TW201006938A - Molybdenum-niobium alloys, sputtering targets containing such alloys, methods of making such targets, thin films prepared therefrom and uses thereof - Google Patents

Abstract

Alloys comprising: (a) molybdenum present in a majority portion; (b) niobium present in an alloying amount; and (c) a third metal selected from the group consisting of nickel, chromium, titanium, zirconium, hafnium, vanadium and mixtures thereof, wherein the third metal is present in a doping amount; along with sputtering targets prepared therewith, films sputtered using such targets and thin film devices containing such films.

Description

201006938 VI. INSTRUCTIONS · · [Prior Art] Sputtering is a technique for producing a metal layer in various manufacturing processes used in the semiconductor and optoelectronic industries. The nature of the film formed during sputtering is related to the nature of the sputter dry material itself, such as the size of the individual grains and the formation of secondary phases with distribution characteristics. There is a need to create a sputtering target that will provide film uniformity, minimal particle generation during sputtering, and desired electrical and physical properties in the resulting film. • Use a variety of sputtering techniques to achieve film deposition on the surface of the substrate. A deposited metal film, such as a metal film on a flat panel display device, can be formed by a magnetron sputtering device or other sputtering technique. The magnetron sputtering device induces plasma ions of the gas to bombard the target, causing surface atoms of the target material to be ejected and deposited as a film or layer on the surface of the substrate. Conventionally, a sputtering source in the form of a flat disk or a rectangle is used as a target, and the exiting atoms travel along a line of sight trajectory for deposition on the top of the wafer, and the deposition surface of the wafer is parallel to the target. The erosion surface. A tubular sputter target can also be used, as described in U.S. Patent Application Publication No. 2007/0042, the entire disclosure of which is incorporated herein by reference. It may be desirable to include a sputter target that cannot be made of a material or combination of materials that is manufactured by conventional means such as rolling. In such cases, the target is produced by thermally equalizing pressurized (HIP) powder. Ideally, the target is fabricated in a single step. However, the physical limitations of the powder loading density and size of the HIP device necessitate the addition of smaller sections to create a large sputter target. For single-phase targets, conventional treatments such as welding can be used; solid-state edge-to-edge bonding is preferred for multi-phase materials or where alloy formation is avoided for any reason at 139600.doc 201006938. The interconnections in semiconductors and TFT-LCDs evolved from aluminum and toward copper, so new diffusion barriers were needed. Titanium provides excellent adhesion properties, while turning helps with dense barrier stability. Integral circuits (for semiconductors and flat panel displays) use Mo—Ti as the underlayer or overlay for aluminum, copper and aluminum alloys to minimize small bump formation, control reflectivity and provide protection during photolithography Invade the surname in physics and chemistry. SUMMARY OF THE INVENTION The present invention generally relates to molybdenum alloys, their use in the preparation of sputter targets, methods of making films using such sputter targets, and films prepared thereby. More specifically, the present invention relates to a molybdenum alloy comprising a majority of molybdenum, an amount of the alloy, and a doping amount of the third metal 'the third metal is selected from the group consisting of: recording, complex, titanium, error, giving, and/or Or a group of slaves. An embodiment of the invention includes an alloy comprising: molybdenum present; : (a) in a majority

When it is 鍅, the doping amount is less than 0.01% by weight or more than 1% by weight. The second metal lanthanum in chromium, titanium and lead. (a) in most parts

