Abstract:
Improvements to chemical vapor deposition processes are taught for depositing tungsten nitride in semiconductor manufacturing processes. In one irmproved process NF 3  is used as a source of nitrogen, and a plasma is introduced under controlled conditions to control particle formation and lower the temperature at which acceptable films may be produced. In another set of processes substantially pure tungsten is produced by rapid thermal annealing of substantially amorphous tungsten nitride at temperatures lower than achieved in the art, by using hydrogen in the ambient atmosphere. In yet another set of new processes particle formation and step coverage enhancement when using NH 3  as a nitrogen source is controlled by limiting the pressure at which source gases mix, by unique wall coating technique, and by controlling chamber wall temperature. In still another set of unique processes a graded film on oxide, starting with tungsten silicide quickly grading to tungsten nitride is produced by introducing silane in the NH 3  chemistry under controlled conditions.

Description:
FIELD OF THE INVENTION 
     The present invention is in the area of methods and apparatus for processing wafers as a step in manufacturing integrated circuits (ICs), and relates in particular to chemical vapor deposition (CVD) processes for depositing tungsten and alloys and mixtures of tungsten with other elements such as, in particular, silicon and nitrogen, using NF 3  and in some cases, NH 3  as a gaseous source of nitrogen in the processes. 
     BACKGROUND OF THE INVENTION 
     Manufacturing of integrated circuits is historically a procedure of forming thin films and layers of various materials on wafers of base semiconductor material, and then selectively removing areas of the films to produce structures and circuitry. Doped silicon is a typical base wafer material, and in various process schemes, metal layers are formed on the doped silicon or on polysilicon or silicon oxide formed from the base material. It is well known in the art that there are many difficulties in forming thin metal films and in particular in forming such films on non-metallic base materials. Among these difficulties are problems of adhesion and problems related to diffusion and reaction of materials across material boundaries. 
     There are a number of well-developed technologies for deposition of materials in the ultra-thin layers required for IC fabrication schemes. The deposition techniques can be roughly classed as either physical vapor deposition (PVD) or Chemical Vapor Deposition (CVD) techniques. PVD processes include such processes as evaporation and re-condensation, wherein a material, typically a metal, is heated to a temperature at which the metal melts and vaporizes. The metal then condenses on surfaces generally in line-of sight of the evaporation, forming a film. 
     Another PVD process is the well-known sputtering process, wherein plasma of usually an inert gas is formed near a target material, and the target is biased to attract ions from the plasma to bombard the target. Atoms of the target material are dislodged by momentum transfer, and form an atomic flux of particles, which coalesce on surrounding surfaces generally in line-of-sight of the target surface eroded by the sputtering process. 
     PVD processes have distinct advantages for some processes, such as high rate of deposition, and relatively simple coating apparatus. There are drawbacks as well, notably an inherent inability to provide adequate step coverage. That is, on surfaces having concavities as a result of previous coating and etching steps, PVD processes are prone to shadowing effects resulting in local nonuniformity of coating thickness. This problem has grown in importance as device density has increased and device geometry has shrunk in size with multi-level interconnect schemes involving vias and trenches on microscopic scale. 
     CVD processes comprise deposition from gases injected into a chamber, wherein the gases or components of the gases are chemically decomposed and/or recombined by energy input. In typical CVD processes the substrate to be coated is heated, and gases introduced into a chamber holding the substrate react at or very near the substrate surface in a manner to deposit a film of material on the surface. For example, a film of metallic tungsten may be deposited on a heated substrate surface by flowing Tungsten hexafluoride to the surface in conjunction with a reducing gas such hydrogen. Resulting chemical reaction at a hot substrate surface reduces the tungsten hexafluoride, depositing a film of tungsten on the substrate, and producing HF gas. 
     It is well-known in the art that there are a wide variety of CVD processes known and available for semiconductor circuit processes, including deposition from organo-metallic materials and plasma-enhanced CVD, wherein energy is added to the process by exciting the gas above the deposition surface with a high-frequency discharge (plasma). 
     In the fabrication of an integrated circuit, transistors are developed on the surface of a doped silicon substrate. Once transistors are formed, to make a circuit, gates and drains have to be interconnected with electrically conductive tracks. This point in the overall IC fabrication process serves as perhaps the best example of a thin-film interface between a substrate material and an electrically conductive metal. 
