substrate surface cleaning treatments.

As noted above, environmental control systems are of great importance for the preparation of copper surfaces for cobalt alloy deposition, especially after H-plasma reduction of copper surfaces. Figure 6B shows an overview of an exemplary integrated system 650 that minimizes oxygen exposure of the substrate surface after critical surface treatment. The integration system 650 can be used to process the substrate through the entire process of the process 600 of FIG. 6A.

Similar to the integrated system 450, the integrated system 650 has three substrate transport modules 660, 670, and 680. Transport modules 660, 670, and 680 can be equipped with automatic controls to move substrate 655 from one processing area to another. The substrate transport module 660 operates in a laboratory environment. The module 660 uses a substrate loader (or substrate carrier) 661 as an interface to bring the substrate 655 into the integrated system, or return the substrate to the carrier 661 to continue processing outside of the system 650.

As described above in process flow 600, as shown in FIG. 5A, the substrate has been planarized by copper CMP to remove excess copper from the surface of the substrate, and leaving barrier layers and trenches on the surface of the dielectric layer. Subsequent to the copper, substrate 655 is brought to integration system 650 for cobalt alloy deposition, such as CoWB, CoWP, or CoWBP. As described in step 601 of process flow 600, surface contaminants such as Cu-BTA, metal oxides, and organic residues must be removed from the surface of the substrate. Cu-BTA and metal oxides can be removed by a wet cleaning process comprising a cleaning solution, such as a solution comprising TMAH. The wet cleaning reactor 663 can be integrated with the laboratory environment transport module 660. Although the wet cleaning reactor 663 can be integrated with the laboratory environment transport module 660 during process flow 600, this processing step can also be performed immediately after the metal CMP and before the substrate is brought to the integrated system for cobalt alloy deposition. Alternatively, the wet cleaning process can also be performed in a controlled ambient processing environment where the control environment is maintained during and after the wet cleaning step.

At step 602, the organic residue (or contaminant) that has not been removed by the wet cleaning process performed in reactor 663 can be treated by dry plasma such as O ₂ plasma or O ₂ /Ar sputtering. Remove it. As noted above, most of the plasma or sputtering processes operate at pressures below 1 Torr; therefore, it is desirable to couple such systems to a transport die that operates at a vacuum pressure of, for example, 1 Torr. group. Assuming O ₂ plasma treatment is selected to clean up organic residues, the O ₂ plasma treatment reactor 671 can be coupled to the vacuum transport module 670.

The O ₂ plasma treatment can be processed by downstream plasma. Although the O ₂ plasma reactor 671 can be integrated with the vacuum transport module 670 in process flow 600, this processing step can also be performed immediately after the metal CMP and before the substrate is brought to the integrated system for cobalt alloy deposition.

Since the laboratory environment transport module 660 is operated under atmospheric pressure, and the vacuum transport module 670 is operated under vacuum (<1 Torr), the load compartment 665 is disposed between the two modules to The substrate 655 can be transported between the two modules 660 and 670.

As shown in step 603, after the O ₂ plasma treatment is completed on the substrate 655, the substrate 655 is moved into the processing system for barrier layer etching. The barrier etch chamber (or module) 673 can be coupled to the vacuum transport module 670 if a dry barrier plasma etch process is selected. This dry barrier plasma treatment can be CF ₄ plasma treatment or O ₂ /Ar sputtering treatment.

The treatment after the barrier layer etch can be selected to ensure that there is no H plasma reduction of copper oxide remaining on the copper surface. The H ₂ plasma reduction can be performed in a plasma chamber (or module) 674 that is coupled to a vacuum delivery module 670. Alternatively, in a O ₂ plasma reactor 671 for removing organic residues, hydrogen plasma reduction may be successively performed after cleaning the chamber of residual oxygen species.

As described above, electroless deposition of cobalt alloy is a wet chemical treatment. Since the wet process is typically carried out at atmospheric pressure, the transport module 680 coupled to the electroless deposition reactor should be operated at near atmospheric pressure. To ensure that the environment is controlled to an anaerobic condition, the control environment transport module 680 can be filled with inert gas. In addition, all of the liquid used in this treatment needs to be degassed, i.e., the dissolved oxygen is removed by a commercially available degassing system.

The wet cobalt alloy electroless deposition reactor must be coupled to the rinsing and drying system to deliver the substrate to the electroless deposition system 681 in a dry state and to the system 681 (dry/dry) in a dry state. As described above, this dry/out of demand requires the electroless deposition system 681 to be integrated with the control environment transport module 680. The inert gas filling system 681 can be used to ensure that low (or limited, or controlled) concentrations of oxygen are maintained in the system.

Subsequent to the cobalt alloy deposition in system 681, substrate 655 can be sent to post deposition cleaning reactor 683. The rinsing and drying system must also be integrated with the scrubbing system to allow the substrate 655 to dry into/out of the wet cleaning system 683. We can fill the system 683 with an inert gas to ensure that no oxygen is present. As described above with respect to Figure 6A, since post-deposition cleaning is optional, the system 683 is constructed in dots to indicate that it is optional. Since the post deposition cleaning step is the final processing to be operated by the integration system 650, the substrate 655 must be brought back into the carrier 661 after processing. The cleaning system 683 can alternatively be coupled to the laboratory environment transport module 660.

Case III: When metal CMP stops on a thin copper layer

Figures 7A-7C show cross-sections of interconnect structures at various different interconnect processing stages. The substrate of Figure 7A has just completed copper planarization, but copper has not been completely cleaned from the substrate. The thin copper layer 132 remains on the surface of the substrate. Figure 8A shows an embodiment of a process flow for the preparation of a surface for electroless deposition of a cobalt alloy over copper in a dual damascene metal trench. The substrate used in the process flow 800 of FIG. 8A has just completed a copper CMP process to remove most of the copper above the barrier layer overlying the dielectric layer. As shown in FIG. 7A, a thin copper layer ranging from about 100 angstroms to about 1000 angstroms is left on the surface of the barrier layer. The difference between Case III and Case I and Case II is: In Case III, the thin copper layer covers the entire substrate surface; therefore, there is no Giovanni due to the exposure of the dissimilar materials in the copper CMP solution. Copper corrosion problem. Since the thin copper layer and other surface contaminants present will be removed in an oxygen-free environment, there is no problem with copper oxidation. Therefore, we do not need H ₂ plasma reduction. Case II and Case III do not have barrier CMP; therefore, the processing cost of metal CMP can be reduced. The copper surface prepared by this treatment provides excellent selectivity to copper on the dielectric layer on the copper layer.

Processing begins in step 801 where contaminants comprising organic residues and inorganic metal oxides are removed from the surface of the substrate. These organic contaminants can be removed by oxidizing plasma, such as dry oxygen (O ₂ ) plasma treatment, H ₂ O plasma treatment, H ₂ O ₂ plasma treatment, or plasma with ozone vapor. As noted above, the O ₂ plasma treatment is preferably carried out at relatively low temperatures of less than 120 °C. The O ₂ plasma treatment can be processed by downstream plasma. Alternatively, organic residues (or contaminants) can also be removed using an O ₂ /Ar sputtering process that physically removes the organic contaminants. As noted above, the O ₂ plasma treatment and the O ₂ /Ar sputtering process are typically operated at pressures less than 1 Torr.

Once the substrate surface is free of contaminants, the substrate should be exposed to an oxygen-free environment to protect the copper surface from oxidation. After removing the surface contaminants, in step 803, the thin copper layer overlying the barrier layer and the dielectric layer is removed. We can use O ₂ /A _r sputtering, O ₂ /hexafluoropentanedione (HFAC, hexafluoroacetylacetone) plasma etching, wet chemical etching using chemicals such as sulfuric acid and hydrogen peroxide, or use of misfit chemistry Remove the thin copper layer. Both O ₂ /Ar sputtering and O ₂ /HFAC plasma treatments operate at low pressures, for example, below 1 Torr.

Then, at step 805, a barrier layer such as Ta, TaN, or a combination of both films is removed from the surface of the substrate. The cross-section of the interconnect structure after removal of the thin copper layer and the barrier layer is shown in Figure 7B. The barrier layer can be removed by CF ₄ plasma, O ₂ /Ar sputtering, CMP, or wet chemical etching. Both the CF ₄ plasma etch and the O ₂ /Ar sputtering process operate at pressures below 1 Torr.

Since the copper surface for selectively depositing the cobalt alloy is produced by etching a thin copper layer and a barrier layer located above the dielectric layer in a controlled environment, most of the copper surface used for reducing the surface of the copper is not required. The step of the slurry. However, to ensure that the copper surface is free of copper oxide, the surface of the substrate can optionally be reduced in step 807 to convert any residual copper oxide to copper. The copper surface reduction treatment has been described above. Once the substrate has been subjected to a hydrogen reduction treatment, the substrate is ready for cobalt alloy deposition. The copper surface must be carefully protected from the formation of copper oxide. At the next processing step 809, a cobalt alloy such as CoWP, CoWB or CoWBP is electrolessly deposited on top of the copper surface. The cobalt alloy system shows layer 135 as in Figure 7C. Electroless deposition of cobalt alloys is selective deposition and is a wet process. The cobalt alloy is only deposited on the copper surface.

As in Case I and Case II above, after the electroless deposition of the cobalt alloy, the process flow can proceed to a process step 811 of optional deposition and deposition. The deposition has been cleaned up as described in Case I and Case II above.

As noted above, environmental control systems are of great importance for the preparation of copper surfaces for cobalt alloy deposition, especially after H-plasma reduction of copper surfaces. Figure 8B shows an overview of an exemplary integrated system 850 that minimizes oxygen exposure of the substrate surface after critical surface treatment. The integration system 850 can be used to process the substrate through the entire process of the process 800 of FIG. 8A.

The integrated system 850 has three substrate transport modules 860, 870, and 880. Transport modules 860, 870, and 880 can be equipped with automatic controls to move substrate 855 from one processing region to another. The substrate transport module 860 operates in a laboratory environment. The module 860 employs a substrate loader (substrate carrier) 861 as an interface to bring the substrate 855 into the integrated system, or to return the substrate to the carrier 861 and continue processing outside of the system 850.

As described in process flow 800 above, as shown in FIG. 7A, the substrate has been planarized by copper CMP to remove excess copper from the surface of the substrate and leave a thin layer over the barrier layer overlying the surface of the dielectric layer. Subsequent to the copper layer, substrate 855 is brought to integration system 850 for deposition of a cobalt alloy such as CoWB, CoWP, or CoWBP. As described in step 801 of process 800, surface contaminants such as organic residues and non-copper metal oxides must be removed from the surface of the substrate. In contrast to Case I and Case II, the laboratory environment transport module 860 may be omitted to allow the carrier 861 to be directly coupled to the load compartment 865 due to the need to omit wet Cu-BTA cleanup.