Another embodiment of the first invention includes an alloy comprising: and the presence of ruthenium chromium, titanium, and a trimetallic system present in a doping amount. Sputtering target comprising densification Another embodiment of the invention includes a sputter target, 139600.doc 201006938 alloy 'densified alloy comprising: (4) molybdenum niobium (n) present in a majority portion is sharp in the amount of alloy; (4) A third metal selected from the group consisting of a mixture of nickel, chromium, hexagram, dynamite, and hunger, wherein the third metal is present in a doping amount. In various preferred embodiments, the present invention includes a dry-dissolved material, the sputter target comprises a densified alloy, and the densified alloy is also composed of Q gold. (a) indium present in a majority portion; (b) a sharp metal present in the amount of alloy; and (10) a third metal of a group consisting of free zinc, chromium, chin, erroneous, giving, hunger, and mixtures thereof, wherein the second metal is present in a doping amount; the limiting condition is: When the third metal is zirconium, the doping amount is less than 0.01% by weight or more than 丄% by weight. - Further embodiments of the present invention include a method comprising: providing a crucible in a majority portion, presenting in an amount of alloy a sharp powder and a blend of a third metal powder selected from the group consisting of nickel, road, titanium, niobium, niobium, ruthenium, and mixtures thereof, wherein the ri is a doping amount, limiting When the second metal powder is lead, the doping amount is less than qgi wt% or 00, and the compound is subjected to heat and late force to form a densified splashing dry material. Still another embodiment of the present invention includes a method, Including (4) Providing a permafrost dry material containing a densified alloy (1) indium present in a majority portion, (8) sharp in the presence of an alloy amount; and (d) a third metal selected from the group consisting of chrome, chromium, titanium, erroneous, agglomerate, sharp, and mixtures thereof, wherein Providing a doping amount; (8) providing a substrate; and (4) subjecting the extrudate to a debonding condition to form a coating comprising a free material on the substrate. Another embodiment of the invention includes a thin film device comprising a substrate and disposed on The film 'film on top of the substrate is prepared according to any one of the methods of mineral reduction of the present invention, 139600. doc 201006938. Various embodiments of the present invention may provide a sputtering target, which may be in accordance with the present invention. Other method embodiments are used to provide films for use in various devices also embodied by the present invention, wherein the performance properties of the film device are at least comparable to, and in some cases superior to, the thin film devices known in the art. a thin film device known in the art, and wherein the film exhibits excellent adhesion to the substrate. The thin medium according to the present invention and the device containing the film according to the present invention can also be provided with an improved system. A favorable photolithographic feature of productivity. The advantage provided by the film according to the invention is a uniform, fast and controllable etch rate, which is improved adhesion (between the substrate and the thin mold of the invention) and The combination of the inventive film and a later deposited metal film (for example, copper) can greatly improve the photolithography operation. [Embodiment] The foregoing overview can be better understood when combined with additional patterns. The detailed description of the present invention is set forth in the accompanying drawings. As used herein, the singular terms "a" and "an" and "the" and "the" and "the" and "the" are used interchangeably and interchangeably. For the sake of &amp;, the reference to "_metal" in the scope of additional patent application may be: or more than one metal. All numbers I39600.doc 6 - 201006938 or the expressions of the components, reaction conditions, etc. used in this specification outside the operating example t or other indications should be understood as terms in all cases. "about" modification. Various numerical ranges are disclosed in this patent application. Because these ranges are continuous, they include every value between the minimum and maximum values. In addition, all ranges disclosed herein are intended to encompass the same <RTI ID=0.0> </ RTI> <RTIgt; </ RTI> <RTIgt; </ RTI> <RTIgt; lower limit. References to &lt;RTI ID=0.0&gt;&gt;&quot;&quot;&quot;&quot;&quot;&quot; Alloys in accordance with various embodiments of the present invention include a majority portion of molybdenum. As used herein, the term "majority" refers to a weight percent content greater than 5%. Preferably, the majority is 75% or more, and even more preferably, the majority is 94% to 99%. In an even more preferred embodiment of the alloy of the present invention, the molybdenum is 95. /. It exists in most parts of 98%, and is optimally 95% to 97%. Alloys in accordance with various embodiments of the present invention include an amount of alloy. As used herein, the term "alloy amount" refers to a weight percent content of from about 〇5〇/〇 to 6〇/〇. Preferably, the amount of the alloy is from 1% to 5%, and even more preferably 2%/. Up to 4%, and optimally 3. /. Up to 4%. Alloys in accordance with various embodiments of the present invention include a doping amount of a third metal. As used herein, the term "doping amount" refers to a content by weight which is generally less than the amount of the alloy. Preferably, the amount of doping is at most about 2%. In various embodiments, the amount of doping can be up to about 1 ^. In various embodiments, the amount of doping can range from 100 ppm to 1%. In various embodiments, the amount of doping can be up to 1 〇〇 ppm. In various embodiments, the amount of doping can be any amount greater than 139600.doc 201006938 1 〇 / 直至 up to an amount less than the amount of alloy. The third metal present in the alloys according to various embodiments of the present invention may be selected from the group consisting of nickel, chromium, titanium, niobium, tantalum, vanadium, and mixtures thereof. In various preferred embodiments of the invention, the third metal comprises zirconium. An embodiment according to an embodiment of the invention comprises an alloy comprising: (a) molybdenum present in a majority; (b) niobium present in an amount of alloy; and (e) zirconium in an amount less than 100 ppm. Another embodiment according to the invention comprises an alloy&apos; alloy comprising: (4) molybdenum present in a majority; (b) bismuth in the amount of alloy; and (C) greater than 1 weight. /. The amount of zirconium. The alloy according to various embodiments of the present invention may be characterized in that the niobium and the third metal are mainly combined with molybdenum in the displacement type solid solution, or as a mixture of alloys of various metals in the crystal structure, or as a partial alloy. a mixture. Alloys in accordance with various embodiments of the present invention may be prepared by any suitable molten metallurgical process. The alloy according to the invention may be further milled and/or ground to produce a powder for forming a sputter target according to the invention. The powder can also be prepared using an atomization process (e.g., a rotating electrode process). A suitable molten metallurgy process for the preparation of the alloys according to the present invention is described in U.S. Patent Application Publication No. US2006/0172454, the entire disclosure of which is incorporated herein by reference. Alternatively, for example, a suitable amount of molybdenum powder, niobium powder, and third metal powder may be blended, vacuumed, vacuum hot pressed, or thermally evenly pressurized (HIP). The parisons can then be compacted by a thermal deformation process such as extrusion, forging and/or rolling. The invention also encompasses (4) (four) materials comprising a densified alloy of any of the various alloys of the invention 139600.doc 201006938. The finished sputter target of the present invention has a theoretical density greater than about 90%, preferably a theoretical density of at least 95%, more preferably a theoretical density of at least 98%, and most preferably a theoretical density of at least 99.5%. density. The sputter target according to the present invention can be provided via suitable conventional techniques such as a melt process or a powder metallurgy process. Various scale metallurgy processes are known in the art including, but not limited to, methods such as electron beam melting processes, electrospinning, plasma melting, and the like. Melting can be performed under extreme vacuum conditions equal to or lower than 4 χ 10·5 Torr in a suitable electron beam melting process. In a suitable plasma melting process, melting can be carried out in an atmosphere between 8 χ 1 〇 4 and 4 χ 1 〇 - 3 Torr. In a suitable powder metallurgy process, the constituent powders (i.e., 'molybdenum powder, tantalum powder and third metal powder or previously ground and ground alloy powder as described above) are blended in the proportions previously described, and Compaction and sintering are carried out by various means known in the art. Further, a powdery alloy produced by a predetermined component via an atomization method or the like may be used instead of the elemental powder, or the powdery alloy and the elemental powder may be used. The average particle size of the molybdenum powder is preferably between _ 1 - 25 μm, more preferably less than 5 μm. For the niobium and the third metal powder, the average particle size is preferably from 5 to 50 μm, more preferably from 20 to 35 μm. The powder can be blended according to well known powder blending techniques in the art. For example, mixing can occur by placing molybdenum, niobium, and third metal powder in a dry container and rotating the closed container about its central axis. The mixing will continue for a period of time sufficient to result in a fully blended and uniformly distributed powder 139600.doc 201006938. A ball mill or similar device can also be used to complete the blending step. The invention is not limited to any particular mixing technique, and other mixing techniques may be selected (if it will be sufficiently blended to form the starting powder). Optionally, the powder blend is then compacted to 60/ in the preliminary compacting step. Density of theoretical density of -85 ° / ◦. Compaction can be accomplished by any means known to those skilled in the art of powder metallurgy, for example, cold equalization pressurization, rolling, or die compaction. The length and amount of pressure used will vary depending on the desired pressure density to be achieved in this step. For some types of targets (e.g., tubular targets) this step may not be necessary. After the preliminary compacting step, the compacted powder is encapsulated, for example, in a mild steel can. Encapsulation can also be accomplished by any method that will provide a compacted workpiece with no interconnected surface porosity, such as by sintering, thermal spraying, and the like. As used herein, the term "encapsulated" will refer to any method known to those skilled in the art for providing a compression member having no interconnected surface porosity. A preferred method of encapsulation is by using a steel can. After encapsulation, the encapsulated member is compressed under heat and pressure. Various compression methods are known in the art including, but not limited to, methods such as inert gas uniaxial hot pressing, vacuum hot pressing and thermal equalizing press, and rapid omni compaction (Ceracon process). Preferably, the encapsulate is thermally isostatically pressurized to the desired target shape, as the method is known in the art and is 75-300 MPa (more preferably 1 〇〇 175). The pressure under Mpa) is 2 16 hours (more preferably 4-8 hours) at a temperature of 10 ° C - 1500 ° C (more preferably (1) generation seven (10)). As long as the proper temperature is maintained and then the other conditions are used to produce the M〇_Nb_ 139600.doc 201006938 of the present invention.