     Over several years in the IC industry, a variety of materials have been tested for interconnecting tracks. Among these are aluminum, titanium. tungsten, and gold. Each has advantages and drawbacks, and different characteristics related to interaction with silicon, electrical conductivity, and electromigration, among others. Also, specific deposition processes have been developed suitable for specific materials. Aluminum, for example is typically deposited by the PVD process of sputtering, and there is currently no commercialized process for CVD deposition of aluminum as an interconnect material. A CVD process, on the other hand, can conveniently deposit tungsten. 
     There are a variety of known CVD processes employing variations of known chemistries to produce a variety of films of a single element, or a combination of two or more elements. Tungsten is deposited as a continuous (blanket) film on substrates for example to provide, after etching, both via plugs and interconnect tracks between devices implemented in doped silicon. Combinations of tungsten with other elements are deposited for other purposes, such as adhesion and barrier layers on gates of transistors implemented in silicon as an intermediate layer to improve adhesion and combat diffusion, for example, of silicon from the gates into the interconnect film. In these applications the films deposited directly on the gates prior to the interconnect material are called barrier layers. 
     One of the elements frequently combined with tungsten to provide specific desirable characteristics of a resulting film for adhesion and barrier purposes is Nitrogen to form tungsten nitride. The inventors are aware of conventional chemistry and processes for deposition of WN x  (Tungsten Nitride). In some instances it is desirable to combine tungsten with other elements as well as Nitrogen. One such combination of interest and potential use in gate technology is Tungsten-Silicon-Nitride. 
     There are also elements competitive to tungsten for gate processes. One of these is Titanium, and materials of interest in combination with Titanium are Titanium Nitride (TiN) and Titanium Silicon Nitride (Ti x Si y N z ). 
     The common element among the materials described above is Nitrogen, and perhaps the most common gas utilized as a source of Nitrogen in the CVD processes is ammonia (NH 3 ). It is well known in the art that there are many problems with handling NH 3  and mixing NH 3  with other gaseous components for CVD processes. One such component is WF 6  which, when combined with NH 3  at room temperature produces an instantaneous and highly exothermic chemical reaction. Such a gas phase reaction is highly undesirable because it leads to serious complications in CVD reactor design and operation. Also an undesirable gas phase reaction leads to particulate formation, powdery deposits, and poor adhesion of films to the substrate. In addition to this, the instantaneous reaction between WF 6  and NH 3  leads to coating on the reactor (process chamber) walls. This coating contributes significantly to particles due to peeling, and hence reactors must be completely and periodically cleaned for operation in the actual production environment. 
     The processes with which the present patent application is concerned pertain to the art of depositing layers of materials typically less than 1 μm thick, which are used to manufacture semiconductor integrated circuits. These processes are generally termed thin film deposition. The teachings of this disclosure address improvements to the art of chemical vapor deposition (CVD) for thin films consisting generally of the two elements tungsten and nitrogen. 
     The films in the processes of interest are typically deposited on silicon wafers placed in reaction chambers that provide a highly controlled gaseous ambient atmosphere. Inside these reaction chambers there is apparatus, such as a resistance heated plate, to heat the silicon wafers to provide energy to cause the gases to react to form thin layers on the wafer surface. 
     Process chambers for such processes are typically attached to a larger chamber, which contains a robotic transfer mechanism also operating under highly controlled ambient atmosphere, usually a high vacuum. The process chambers are typically arranged around a single centrally located robot to allow transfer of wafers between process chambers and load-lock chambers, which are isolated from the larger, general chamber by slit valves. Load-lock chambers are needed to allow introduction of the silicon wafers in to the controlled ambient. The arrangement often ends up looking like a cluster of smaller chambers surrounding a larger central chamber containing the robot, hence the popular term “cluster tool” to describe the type of equipment that is used often used 
     The generic terminology for thin films made up of tungsten and nitrogen is tungsten nitride. The actual films covered by the name tungsten nitride covers a wide range of nitrogen content and morphology. Nitrogen content can vary from a few atomic % to as much as 70 atomic %. The film morphology can range from a fully crystallized structure consisting of grains 10 nm and larger (polycrystalline) to an almost amorphous structure consisting of no long range order at all, or grains less than 1 nm, which is highly nano-crystalline. 