Surface contaminants comprising organic residues and metal oxides can be removed by treatment with an oxidative plasma such as O ₂ plasma or O ₂ /Ar sputtering. As noted above, most of the plasma or sputtering processes operate at pressures below 1 Torr; therefore, it is desirable to couple such systems to a transport die that operates at a vacuum pressure of, for example, 1 Torr. group. The O ₂ plasma processing reactor 871 can be coupled to the vacuum transport module 870 assuming an O ₂ plasma treatment is selected to clean up the organic residue.

The O ₂ plasma treatment can be processed by downstream plasma. Although the O ₂ plasma processing reactor 871 can be integrated with the vacuum transport module 870 in process 800, this processing step can also be performed immediately after the metal CMP and before the substrate is brought to the integrated system for cobalt alloy deposition. .

Since the laboratory environment transport module 860 is operated under atmospheric pressure and the vacuum transport module 870 is operated under vacuum (<1 Torr), the load compartment 865 is disposed between the two modules to The substrate 855 can be transported between the two modules 860 and 870.

As shown in step 803, after the O ₂ plasma treatment is completed on the substrate 855, the substrate 855 is moved into a processing system for copper etching. If a dry copper plasma etch process is selected, a copper etch chamber (or module) 873 can be coupled to the vacuum transport module 870. If a wet process is selected, the wet copper etch reactor can be integrated with the rinsing/drying system to form a wet copper etch system 873' that can be coupled to the control environment transport module 880. In order to integrate the wet copper etching system 873' with the control environmental group 880, for the system 873', dry/drying of the substrate is necessary. In one embodiment, the rinsing and drying system can be integrated with the wet copper etch system 873' to meet dry/dry out requirements. The environment of system 873' must also be controlled in an anaerobic state. We can also fill this system with inert gas to ensure there is no oxygen in this treatment environment.

As shown in step 805, barrier layer etching is performed after copper etching. If a dry barrier plasma etch process is selected, the barrier etch chamber 874 can be coupled to the vacuum transport module 870. If a wet barrier etch process is selected, the wet barrier etch reactor can be integrated with the rinsing/drying system to form a wet barrier etch system 874' that can be coupled to the control environment transport module 880. In order to integrate the wet barrier etch system 874' with the control environment transport module 880, for the system 874', dry/drying of the substrate is necessary. The environment of system 874' must also be controlled to provide low (or limited, or controlled) concentrations of oxygen. We can also fill this system with inert gas to ensure that low concentrations of oxygen are achieved in this treatment environment.

The treatment after the barrier layer etch is a H-containing plasma reduction as described above. H ₂ plasma reduction can be performed in a plasma chamber 877 that is coupled to a vacuum delivery module 870.

As described above, the electroless deposition of the cobalt alloy is a wet treatment. Since the wet process is typically carried out at atmospheric pressure, the transport module 880 coupled to the electroless deposition reactor should be operated at near atmospheric pressure. To ensure that the environment is controlled to provide low concentrations of oxygen, the control environment transport module 880 can be filled with inert gas. In addition, all of the liquid used in this treatment needs to be degassed, i.e., the dissolved oxygen is removed by a commercially available degassing system. Exemplary inert gases include: nitrogen (N ₂ ), helium (He), neon (Ne), argon (Ar), krypton (Kr), and xenon (Xe).

The wet cobalt alloy electroless deposition reactor must be coupled to the rinsing and drying system to allow the substrate to enter the electroless deposition system 881 in a dry state and to be sent out of the system 881 (dry/dry) in a dry state. This dry/dry demand requires the electroless deposition system 881 to be integrated with the control environment transport module 880. We can fill the system 881 with an inert gas to ensure that there is a low concentration of oxygen in this system.

After deposition of the cobalt alloy in system 881, substrate 855 can be sent to a post deposition cleaning reactor. The rinsing and drying system must also be integrated with the scrubbing system to allow the substrate 855 to dry into/out of the wet cleaning system 883. We use an inert gas filling system 883 to ensure that no oxygen is present. As described above with respect to Figure 8A, since post-deposition cleaning is optional, the system 883 is constructed in dots to indicate that it is optional. Since the post deposition cleaning step is the final processing to be operated by the integration system 850, the substrate 855 must be returned to the carrier 861 after processing. The cleaning system 883 can alternatively be coupled to the laboratory environment transport module 860.

2. Arranging the surface of the barrier layer for electroless copper deposition

The above system concept can be used to prepare the barrier layer surface for copper plating. If a barrier layer such as Ta, TaN or Ru is exposed to air for a long period of time, it will form Ta _x O _y (钽 oxide), TaO _x N _y (钽 钽 氧化物), or RuO ₂ (钌 钌). The electroless deposition of the metal layer on the substrate is highly dependent on the surface characteristics and composition of the substrate. Copper electroless deposition on the surface of Ta, TaN or Ru belongs to the result of the participation of the seed layer formation prior to electroplating and the selective deposition of copper lines within the lithographic definition pattern. There is a problem in that the electroless deposition treatment is suppressed by the atomic-scale thin primary metal oxide layer formed by the presence of oxygen (O ₂ ).

In addition, the copper film cannot be attached to, for example, tantalum oxide, niobium oxynitride, as it is attached to a pure barrier metal film (for example, Ta, Ru film) or a barrier-rich film (for example, a Ta-rich TaN film). a barrier oxide layer of a substance or a tantalum oxide. The Ta and/or TaN barrier layers are only used as an example. This description and concept can be applied to other types of barrier metals, such as Ta or TaN covered with a thin Ru layer. As described above, poor adhesion can adversely affect EM performance. In addition, the formation of tantalum oxide or niobium oxynitride on the surface of the barrier layer increases the resistivity of the barrier layer. Due to these problems, it is desirable to use this integrated system to prepare a barrier/copper interface while ensuring good adhesion between the barrier layer and copper and ensuring low barrier layer resistivity.

Case I: the formation of metal wires

Figure 9A shows an exemplary cross-section of a metal line structure after patterning with dielectric etching and removing photoresist. The metal wire structure is on the substrate 900 and has a germanium layer 110 which is previously fabricated to form a gate structure 105 having a gate oxide layer 121, a spacer 107, and a contact portion 125 therein. The contact portion 125 is typically formed by etching a contact hole in the oxide layer 103 and then filling the contact hole with a conductive material such as tungsten. Alternative materials may include copper, aluminum or other electrically conductive materials. The barrier layer 102 is also used as a function of the selective trench etch stop layer. The barrier layer 102 may be composed of a material such as tantalum nitride (SiN) or tantalum carbide (SiC).

A metal line dielectric layer 106 is deposited overlying the barrier layer 102. Materials that can be used to deposit the dielectric layer 106 have been described above. After depositing the dielectric layer 106, the substrate is patterned and etched to create metal trenches 116. FIG. 9B shows deposition of a metal barrier layer 130 along the metal trench 116 after the metal trench 116 is formed. FIG. 9C shows deposition of a copper layer 132 overlying the barrier layer 130 after deposition of the barrier layer 130. The barrier layer 130 may be composed of tantalum nitride (TaN), tantalum (Ta), Ru, or a combination of these films. A copper film 132 is then deposited to fill the metal trenches 116. In one embodiment, the copper film 132 includes a thin copper seed layer 131 beneath it.

As shown in FIG. 9D, after the plasma surface is pretreated to prepare a catalytic surface for deposition of the positive and thin electroless Cu seed layer 131, and after the trench 116 is filled with the copper film 132, the substrate 900 is subjected to chemical mechanical treatment. A polishing (CMP) or wet etching is performed to remove the copper material (or copper overlying layer) overlying the surface of the dielectric layer 106 from the barrier layer (or barrier overlayer). In one embodiment, the thickness of the thin copper seed layer is between about 5 angstroms and about 300 angstroms. As shown in FIG. 9E, the next step covers the copper surface 140 with a copper/SiC interface adhesion promoting layer 135 such as a cobalt alloy. Examples of cobalt alloys include: CoWB, CoWP, or CoWBP, which can be selectively deposited over copper by electroless treatment. The thickness of the adhesion promoting layer may be as thin as a single molecular layer, which is only a few angstroms, for example 5 angstroms; and for thicker layers, it may be, for example, 200 angstroms.

Figure 10A shows an embodiment of a process flow 1000 for preparing a barrier (or liner) layer surface for electroless copper deposition after a trench has been formed. However, it should be noted that the barrier (or liner) layer can be prepared separately in a non-integrated deposition system, such as an ALD or PVD deposition reactor. In this case, the surface preparation for depositing the thin copper seed layer will not include the metal plug cleaning and barrier deposition processing steps. At step 1001, the contact plug is cleaned to remove the original metal oxide. The metal oxide can be removed by various methods: Ar sputtering treatment; plasma treatment using a fluorine-containing gas such as NF ₃ , CF ₄ , or a combination thereof; wet chemical etching treatment; or, for example, using hydrogen Reduction treatment of plasma. At step 1003, a barrier layer is deposited. According to the technology node, the barrier layer can be deposited by atomic layer deposition (ALD) due to the reduction of the critical dimensions of the metal lines and vias. The barrier layer 130 has a thickness between about 20 angstroms and about 200 angstroms. As described above, it is essential to prevent the barrier layer from being exposed to oxygen in order to ensure that the electroless copper is deposited on the barrier layer with good adhesion between the copper and the barrier layer. Once the barrier layer is deposited, the substrate should be transported or treated in a controlled environment to limit exposure to oxygen. In optional step 1005, the barrier layer is subjected to a hydrogen plasma treatment to produce a metal-rich surface on the Ta, TaN, or Ru layer to provide a catalytic surface for subsequent copper seed deposition steps. Whether or not this step is required depends on the extent to which the surface is rich in metals.

Then, a positive copper seed layer is deposited on the surface of the barrier layer at step 1007, followed by a thick trench fill (or bulk fill) process at step 1008. In one embodiment, the positive copper seed layer can be deposited by electroless treatment. The thick copper bulk filling treatment may be an electroless deposition (ELD) treatment or an electrochemical plating (ECP) treatment. Electroless copper deposition and ECP are well known wet treatments. As explained above, for wet processing to be integrated into a system with control processing and shipping environment, the reactor must be integrated with the rinsing/drying system to have dry/dry out processing capabilities. In addition, this system must be filled with an inert gas to ensure minimal exposure of the substrate to oxygen. In recent years, dry/dry copper-free treatment has been developed. Again, all of the liquid used in this treatment is degassed, i.e., the dissolved oxygen is removed by a commercially available degassing system.