Zr sputtering target. The sputter target according to various embodiments of the present invention can be prepared into a rectangular plate or other suitable shape using the compacting and sintering methods described above, or can be prepared as a tubular sputter target. Larger targets can be prepared by bonding a plurality of sheets, as described in U.S. Patent Application Publication No. US2007/0089984, the entire disclosure of which is incorporated herein by reference. Suitable methods for the preparation of the official target are described in U.S. Patent Application Publication No. US 2006/0172454, the entire disclosure of which is incorporated herein by reference. A method of making a tubular sputter target, which can also be used to prepare a target according to the present invention, is disclosed in U.S. Patent Application Publication No. US 2006/0042, the entire disclosure of which is incorporated herein by reference. . The invention also includes films prepared by sputtering targets of various embodiments of the targets of the invention as described herein. The film according to the invention can be prepared by sputtering a target according to the invention comprising an alloy of molybdenum, niobium and a third metal. Sputtering the target of the present invention involves subjecting the target to sputter conditions. Magnetron sputtering can be preferred using any suitable sputtering method. Suitable sputtering conditions that can be used in accordance with the methods of the present invention can include a preliminary burn-in procedure that can include power application to the target, with a watt rise of, for example, 〇 to (10) w, and maintaining the power of the shirt for 1 〇. Minutes, rise to _ w for a period of 50 minutes and then maintain the power at face | for 2 hours. Splashing can be performed after the burn-in procedure and any optional substrate cleaning. Prior to deposition, the substrate can be subjected to chemical cleaning by continuous rinsing in an ultrasonic bath of propylene and ethanol. The 139600.doc 201006938 substrate can then be blow dried in nitrogen and loaded into a deposition chamber for sputtering. The deposition of the splash to the center can be carried out under various parameters or power applied to the material and the gas pressure in the chamber. The appropriate power level applied to the dry material can range from 500 to 2000 W, and is preferably about 1 〇〇〇 w. The substrate is preferably grounded at 〇 V and the substrate source spacing (sss) is maintained at about 5 Å. The gas pressure is usually from about 1 to 10 mTorr' and more preferably from 1 to 5 mTorr. The present invention also encompasses a film device having a film produced by the method of sputtering a dry material according to the present invention as described above. As used herein, a "thin film device" includes electronic components such as a semiconductor device, a thin film transistor, a TFT-LCD device, a black matrix device that enhances image contrast of a flat panel display, a solar cell, a sensor, and A CMOS (Complementary Metal Oxide Semiconductor) gate device with a tunable work function. Films prepared by sputtering a target according to the present invention in accordance with the method of the present invention can be used in any of the above-described thin film devices in any suitable manner. Thus, for example, a tantalum, niobium, film prepared from the target of the present invention (Μ3 represents a third metal and x+y+z is preferably equal to 1% by weight) can serve as a barrier layer, in etching Subsequent conductive wiring, gate electrode, source electrode and/or germanium electrode 'etc. Films in accordance with various embodiments of the present invention are preferably used in flat panel displays and solar cells. Any suitable process for fabrication by etching, photolithography, and other electronic device architectures can be used to form suitable wiring, electrodes or transistor components from films deposited in accordance with the present invention. As a barrier layer, a film according to various embodiments of the present invention may serve as a diffusion barrier layer (for example, between a Si substrate and a metal layer disposed above the Si substrate), and the bite St is placed above the underlying layer in the device. The protective layer, or the barrier layer and the protective layer that act as the diffusion 139600.doc 12 201006938. The use of a molybdenum layer as a barrier layer is described, for example, in U.S. Patent No. 7,352,417, the disclosure of which is incorporated herein in its entirety. The film of the present invention can be deposited on any suitable substrate that can be sputtered over the material. In various preferred embodiments of the invention, the substrate on which the film according to the present invention is sputtered comprises glass, tantalum, steel or polymeric material. Alternatively, the film according to the present invention can be deposited onto other film tantalum/niobium alloy layers. In various preferred embodiments, the substrate can comprise glass, tantalum and/or stainless steel. In various particularly preferred embodiments, the substrate can comprise low sodium glass, other non-indicating LCD substrate glass (e.g., &apos; Corning® 1737), or a combination thereof. The M〇NbM3 film prepared according to the present invention can be advantageously used in various film placements', particularly preferably used as wiring in flat panel displays. The MoNbM3 film exhibits minimal particle generation, good substrate adhesion and low resistivity. As discussed below, the uniformity of the MoNbM3 film is comparable to known M〇 and ΜοΤι films, or even better than known m〇 and M〇Ti films. The invention will now be described in more detail with reference to the following non-limiting examples. Instance

Comparative sputtering targets 丨, 2, 3A, and 3B are prepared based on known high purity molybdenum alloys, wherein the molybdenum comprises substantially the entire target. Additional comparative targets based on known molybdenum-titanium alloys were also prepared. Finally, a target comprising molybdenum, niobium and lead is prepared for the preparation of a film according to an embodiment of the invention. The crucible was then deposited on various substrates under various conditions and evaluated for morphology, particle generation, accumulation rate, microstructure, adhesion, (iv) rate, and resistivity. 139600.doc -13- 201006938 Target preparation: Known melting, annealing, each. In protection. In the target used, all of the annealing steps are carried out by combining appropriate metals and extruding, annealing, forging and annealing by electron beam irradiation or in vacuum, each having a 〇·25吋The thickness of the circle. Substrate and substrate preparation: Before the substrate is sunk (4), the film is subjected to ultrasonic bath with acetone and ethanol in each of the 7, not (fine 3〇4), limestone glass and ~ning 1737 glass substrates. The continuous rinse of the chemical clear I then uses nitrogen to dry each of the substrates and load them into the deposition chamber. The chamber is then vented to a low W, pressure, and then filled with argon to 65 ton; the pressure of the susceptor is applied by a negative voltage of 4 〇〇v and pulsed at 100 kHz for 3 〇. The substrate was sputter-etched by accelerating chloride ions to the substrate in minutes. After the substrate was sputter cleaned, the argon flow was reduced to 2 mTorr and the target was sputter cleaned at 500 W (DC) for 5 minutes. During the sputter cleaning of the target, the baffle is positioned in front of the dry material to prevent deposition on the substrate. Deposition on the substrate is performed by application to the fixed power of the material and under varying gas pressure and time conditions. The conditions are shown below in the table. Table 1. Parameters for deposition of the substrate at 0 V (ground) at 1000 W

Time tk body pressure (millimeter: te) 1 2 3 4 5 1 hour XXXXX ~ 2 minutes XXX Maintain the substrate source spacing at 5". The power applied to the target is 1 〇〇〇W and 139600.doc 201006938 Maintain the substrate The deposition chamber used is a cylindrical vessel having a base pressure of ΐχΐ〇.6 Torr, which is manufactured by ACSEL and is powered by a dual-channel DC 6 kw power source manufactured by Advanced Energy. : Using each of the prepared &lt;贱 plated materials, a film is provided to each of the + substrates. The coated substrate is then evaluated as follows. Shape of the material: Erosion of comparative molybdenum titanium film Some micropores are observed in the orbit. Based on backscattered electron images, it seems that some molybdenum grains are segregated with titanium grains and most of the micropores are present in brighter regions (composed of molybdenum grains with a larger atomic number) In contrast, micropores or segregation of molybdenum, niobium and tantalum grains were not observed in films prepared from M〇NbZr sputtering targets. In addition, the grain size in MoNbZr sputtering targets is much larger than Grain in a comparative target Dimensions. Referring to Figures la, lb, 2a and 2b, micropores can be identified in MoTi targets, especially at 5000X magnification, such as shown in Figure 2 &amp; ^ MoTi at 50〇X magnification Backscattered electron imaging of the target shows that most of the micropores are between the Mo grains. Referring to Figures 3a, 3b, 4a and 4b, micropores are not identified in the MoNbZr target. 5a, 5b, 6a, 6b and 7, also in the film produced using the comparative MoTi target. The diameter of the particles encountered has an amount between 2 and 5 μηη. The macroparticle density is estimated to be about 4 macroparticles in an area of 50 μπιχ50 μπι. In contrast, the MoNbZr dry material is not used on a broken substrate at 5 mTorr, 3 mTorr or 1 mTorr. 139600.doc 15 201006938 Macroscopic particles were observed in the prepared film. Accumulation rate: Scanning electron microscopy (SEM) was used to measure each of the targets used in both the ruthenium substrate and the Corning 1737 glass substrate. The rate of accumulation of the coating prepared above. The following is presented in Table 2. Table 2. At 0 V Accumulation rate of film deposited under ground (μιη/h) gas pressure (mTorr) 1 2 3 4 5 mean standard deviation material 1 (μιη/h) 5.5 5.1 5 5 6 5.32 0.43 dry material 2 (μιη/h) 5.8 6 6.6 6.5 6.5 6.28 0.36 Δ accumulation rate (μιη/h) 0.3 0.9 1.6 1.5 0.5 0.96 About % change of Ding 1.5.4 17.65 32.00 30.00 8.33 18.69 Dry material 3A (ftm/h) 5.7 6.0 5.4 6.4 6.9 6.08 0.59 About Δ accumulation rate of T1 (μιη/h) 0.2 0.9 0.4 1.4 0.9 0.76 About D1 change of 3.64 17.65 8.00 28.00 15.00 14.46 Dry material 3B (μπι/h) 6.16 6.4 6.1 6.25 5.8 6.14 0.22 About Ή之Δ accumulation rate (μιη/h) 0.66 1.3 1.1 1.25 -0.2 0.82 About D1 change of 12.00 25.49 22.00 25.00 -3.33 16.23 Coming 1737 dry material Mo-Ti (μπι/h) 5.85 6.04 6.43 6.28 6.55 6.23 0.255 About Δ accumulation rate of T1 (μπι/h) 0.35 0.94 1.43 1.28 0.55 0.91 About % change of Ding 1.6.3 18.4 28.6 25.6 9.17 17.6% The material on Si Μο-Ή(μηι/1ι) 5.66 5.64 6.5 6.5 6.08 0.425 About Τ1 Δ accumulation rate (μπι/h) 0.16 0.54 1.5 1.5 0.925 About % change of Ding 1 2.9 10.5 30 30 18.35 Coming 1737 on Mo-NbZr(pm/h) 5.47 6.52 6.7 6.23 0.54 About Δ accumulation rate of T1 (μιη/h) -0.03 1.52 0.7 0.73 About 11 %Change -0.55 30 11.6 13.6 Dry material on Si Mo-NbZr(|im/h) 6.19 6.67 6.39 6.33 6.74 6.46 0.208 About Δ accumulation rate of T1 (μιη/h) 0.69 1.57 1.9 1.33 0.67 1.23 About Ding 1% Variation 12.5 30.8 38 26.6 11.2 23.8 139600.doc -16- 201006938 Microstructure: The microstructure of the thin crucible prepared on the # substrate and Corning 173 7 glass substrate using MoTi and MoNbZr sputtering targets was also observed using SEM. As the deposition pressure is reduced, the coatings prepared using the two materials become increasingly dense. The coating on the 1737 glass substrate is denser than the coating on the Shixi substrate. • Referring to Figures 8a to 24b, a similar density of films is shown. Adhesion (band test): The tape test was used to measure the adhesion of the scented coating using MoTi and MoNbZr sputter targets. A coating having a thickness of about 200 nm prepared on Corning 1737 glass demonstrated significantly better adhesion than a coating having a thickness of about 5 μηι on a stainless steel and soda lime glass substrate. The results are shown below in Tables 3a and 3b. Table 3a. Tape test: Mo-Ti and Mo-NbZr coating; thickness of ~2〇〇 nm on Corning 1737

1 mTorr 3 mTorr 5 mTorr Target Mo-Ti 5B 5B 5B Dry material Mo-NbZr 5B 5B 5B Table 3b. Tape test: Mo-Ti and Mo-NbZr coating; thickness of ~5 μπι.

1 mTorr 2 mTorr 3 mTorr 4 mTorr 5 mTorr stainless steel target Mo-Ti 0B 0B 1B 0B 1B Alkali lime glass target Mo-Ti 0B 0B 0B 0B 0B Stainless steel target Mo- NbZr 2B 5B 4B 5B Target on soda lime glass Mo-NbZr 0B 0B 0B 0B Etching rate: Immersion of the coating prepared by sputtering the target on the tantalum substrate with MoTi at 25 ° C in the ferric cyanide The etch of the coating 139600.doc 201006938 was measured over 30 minutes in the solution. The etch rate of the coating was measured by immersing the coating prepared on the ruthenium substrate with a MoNbZr target at 25 ° C for 5 minutes in a ferricyanide solution. The etch rate of the coating prepared using the MoTi target is much lower than that of the coating prepared using the MoNbZr target and the coating prepared from the pure molybdenum target. The results are shown in Table 4 below. Table 4. Etch rate; Mo coating produced at 1 kW for 1 hour, 〇V bias (ground) in ferricyanide solution at 25 °C. Deposition pressure (mTorr) Etching rate Target axis engraving rate target Mo-Ti (μπι/min) Mo-NbZr (μιη/ηιΐη) 1 0.063 0.64 2 0.064 0.87 3 0.098 0.56 4 0.081 0.67 5 0.078 0.76 Average 0.077 0.71 Resistivity: A four-point probe is used to measure the sheet resistance of a selected molybdenum film. The results are presented in Table 5 below. As shown in Table 5, the resistivity of the coating prepared using the MoTi target was much higher than that of the coating prepared using the MoNbZr sputtering target. Table 5. Sheet Resistance &amp; Resistivity Parameter Measurement Pressure Power Time Thickness Sheet Resistance Resistivity (mTorr) (W) (S) (nm) (Ω/D) (μΩ.οπι) Target 1 1000 117 179 4.45 79.6 Mo-Ti 2 1000 109 182 4.50 81.9 5 1000 108 170 4.58 78 Target 1 1000 127 191 0.745 14.2 Mo-NbZr 3 1000 133 247 0.642 15.8 5 1000 112 193 0.697 12.3

139600.doc -18- 201006938 Determine the uniformity of the film by measuring the sheet resistance of 37 points of the coating produced on the 4&quot; wafer at the 5" position of the target. Using each of the targets The uniformity of the coatings prepared was comparable. The results of the uniformity evaluation are shown graphically in Table 6 and with reference to Figures 25, 26a and 26b. Table 6. Uniformity of all coatings produced. All points 4 are not divided by 6 external 咅 1 point target standard deviation mean non-uniform standard deviation mean non-uniformity (Ω/sq.) (Ω/sq.) bisexuality (Ω/sq.) (Ω/ Sq.) One nature 1 0.0301 0.0860 0.105 0.0193 0.2761 0.070 2 0.0255 0.2298 0.111 0.0171 0.2214 0.077 3A 0.0236 0.2354 0.100 0.0157 0.2277 0.069 3B 0.0278 0.2750 0.101 0.0155 0.2656 0.058 MoTi 0.37 4.37 0.082 0.219 4.34 0.050 MoNbZr 0.095 0.80 0.119 0.0577 0.769 0.075 It will be appreciated by those skilled in the art that the above-described embodiments may be varied without departing from the broad inventive concepts thereof. It is therefore to be understood that the invention is not limited Modifications within the spirit and scope of the invention as defined by the scope of the patent [Simplified illustration] Figure la is a secondary electron image of a comparative Mo-Ti target at 1000X magnification; Figure lb is at 1000X magnification Figure 2a shows the secondary electron image of the comparative Mo-Ti target in Figure la at 1000X magnification; Figure 2b shows the magnification at 1000X. Figure 2b shows the backscattered electron image of the comparative Mo-Ti target in Figure la; The backscattered electron image of the comparative Mo-Ti target in the following figure la; Figure 3a is 139600.doc -19· 201006938 according to an embodiment of the invention at 200X magnification

Secondary electron image of MoNbZr target; Figure 3b shows backscattered electron image of MoNbZr target in Figure 3a at 200X magnification; Figure 4a shows secondary electron of MoNbZr target in Figure 3a at 1000X magnification Figure 4b is a backscattered electron image of the MoNbZr target in Figure 3a at 1000X magnification; Figure 5a is a film prepared on a Si substrate using a comparative Mo-Ti target at 1000X magnification. Secondary electron image; Figure 5b is a backscattered electron image of the film of Figure 5a at 1000X magnification; Figure 6a is another sample prepared on a Si substrate using a comparative Mo-Ti target at 20,000X magnification A secondary electron image of a film; Figure 6b is a backscattered electron image of the film of Figure 6a at 20,000X magnification; Figure 7 is a backscattered electron image of the film of Figure 7a at 1000X magnification; Figure 8a Secondary electron image of a film prepared on a Corning 173 7 glass substrate using a comparative Mo-Ti target at 10000X magnification; Figure 8b is a secondary electron image of the film in Figure 8a at 5000X magnification Figure 9a shows the use of comparative Mo-Ti at 10000X magnification Secondary electron image of another film prepared on a Corning 1737 glass substrate; 139600.doc -20· 201006938 Figure 9b is a secondary electron image of the film of Figure 9a at 5000X magnification; Figure 10a is Secondary electron image of another film prepared on a Corning 1737 glass substrate using a comparative Mo-Ti target at 10000X magnification; • Figure l〇b is the film of Figure 10a at 5000X magnification Secondary electron image; Figure 11a is a secondary electron image of another film prepared on a ❹ Corning 1737 glass substrate using a comparative Mo-Ti target at 10000X magnification; Figure lib is at Figure 5000a at 5000X magnification Secondary electron image of the film in the film; Figure 12a is a secondary electron image of another film prepared on a Corning 173 7 glass substrate using a comparative Mo-Ti target at 10000X magnification; Figure 12b is at 5000X Secondary electron image of the film in Figure 12a at magnification; Figure 13a is a secondary electron image of the film prepared on the Si' substrate using a comparative Mo-Ti target at 10000X magnification; Figure 13b For Figure 5a at 5000X magnification Secondary electron image of the film; Figure 14a is a secondary electron image of another film prepared on a Si substrate using a comparative Mo-Ti target at 10000X magnification; Figure 14b is Figure 14a at 5000X magnification Secondary electron image of film in 139600.doc •21 · 201006938 Image; Figure 15a is a secondary electron image of another film prepared on a Si substrate using a comparative Mo-Ti target at 10000X magnification; Figure 15b is a secondary electron image of the film of Figure 15a at 5000X magnification; Figure 16a is a secondary electron of another film prepared on a Si substrate using a comparative Mo-Ti target at 10000X magnification. Figure 16b is a secondary electron image of the film of Figure 16a at 5000X magnification; Figure 17a is prepared on a Corning 1737 glass substrate using a MoNbZr target according to an embodiment of the present invention at 10000X magnification. Secondary electron image of the film; Figure 17b is a secondary electron image of the film of Figure 17a at 5000X magnification; Figure 18a is a use of a MoNbZr material according to an embodiment of the present invention at 10000X magnification in Corning 1737 glass substrate Secondary electron image of another film prepared; Fig. 18b is a secondary electron image of the film of Fig. 18a at 5000X magnification; Fig. 19a is a MoNbZr target according to an embodiment of the present invention at 10000X magnification a secondary electron image of another film prepared on a Corning 173 7 glass substrate; Figure 19b is a secondary electron image of the film of Figure 19a at 5000X magnification; 139600.doc -22-201006938 Figure 20a is at Secondary electron image of a film prepared on a Si substrate using a MoNbZr target according to an embodiment of the present invention at 10000X magnification; Figure 20b is a secondary electron image of the film of Figure 20a at 5000X magnification; Figure 21a is a secondary electron image of another film prepared on a Si substrate using a MoNbZr target according to an embodiment of the present invention at 10000X magnification; Figure 2b is at 5000X magnification in Figure 21a Secondary electron image of the film; Figure 22a is a secondary electron image of another film prepared on a Si substrate using a MoNbZr target according to an embodiment of the present invention at 10000X magnification; Figure 22b is at 5000X put Figure 2a shows a secondary electron image of another film prepared on a Si substrate using a MoNbZr target of the stomach according to an embodiment of the present invention at 10000X magnification. Figure 23b is a secondary electron image of the film of Figure 23a at 5000X magnification; Figure 24a is another sample prepared on a Si substrate using a MoNbZr target according to an embodiment of the present invention at 10000X magnification. Secondary electron image of a film; Figure 24b shows the secondary electron image of the film in Figure 24a at 5,000X magnification 139600.doc • 23· 201006938 image; Figure 25 shows the position of the sheet resistance measurement point on the wafer Schematic representation; Figure 26a is a schematic representation of sheet resistance measurement at the location identified in Figure 25 on a Si wafer coated with a film prepared using a comparative MoTi target; and Figure 26b is in coating A schematic representation of the sheet resistance measurement at the location identified in Figure 25 on a Si wafer having a film prepared using an M〇NbZr target in accordance with an embodiment of the present invention. 139600.doc 24·

Claims (1)

201006938 VII. Patent application scope: Two kinds of alloys, which contain: (4) molybdenum in the presence of - majority; 〇 &gt;) bismuth in the amount of - alloy; and (4) selected from nickel, chromium, titanium, zirconium, hafnium a third metal of a group consisting of vanadium and a mixture thereof, wherein the third metal is present in a doping amount; the limiting condition is: when the third metal is zirconium, the doping amount is less than 0.01% by weight or More than 丨% by weight. 2. φ 3. 4. 5. 6. 7. The alloy of claim 1, wherein the third metal is selected from the group consisting of nickel, chromium, condensate, feed, vanadium, and mixtures thereof. The alloy of claim 1, wherein the doping amount is less than 〇 01% by weight. The alloy of claim 1, wherein the doping amount is greater than 1 weight 〇/〇. The alloy of claim 2, wherein the doping amount is less than 〇〇1% by weight. An alloy such as β, wherein the doping amount is greater than 丨% by weight. For example, the alloy of Item 2, wherein the doping amount is from 重量1% by weight to 重量%. 8. The alloy of claim 1, wherein the amount of the alloy is from 5% by weight to 5% by weight. _ 9. * The alloy of claim 2, wherein the amount of the alloy is from 5% by weight to 1% by weight. 10. A sputter target comprising a densified alloy as claimed. 11. A sputtering target comprising the densified alloy of claim 2. 12. A method comprising: (a) providing a blend comprising: a molybdenum powder present in a plurality of knives, a bismuth powder present in an alloy amount, and selected from the group consisting of chromium and rhenium a third metal powder of zirconium, zirconium, feed, hunger and a mixture thereof, wherein the third metal is stored as a doping amount 139600.doc 201006938 in the 'restricted condition is · · when the third gold (four) The secret amount is less than 0.01% by weight or more than 1% by weight; and (b) the composition is subjected to heat and pressure to form a densified sputtering target. 13. A method comprising: (4) providing a ruthenium bond material comprising a densified alloy, the densified alloy comprising: (1) being present in a majority; (8) being present in an alloy amount; and (iv) being selected a third metal of a group consisting of nickel, chromium, titanium, erbium, strontium, hunger and a mixture thereof, wherein the third metal is present in a doping amount; (b) providing a substrate; and (4) making the stem The material is subjected to splashing conditions to form a coating of the material of the sister material on the substrate. 14. a method comprising: (4) providing a sputtering target as claimed in claim 1; (8) providing a substrate; and (4) subjecting the dry material to (10) conditions to form one of the target materials formed on the substrate coating. A film device comprising a substrate and a film disposed above the substrate and prepared according to the method of claim 13. 16. A film device comprising: a substrate and a film disposed over the substrate and prepared according to the method of claim M. 17. 18. 19. The film device of claim 15, wherein the substrate is transparent. The film device of claim 17, wherein the transparent substrate comprises glass and the film device is a flat panel display. The thin (four) of claim 15 wherein the substrate comprises one or more selected from the group consisting of glass, polymer, and combinations thereof and the film is a solar cell. 20. The film device of claim 16, wherein the substrate is transparent 〇 600 600 600 600 600 600 600 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如 如The steel, polymer and combinations thereof are placed in a solar cell. The transparent substrate comprises glass and the substrate comprises one or more selected from the group consisting of glass, and the film device of claim 15, wherein the substrate comprises ruthenium. 24. The film device of claim 16, wherein the substrate comprises ruthenium. ❹ 139600.doc