     Nitrogen in the tungsten nitride film can be bonded in a stochiometric arrangement with tungsten, and also concentrated at discontinuities in the film such as at grain boundaries. When crystallized at least the following phases can be present: W, W 2 N, WN, or WN 2 . The relative amounts of these phases in the film depends in part on the relative concentrations of W and N, which in turn can be controlled by adjusting the relative partial pressures of the source gases in the ambient atmosphere during deposition. The most stable phase of crystallized tungsten nitride is W 2 N. This is also the phase with the lowest electrical resistance which is an important parameter for many applications. 
     An important application of tungsten nitride films to semiconductor integrated circuit manufacturing is in the role popularly known as a barrier film. The use of barrier films occurs at many steps in the manufacture of semiconductor devices because of a need to achieve stable interaction between dissimilar materials on a microscopic scale, even when exposed to processing temperatures that can range at least as high as 1000° C. The role of the barrier layer is to improve the following specific characteristics for a subsequent film deposition: promote nucleation, increase adhesion, and prevent intermixing. These attributes should in general be obtained by the barrier film while contributing minimally to increased resistance and thickness of the finished structure. 
     The transition metals in the periodic table are generally suitable as base material for barrier films based on their high melting points and suitable formation of a compound with silicon (silicide). To reduce intermixing due to diffusion aided by defects and grain boundaries the formation of a stable nitride is also a desired characteristic for a barrier film. Elements such as titanium, tantalum, and tungsten are good candidates. 
     Historically the most commonly used barrier film in the silicon-based semiconductor manufacturing industry is titanium nitride. Tungsten nitride was not thought to have the needed qualities needed by the industry. However, economic progress in the manufacturing industry of integrated circuits is based on continually shrinking the dimensions of the features on these integrated circuits. As the dimensions continue to decrease, the thickness allowed for a barrier layer also decreases. In addition new materials such as copper and tantalum pentoxide (Ta 2 O 5 ) may be introduced in to the manufacturing process. These new materials require enhanced requirements of the barrier layers, such as very strong ability to block diffusion in the case of copper, and low tendency to remove oxygen in the case of tantalum pentoxide. 
     Based on the above, tungsten, as a denser material with lower tendency for oxidation than titanium, has become a potential candidate for several important applications in the industry. These applications include low resistance gate, capacitor electrode, and copper diffusion barriers. 
     Implementation of tungsten nitride in many potential applications is hindered by the common perception that suitable deposition methods for tungsten nitride may not exist. A survey of the literature of the deposition arts indicates very few papers depositing tungsten nitride by means other than physical sputtering. Few papers deal with chemical vapor deposition methods. Furthermore, the general conclusion of the art appears to be that chemical vapor deposition methods for tungsten nitride, especially those based on the simple reaction with ammonia are not suitable for manufacturing of integrated circuits, because of the extreme reactivity of the constituent gases in such processes that leads to particulate formation. 
     It is important to note that chemical vapor deposition methods as a class exhibit properties such as production stability and conformality in small features that are desired by the industry. The ability to deposit conformably in small features is very important, especially as the industry need is to shrink the dimensions of features on the integrated circuits. Therefore, it is significant that contrary to common teaching in the art, the present inventors have discovered principles and developed processes that provide several significant improvements to the methods of depositing tungsten nitride by chemical vapor deposition. 
     What is clearly needed are new processes for chemical vapor deposition to accomplish the needs of the industry in the several areas described, as the existing methods are not adequate. 
     SUMMARY OF THE INVENTION 
     In a preferred embodiment of the present invention a method for depositing Tungsten Nitride (WNx) using NF 3  as a source of nitrogen is provided, comprising steps of (a) exposing a substrate surface to be coated in a CVD chamber, maintaining temperature of the substrate in a range of 300 to 450 degrees centigrade, inclusive; (b) flowing WF 6  into the CVD chamber at a flow rate between 3 and 12 sccm inclusive; (c) flowing NF 3  into the CVD chamber at a flow rate between 1.5 and 15 sccm inclusive; (d) flowing H 2  into the CVD chamber at a flow rate between 200 and 500 sccm inclusive; (e) pumping the chamber to maintain a total pressure of from 50 to 500 mtorr; and (f) striking a plasma in the CVD chamber using a plasma power supply at a power level of from 50 to 300 watts inclusive. In different embodiments films of different thickness are produced by maintaining conditions listed for different lengths of time. 
     In some embodiments, in steps (b), (c) and (d) the elements are flowed to a premixing apparatus, and thence to the CVD chamber. In others there is a step for flowing argon to the CVD chamber to aid in supporting the plasma of step (f). 