The electroless deposition process can be carried out in a number of ways, such as puddle-plating, in which a liquid is dispensed onto a substrate and reacted in a static mode, after which the reactants are removed and discarded, or recycled. . In another embodiment, this process uses a proximity processing head to limit the electroless treatment fluid to only contact the substrate surface on the defined area. The surface of the substrate other than the one below the processing head is dried. The details of such a process and system are known from the following U.S. Patent Application Serial No. 10/607,611, entitled "Apparatus And Method For Depositing And Planarizing Thin Films Of Semiconductor Wafers", filed on June 27, 2003; No. 10/879,263, entitled "Method and Apparatus For Plating Semiconductor Wafers", filed on June 28, 2004, the contents of which are incorporated herein. The electroless plating of the cobalt alloy described above can use a similar proximity processing head to facilitate the initiation of the dry/dry process.

After depositing copper in steps 1007 and 1008, the substrate can be subjected to optional substrate cleaning in step 1009. Post-copper deposition cleaning can be accomplished using a brush cleaning process with a chemical solution, for example, comprising a solution of CP72B supplied by Air Products and Chemicals, Inc. of Allentown, Pennsylvania. I may also use other substrate surface cleaning process, for example, Lam, C3 ^TM or P3 ^TM cleaning technology.

FIG. 10B shows an overview of an integrated system 1050 that minimizes oxygen exposure of the substrate surface in a critical step after preparing the surface of the barrier layer. In addition, since this is an integrated system, the substrate is immediately transported from one processing station to the next to limit the period of exposure of the cleaned copper surface to low concentrations of oxygen. The integration system 1050 can be used to process the substrate through the entire process of the process 1000 of FIG. 10A.

As noted above, surface preparation for copper electroless deposition and, optionally, cobalt alloy deposition processing, includes mixed dry and wet processing. This wet process is typically operated at near atmospheric pressure, while the dry process operates at pressures less than 1 Torr. Therefore, this integrated system must be capable of operating a mix of dry and wet processes. The integration system 1050 has three substrate transport modules 1060, 1070, and 1080. Transport modules 1060, 1070, and 1080 can be equipped with automatic controls to move substrate 1055 from one processing area to another. This processing area can be a substrate carrier, a reactor, or a carrier chamber. The substrate transport module 1060 operates in a laboratory environment. The module 1060 uses a substrate loader (or substrate carrier) 1061 as an interface to bring the substrate 1055 into the integrated system or return the substrate to one of the carriers 1061.

In process flow 1000 as described above, substrate 1055 is brought to integrated system 1050 to deposit a barrier layer and a copper layer. The upper tungsten surface 124a of the contact portion 125 is etched to remove the original tungsten oxide as described in step 1001 of process flow 1000. Once the tungsten oxide is removed, it is necessary to protect the exposed tungsten surface 124a of Figure 9A from exposure to oxygen. If the removal process is an Ar sputtering process, the reactor 1071 can be coupled to the vacuum transport module 1070. If a wet chemical etch process is selected, the reactor should be coupled to the control environment transport module 1080 instead of being coupled to the laboratory environment transport module 1060 to limit the exposure of the tungsten surface to oxygen.

Then, as described in step 1003 of FIG. 10A, the substrate is deposited with a metal barrier layer such as Ta, TaN, Ru, or a combination of these films. The barrier layer 130 of Figure 9B can be deposited by ALD or PVD processing. In one embodiment, the ALD process operates at a pressure of less than 1 Torr. The ALD reactor 1073 is coupled to the vacuum transport module 1070. In another embodiment, the deposition process using supercritical CO ₂ and a high pressure process for forming the barrier metal organometallic precursor. In yet another embodiment, the deposition process is a physical vapor deposition (PVD) process operating at a pressure of less than 1 Torr. The exemplary reactor details of the high pressure treatment using supercritical CO ₂ are described in co-pending U.S. Patent Application Serial No. 10/357,664, entitled "Method and Apparatus for Semiconductor Wafer Cleaning Using High-Frequency Acoustic Energy with Supercritical Fluid". , filed on February 3, 2003, which is incorporated herein by reference.

As described in step 1005 of Figure 10A, the substrate is capable of undergoing an optional reduction treatment, such as the use of a hydrogen containing plasma. Hydrogen reduction reactor 1074 can be coupled to vacuum delivery module 1070. At this stage, the substrate is ready for electroless copper deposition. Electroless copper plating can be performed in the electroless copper plating reactor 1081 to deposit a positive seed layer. After depositing the seed layer, a large amount of copper can be filled in the same electroless copper deposition reactor 1081 used to deposit the positive seed layer, but a large amount of filling is achieved with different chemicals. Alternatively, a large amount of copper can be filled in a separate ECP reactor 1081'.

Prior to exiting the integrated system 1050, the substrate optionally undergoes a surface cleaning process that cleans residues from previous copper deposition processes. For example, the substrate cleaning process can be a brush cleaning process. The substrate cleaning reactor 1083 can be integrated with the control environment transport module 1080. Alternatively, the substrate cleaning reactor 1083 can be integrated with the laboratory environment transport module 1060.

Alternatively, the barrier layer 130 of FIG. 9B can be deposited in the processing chamber before the substrate 900 is brought into a system for surface treatment and deposition of copper. Figure 10C shows an embodiment of a process flow 1090 for preparing a barrier (or liner) layer surface for electroless copper deposition. In optional step 1095, the barrier layer is subjected to a hydrogen plasma treatment to produce a metal-rich surface on the Ta, TaN, or Ru layer to provide a catalytic surface for subsequent copper seed deposition steps. Whether or not this step is required depends on the extent to which the surface is rich in metals.

Then, at step 1097, a conformal copper seed layer is deposited on the surface of the barrier layer, followed by a thick copper trench fill (or bulk fill) process at step 1098. In one embodiment, the positive copper seed layer can be deposited by electroless treatment. The thick copper bulk filling process can be an electroless deposition (ELD) process or an electrochemical plating (ECP) process. After the copper is deposited in steps 1097 and 1098, the substrate can be subjected to the optional substrate cleaning in step 1099. Post-copper deposition cleaning can be accomplished using a brush cleaning process with a chemical solution, for example, comprising a solution of CP72B supplied by Air Products and Chemicals of Allentown, Pennsylvania. I may also use other substrate surface cleaning process, for example, Lam, C3 ^TM or P3 ^TM cleaning technology.

Figure 10D shows an overview of an integrated system 1092 that minimizes the exposure of the substrate surface to oxygen after critical steps in the preparation of the barrier layer. In addition, since this is an integrated system, the substrate is immediately transported from one processing station to the next to limit the exposure of the cleaned copper surface to low concentrations of oxygen. The integration system 1092 can be used to process the substrate through the overall processing of the process 1090 of FIG. 10C.

As described above, the surface preparation for the electroless deposition of copper and the cobalt alloy deposition treatment after the selection involves dry and wet mixing treatment. This wet process is typically operated at near atmospheric pressure while the dry plasma process is operated at a pressure of less than 1 Torr. Therefore, this integrated system must be capable of operating a mix of dry and wet processes. The integration system 1092 has three substrate transport modules 1060, 1070, and 1080. Transport modules 1060, 1070, and 1080 can be equipped with automatic controls to move substrate 1055 from one processing area to another. This processing area can be a substrate carrier, a reactor, or a carrier chamber. The substrate transport module 1060 operates in a laboratory environment. The module 1060 uses a substrate loader (or substrate carrier) 1061 as an interface to bring the substrate 1055 into the integrated system or return the substrate to one of the carriers 1061.

In process flow 1090, as described above, after depositing the barrier layer to prepare the barrier layer surface for electroless copper deposition, substrate 1055 is brought to integration system 1092. As described in step 1095 of Figure 10C, the substrate is first subjected to a reduction treatment, such as the use of a hydrogen-containing plasma. The hydrogen reduction reactor 1074 can be coupled to the vacuum transport module 1070. At this stage, the substrate is ready for electroless copper deposition. Electroless copper plating can be performed in the electroless copper plating reactor 1081 to deposit a positive seed layer. After depositing the seed layer, a large amount of copper can be filled in the same electroless copper deposition reactor 1081 used to deposit the positive seed layer, but a large amount of filling is achieved with different chemicals. Alternatively, a large amount of copper can be filled in a separate ECP reactor 1081'.

This substrate optionally undergoes a surface cleaning process prior to exiting the integrated system 1092, which cleans the residue from previous copper deposition processes. For example, the substrate cleaning process can be a brush cleaning process. The substrate cleaning reactor 1083 can be integrated with the control environment transport module 1080. Alternatively, the substrate cleaning reactor 1083 can also be integrated with the laboratory environment transport module 1060.

Figure 11A shows an embodiment of a process flow for preparing a barrier (or liner) layer surface for electroless copper deposition and for preparing a CMP copper surface after electroless cobalt alloy deposition. At step 1101, the upper surface 124a of the contact plug is cleaned to remove the original tungsten oxide. The metal oxide can be removed by the following methods: Ar sputtering treatment, plasma reduction treatment, reactive ion etching treatment, or wet chemical etching treatment. At step 1103, a barrier layer is deposited. In the optional step 1105, the barrier layer is subjected to a hydrogen plasma treatment to produce a metal-rich surface on the Ta, TaN, or Ru layer to provide a catalytic surface for subsequent copper seed deposition steps. Whether or not this step is required depends on the extent to which the surface is rich in metals.

However, it should be noted that the barrier (or liner) layer can be prepared separately in a non-integrated deposition system, such as an ALD or PVD deposition reactor. In this case, the surface preparation for depositing the thin copper seed layer will not include the metal plug cleaning and barrier deposition processing steps, steps 1001 and 1003 as illustrated in FIG. 10A, and steps 1101 and 1103 of FIG. 11A. . In these cases, the illustrated processes begin at step 1005 or 1105.

Then, a positive copper seed layer is deposited on the surface of the barrier layer at step 1107, followed by a thick copper trench fill (or bulk fill) process at step 1108. In one embodiment, the positive copper seed layer can be deposited by electroless treatment. The thick copper bulk filling process can be an electroless deposition (ELD) process or an electrochemical plating (ECP) process. Electroless copper deposition and ECP are well known wet treatments. As explained above, for wet processing to be integrated into a system with control processing and shipping environment, the reactor must be integrated with the rinsing/drying system to have dry/dry out processing capabilities. In addition, this system must be filled with an inert gas to ensure minimal exposure of the substrate to oxygen. In recent years, dry/dry copper-free treatment has been developed. Again, all of the liquid used in this treatment is degassed, i.e., the dissolved oxygen is removed by a commercially available degassing system.

As shown in FIG. 9D, the substrate is deposited with a positive copper seed layer at step 1107, and after a thick Cu trench fill (mass fill) is performed in step 1108 by electroless or electroplating, in step 1109, from the overlying dielectric layer. The surface of the substrate above the barrier layer 130 of 106 removes the copper layer 132. Then remove the barrier layer. These removal processes are simultaneously performed in process step 1109 of Figure 11A. We can remove copper from the surface above the barrier layer by CMP (this is a wet process). The barrier layer can be removed by reactive ion etching, O ₂ /Ar sputtering, CMP, or wet chemical etching, such as CF ₄ plasma. These barrier etch processes have been previously described.