     In another aspect of the invention a process for producing a substantially pure tungsten film is provided, comprising steps of (a) producing first a substantially amorphous tungsten nitride film on a substrate; (b) placing the substrate in a rapid thermal anneal (RTA) apparatus; and (c) establishing an ambient atmosphere other than substantially pure nitrogen or pure argon in the chamber, and annealing the tungsten nitride film by RTA at a temperature at or below 900 degrees centigrade. The other than substantially pure nitrogen or pure argon may comprise nitrogen with at least 5% hydrogen, or argon with at least 5% hydrogen, or H 2 O vapor with at least 5% hydrogen, or other mixtures of gases with hydrogen. 
     In yet another embodiment of the invention a process for controlling particle formation in a chemical vapor deposition (CVD) chamber using WF 6  and NH 3  gases as precursors is provided, comprising steps of (a) injecting the WF 6  and NH 3 gases separately into the chamber; and (b) controlling the pressure at which the WF 6  and NH 3  gases meet and mix to less than 1000 mtorr. 
     In some embodiments there may be a further step for pre-coating walls of the CVD chamber with a hard-anodized aluminum film also substantially crack-free. In others a step for heating walls of the CVD chamber to a temperature between 70 and 90 degrees centigrade inclusive is used. In still other embodiments both steps for heating walls of the CVD chamber to a temperature between 70 and 90 degrees centigrade inclusive, and for pre-coating walls of the CVD chamber with a hard-anodized aluminum film also substantially crack-free may be used. 
     In still another embodiment of the present invention a process for controlling particle formation in a chemical vapor deposition (CVD) chamber using WF 6  and NH 3  gases as precursors is provided, comprising steps of (a) injecting the WF 6  and NH 3  gases into the CVD chamber; and (b) heating walls of the CVD chamber to a temperature between 70 and 90 degrees centigrade inclusive during CVD processing. There may be a further step in alternative embodiments for pre-coating walls of the CVD chamber with a hard-anodized aluminum film also substantially crack-free. In still other embodiments there may be another step for injecting the gases separately and controlling the pressure at the point of mixing to less than 1000 mtorr. In yet other embodiments there may be two further steps one for pre-coating walls of the CVD chamber with a hard-anodized aluminum film also substantially crack-free, and the other injecting the gases separately and controlling the pressure at the point of mixing to less than 1000 mtorr. 
     In still another embodiment a process for controlling particle formation in a chemical vapor deposition (CVD) chamber using WF 6  and NH 3  gases as precursors is provided, comprising steps of (a) injecting the WF 6  and NH 3  gases into the CVD chamber; and (b) pre-coating walls of the CVD chamber with a hard-anodized aluminum film also substantially crack-free. In alternative embodiments there may be another step for injecting the gases separately and controlling the pressure at the point of mixing to less than 1000 mtorr. In other alternative embodiments there may be a further step for heating walls of the CVD chamber to a temperature between 70 and 90 degrees centigrade inclusive during CVD processing. In still other embodiments both steps, one for injecting the gases separately and controlling the pressure at the point of mixing to less than 1000 mtorr, and the other for heating walls of the CVD chamber to a temperature between 70 and 90 degrees centigrade inclusive during CVD processing may be incorporated. 
     In still another embodiment a process for depositing Tungsten Nitride (WNx) using NH3 as a source of nitrogen is provided, comprising steps of (a) exposing a substrate surface to be coated in a CVD chamber, maintaining temperature of the substrate in a range of 300 to 450 degrees centigrade, inclusive; (b) flowing WF 6  NH 3 , and H 2  into the CVD chamber; and (c) striking a plasma in the CVD chamber. In this process in some embodiments the substrate temperature is maintained in a range of from 300 to 450 degrees centigrade, the WF 6  is flowed to the chamber at from 3-12 sccm inclusive, the NH 3  is flowed to the chamber in a range of from 1.5 to 24 sccm, the H 2  is flowed to the chamber at from 200 to 500 sccm, and the chamber is pumped to maintain the total pressure below 1000 torr. In some embodiments the plasma may be pulsed. 
     In still another embodiment a process for forming a tungsten nitride film on an oxide surface of a substrate, with a graded interface of tungsten silicide at the oxide surface is provided, comprising steps of (a) heating a substrate having an oxide surface to a temperature of from 500 to 600 degrees Centigrade in a reactor chamber; (b) flowing WF 6 , NH 3 , H 2  and SiH 4  into a reactor chamber; and (c) pumping the chamber to maintain a total pressure of from 100 to 500 mtorr. In this embodiment WF 6  may be flowed into the chamber at from 3-12 sccm inclusive, NH 3  may be flowed into the chamber at from 1.5 to 50 sccm, and H 2  may be flowed into the chamber at from 200 to 500 sccm. 
     The process improvements taught in enabling detail in the descriptions herein and below provide contributions in the art for improving processes in chemical vapor deposition for processes related t tungsten nitride, and afford new and better ways for manufacturers to produce integrated circuits. 
    
    
     BRIEF DESCRIPTION OF THE DRAWING FIGURES 
     FIG. 1 is a cross-section elevation view of a single wafer CVD deposition reactor for practicing the present invention. 
     FIG. 2 is a process diagram for deposition of WN x  in an embodiment of the present invention, with plasma enhancement. 
     FIG. 3 is a graph of film content for tungsten nitride films made with NF 3  chemistry according to an embodiment of the present invention, and with conventional NH 3  chemistry. 
    
    
     DESCRIPTION OF THE PREFERRED EMBODIMENT 
     FIG. 1 is a simplified cross-section elevation view of a single wafer CVD reactor chamber  11  for practicing the present invention. Single wafer chambers are highly desirable in current art for adaptation to processing systems known generally as cluster tools, wherein one wafer at a time may be moved through vacuum load locks and sequentially through a number of individual processes before again being exposed to air. Pick-and-place transfers, not shown in FIG. 1, operating in a transport volume maintained at a high vacuum level, move wafers from one chamber to another for processing, and the individual processing chambers are isolated from the transport volume during processing. In FIG. 1 transfer of wafers is made through valved port  28 . A number of such machines are known to the inventors, and among them is the Genus Series 7000™ machines, made by Genus, Inc. of Sunnyvale, Calif. 
     In the reactor of FIG. 1 a hermetically sealed chamber  13  is pumped through a pumping port  15  by a vacuum pumping system not shown, and gaseous process material are introduced via a manifold arrangement  17  and a showerhead manifold arrangement  19  from a remote gas supply system through manifolding  23 . The showerhead is typically electrically isolated from other metallic portions of the chamber, and may be grounded or connected to high-frequency power supplies for electrical biasing. A gas-mixing manifold (not shown) in this arrangement ensures that gases introduced into the showerhead manifold are thoroughly mixed. 
     Susceptor  23  is the CVD hearth in this embodiment, and supports a wafer  25  for processing. The hearth, and hence the wafer, is heated by a plate heater  27  within an enclosure volume  29 , and arrangements provide for an ability to flow gases into this volume and onto the backside of a wafer during processing. Susceptor  23  is also electrically isolated and may be either grounded or biased as desired, such as by a high frequency power supply not shown. Various sensors for measuring process parameters such as temperature and pressure are also interfaced with the CVD reactor, although not specifically shown in FIG.  1 . 
     CVD reactor  11  depicted in FIG. 1 is well suited for conducting CVD processes according to the present invention. It will be apparent to those with skill in the art, however, that the invention is not limited to the reactor shown, and may be practiced in a wide variety of CVD reactors, including those reactors known as batch reactors in the art, wherein several wafers at a time are transferred into a reactor chamber, and processed in the reactor simultaneously. 
     CVD Process for Deposition of Tungsten Nitride as Low-Resistance Gate Material 
     In some applications, such as low resistance gates, a low-fluorine content in the barrier film is desired. In the case of a low-resistance gate, high fluorine content greater than ˜10 19  atoms per cm 3  can have a detrimental effect on the electrical characteristics of the capacitor formed by the structure. This effect adds an additional variability, which is desirable to eliminate if possible. 
     It is known to the inventors that there are several chemistries possible for producing tungsten nitride in a CVD process these are: 
     