After removing the barrier layer, a cleaning process to remove the Cu-BTA complex is performed, and a metal oxide (step 1110) and an organic contaminant removal process (step 1111) are performed to remove from the substrate surface. Contaminants. Details of substrate surface cleaning using these two steps after metal CMP have been described above.

After removing surface contaminants from the surface of the substrate, in step 1112, the substrate is treated with a (hydrogen containing) reduction plasma to reduce all of the residual metal oxide to metal. After hydrogen reduction, the copper surface is very clean and catalytic, and is ready for electroless deposition of cobalt alloy. At step 1113, the substrate is subjected to electroless deposition of cobalt alloy and rinsing and drying of the substrate. A final processing step 1115 is an optional substrate cleaning step to clean any residual contaminants from previous electroless cobalt alloy deposits.

Figure 11B shows an overview of an integrated system 1150 that minimizes oxygen exposure of the substrate surface in a critical step after preparing the barrier layer and the copper surface. In addition, this is an integrated system so that the substrate is immediately transported from one processing station to the next, which limits the exposure of the cleaned copper surface to low concentrations of oxygen. The integration system 1150 can be used to process the substrate through the entire processing of the process 1100 of FIG. 11A.

The integration system 1150 has three substrate transport modules 1160, 1170, and 1180. Transport modules 1160, 1170, and 1180 can be equipped with automatic controls to move substrate 1155 from one processing region to another. This processing area can be a substrate carrier, a reactor, or a carrier chamber. The substrate transport module 1160 operates in a laboratory environment. The module 1160 uses a substrate loader (or substrate carrier) 1161 as an interface to bring the substrate 1155 into the integrated system or return the substrate to one of the carriers 1161.

As described above, in the process flow 1100 of FIG. 11A, the substrate 1155 is brought to the integration system 1150 to deposit a barrier layer, to prepare a barrier layer surface for copper layer deposition, and to prepare a post-CMP copper surface for electroless cobalt alloy deposition. . The upper metal plug surface 124a of the contact 125 is etched to remove the original metal oxide as described in step 1101 of process flow 1100. Alternatively, a reducing plasma such as a hydrogen-containing plasma can be used to remove the metal plug surface oxide. Once the metal plug surface oxide is removed, the exposed metal surface 124a of Figure 9A must be protected from oxygen exposure. If the removal process is an Ar sputtering process, the Ar sputtering reactor 1171 can be coupled to the vacuum transport module 1170. If a wet chemical etch process is selected, the reactor should be coupled to the control environment transport module 1180 rather than to the laboratory environment transport module 1160 to limit the exposure of the cleaned metal plug surface to oxygen.

Then, as described in step 1103 of FIG. 11A, the substrate is deposited with a metal barrier layer such as Ta, Ru, TaN, or a combination of these films. The barrier layer 130 of FIG. 9B can be deposited by ALD processing or PVD processing. In an embodiment, the ALD process operates at a pressure of less than 1 Torr. The ALD reactor 1173 is coupled to the vacuum transport module 1170. In another embodiment, the deposition process using supercritical CO ₂ and a high pressure process for forming the barrier metal organometallic precursor. In yet another embodiment, the deposition process is a physical vapor deposition (PVD) process operating at a pressure of less than 1 Torr. As described in step 1105 of Figure 11A, the substrate can be subjected to an optional reduction treatment, such as the use of a hydrogen containing plasma. Hydrogen reduction reactor 1174 can be coupled to vacuum delivery module 1170. At this stage, the substrate is ready for electroless copper deposition. Electroless copper plating can be performed in the electroless copper plating reactor 1181 to deposit a positive seed layer. After depositing the seed layer, we can perform a large amount of copper filling in the same electroless copper deposition reactor 1181 used to deposit the positive seed layer, but achieve a large amount of filling with different chemicals. Alternatively, a large amount of copper can be filled in a separate ECP reactor 1181 '.

Then, as described in step 1109 of FIG. 11A, the copper overlying layer and the barrier overlayer are removed from the substrate. The removal of the copper overlayer and the barrier overcoat can be achieved in one CMP system 1183, or in two CMP systems. In the embodiment shown in Figure 11A, we only use one CMP system 1183. After the CMP removes the copper and barrier overcoat, the substrate surface must be cleaned to remove surface contaminants. A wet cleaning system 1185 is used to remove copper BTA complexes as well as metal oxides. An O ₂ plasma system 1177 is used to remove organic contaminants. In one embodiment, an O ₂ plasma treatment to remove organic contaminants can be performed in the hydrogen reduction chamber 1174.

As described in step 1112 of Figure 11A, the substrate is subjected to a reduction process after removal of contaminants. Hydrogen reduction treatment can occur in the same reduction reactor 1174 used to reduce the barrier layer to Ta-rich. After the hydrogen reduction treatment, the copper surface is ready for electroless cobalt alloy deposition, which can be carried out in reactor 1187.

Prior to exiting the integrated system 1150, the substrate can optionally undergo a surface cleaning process that cleans residues from previous copper plating processes. This substrate cleaning process can be a brush cleaning process, and the reactor 1163 can be integrated with the laboratory environment transport module 1160.

The wet processing system described in Figure 11B coupled to the control environment transport module 1180 must be fully compliant with dry/dry out requirements to provide system integration.

Case II: Dual Tessellation Interconnect Procedure

Figure 12A shows an exemplary cross-section of an interconnect structure after patterning via a dual damascene process. This interconnect structure is located on the substrate 1200 and has an oxide layer 100 that is previously fabricated to form metallized wires 101 therein. The metallized wire is typically made by etching a trench into the oxide layer 100 and then filling it with a conductive material such as copper.

In this trench, there is a barrier layer 120 for preventing the copper material 122 from diffusing into the oxide layer 100. The barrier layer 120 may be composed of tantalum nitride (TaN), tantalum (Ta), ruthenium (Ru), or a combination of these films. We can also use other barrier materials. The barrier layer 102 is deposited over the copper material 122 to provide an etch stop during the via etch process and as a diffusion barrier between the dielectric layers for copper. The barrier layer 102 may be composed of a material such as tantalum nitride (SiN) or tantalum carbide (SiC), or other materials suitable for integration with a dual damascene process.

I deposited the via dielectric layer 104 over the barrier layer 102. The via dielectric layer 104 may be composed of an inorganic dielectric material such as cerium oxide or, preferably, a low-K dielectric material. Exemplary dielectrics can include undoped TEOS ceria, fluorine-doped bismuth glass (FSG), organic bismuth glass (OSG), and porous OSG. Commercially available dielectric materials include Aurora, Coral, Black Diamond (I) and Black Diamond (II). After depositing the via dielectric layer 104, a patterning and etching process is used to form the vias 114. The copper surface 122a can be protected by a dielectric barrier layer such as SiC or Si ₃ N ₄ . FIG. 12A shows a dual damascene structure after forming vias 114 and trenches 116. The dielectric barrier layer 102 underlying the via hole 114 has been removed.

12B shows that a first barrier layer 130 _I , a second barrier layer 130 _II , and a copper layer 132 are deposited along the via 114 ' and the trench 116 after the via 114 and the trench 116 are formed. Each of the barrier layers 130 _I and 130 _{II may} be composed of tantalum nitride (TaN), tantalum (Ta), or ruthenium (Ru). We can also use other barrier materials. In one embodiment, the first barrier layer 130 _I is a thin TaN layer deposited by ALD; and the second barrier layer 130 _II is a very thin Ta layer deposited by flash plating PVD, or by ALD or PVD The deposited Ru layer. In one embodiment, the first barrier layer 130 _{I has} a thickness between about 10 angstroms and about 150 angstroms; and the second barrier layer 130 _{II has} a thickness between about 10 angstroms and about 50 angstroms. . This thin ALD TaN layer can provide a positive coverage of the barrier layer above the via 114' and trench 116. This thin PVD Ta layer or Ru layer can provide good adhesion to the copper film 132 overlying the barrier layers 130 _I and 130 _II . Typically, the barrier layer deposited by PVD processing does not have good step coverage (or the film is not conformal). Therefore, we need an ALD barrier layer to ensure good barrier coverage inside the via and trench. In another embodiment, the first barrier layer 130 _I and the second barrier layer 130 _{II are} combined into a single layer, which can be deposited by ALD or PVD. Such a single layer barrier material may be tantalum, tantalum nitride, niobium, or a combination of these films.

After depositing the first and second barrier layers 130 _I , 130 _II , the substrate is subjected to the desired surface treatment steps described above to ensure that the barrier layer surface is rich in Ta. Then, a person deposits a copper film 132 using one of the PVD seed layer 131 or the electroless seed layer 131, and then fills the via hole 114 and the trench 116 with a thick trench copper filling layer.

As shown in FIG. 12C, after the copper film 132 fills the via 114 and the trench 116, the substrate 1200 is planarized to remove the copper material (or copper overlying layer) overlying the surface of the dielectric layer 106. Barrier layer (or barrier overlayer). This substrate then receives the required surface treatment steps described above to ensure that the substrate surface is clean and that copper oxide is removed from the copper surface. As shown in FIG. 12D, the next step is to cover the copper surface 140 with a copper/SiC interface adhesion promoting layer 135 such as a cobalt alloy. Examples of cobalt alloys include: CoWP, CoWB, or CoWBP, which can be selectively deposited over copper by electroless treatment. The thickness of the adhesion promoting layer may be as thin as a single molecular layer, which is only a few angstroms; and for a thicker layer, it may be, for example, 200 angstroms.

Figure 13A shows an embodiment of a process flow for preparing a barrier (or liner) layer surface for electroless copper deposition and for preparing a CMP copper surface after electroless cobalt alloy deposition. At step 1301, the upper surface 122a of the metal line 101 is cleaned to remove the original copper oxide. The copper oxide can be removed by Ar sputtering or wet chemical etching. In step 1302, a first barrier layer (130 _I of FIG. 12B) is deposited in an ALD system. At step 1303, a second barrier layer (130 _{II of} Figure 12B) is deposited in the PVD system. As described above, it is essential to prevent the barrier layer from being exposed to oxygen in order to ensure that the electroless copper is deposited on the barrier layer with good adhesion between the copper and the barrier layer. Once the barrier layer is deposited, the substrate should be transported or treated in a controlled environment to limit exposure to oxygen. At step 1305, the barrier layer is treated with a reducing plasma (i.e., containing hydrogen) to produce a metal-rich layer that will provide a catalytic surface for subsequent copper seeding deposition steps. This reduction plasma treatment is optional depending on the composition of the surface.