       
         2WF 6 +0.5N 2 +6H 2 →W 2 N(s)+12HF  (1) 
       
     
     
       
         2WF 6 +NH 3 +4.5H 2 →W 2 N(s)+12HF  (2) 
       
     
     
       
         2WF 6 +NF 3 +7.5H 2 →W 2 N(s)+15 HF  (3) 
       
     
     In current art WF 6  with NH 3  is the most common chemistry for Tungsten Nitride thin films by CVD or PECVD, but, because of drawbacks previously discussed, an undesirable process. There is, as also described above, a serious drawback to this chemistry. That is the fact that mixing these two gases at room temperature causes an instantaneous and highly exothermic reaction. This fact leads to considerable complications in CVD reactor design and operation. The undesirable gas phase reactions, even where the gases are not premixed, causes particulate formation, powdery deposits, coating of chamber walls, and to poor film adhesion to the substrate. For these reasons such processes are not seriously considered as serious, viable processes in industry at the present. 
     In all of the above reactions it is obvious that a lot of fluorine is available for incorporation due to WF 6 . It would appear to most skilled practitioners in the art of thin film deposition that reaction (3) is likely to lead to the most F incorporation in the film because of the addition of nitrogen trifludride (NF 3 ). Indeed NF 3  broken down by plasma is commonly used to generate fluorine to etch tungsten deposits from the process chamber. Therefore, reaction (3) above has been proposed in the art, but never demonstrated, and the tendency in the art has been away from this process for exactly the reason of surplus fluorine. 
     The inventors have found that thermal CVD using NF 3  in reaction (3) is not very reactive. No significant formation of tungsten nitride at temperatures up to at least 600° C. has been observed, although there may be deposition at even higher temperatures. Much higher temperatures, however, would be a serious drawback for a viable commercial process. However, with the addition of plasma, high quality amorphous tungsten nitride films have been deposited at lower temperatures at rates of 20 to 60 nm/min. The typical process ranges for this exemplary process are: 
     
       
         
               
             
               
               
               
             
           
               
                 TABLE I 
               
             
             
               
                   
               
               
                 (Gate Application) 
               
             
          
           
               
                 Parameter 
                 Units 
                 Range 
               
               
                   
               
               
                 Total Pressure 
                 mtorr 
                  50-500 
               
               
                 Plasma Power 
                 Watts 
                  50-200 
               
               
                 Temperature 
                 ° C. 
                 300-450 
               
               
                 WF 6   
                 sccm 
                  3-12 
               
               
                 NF 3   
                 sccm 
                 1.5-24  
               
               
                 H 2   
                 sccm 
                 200-500 
               
               
                   
               
             
          
         
       
     
     In addition to the above Table I, FIG. 2 shows a particular process verified by the inventors within the ranges of Table I. 
     Three important improvements have been observed if NF 3  is used as a nitrogen source compared to NH 3  under the same conditions described above: 
     1) An approximately 2 times increase in the effectiveness in the utilization of the nitrogen gas 
     2) An increase of the number of wafer depositions from less than 50 to over 400 before the process chamber needs cleaning to reduce particles 
     3) An approximately 2 order of magnitude decrease in fluorine level 
     The above methods and benefits obtained with the exemplary NF 3  were are not obvious to those skilled in the art since no actual deposition results have been demonstrated prior to our discoveries, or reported in the literature. Only after obtaining the surprising results were the inventors able to realize that the improvements can be explained by the elimination of a direct reaction between WF 6  and NH 3 . 
     The plasma enhanced CVD process described above involving NF 3  may be modified by an addition of an inert gas such as Helium or Argon. It is well known that a deposition plasma consists of highly energetic free electrons that are necessary to sustain a plasma. In NF 3 , the highly electronegative character of F tends to extract electrons from the plasma and make it unstable. Such plasma instabilities in turn tend to adversely affect the PECVD process repeatability and also film uniformity. Addition of an inert gas such as He or Ar (preferably Ar) supplies electrons by ionization in the plasma. The mechanism is described below: 
     
       
         
               
               
               
             
           
               
                   
                   
               
             
             
               
                   
                 NF 3  −−−&gt; NF 2  + F 
                   
               
               
                   
                 F + e −−−&gt; F −   
                 (electron abstracted from the plasma) 
               
               
                   
                 Ar −−−&gt; Ar +  + e 
                 (electron supplied to plasma) 
               
               
                   
                   
               
             
          
         
       
     
     It will be understood by those with skill in the art that the addition of inert gas into the chamber to support a plasma for PECVD processing is well known in the art. 
     A significant advantage of NF 3  chemistry in the present disclosure is the co-reduction characteristic as described above. Because each of the desired products of the composite films is formed in an essentially independent chemical reaction, control of film composition is straightforward and predictable. 
     The inventors have also have discovered, as an added advantage in the NF 3  process, that NF 3  chemistry is more efficient than NH 3  chemistry for providing nitrogen in the desired film. FIG. 8 is a graph prepared from experimental data collected in practicing the tungsten nitride NF 3  processes described above and in practicing conventional tungsten nitride NH 3  processes. As is well known in the art from the conventional processes, the films prepared are a mixture of tungsten and tungsten nitride (W 2 N) after annealing. The ordinate in the graph represents film content by percent for materials represented in the graph, while the abscissa represents the ratio of nitrogen-bearing gas in the process (either NH 3  or NF 3 ) to tungsten hexafluoride (WF 6 ). 
     Curve  35  indicates W 2 N percent content for the unique NF 3  process of the present invention, and curve  37  represents W 2 N percent for conventional NH 3  processing. It is readily apparent that the W 2 N content increases more rapidly for the unique NF 3  process than for the conventional process. For example, a 50% level is reached for NF 3  processing at a ratio of about 0.6, while for conventional NH 3  processing a ratio of about 1.1 is needed for a 50% level. 
     Low Temperature Conversion of WNx to W 
     Rapid Thermal Annealing (RTA) is known in the art to anneal tungsten nitride in an ambient gas to reduce the Nitrogen and Fluorine to form pure W. Converting WNx to pure W through RTA is more successful, in terms of quality, than directly depositing pure W on the substrate. A temperature of approximately 1000° C. is required for about 60 seconds to fully convert WNx to W in known processes. In this process, an N2 ambient gas is employed. 
     Using the PECVD process for tungsten nitride described above allows a much purer (lower Nitrogen and Fluorine) amorphous WN film to be deposited on a substrate than has been possible by previous CVD processes, and this starting point helps in further annealing to form pure tungsten. 
     Further to the above, the inventors have discovered that inclusion of at least 5% H2 in an ambient such as Argon (Ar), Nitrogen or water vapor reduces the temperature requirement for the annealing from 1000° C. to a range of 850° C. to 900° C. for the same time period (about 60 seconds). 
     Moreover, by starting with an amorphous tungsten nitride layer preferably formed by the NF 3  process described above, and adjusting the annealing ambient to a lower nitrogen content, for example 10% hydrogen with the balance argon, a built-in barrier is self-formed. The barrier is either tungsten nitride or tungsten-silicon-nitride with a layer thickness of from about 10 to 30 Angstroms. The rest of the film is pure tungsten with resistivity about 10-15 micro-ohm cm. 
     Particle Control for WNx Deposition Using WF 6  and NH 3    
     It has been taught above that NF3 may be used successfully in place of NH 3  for eliminating gas phase reactions in both CVD and PECVD processes wherein the deposition film is WNx. As described above there exists a direct and kinetically-favored reaction between WF 6  and NH 3  without the need for H 2 . This reaction occurs spontaneously and exothermically even at room temperature. If WF 6  and NH 3  are allowed to mix at 10 torr and room temperature, the mixing point will easily reach temperatures above 100° C. The result is a white solid powder consisting of fluorinated tungsten complex containing W, N, F, and H. The ability to form solid particles from a gaseous mixture is why reaction (2), shown above, is considered in the art to be a “dirty”chemistry not suitable for manufacturing integrated circuits. 
     The tendency to form a direct CVD reaction is, however, a favorable trait to accomplish a deposition process to conformably coat small features, both with and without plasma. The present inventors have therefore developed methods to take advantage of the potential for conformal coating of small features with reaction (2) by finding solutions to the particulate formation. 
     To combat the particulate formation tendencies of the gas phase reaction using NH 3  the inventors have undertaken several steps, as follows: 
     1) Process chamber wall coating by a 0.5 mil hard-anodized aluminum oxide layer especially developed to not have any cracks that allow fluorine attack. Hard anodized films substantially above 0.5 mil typically form microcracks allowing an exposed aluminum surface to the process. This layer improves the adhesion of wall coatings thus reducing particles formed by flaking deposits on the chamber walls. 
     2) Separate injection of WF 6  and NH 3  that prevents mixing of the two gasses above 1 torr. We have found that a mixing pressures less than 1 torr eliminates formation of particles in the gas phase by direct reaction between WF 6  and NH 3 . 
     3) Elevating the chamber wall temperature to maintain within a range of from 70-90 degrees centigrade. Counter to expectation that an elevated temperature would enhance wall reactions due to the direct reaction between WF6 and NH 3  the elevated temperature actually reduces the amount of wall depositions as evidenced by a increased utilization of NH 3  by at least a factor of 2. 
     The inventors have discovered that each of the steps is beneficial, and combinations of these steps are even more beneficial in reducing particulate formation when using the NH 3  process. 
     In the processes performed according to equation (2) above, the process parameters are preferably within the ranges shown in Table 11 following: 
     
       
         
               
               
               
             
           
               
                 TABLE II 
               
               
                   
               
               