Then, in step 1307, a person deposits a layer of a positive copper seed on the surface of the barrier layer, followed by a thick copper bulk fill (or trench fill) process at step 1308. This positive copper seed layer can be deposited by electroless treatment. This thick copper bulk fill (also trench fill) layer can be deposited by ECP processing. Alternatively, such a thick copper bulk (also trench fill) layer can be deposited by electroless treatment in a identical electroless system for a positive copper seed layer but with different chemicals.

As shown in FIG. 11C, the substrate is deposited in a stepped copper seed layer at step 1307, and after a large amount of thick Cu is filled in a step 1308 by electroless or electroplating, in step 1309, from the barrier at the capping dielectric layer 106. The surface of the substrate above layer 130 removes copper layer 132. Then remove the barrier layer. These removal processes are simultaneously performed in process step 1309 of Figure 13A. We can remove copper from the surface above the barrier layer by CMP (this is a wet process). The barrier layer can be removed using CF ₄ plasma, O ₂ /Ar sputtering, CMP, or wet chemical etching. These barrier etch processes have been previously described.

After removing the barrier layer, a cleaning process to remove the Cu-BTA complex and metal oxide (step 1310) and organic contaminant removal process (step 1311) are performed to remove contaminants from the substrate surface. . Details of the surface cleaning of the substrate using this two-step process after metal CMP have been described above.

At step 1312, after removing surface contaminants from the surface of the substrate, the substrate is treated with a reducing plasma such as a hydrogen-containing plasma to reduce all of the residual metal oxide to metal. After the hydrogen reduction treatment, the copper surface is very clean and catalytic, and preparation for electroless deposition of the cobalt alloy has been made. At step 1313, the substrate receives electroless deposition of the cobalt alloy and rinsing and drying of the substrate. The final processing step 1315 is an optional substrate cleaning step to clean any residual contaminants from previous electroless cobalt alloy deposits.

Figure 13B shows an overview of an integrated system 1350 that minimizes oxygen exposure of the substrate surface in a critical step after preparing the barrier layer and the copper surface. Moreover, since this is an integrated system, the substrate is immediately transported from one processing station to the next, which limits the exposure of the cleaned copper surface to low concentrations of oxygen. The integration system 1350 can be used to process the substrate through the entire process of the process 1300 of FIG. 13A.

The integration system 1350 has three substrate transport modules 1360, 1370, and 1380. Transport modules 1360, 1370, and 1380 can be equipped with automatic controls to move substrate 1355 from one processing region to another. This processing area can be a substrate carrier, a reactor, or a carrier chamber. The substrate transport module 1360 operates in a laboratory environment. The module 1360 uses a substrate loader (or substrate carrier) 1361 as an interface to bring the substrate 1355 into the integrated system or return the substrate to one of the carriers 1361.

As described above, in the process flow 1300 of FIG. 11A, the substrate 1355 is brought to the integration system 1350 to deposit a barrier layer to prepare a barrier layer surface for copper layer deposition, and a post-CMP copper surface for electroless cobalt alloy deposition is prepared. . The upper end copper surface 122a of the metal line 101 is etched to remove the original copper oxide as described in step 1301 of process flow 1300. Once the copper oxide is removed, the exposed tungsten surface 122a of Figure 12A must be protected from exposure to oxygen. If the removal process is an Ar sputtering process, the Ar sputtering reactor 1371 can be coupled to the vacuum transport module 1370. If a wet chemical etch process is selected, the reactor should be coupled to the control environment transport module 1380 rather than to the laboratory environment transport module 1360 to limit the exposure of the cleaned tungsten surface to oxygen.

Then, the substrate is deposited with the first and second barrier layers. The first barrier layer 130 _{I of} Figure 12B can be deposited by ALD processing, which is dry processing and operates at a pressure of less than 1 Torr. The ALD reactor 1372 is coupled to the vacuum transport module 1370. The second barrier layer 130 _{II of} Figure 12B can be deposited by PVD or ALD processing, which is dry processing and operates at a pressure of less than 1 Torr. The PVD reactor 1373 can be coupled to the vacuum transport module 1370. The substrate is capable of undergoing an optional hydrogen reduction treatment to ensure that the surface of the barrier layer is rich in metal for the electroless copper deposition system. Hydrogen reduction reactor 1374 can be coupled to vacuum delivery module 1370. At this stage, the substrate is ready for electroless copper deposition. As described in step 1307 of Figure 13A, electroless copper plating can be performed in an electroless copper plating reactor 1381 to deposit a positive copper seed layer. As noted above, the trench fill layer deposition of step 1308 of Figure 13A can be performed in the same electroless plating reactor 1381 with different chemicals, or in a separate ECP reactor 1381'.

Then, as described in step 1309 of FIG. 13A, the copper overlying layer and the barrier overlayer are removed from the substrate. The removal of the copper overlying layer and the barrier overcoat can be achieved in one CMP system 1383 or in two CMP systems. In the embodiment shown in Figure 13A, we only use one CMP system 1383. After the CMP removes the copper and barrier overcoat, the substrate surface must be cleaned to remove surface contaminants. Wet cleaning system 1385 is used to remove copper BTA complexes as well as metal oxides. The O ₂ plasma system 1377 is used to remove organic contaminants. In one embodiment, we may perform an O ₂ plasma treatment to remove organic contaminants in a hydrogen reduction chamber 1374.

As described in step 1312 of Figure 13A, after removal of the contaminants, the substrate is subjected to a reduction process. This hydrogen reduction treatment is used to reduce copper oxide to copper and can occur in the same reduction reactor 1374 used to reduce the barrier layer to Ta-rich. After the hydrogen reduction treatment, the copper surface is ready for electroless cobalt alloy deposition, which can be carried out in reactor 1387.

Prior to exiting the integrated system 1350, the substrate can optionally undergo a surface cleaning process that cleans residues from previous copper plating processes. The substrate cleaning process can be a brush cleaning process, and the reactor 1363 can be integrated with the laboratory environment shipping module 1360.

The wet processing system described in Figure 13B coupled to the control environment transport module 1380 must be fully compliant with dry/dry out requirements to provide system integration.

The above apparatus and method (or process) can be applied to the preparation of metal surfaces for subsequent metal deposition to improve metal-to-metal adhesion and EM properties.

3. Arranging a crucible surface for selective electroless metal deposition for forming a metal deuteration layer

We can use the processes described so far to improve EM performance, metal resistivity, and to create copper interconnects such as contacts, vias, and metal lines. In earlier integrated circuit fabrication procedures, another metal deposition was applied to the surface of the germanium or polysilicon to contact the landing region of the source/drain/gate, resistor, structure (eg, contact landing area of the resistor) A metal deuteration layer is formed in the gate portion, the capacitor portion, or the inductor portion of the device, and provides good ohmic contact. 14A is a cross section of a gate structure 127 including a thin gate oxide layer 121, a polysilicon layer 115, and a nitride spacer 107 on the germanium substrate 110. STP (shallow trench isolation) 65 is used to separate the active components. At both ends of the gate structure are a source region 61 and a drain region 63. On the source region 61, there is an exposed crucible surface 62. On the drain region 63, there is an exposed crucible surface 64. On the polysilicon layer 115, there is an exposed polysilicon 109. We form a metal deuteration layer to reduce the surface resistance.

As shown in FIG. 14B, in order to form a metal deuterated layer, a metal 111 such as nickel (Ni), titanium (Ti), or cobalt (Co) is first deposited on the surface of the crucible. Currently, metal 111 is deposited on the surface of the substrate by PVD processing and is not selective for germanium or dielectric regions. The metal is then tempered to form a metal ruthenium alloy (telluride) in the region where the metal is in contact with the tantalum or polycrystalline germanium substrate. No telluride is formed in the dielectric region. The metal that is not reacted to the telluride is selectively removed, including the metal in the dielectric region and the remaining unreacted metal above the deuterated region. An electroless metal deposition system can be used to replace the current alternative process for deposition of Co or Ni. These advantages are: a thicker metal deuteration layer can be produced as well as providing improved etch stop characteristics and allowing the formation of metal-to-metal contacts. In order to ensure the deposition of electroless metal, the surface of the crucible must be very clean and free of the original niobium oxide. As shown in FIG. 14C, after the metal 111 is selectively deposited on the crucible surfaces 62, 64, the substrate is subjected to a heat treatment at a high temperature, for example, between about 800 ° C and about 900 ° C to form a metal deuterated layer 113. As shown in FIG. 14D, the formed deuterated layer 113 can electrically connect the contact portion 125 with the drain region 61.

As noted above, surface preparation prior to electroless metal deposition must be performed in a controlled ambient environment to ensure that the surface on which electroless deposition will occur is not exposed to oxygen. Figure 15A shows an embodiment of a process flow 1500 for forming a metal deuterated layer. At step 1501, metal contaminants are removed from all of the dielectric layer surfaces; this can be done using known methods and chemicals. Step 1501 is an optional step that is required only if there is a problem with surface metal contaminants. At step 1502, organic contaminants are then removed from the surface of the substrate. As noted above, organic contaminants can be removed by a variety of different dry or wet treatments. Then, at step 1503, the surface is reduced to convert the native cerium oxide into cerium. The native niobium oxide is a self-limiting process; therefore, this oxide layer is rather thin and does not require an oxide removal step prior to the reduction treatment. As described above, this reduction treatment can be a hydrogen plasma treatment.

After surface reduction, the surface of the crucible is ready for electroless metal deposition. A metal such as Ni, Ti, or Co at step 1505 is selectively deposited over the exposed surface of the germanium (including polysilicon). Selective metal deposition can be achieved by electroless processing. After electroless metal deposition, the substrate is subjected to optional substrate cleaning using known methods and chemicals in step 1507. At step 1509 the substrate is then subjected to a high temperature treatment (or tempering) to form a metal deuteration layer.

15B shows an embodiment of an integrated system 1550 that includes a laboratory environment transport module 1560, a vacuum transport module 1570, and a control environment transport module 1580. The laboratory environment transport module 1560 can be coupled to the carrier 1561 holding the substrate 1555. In one embodiment, the metal contaminants may be removed by a wet cleaning process, such as one of the wet cleaning processes described above to remove metal contaminants. This wet cleaning can be performed in chamber 1563 coupled to laboratory environment transport module 1560. Since this processing step is optional, the chamber 1563 of Fig. 15B is formed in dots. After removing metal contaminants, remove organic contaminants. In one embodiment, organic contaminants may be removed in an oxidizing plasma such as O ₂ , H ₂ O, or ozone plasma in reactor 1571 due to O ₂ plasma treatment at pressures below 1 Torr The low pressure dry process of operation is such that the reactor is coupled to the vacuum transport module 1570.

Then, we can perform the ruthenium surface reduction of step 1503 of Scheme 1500 in reactor 1573. The substrate is then transported to the next system for deposition with a metal used to form a metal deuteration layer (or deuterated metal) in the electroless treatment reactor 1581. The substrate is transported through the vacuum transport module 1570, the load compartment 1575, and the control environment transport module 1580, and finally reaches the reactor 1581 for processing. The electroless metal deposition reactor 1581 can be equipped with a rinsing/drying system. As described in process step 1507 of Figure 15A, the substrate can be subjected to an optional substrate cleaning in the wet cleaning chamber 1583 after metal deposition. After electroless deposition, the substrate is sent to a thermal reactor 1576, such as a rapid thermal processing (RTP) reactor, to form a metal deuterated layer.

These systems provide substrate processing requiring low pressure dry processing, high pressure processing, and wet processing, which are to be integrated to limit oxygen exposure with critical processing steps. Figure 16 shows an overview of how to integrate different processes. This laboratory environmental transport module can be integrated with carriers, wet processing, and dry processing that do not necessarily limit oxygen exposure (or uncontrolled disposal). This vacuum transport module can be integrated with low pressure dry processing. The vacuum transport module operates at a vacuum of, for example, less than 1 Torr; therefore, we can limit and control the exposure to oxygen. The carrier chamber I allows the substrate to be transported between the laboratory environment transport module and the vacuum transport module. The control environment transport module can be integrated with wet processing, near atmospheric pressure processing, and high pressure processing. The term "high pressure" is used to distinguish between low pressure treatment. The pressure of the high pressure treatment is related to the pressure greater than atmospheric pressure treatment, such as the supercritical CO ₂ treatment described above. In one embodiment, a load compartment (no display) is present between the high pressure processing chamber and the control environment transport module to ensure that the substrate is effectively transported between the transport module and the processing chamber. The carrier chamber II allows the substrate to be transported between the vacuum transport module and the control environment transport module. The control environment transport module and the reactor coupled to the control environment transport module are filled with inert gas to limit exposure to oxygen. The load bearing chamber II can be evacuated to receive the substrate from the vacuum transport module. We can also fill the load compartment II with inert gas and exchange the substrate with the control environment transport module.

While the invention has been described with respect to the embodiments the embodiments of the present invention Therefore, it is intended that the present invention include all such modifications, additions, modifications, and In the context of the patent application, the elements and/or steps do not imply any order of operation unless explicitly stated in the scope of the claims.

20. . . Cobalt alloy coating

twenty three. . . Copper layer

twenty four. . . Barrier layer

25. . . Dielectric covering SiC layer

30. . . Cobalt alloy coating

33. . . Copper layer

34. . . Barrier layer

35. . . Dielectric covering SiC layer

50. . . Substrate

60. . . Substrate

61. . . Source area

62. . .矽 surface

63. . . Bungee area

64. . .矽 surface

65. . . Shallow trench isolation

100. . . Dielectric layer

101. . . Metallized wire

102. . . Barrier layer

103. . . Oxide layer

104. . . Through hole dielectric layer

105. . . Gate structure

106. . . Trench dielectric layer

107. . . Partition

109. . . Exposed polycrystalline germanium

110. . .矽 substrate

111. . . metal

113. . . Metal deuterated layer

114. . . Through hole

114’. . . Through hole

115. . . Polycrystalline layer

116. . . Trench

120. . . Barrier layer

121. . . Gate oxide layer

122. . . Copper material

122a. . . Copper surface

124a. . . Exposed metal surface

125. . . Contact

127. . . Gate structure

130. . . Barrier layer

130 _I . . . First barrier layer

130 _II . . . Second barrier layer

131. . . Copper seed layer

132. . . Copper layer

135. . . Interface adhesion promoting layer

140. . . Copper surface

140’. . . Reduced copper surface

400. . . Processing flow

401. . . Step of removing metal organic complex and metal oxide from the surface of the substrate

403. . . Steps to remove organic contaminants from the surface of the substrate

405. . . Steps to reduce the copper surface

407. . . Step of depositing a cobalt alloy and performing rinsing and drying

409. . . Step of cleaning the surface of the substrate after the cobalt alloy deposition cleaning process

450. . . Integrated system

455. . . Substrate

460. . . Laboratory environment transport module

461. . . Substrate loader

463. . . Wet cleaning reactor

463’. . . Wet cleaning reactor

465. . . Carrying room

470. . . Vacuum transport module

471. . . O ₂ plasma treatment reactor

473. . . Hydrogen reduction plasma reduction chamber

475. . . Carrying room

480. . . Control environment transport module

481. . . Electroless deposition system

483. . . Wet cleaning system

490. . . Control environment

600. . . Processing flow

601. . . Step of removing copper complex and metal oxide from the surface of the substrate

602. . . Steps to remove organic contaminants from the substrate surface

603. . . Steps to remove the barrier layer above the dielectric layer

605. . . Steps to reduce the copper surface

607. . . Step of depositing cobalt alloy and rinsing/drying

609. . . Step of cleaning the surface of the substrate after the cobalt alloy deposition cleaning process

650. . . Integrated system

655. . . Substrate

660. . . Laboratory environment transport module

661. . . Substrate loader

663. . . Wet cleaning reactor

665. . . Carrying room

670. . . Vacuum transport module

671. . . O ₂ plasma treatment reactor

673. . . Barrier layer etching chamber

674. . . H ₂ plasma reduction chamber

675. . . Carrying room

680. . . Control environment transport module

681. . . Electroless deposition system

683. . . Post-deposition cleaning reactor

800. . . Processing flow

801. . . Steps to remove contaminants from the surface of the substrate

803. . . Removing the thin copper layer to clean the copper over the barrier layer overlying the dielectric layer

805. . . Step of removing the barrier layer covering the dielectric layer

807. . . Steps to reduce the copper surface

809. . . Step of depositing cobalt alloy and rinsing/drying

811. . . Step of cleaning the surface of the substrate after the cobalt alloy deposition cleaning process

850. . . Integrated system

855. . . Substrate

860. . . Laboratory environment transport module

861. . . Substrate loader

865. . . Carrying room

870. . . Vacuum transport module

871. . . O ₂ plasma treatment reactor

873. . . Copper etching chamber

873’. . . Wet copper etching system

874. . . Barrier layer etching chamber

874’. . . Wet barrier etching system

875. . . Carrying room

877. . . H ₂ plasma reduction chamber

880. . . Control environment transport module

881. . . Electroless deposition system

883. . . Cleaning system

900. . . Substrate

1000. . . Processing flow

1001. . . Steps to clean the upper surface of the contact

1003. . . Step of depositing a barrier layer

1005. . . Step of reducing barrier oxide to a metal rich layer

1007. . . Step of depositing a positive copper seed layer

1008. . . Step of depositing a copper layer in the trench

1009. . . Steps to clean the surface of the substrate

1050. . . Integrated system

1055. . . Substrate

1060. . . Laboratory environment transport module

1061. . . Substrate loader

1065. . . Carrying room

1070. . . Vacuum transport module

1071. . . reactor

1073. . . ALD reactor

1074. . . Hydrogen reduction reactor

1075. . . Carrying room

1080. . . Control environment transport module

1081. . . Electroless copper deposition reactor

1081’. . . ECP reactor

1083. . . Substrate cleaning reactor

1090. . . Processing flow

1092. . . Integrated system

1095. . . Step of reducing barrier oxide to a metal rich layer

1097. . . Step of depositing a positive copper seed layer

1098. . . Step of depositing a copper layer in the trench

1099. . . Steps to clean the surface of the substrate

1100. . . Processing flow

1101. . . Steps to clean the upper surface of the contact

1103. . . Step of depositing a barrier layer

1105. . . Step of reducing barrier oxide to a metal rich layer

1107. . . Step of depositing a positive copper seed layer

1108. . . Step of depositing a copper layer in the trench

1109. . . Steps to remove the Cu overlayer and the barrier overlayer

1110. . . Step of removing copper complex and metal oxide from the surface of the substrate

1111. . . Steps to remove organic contaminants from the surface of the substrate

1112. . . Steps to reduce the copper surface

1113. . . Step of depositing a cobalt alloy and performing rinsing and drying

1115. . . Step of cleaning the surface of the substrate after the cobalt alloy deposition cleaning process

1150. . . Integrated system

1155. . . Substrate

1160. . . Laboratory environment transport module

1161. . . Substrate loader

1163. . . Clean up the reactor

1165. . . Carrying room

1170. . . Vacuum transport module

1171. . . Ar sputtering reactor

1173. . . ALD reactor

1174. . . Hydrogen reduction reactor

1175. . . Carrying room

1177. . . O ₂ plasma reactor

1180. . . Control environment transport module

1181. . . Electroless copper plating reactor

1181’. . . ECP reactor

1183. . . CMP system

1185. . . Wet cleaning system

1187. . . Electroless cobalt alloy deposition reactor

1200. . . Substrate

1300. . . Processing flow

1301. . . Steps to clean the exposed surface of the wire

1302. . . Step of depositing barrier layer I

1303. . . Step of depositing barrier layer II

1305. . . Step of reducing barrier oxide to a metal rich layer

1307. . . Step of depositing a positive copper seed layer

1308. . . Step of depositing a copper layer in the trench

1309. . . Steps to remove the Cu overlayer and the barrier overlayer

1310. . . Step of removing Cu complex and metal oxide from the surface of the substrate

1311. . . Steps to remove organic contaminants from the surface of the substrate

1312. . . Steps to reduce the copper surface

1313. . . Step of depositing a cobalt alloy and performing rinsing and drying

1315. . . Step of cleaning the surface of the substrate after the cobalt alloy deposition cleaning process

1350. . . Integrated system

1355. . . Substrate

1360. . . Laboratory environment transport module

1361. . . Substrate loader

1363. . . Clean up the reactor

1365. . . Carrying room

1370. . . Vacuum transport module

1371. . . Ar sputtering reactor

1372. . . ALD reactor

1373. . . PVD reactor

1374. . . Hydrogen reduction reactor

1375. . . Carrying room

1377. . . O ₂ plasma system

1380. . . Control environment transport module

1381. . . Electroless copper plating reactor

1381’. . . ECP reactor

1383. . . CMP system

1385. . . Wet cleaning system

1387. . . Electroless cobalt alloy deposition reactor

1500. . . Processing flow

1501. . . Steps to remove metal contaminants

1502. . . Steps to remove organic contaminants

1503. . . Steps to restore the surface of the crucible

1505. . . Steps of selectively depositing metal over the crucible

1507. . . Step of cleaning the surface of the substrate after metal deposition

1509. . . Step of forming a metal deuteration layer

1550. . . Integrated system

1555. . . Substrate

1560. . . Laboratory environment transport module

1561. . . Substrate carrier

1563. . . Wet cleaning room

1565. . . Carrying room

1570. . . Vacuum transport module

1571. . . Oxidation plasma reactor

1573. . . Reduction reactor

1575. . . Carrying room

1576. . . Thermal reactor

1580. . . Control environment transport module

1581. . . Electroless metal deposition reactor

1583. . . Wet cleaning room

The invention will be more apparent from the following detailed description of the embodiments of the invention.

Figure 1 shows an exemplary cross-sectional interconnect; Figures 2A-2D show cross-sections of interconnect structures at various different interconnect processing stages; Figure 3 shows various different forms of contaminants on the surface of the substrate after metal CMP; Figure 4A An exemplary process flow for preparing a copper surface for electroless deposition of a cobalt alloy is shown; Figure 4B shows an exemplary system for processing a substrate through the process flow of Figure 4A; Figures 5A-5C show interconnections at various different interconnect processing stages Cross-section of the structure; Figure 6A shows an exemplary process flow for preparing a copper surface for electroless deposition of cobalt alloy; Figure 6B shows an exemplary system for processing a substrate through the process flow of Figure 6A; Figures 7A-7C show various Cross-section of the interconnect structure of the interconnect processing stage; FIG. 8A shows an exemplary process flow for preparing a copper surface for electroless deposition of a cobalt alloy; FIG. 8B shows an exemplary system for processing a substrate through the process flow of FIG. 8A; 9A-9E shows the cross section of the metal line structure at various processing stages; FIG. 10A shows an exemplary process flow for preparing the surface of the barrier layer for the electroless deposition of copper layer; 0B shows an exemplary system for processing a substrate through the process flow of FIG. 10A; FIG. 10C shows an exemplary process flow for preparing a barrier layer surface for an electroless copper layer; FIG. 10D shows a process flow through FIG. 10C. An exemplary system for processing a substrate; FIG. 11A shows an exemplary process flow for preparing a barrier layer surface for an electroless deposition of a copper layer and a copper surface for preparing an electrolessly deposited cobalt alloy; FIG. 11B is shown for use in the process flow of FIG. An exemplary system for processing a substrate; Figures 12A-12D show cross-sections of interconnect structures at various processing stages; Figure 13A shows the surface of a barrier layer for preparing an electrolessly deposited copper layer and for preparing an electrolessly deposited cobalt alloy An exemplary process flow for the copper surface; FIG. 13B shows an exemplary system for processing the substrate through the process flow of FIG. 13A; FIGS. 14A-14D show a cross-sectional view of the gate structure at various stages of forming the metal germanide layer; FIG. 15A shows An exemplary process flow for preparing an exposed tantalum surface to form a metal deuterated layer; FIG. 15B shows an illustration for processing a substrate through the process flow of FIG. 15A System; and Figure 16 shows a schematic view around a system having integrated control of the processing environment of the integrated system.

850. . . Integrated system

855. . . Substrate

860. . . Laboratory environment transport module

861. . . Substrate loader

865. . . Carrying room

870. . . Vacuum transport module

871. . . O ₂ plasma treatment reactor

873. . . Copper etching chamber

873’. . . Wet copper etching system

874. . . Barrier layer etching chamber

874’. . . Wet barrier etching system

875. . . Carrying room

877. . . H ₂ plasma reduction chamber

880. . . Control environment transport module

881. . . Electroless deposition system

883. . . Cleaning system

Claims (37)

A method for preparing a surface of a substrate for selectively depositing a thin layer of a cobalt alloy material on a copper surface of a copper interconnect of the substrate in an integrated system to improve electromigration performance of the copper interconnect; The method includes: removing contaminants and metal oxides from a dielectric region of a surface of the substrate in a wet processing module coupled to a first transport module of the integrated system; removing contaminants and metal oxides Thereafter, in a plasma module connected to a second transport module of the integrated system, a copper surface of the copper interconnect is reconstructed using a reducing environment; and after the surface of the substrate is reconstructed, the cobalt alloy is selectively deposited a thin layer of material on the copper surface of the copper interconnect, more than one processing module of the integrated system and the transport modules are filled with an inert gas to reduce oxygen during transport of the substrate within the integrated system Exposure, the transport of the substrate comprises transport between the transport modules of the integrated system, and wherein a thin layer of the cobalt alloy material is deposited on one of the processing modules, one of which is a wet No electricity a processing module, the wet electroless deposition processing module is filled with an inert gas to maintain a lower oxygen concentration in the processing environment than in a surrounding environment, and after removing contaminants and metal oxides from the surface of the substrate and The copper surface is protected from oxidation by transport in a transport module filled with an inert gas prior to selectively depositing a thin layer of the cobalt alloy material on the copper surface. The method for preparing a surface of a substrate according to claim 1, wherein the surface of the substrate is reconstructed by a hydrogen-containing plasma, which is composed of hydrogen (H ₂ ), ammonia (NH ₃ ), or two gases. The combination is produced. The method for preparing a surface of a substrate according to claim 1, wherein the step of reconstructing the surface of the substrate substantially converts the surface copper oxide into copper, and after reconstructing the surface of the substrate, the substrate is transported in a controlled environment and The treatment is such that the formation of copper oxide overlying the copper surface is minimized. A method of preparing a substrate surface according to claim 3, wherein after the copper surface is reduced, the substrate is transported and treated under a limited exposure of oxygen to enable selective deposition of a thin layer of the cobalt alloy material. On the copper surface. A method of preparing a substrate surface according to claim 1, wherein the thin layer of the cobalt alloy material is selectively deposited on the copper surface by an electroless deposition treatment to promote the copper surface of the copper interconnect line. Adhesion to the dielectric cap layer of the copper interconnect. A method of preparing a substrate surface according to claim 1, wherein the cobalt alloy material is selected from the group consisting of CoWP, CoWB, and CoWBP. An integrated system for transporting and processing substrates in a controlled environment that selectively deposits a thin layer of cobalt alloy material on the copper surface of the copper interconnect to improve electromigration of the copper interconnect. The system includes: a laboratory environment transport chamber for feeding the substrate from a substrate carrier coupled to the laboratory environment transport chamber to the integrated system; a substrate cleaning reactor coupled to the laboratory environment a transport chamber, wherein the substrate cleaning reactor cleans the surface of the substrate to remove metal-organic mis-contaminants on the surface of the substrate; a vacuum transfer chamber is operated under a vacuum of less than 1 Torr; a vacuum processing module For removing organic contaminants from the surface of the substrate, wherein at least one vacuum processing module is coupled to the vacuum transfer chamber and the vacuum processing module is coupled to the at least one vacuum processing module of the vacuum transfer chamber First, and operating under a vacuum of less than 1 Torr; a control environment transport chamber, filled with an inert gas selected from the group of inert gases; a controlled environment treatment a module coupled to the control environment transport room; and An electroless cobalt alloy material deposition processing module for depositing a thin layer of the cobalt alloy on the copper after the metal contaminants and organic contaminants have been removed on the surface of the substrate, and the copper surface has been removed from the copper oxide The electroless cobalt alloy material deposition processing module is one of the at least one control environment processing module coupled to the control environment transport chamber on the copper surface of the connection, and is selected from the group consisting of inert gas groups The inert gas is filled and has a fluid delivery system in which the treatment fluid is degassed. An integrated system for transporting and processing a substrate in a controlled environment, as in claim 7, further comprising: a hydrogen-containing reduction processing module for reducing residual copper oxide on the copper surface to copper, wherein A hydrogen reduction treatment module is coupled to the vacuum transfer chamber, and the hydrogen reduction treatment module operates at a vacuum of less than 1 Torr. An integrated system for transporting and processing substrates in a controlled environment, as in claim 7, further comprising: a substrate cleaning reactor coupled to the laboratory environmental transport chamber, wherein the substrate cleaning reactor is wet cleaned The liquid cleans the surface of the substrate to remove metal oxide on the surface of the substrate, wherein the cleaning liquid comprises one of citric acid, sulfuric acid, or sulfuric acid having hydrogen peroxide. An integrated system for transporting and processing a substrate in a controlled environment, as in claim 7, further comprising: a first load lock coupled to the vacuum transfer chamber and the control environment transport chamber, wherein the first load A chamber assists transport of the substrate between the vacuum transfer chamber and the controlled environment transport chamber, the first load chamber being configured to operate at a vacuum of less than 1 Torr, or an inert selected from the group of inert gases The gas is filled to operate at the same pressure as the controlled environment transport module; and a second load chamber coupled to the vacuum transport chamber and the laboratory environmental transport chamber, wherein the second load chamber assists the substrate In the vacuum transfer chamber and the laboratory The transport between the environmental transport chambers is arranged to operate under a vacuum of less than 1 Torr or in a laboratory environment. An integrated system for transporting and processing a substrate in a controlled environment as in claim 7, wherein the vacuum transfer chamber and the at least one vacuum processing module coupled to the vacuum transfer chamber operate at a pressure of less than 1 Torr, To limit the exposure of the substrate to oxygen. An integrated system for transporting and processing substrates in a controlled environment, according to claim 7, wherein the control environment transport chamber and the control environment transport chamber are filled with one or more inert gases selected from the group consisting of inert gases. The at least one control environment processing module limits the exposure of the substrate to oxygen. An integrated system for transporting and processing substrates in a controlled environment, as in claim 7, wherein the substrate is transported and processed in the integrated system to limit the duration of exposure of the substrate to oxygen. An integrated system for transporting and processing a substrate in a controlled environment according to claim 13 wherein limiting the exposure of the substrate to oxygen reduces the induction time of the deposition reaction and enhances selective deposition on the copper surface. A thin layer of the cobalt alloy material. An integrated system for transporting and processing a substrate in a controlled environment according to claim 7, wherein the at least one processing module coupled to the control environment transport chamber is capable of performing dry/out process of the substrate, wherein the substrate It enters in a dry state and comes out in a dry state. A method for preparing a surface of a substrate for depositing a metal barrier layer in an integrated system to align a copper interconnect structure of the substrate, and depositing a thin copper seed layer thereon a surface of the metal barrier layer to improve electromigration performance of the copper interconnect, the method comprising: cleaning an exposed surface of the underlying metal to remove surface metal in a first module of the integrated system An oxide, wherein the underlying metal is electrically connected to a portion of the underlying interconnect of the copper interconnect structure; in the integrated system, the surface of the metal barrier layer is reduced such that the metal barrier layer is located The metal barrier oxide on the surface produces a transition, and the surface of the metal barrier layer is rich in metal, wherein after cleaning the exposed surface of the underlying metal, the surface of the metal barrier layer is reduced; Depositing the metal barrier layer to align the copper interconnect structure in a second module of the integrated system; depositing the thin copper seed layer in a third module of the integrated system; and in the integrated system a fourth module, wherein a trench copper layer is deposited over the thin copper seed layer, wherein the first, second, third, and fourth module transport lines are performed Inert gas filled environment, and where it is deposited Carrying in the environment filled with the inert gas before the trench filling layer reduces the formation of metal oxide on the copper interconnect structure, the metal barrier layer, and the thin copper seed layer, and wherein The fourth module is a copper plating treatment system for depositing the trench copper layer, and the copper plating processing system is filled with an inert gas to ensure a low oxygen concentration in the processing environment, and wherein the substrate is used for processing the substrate The copper plating process utilizes a dry/dry process of the substrate to allow the substrate to enter and exit the copper plating process in a dry state. A method of preparing a substrate surface according to claim 16, wherein the copper interconnect structure comprises a metal line overlying a via, and the lower interconnect comprises a metal line. A method of preparing a surface of a substrate according to claim 16, wherein the step of removing the exposed surface to remove the surface metal oxide is achieved by using an Ar sputtering process or a plasma treatment using a fluorine-containing gas. The method for preparing a surface of a substrate according to claim 16, wherein the step of depositing the metal barrier layer further comprises: depositing a first metal barrier layer; and depositing a second metal barrier layer. A method of preparing a substrate surface according to claim 16, wherein the substrate is transported and processed in a controlled environment to prevent formation of a metal barrier oxide, and a thin layer of the copper seed layer is selectively deposited. To improve the electromigration performance of the copper interconnect. A method for preparing a metal barrier surface of a substrate for depositing a thin copper seed layer on a surface of a metal barrier layer of a copper interconnect structure in an integrated system to improve the copper interconnect structure Electromigration performance, the method comprising: reducing a surface of the metal barrier layer in a first module of the integrated system to cause a transition of a metal barrier oxide on the surface of the metal barrier layer And depositing the surface of the metal barrier layer with a metal; depositing the thin copper seed layer in a second module of the integrated system; and depositing a trench in a third module of the integrated system a copper layer overlying the thin copper seed layer, wherein the transport along the first, second, and third modules is performed in an atmosphere filled with an inert gas, and wherein the trench is deposited The transport of the layer prior to the inert gas filling environment reduces the formation of metal oxide over the copper interconnect structure, the metal barrier layer, and the thin copper seed layer, and wherein the third mode a copper plating treatment system for depositing the trench copper layer And the copper plating treatment system is filled with an inert gas to ensure a low oxygen concentration in the processing environment, and wherein the copper plating processing system for processing the substrate utilizes dry/dry processing of the substrate to make the substrate The copper plating treatment system is fed in and out in a dry state. An integrated system for processing substrates in a controlled environment that enables a thin copper seed layer Deposited on the surface of a metal barrier layer of a copper interconnect, the system comprising: a laboratory environment transport chamber for feeding the substrate from the substrate carrier coupled to the laboratory environment transport chamber into the integrated system a vacuum transfer chamber operating at a vacuum of less than 1 Torr; a vacuum processing module for cleaning the metal oxide of the exposed surface of the underlying metal in the integrated system, wherein the underlying metal is a lower layer interconnect a portion of the wire, the copper interconnect is electrically connected to the lower interconnect, wherein at least one vacuum processing module is coupled to the vacuum transfer chamber and the vacuum processing module for cleaning is coupled to the vacuum transfer chamber One of the at least one vacuum processing module and operating under a vacuum of less than 1 Torr; a vacuum processing module for depositing the metal barrier layer, wherein the vacuum is used to deposit the metal barrier layer The processing module is coupled to one of the at least one vacuum processing module of the vacuum transfer chamber and operates at a vacuum pressure of less than 1 Torr; a control environment transport chamber selected from the group consisting of inert gases An inert gas is filled therein; a control environment processing module coupled to the control environment transport chamber; and an electroless copper deposition processing module for depositing a thin layer of the copper seed layer on the metal barrier layer The surface of the electroless copper deposition processing module is one of the at least one control environment processing module coupled to the control environment transport chamber. An integrated system for processing a substrate in a controlled environment, as in claim 22, further comprising: a hydrogen reduction processing module for reducing metal oxide or metal nitride on the surface of the metal barrier layer The hydrogen reduction treatment module is coupled to the vacuum transfer chamber, and the hydrogen reduction treatment module is operated under a vacuum of less than 1 Torr. The integrated system for processing substrates in a controlled environment, as in claim 22, further includes: a first load-bearing chamber coupled to the vacuum transfer chamber and the control environment transport chamber, wherein the first load-bearing chamber assists in transporting the substrate between the vacuum transport chamber and the control environment transport chamber, the first load chamber Arranged to operate under a vacuum of less than 1 Torr, or to be filled with an inert gas selected from the group of inert gases; and a second carrier chamber coupled to the vacuum transfer chamber and the laboratory environment transport chamber, wherein The second carrier chamber assists in transporting the substrate between the vacuum transfer chamber and the laboratory environment transport chamber, the second load chamber being configured to operate under a vacuum of less than 1 Torr or in a laboratory environment, or The filling is carried out with an inert gas selected from one of the inert gas groups. An integrated system for processing a substrate in a controlled environment as in claim 22, wherein the vacuum transfer chamber and the at least one vacuum processing module coupled to the vacuum transfer chamber are operated at a pressure of less than 1 Torr to control The substrate is exposed to oxygen. An integrated system for processing a substrate in a controlled environment as in claim 22, wherein the control environment transport chamber and the at least one of the inert gas groups selected from the group of inert gases are filled with the control environment transport chamber Each of the processing modules controls the exposure of the substrate to oxygen. An integrated system for processing a substrate in a control environment as claimed in claim 22, wherein the at least one processing module coupled to the control environment transport chamber is capable of performing dry/dry processing of the substrate, wherein the substrate is The at least one processing module is accessed in a dry state. An integrated system for processing a substrate in a controlled environment, wherein a thin copper seed layer is deposited on a surface of a metal barrier layer of a copper interconnect, the system comprising: a laboratory environment transport chamber The substrate is fed into the integrated system from a substrate carrier coupled to the laboratory environment transport chamber; a vacuum transfer chamber operating at a vacuum of less than 1 Torr; a vacuum processing module for reducing the metal barrier layer, wherein at least one vacuum processing module is coupled to the vacuum transfer chamber and used to reduce the metal The vacuum processing module of the barrier layer is coupled to one of the at least one vacuum processing module of the vacuum transfer chamber and operates under a vacuum of less than 1 Torr; a control environment transport chamber is selected from the group consisting of An inert gas group of the inert gas group is filled, wherein at least one control environment processing module is coupled to the control environment transport chamber; and an electroless copper deposition processing module is configured to deposit a thin layer of the copper seed layer on the metal The surface of the barrier layer, wherein the electroless copper deposition processing module is one of the at least one control environment processing module coupled to the control environment transport chamber. A method of preparing a substrate surface for selectively depositing a metal layer on a tantalum or polysilicon surface of the substrate in an integrated system for performing both dry and wet processing to form a metal germanium layer, and The substrate is operated while being maintained in the integrated system, the operations comprising: removing organic contaminants from the surface of the substrate in the integrated system for performing both dry and wet processing; removing organic contamination Thereafter, the surface of the tantalum or polysilicon is reduced in the integrated system to convert the tantalum oxide on the surface of the tantalum or polysilicon into a tantalum, and wherein the surface of the tantalum or polysilicon is reduced to increase the metal on the surface of the tantalum Selectively, and wherein the surface of the tantalum or polysilicon is reduced in a hydrogen-containing plasma system connected to a vacuum transport module; the substrate is immediately moved into the reduction operation after completion of the reduction operation in the hydrogen-containing plasma system Operating the vacuum transport module under vacuum; moving the substrate from the vacuum transport module into a load chamber under vacuum, and supplying inert gas to the load chamber, the load chamber For conveying away from the vacuum control module into a conveying environment of the transport module; the carrier substrate from the chamber to move the transport module control environment, the environment control The transport module is supplied with the inert gas; the substrate is transported into an electroless deposition module in the control environment transport module having the inert gas, and the electroless deposition module is coupled to the control environment transport module And selectively depositing the metal layer on the surface of the germanium or polysilicon of the substrate by electroless deposition in the electroless deposition module, the inert gas in the control environment transport module being limited after the reducing operation Oxidation of the surface of germanium or polycrystalline germanium. The method for preparing a surface of a substrate according to claim 29, further comprising: after selectively depositing the metal layer on the surface of the crucible in the integrated system, forming the metal deuterated layer to bond the metal deuterated layer Formed in a rapid thermal processing (RTP) system. The method of preparing a substrate surface according to claim 29, further comprising: removing metal contaminants from the surface of the substrate before the surface of the crucible is reduced in the integrated system. A method of preparing a substrate surface according to claim 29, wherein the hydrogen-containing plasma of the hydrogen-containing plasma system is produced by hydrogen (H ₂ ), ammonia (NH ₃ ), or a combination of two gases. A method of preparing a substrate surface according to claim 29, wherein the metal is selected from the group consisting of Ni or Co. The method for preparing a surface of a substrate according to claim 29, wherein the substrate is in a controlled environment of the integrated system after the surface of the crucible has been reduced by being transported or treated in a vacuum environment or an environment filled with an inert gas. The transportation and processing are carried out to control the exposure of the substrate surface to oxygen. An integrated system for processing a substrate in a controlled environment, wherein a metal layer is selectively deposited on the surface of the substrate to form a metal germanium layer, the system comprising: a laboratory environment transport chamber, which can The substrate is fed into the integrated system from a substrate carrier coupled to the laboratory environment transport chamber; a vacuum transport chamber operating at a vacuum of less than 1 Torr; and a vacuum processing module for removing from the substrate surface An organic contaminant, wherein the vacuum processing module is coupled to the vacuum transfer chamber and the vacuum processing module for removing organic contaminants is coupled to one of the at least one vacuum processing module of the vacuum transfer chamber And operating at a vacuum pressure of less than 1 Torr; a vacuum processing chamber for reducing the surface of the crucible, wherein the vacuum processing chamber for reducing the surface of the crucible is coupled to the at least one vacuum processing module of the vacuum transfer chamber One of the group, and operating at a vacuum pressure of less than 1 Torr; a control environment transport chamber, filled with an inert gas selected from the group of inert gases, and At least one control environment processing module coupled to the control environment transport chamber; and an electroless metal deposition processing module for selectively depositing a thin layer of the metal on the surface of the crucible after the surface of the crucible has been restored, the electroless The metal deposition processing module is one of the at least one control environment processing module coupled to the control environment transport chamber. An integrated system for processing a substrate in a controlled environment as in claim 35, wherein the vacuum processing chamber for forming the metal deuteration layer is an RTP chamber. An integrated system for processing a substrate in a controlled environment as in claim 35, wherein the control environment transport chamber and the at least one coupled to the control environment transport chamber are filled with one or more inert gases selected from the group consisting of inert gases The module is processed to control the exposure of the substrate to oxygen.