                 Parameter 
                 Units 
                 Range 
               
               
                   
               
             
             
               
                 Total Pressure 
                 mtorr 
                  50-500 
               
               
                 Power 
                 Watts 
                  50-200 
               
               
                 Temperature 
                 ° C. 
                 300-450 
               
               
                 WF 6   
                 sccm 
                  3-12 
               
               
                 NH 3   
                 sccm 
                 1.5-24  
               
               
                 H 3   
                 sccm 
                 200-500 
               
               
                   
               
             
          
         
       
     
     High Step Coverage Low-Temperature Deposition 
     The inventors have determined that reaction (2) does not react fully to form a good quality W 2 N unless the reaction temperature is above 500° C. For some applications, notably with devices with copper metalization, deposition temperatures less than 400° C. are required. Plasma enhanced chemical vapor deposition (PECVD) is used in such processes according to the invention to drive reaction (2) very efficiently at temperatures above about 290° C. If the wafer temperature is maintained between 300 and about 450° C. as seen in Table II, an amorphous WN x  (x=0.2 to 0.5) film results. The amorphous morphology is inherently a good characteristic for reducing diffusion due to film defects and grain boundaries. However, PECVD processes do not typically exhibit ability to coat small features conformably. The inventors discovered that when the utilization of the NH 3  was increased through controlling the wall temperature to 70-90degrees centigrade the step coverage was also enhanced. Step coverage of 30% in a 9:1 (depth:width) trench structure has been obtained under the conditions described in table II when combined with a wall temperature of 70-90degrees centigrade. This result is much improved over a process where the wall temperature is nominal room temperature, 30 degrees centigrade, and NH 3  is utilized less efficiently 
     Improving Nucleation of CVD Deposited WN on Oxide Surfaces 
     As scaling of integrated circuits to smaller and smaller dimensions continues, dielectric layers also must become thinner to concomitantly increase the capacitance per unit area. This leads to need for of high capacitance layers, such as Ta 5 O 5 . Tungsten bonds less strongly to nitrogen or oxygen than titanium or tantalum, which leads to the potential of using the tungsten nitride as a barrier layer in this application. 
     However, in the new metal to dielectric structures that are desired by the industry, there needs to be a very thin barrier layer with high ability to coat small features. A significant challenge is that this thin layer will also have to be able to deposit directly on an underlying oxide and also without attacking silicon used to contact the barrier. 
     The inventors have developed a method that can be used to deposit a 25 to 50 nm thin tungsten nitride layer using a thermally activated version of reaction (2) by first forming a thin mono-layer to 6nm tungsten silicide nucleation layer. The typical temperature of 525° C. required for the efficient use of reaction (2) is well outside the range of parameters that most would consider feasible for using silane (SiH 4 ) to form a tungsten silicide. Typically silane deposited tungsten silicide is deposited at only 390° C. or less. 
     Table IV shows the parameter ranges for the process to perform the thin tungsten silicide layer changing quickly to tungsten nitride: 
     
       
         
               
             
               
               
               
             
           
               
                 TABLE IV 
               
             
             
               
                   
               
               
                 (Capacitor Electrode Silicide Nucleation) 
               
             
          
           
               
                 Parameter 
                 Units 
                 Range 
               
               
                   
               
               
                 Total Pressure 
                 mtorr 
                 100-500 
               
               
                 Temperature 
                 ° C. 
                 500-600 
               
               
                 WF 6   
                 sccm 
                 0.1-5   
               
               
                 NH 3   
                 sccm 
                  0-20 
               
               
                 H 3   
                 sccm 
                 200-500 
               
               
                 SiH 4   
                 sccm 
                 20-50 
               
               
                   
               
             
          
         
       
     
     In order to combat this problem, the inventor provides a method that uses SiH 4  to reduce the WF 6  in the gaseous phase. In this method, a thin Tungsten silicide layer forms on the oxide surface. After the layer is completely formed on the oxide surface, conformal deposition of WNx by CVD may commence. 
     It will be apparent to those with skill in the art that there are many alternative to the embodiments of the invention as described above without departing from the spirit and scope of the invention. For example, there are a variety of reactors that might be used, including both single-chamber and batch reactors. There are process variations that may be made as well, including variations in preparatory and finishing steps before and after the principle deposition step in each exemplary process, and there are broad ranges, as have been detailed above, of process characteristics within which successful process has been demonstrated and may be repeated. As there are many such variations within the spirit and scope of the invention, the invention is limited only by the claims which follow: