JP5203908B2 - Ni-Mo alloy sputtering target plate - Google Patents

Description

  The present invention relates to a Ni—Mo alloy material, and more particularly, to a Ni—Mo alloy sputtering target plate used when a Ni—Mo alloy thin film is applied to a plate-like substrate by sputtering film formation.

  For example, since the organic EL display element is a current-driven display that emits light by passing a current through each pixel made of an organic EL material, a larger current flows through the electrodes during driving as compared to a voltage-driven LCD or the like. For this reason, low electrical resistance Al or Al alloy is often used as a wiring material in the organic EL display element. However, Al or Al alloy tends to generate hillocks, which is a phenomenon that rises when aluminum growth parts collide with each other, and Al oxide is easily formed on the surface. In addition, even when trying to make electrical contact with other metals, the contact resistance is large and it is difficult to use as it is.

  Furthermore, a low resistance wiring technique is required between the cathode in each pixel of the organic EL display element and the connection terminal for connecting to the signal matrix wiring to suppress a voltage increase due to a large current. . In general, an auxiliary wiring is provided between the cathode and the connection terminal, and a structure is introduced in which current flows to the connection terminal via the auxiliary wiring.

  Patent Document 1 discloses an invention of a liquid crystal display device and a method for manufacturing the same, and is Mo or Mo alloy (alloy of Cr, Ti, Ta, Zr, Hf or V and Mo) and Al or Al alloy. A method of covering (capping) the wiring is described. In the case of a combination of Mo and Al, a pattern of Al and Mo can be formed in a lump in a photolithography process for forming a display panel.

  In general, Mo has low moisture resistance and is easily corroded by moisture in the air. Therefore, when Mo is used as a wiring material for FPD (Flat Panel Display), there is a problem that wiring tends to deteriorate. Therefore, Patent Document 2 describes a technique of using a transparent electrode material for the drive circuit and the connection terminal in the invention of the organic EL element, and integrating the cathode material and the auxiliary wiring material. As a result, there is no connection between the cathode material and the auxiliary wiring material, and the cathode surface or auxiliary wiring surface, which is the connection location, is not oxidized, so that there is no problem of contact resistance between the cathode and the auxiliary wiring. .

  Patent Document 3 discloses a technique for reducing the contact resistance between the cathode and the auxiliary wiring in the invention of the organic EL display device and the manufacturing method thereof, and the auxiliary wiring has a two-layer structure of a base pattern and an electrode pattern. And divided into two. It is said that contact characteristics with low resistance can be obtained by using TiN or Cr for the base pattern and Al for the electrode pattern to make contact with the cathode Al.

  In the method described in Patent Document 3, two photolithography processes are required to form the auxiliary wiring. In addition, in order to use TiN as a wiring material, it is necessary to apply dry etching for patterning, which causes a problem in productivity. Therefore, Patent Document 4 discloses an appropriate combination of auxiliary wirings using Al or an Al alloy as a wiring material and a Ni-Mo alloy as a cap metal. The Ni—Mo based alloy layer can be etched at approximately the same rate with the same etching solution as the Al electrode layer. Furthermore, since the Ni-Mo alloy layer is excellent in moisture resistance, the cap layer maintains the low resistance of the wiring and suppresses the generation of an Al oxide layer on the surface of the Al-based metal layer. It has a function to prevent an increase in contact resistance. In Patent Document 4, the Ni content of the Ni—Mo alloy layer is preferably 20 to 90% by mass with respect to all components, or the Mo content is preferably 10 to 80% by mass with respect to all components. There is a statement to that effect.

By the way, as for a method for producing a Ni-Mo alloy sputtering target, a technique is disclosed in which metal Ni and metal Mo as raw materials are melted and cast in a high-frequency melting furnace, then forged and rolled, and then cut into a desired target shape. It is disclosed in Document 5. Patent Document 6 discloses a technique for producing a sputtering target containing a trace amount (50 ppm to 1000 ppm) of a metal such as Ni in Mo by a hot isostatic press (HIP) method.
Japanese Patent Application Laid-Open No. 2001-311954 JP 11-317292 A JP 11-329750 A JP 2004-158442 A JP 2000-169922 A JP 2005-154814 A

  By the way, in order to obtain a Ni—Mo alloy film for wiring, a sputtering film is formed on a substrate surface using a Ni—Mo alloy target plate produced by melting (casting + machining) or the like. Conventionally, it has been known as a problem that the number of particles containing Ni-Mo in the chamber of the sputtering apparatus increases remarkably with increasing time. The generation of particles not only induces abnormal discharge during sputtering and lowers the film formation efficiency, but also causes a problem that the particles adhere to the Ni—Mo alloy thin film and the quality of the thin film decreases.

  In view of the above problems, the present invention provides a Ni—Mo based alloy target plate containing about 20% of Ni and about 10% or more of Mo for producing a Ni—Mo alloy film for FPD wiring or the like. In the used sputtering, it aims at providing the technique which can suppress generation | occurrence | production of the particle | grains containing Ni-Mo accompanying the increase in sputtering time.

In the case of performing sputtering film formation with a Ni—Mo based alloy target plate, the present inventors are concerned with the problem that the number of particles increases with an increase in sputtering time, and Ni and Mo elements in the thickness direction of the target material. It was found that this problem can be solved by adjusting the concentration distribution. The gist of the present invention is shown below.
(1) A sputtering target plate of a Ni-Mo alloy composed of Ni, Mo and unavoidable impurity elements,
The Ni concentration and the Mo concentration at a position of 10 μm in the thickness direction from the surface of the surface of the sputtering target plate are Ni (10) and Mo (10) in mass%, respectively, and the Ni at a position of 100 μm from the surface in the thickness direction. A Ni—Mo-based sputtering target plate characterized by satisfying the relationship of the following formula, with Ni and M concentration being 100% by mass and Mo (100), respectively.

−2.0 ≦ ΔNi ≦ 0.2
−0.2 ≦ ΔMo ≦ 2.0
and,
−0.2 ≦ ΔNi + ΔMo ≦ 0.2
Here, ΔNi = Ni (10) −Ni (100)
ΔMo = Mo (10) −Mo (100)
(2) The Ni—Mo based alloy sputtering target plate according to (1) above, wherein the Ni concentration is 20 mass% or more and the Mo concentration is 10 mass% or more.
(3) In the sputtering target plate of the Ni—Mo alloy according to (2) above, further, groups IVa, Va, VIIa, VIII, Ib, IIb, IIIb, IVb of the periodic table Ni-Mo type alloy sputtering target board which has 1 type or multiple types of metal elements except Ni among them by the sum total with an average density of 0.2 mass% or more and 15 mass% or less.

(4) One or a plurality of metal elements other than Ni among the groups IVa, Va, VIIa, VIII, Ib, IIb, IIIb, and IVb are Ti, V, Fe 2 , Ta The sputtering target plate of a Ni—Mo alloy according to (3), wherein the sputtering target plate is one or a plurality of metal elements of Zr, Zr, and Hf.

  (5) The sputtering target plate according to any one of (1) to (4) above, wherein the Ni—Mo alloy sputtering target plate satisfies the relationship of the following formula.

−0.2 ≦ ΔNi ≦ 0.2
−0.2 ≦ ΔMo ≦ 0.2

  According to the Ni—Mo based alloy sputtering target plate of the present invention, the changes in the Ni concentration and the Mo concentration in the vicinity of the surface of the target plate are made smaller than before, so that the generation of particles in the sputtering process is suppressed, and as a result. , Abnormal discharge is eliminated and the efficiency of sputtering work is improved. Furthermore, since the adhesion of particles is drastically reduced in the thin film formed by film formation, a very high quality Ni—Mo alloy thin film can be obtained.

  Below, embodiment of the Ni-Mo type alloy sputtering target board of this invention is described in detail using figures.

In film formation by sputtering, as is well known, Ar, which is a normal atmospheric gas, is ionized under reduced pressure to become Ar ⁺ ions, which collide with the Ni—Mo-based target plate surface, which is one of the electrodes, to form Ni and Mo atoms. Are sputtered and eroded, and the atoms are deposited on the substrate surface placed opposite to the Ni—Mo alloy sputtering target plate to form a film. For example, in a planar type magnetron sputtering apparatus, an erosion portion where sputtering is remarkable on the Ni—Mo alloy sputtering target plate surface due to non-uniform distribution of the magnetic field applied to the Ni—Mo alloy sputtering target plate, etc. Non-erosion part that is not done.

  The present inventors have peeled off the Ni—Mo oxide deposited on the non-erosion portion of the target plate surface by Ar ions generated during sputtering of the Ni—Mo alloy sputtering target plate (hereinafter also simply referred to as “target plate”). It was thought that reducing this separation is effective in suppressing the generation of particles. Therefore, first, the present inventor made a detailed study and estimated the cause of the Ni—Mo oxide peeling as follows. Note that the Ni—Mo oxide is considered to be generated when the sputtered Ni and Mo atoms condense and combine with a trace amount of oxygen in the chamber of the sputtering apparatus.

  The knowledge that the main places where the Ni—Mo oxide deposited on the target plate surface peels is concentrated in the non-erosion portion adjacent to the erosion portion was obtained by a sputtering film formation experiment. FIG. 1 schematically shows a state near the boundary between the non-erosion part 2 and the erosion part 3 in a cross section perpendicular to the target plate surface. Ni—Mo oxide 4 is deposited on the non-erosion portion 2, the erosion portion 3 is hollowed by erosion of Ni—Mo atoms on the target plate 1 by sputtering, and the Ni—Mo oxide 4 is deposited. Absent. The end portion 5 of the deposited Ni—Mo oxide is located at the boundary between the non-erosion portion 3 and the erosion portion 2. In FIG. 1, the end portion 5 is indicated by a circle drawn with a broken line.

  In the vicinity of the surface of the target plate before sputtering, which is prepared by melting or firing a raw material metal to produce a Ni-Mo-based alloy molded body and then flattened by machining, the thickness direction (depth direction is determined). Ni and Mo concentrations at 10 μm and 100 μm locations were measured by GDS (glow discharge emission spectroscopic analyzer). When the measured values at each location were compared, it was found that the Ni concentration of 10 μm decreased compared to the concentration of 100 μm, and conversely, the Mo concentration of 10 μm increased compared to the concentration of 100 μm.

  If the non-erosion portion 3 has such a Ni and Mo concentration distribution, the non-erosion portion 2 and the surface layer portion are removed by sputtering, and there is no concentration distribution except for a portion adjacent to the non-erosion portion 2. It has been found that mechanical failure of the Ni—Mo oxide occurs near the end portion 5 of the Ni—Mo oxide in the vicinity of the boundary with the erosion portion 3, and peeling frequently occurs. By repeating this deposition and peeling during sputtering, particles are generated intermittently.

That is, when the Ni and Mo concentrations near the surface of the target plate have the above characteristics, the reason why the Ni—Mo oxide is easily peeled is estimated as follows. An erosion portion 3 eroded by sputtering exists at a position adjacent to the end portion 5 of the Ni—Mo oxide. In the surface region of the portion of the erosion portion 3 adjacent to the non-erosion portion 2 in the vicinity of the end portion 5 of the Ni—Mo oxide, portions where the Ni concentration and the Mo concentration are different in the thickness direction are exposed. Since each part in the surface region has a different thermal expansion coefficient and thermal conductivity, a thermal strain difference is generated due to heat generated by collision of Ar ⁺ ions during sputtering. This thermal strain is applied as stress to the end portion 5 of the Ni—Mo oxide and is estimated to be sufficient to destroy the oxide during sputtering.

  The concentration distribution of Ni and Mo in the thickness direction of the Ni is generated at the time of manufacturing the Ni-Mo target plate as described above, and cutting and polishing for forming a necessary planar shape on the target plate. If you do, it will always occur. This is caused not only by frictional heat during cutting and polishing, but also by residual strain energy accompanying plastic deformation, and it is thought that Ni and Mo atoms move to the above distribution in order to balance with these energies. ing.

  Based on the detailed examination results as described above, the inventors of the present invention, as a technique for suppressing the exfoliation of the Ni—Mo oxide deposited on the non-erosion part, in the thickness direction of the Ni and Mo elements near the surface of the target plate. It was concluded that it is effective to control the Ni concentration and Mo concentration to be as constant as possible by controlling the concentration distribution in the range. If it can be controlled within the concentration distribution range of the present invention, the distortion generated between the deposited oxide and the target material is reduced, and the exfoliation of the oxide is remarkably suppressed.

  The inventors made a number of Ni—Mo alloy sputtering targets and performed sputtering experiments using the targets, and studied the concentration distribution of Ni and Mo, which makes it difficult for oxides to peel off. The results are shown below.

<Sputtering target plate of Ni-Mo alloy>
Ni (10) and Mo (10) are expressed as Ni (10) and Mo (10), respectively, in terms of mass% at a position of 10 μm from the surface in the thickness direction. (100). Further, ΔNi = Ni (10) −Ni (100) and ΔMo = Mo (10) −Mo (100).

  If controlled so that −2.0 mass% ≦ ΔNi ≦ 0.2 mass% and −0.2 mass% ≦ ΔMo ≦ 2.0 mass% and −0.2 ≦ ΔNi + ΔMo ≦ 0.2, It has been found that peeling of the Ni—Mo oxide deposited on the non-erosion part can be reduced. If it is the said invention range, adhesion to the thin film of a particle can be suppressed without having a big influence on the component density | concentration of the thin film produced by sputtering, and also abnormal discharge prevention during sputtering. The thin film quality can be improved. A sufficient effect can also be obtained by the above numerical range, but preferably -1.9 mass% ≤ΔNi≤0.11 mass%, 0 mass% ≤ΔMo≤1.9 mass%, -0.2≤ ΔNi + ΔMo ≦ 0.16.

  In the target plate, the region having the element concentration distribution remains below the sputtering surface of the non-erosion portion, and can be confirmed by a method of measuring the element concentration distribution in the target depth direction near the surface, such as GDS. Further, the present inventors have confirmed that the effect of the present invention is exhibited even when the erosion part has a slight depth of about several μm at the initial stage of sputtering.

  Hereinafter, the reason for limitation of the present invention will be described in detail.

  In order to apply a Ni-Mo type alloy compact manufactured by a melting method or a powder metallurgy method, which will be described later, to a sputtering target plate, the surface is always processed into a smooth plane. At this time, although cutting and polishing are performed, the above-described ΔNi is less than −2.0 mass% and ΔMo is more than 2.0 mass% regardless of any conventional method. In this region, the larger the absolute value of each region, the easier the oxide peeling occurred. The present inventors have found that by performing heat treatment at an appropriate temperature after cutting and polishing, the absolute values of ΔNi and ΔMo can be reduced, and as a result, oxide peeling can be suppressed.

  When ΔNi is less than −2.0 mass% or ΔMo is more than 2.0 mass%, the Ni—Mo oxide 4 deposited on the non-erosion part 2 during sputtering becomes easy to peel off, and the particles Increases significantly. Therefore, ΔNi is −2.0% by mass or more. ΔMo was set to 2.0% by mass or less. Further, it is desirable that the absolute values of ΔNi and ΔMo are small, and more preferable ranges are ΔNi of −0.2 mass% or more and ΔMo of 0.2 mass% or less.

  On the other hand, it is difficult to control to a combination in which ΔNi is positive and ΔMo is negative in production, and ΔNi is more than 0.2% by mass and ΔMo is less than −0.2% by mass. Therefore, ΔNi is 0.2% by mass or less, and ΔMo is −0.2% by mass or more.

  Next, there is a subordinate relationship between ΔNi and ΔMo, and the sum of both is limited to −0.2 mass% or more and 0.2 mass% or less. Concentration distributions outside this range are limited to this range because it is difficult to achieve with the manufacturing method shown in the present invention.

  Next, if the average concentration of Ni is less than 20% by mass or the average concentration of Mo exceeds 80% by mass, the resulting thin film will not have sufficient moisture resistance. For this reason, the average concentration of Ni is preferably 20% by mass or more, and the average concentration of Mo is 80% by mass or less. Furthermore, if the average concentration of Ni exceeds 90% by mass or the average concentration of Mo is less than 10% by mass, the etching rate by the etching solution is slowed down. Therefore, the average concentration of Ni is 90% by mass or less, and the average concentration of Mo is 10% by mass or more. Here, the average concentration means an average value of Ni or Mo concentration in the thickness direction from one or both surfaces of the target plate to a predetermined depth. And the predetermined depth should just be larger than the depth by which erosion is carried out by sputtering. For example, a target plate having a thickness of 5 mm may be about 1 mm or more, or 5 mm (whole). Wet chemical analysis may be used to measure the average concentration. Alternatively, the average concentration may be derived by measuring the distribution of Ni and Mo in the thickness direction of the target plate by GDS.

  The Ni—Mo based alloy sputtering target plate of the present invention further includes a metal element of any of groups IVa, Va, VIIa, VIII, Ib, IIb, IIIb, IIIb and IVb of the periodic table. In some cases, at least one or more elements (except for Ni and Mo) are contained to further improve etching properties and corrosion resistance. A desirable content of each of these elements is 0.2% by mass or more and 15% by mass or less. If it is less than 0.2% by mass, the effect of improving the etching property and corrosion resistance is small. If it exceeds 15% by mass, the toughness of the Ni—Mo-based target is reduced and troubles such as cracking during use increase. Therefore, it was set as said range. Examples of these elements include Fe, Ti, Cr, V, Zr, and Hf, as well as Mn, Co, Pd, Pt, Cu, Ag, Au, Zn, Al, Ga, and Si.

Among these metal elements, when at least one element of Fe, Ti, Cr, V, Zr, Ta, and Hf is contained, etching properties and corrosion resistance are remarkably improved. A desirable content of each of these elements is 0.2% by mass or more and 15% by mass or less in total. If it is less than 0.2% by mass, the effect of improving the etching property and corrosion resistance is small. If it exceeds 15% by mass, the toughness of the Ni—Mo alloy target will decrease and the troubles such as cracking during use will increase. Therefore, it was set as said range.
<The manufacturing method of a Ni-Mo type alloy sputtering target board>
The above-described method for producing the Ni—Mo alloy sputtering target plate of the present invention includes a step of producing a Ni—Mo alloy molded body using a melting method, a powder metallurgy method, and the like, and a Ni—Mo alloy molded article. It consists of a step of cutting the surface by machining to make it flat and plate-like, and a step of heat-treating the plate-like Ni-Mo alloy compact. Furthermore, the process of removing the oxide layer formed in the outermost surface by heat processing by grinding | polishing etc. is also included. Details of this production method are described below.

  A first method for producing a Ni-Mo alloy compact is a melting method. For example, a raw material containing Ni and Mo is melted and cast in a high-frequency melting furnace. Thereafter, a target material having a desired thickness is obtained by forging or rolling.

  In addition, the process of producing a Ni-Mo alloy compact can be performed by melting, but it is known that it can be applied to sintering of Mo having a high melting point and other high melting point metals. A method of pressure sintering the raw metal powder by a press (hereinafter referred to as “HIP”) method is efficient. Raw material Ni powder, Mo powder, and other additive metal element powders to be used as sputtering target materials are vacuum-sealed in a capsule container for HIP made of SS400 steel plate having a thickness of about 3 mm, and the firing temperature is 600 ° C. or higher. Pressure sintering is performed with HIP under the conditions of 1300 ° C. or less and a pressure of 1000 to 2000 atm. As the firing temperature, an appropriate temperature is selected depending on the metal or alloy. For example, the firing temperature can be a Tamman temperature calculated from the melting point or a range of 100 ° C. before and after the Tamman temperature.

  Thus, the relative density of the pressure sintered body obtained by HIP is 95% or more and 100% or less. Here, it is desirable that the raw metal powder has a size of about 0.1 μm to 50 μm. For example, a powder having an average particle diameter of 6 μm is used. These powders are charged into the HIP container. However, if the powder is temporarily formed by pressing or cold isostatic pressing before being charged into the container, more efficient work can be performed.

  In addition to the compact manufacturing method by HIP, a compact made by consolidating the raw metal powder by CIP (cold isostatic pressing) in a reducing atmosphere in which hydrogen is allowed to flow in a container at normal pressure or reduced pressure is used. It is possible to produce a Ni-Mo-based molded body even if it is sintered. In the sintering process, the average hydrogen concentration in the container is preferably 0.5% or more and 20% or less. The oxygen concentration contained in the Ni—Mo based alloy compact can be controlled by the hydrogen flow rate. The sintering temperature is preferably about 500 to 1800 ° C.

  Further, before performing the sintering at the above-described HIP or normal pressure, the sintered body is controlled by adhering (adsorbing) a desired amount of oxygen in the state of the raw metal powder or the state of the temporary molded body. In addition, it is possible to leave oxygen at an equivalent oxygen concentration. Specifically, when the residual oxygen concentration is less than 10 ppm by mass, the raw metal powder or the temporary molded body is heated to about 200 ° C. to 500 ° C. in the atmosphere to adsorb (oxidize) oxygen. When the oxygen concentration is higher than 1000 ppm by mass, the source metal powder or the temporary molded body may be heated to about 200 ° C. to 500 ° C. in a hydrogen atmosphere to reduce and desorb oxygen.

  The Ni-Mo-based alloy molded body obtained in the process of manufacturing the Ni-Mo-based alloy molded body described above includes a step of flattening the subsequent surface by machining to form a plate shape, The Ni-Mo-based sputtering target plate is finished by a process of heat-treating the compact. By sequentially performing these series of steps, the concentration distribution of Ni and Mo elements in the thickness direction can be adjusted within the scope of the present invention from the surface to the inside of the plate-like Ni—Mo alloy compact. it can. As a result, the Ni and Mo-based alloy sputtering target material of the present invention can be manufactured.

  Examples of the flattening by the machine include known metal material processing methods such as cutting using a milling machine and grinding using a surface grinder. By passing through this step, a plane necessary for the sputtering plate can be obtained, but on the other hand, the distribution of Ni and Mo elements is biased.

  On the other hand, the most important part of the present invention is to flatten the uneven Ni and Mo concentration distribution by performing heat treatment in the next step. When heat treatment is applied, residual strain generated near the surface of the Ni-Mo molded body by machining is released, and at the same time, Ni and Mo elements move during the heat treatment so as to balance the energy with respect to this release. As a result, it is considered that the respective concentrations are flattened.

  The range of the heat treatment temperature in the heat treatment step for obtaining the desired Ni and Mo concentration distribution is desirably 600 ° C. or higher and 1200 ° C. or lower. When the residual stress is applied at a temperature lower than 600 ° C., the Ni and Mo concentration distributions are not rearranged, and the Ni and Mo concentration distributions of the Ni—Mo alloy sputtering target plate of the present invention cannot be obtained. When the temperature exceeds 1200 ° C., rearrangement of Ni and Mo concentration distribution occurs, but coarsening of crystal grains occurs. Therefore, the temperature range in the heat treatment step is set to 600 ° C. or more and 1200 ° C. or less.

  It is not desirable that the surface be oxidized or nitrided during the heat treatment, and the atmosphere may be, for example, a vacuum or an inert gas such as Ar or nitrogen. When heat treatment is performed, an extremely thin oxide or nitride may be formed on the outermost surface even in the above atmosphere. Therefore, if necessary, the thin oxide or nitride is stripped off by extremely slight polishing. Here, if a cutting method using a milling machine or the like is applied to this treatment, care must be taken because the concentration distribution of Ni and Mo that has been adjusted may be broken. Therefore, light polishing using scotch bright or emery paper is preferred in this step.

  In addition, the method of removing the deteriorated layer by a method such as chemical polishing after the flattening process by the machine is also included in the present invention, but industrially because minute irregularities are generated on the surface or the processing takes time. Is not an advantageous method.

Hereinafter, the present invention will be described in more detail with reference to examples.
Example 1
Ni—Mo—Fe alloy powder was produced by the atomization method. The average particle diameter of the alloy powder determined by the line segment method is 6 μm, and the components are component system (i) 81.5 mass% Ni-15.4 mass% Mo-3.1 mass% Fe, component system (ii) 72.4 mass% Ni-24.6 mass% Mo-3.0 mass% Fe, component system (iii) 64.5 mass% Ni-32.3 mass% Mo-3.1 mass% Fe there were.

A SS400 HIP container (inner dimensions: thickness 55 mm × width 400 mm × length 780 mm) having a thickness of 2.5 mm was prepared and filled with the powder. After the inside of the HIP container was evacuated with a rotary pump and an oil diffusion pump, the inside of the HIP container was further evacuated while being heated to 300 ° C. After the degree of vacuum reached about 10 ⁻² Pa, the suction port and the like were sealed with care not to cause pinholes to leak. Then, it hold | maintained for 1180 degreeC * 3 hours, and gave the HIP sintering process on 1000 atmospheres conditions, and obtained the Ni-Mo-Fe type alloy compact. The SS400 iron skin was peeled off from the surface of the obtained specimen to obtain a Ni-Mo alloy molded body. The molded body was cut and then flattened by cutting with a milling machine. The external dimensions of the molded body at this time were 10 mm thick × 150 mm wide × 600 mm long.

  Next, an alloy molded body having the component system (iv) 76.6% by mass, Ni-15.4% by mass, Mo-8.0% by mass Fe was manufactured by a melting method. First, Ni, Mo, and Fe raw materials were melted by high-frequency heating in a vacuum, and then cast into a mold to obtain an alloy compact. Thereafter, the alloy compact was heated to 1000 ° C. and hot-rolled. The total rolling reduction during hot rolling was 60%. The surface of the obtained specimen was flattened by cutting a thickness of 1.2 mm with a milling machine. Thus, the outer dimensions of the obtained alloy compact were 10 mm thick × 150 mm wide × 600 mm long.

  After the above production, planarization, heat treatment, and finishing were performed to finish the target plate. Table 1 shows the details of the manufacturing conditions and evaluation results of each example.

  The element concentration distribution of Ni and Mo in the thickness direction from the surface to the inside of the Ni—Mo based sputtering target plate obtained as described above was measured using a GDS (Glow Discharge Emission Spectrometer). The apparatus used was JY5000RF-PSS manufactured by JOBIN YVON. While removing from the surface to 150 μm in the thickness direction by sputtering, the concentration distribution of each element of Ni, Mo, and Fe in the thickness direction was measured.

  The obtained Ni—Mo based sputtering target plate was bonded to a Cu backing plate to obtain a sputtering target electrode. Using this sputtering target electrode, the abnormal discharge performance during sputtering was evaluated.

The sputtering conditions were as follows. Sputtering gas: Ar, sputtering gas pressure: 0.27 Pa, sputtering power: 2.0 kW, deposition substrate: Corning # 7059 (50 × 50 mm ² ). Further, pre-sputtering was performed for 10 min under the conditions of Ar gas pressure 0.67 Pa and sputtering power 2.0 kW when measuring the film forming rate.

  In order to evaluate the discharge stability during sputtering, the sputtering target was mounted on a sputtering apparatus, and the abnormal discharge characteristics were evaluated. The discharge conditions were sputtering gas: Ar, sputtering gas pressure: 0.27 Pa, sputtering power: 2.0 kW, continuous discharge until the integrated sputtering power reached 5 kWh, and the number of abnormal discharges generated during that time was measured. For abnormal discharge, a coil was directly wound around a DC power supply cable for sputtering discharge to form a CT probe, and an abnormal discharge was detected by observing a pulse signal induced in the probe with an oscilloscope. If there is no abnormal discharge at all, it is evaluated as “Excellent” as “Excellent”, evaluated as “Excellent” when the number of occurrences is 2 times or less, and evaluated as “Poor” when it exceeds 2 times. did.

  In Table 1, the test piece No. 1 to 11 when the component system is (i) and a Ni—Mo target plate is manufactured (molded body manufacturing step), Ni and Mo concentration distribution in the target plate, and abnormal discharge characteristics during sputtering showed that. In either case, the compact was produced by sintering powder produced by atomization with HIP at high temperature and high pressure. As the planarization treatment, test piece No. Nos. 1 to 5 use both milling and surface grinding before heat treatment, and test pieces No. Nos. 6 to 10 are only milling cutters, test pieces No. No flattening treatment was performed before heat treatment. As the heat treatment, test piece No. No. 1 was performed, and the test piece No. 2 and 6 were performed at 400 ° C., and the others were performed at 600 to 1200 ° C.

  In the finishing process after the heat treatment, the test piece No. Nos. 1 to 5 were polished by Scotch Bright manufactured by Sumitomo 3M. Specimen No. 6 to 10 were subjected to scotch bright polishing after surface grinding. Specimen No. No. 11 was subjected to scotch bright polishing after milling and surface grinding.

  When the concentration distribution of Ni and Mo was measured by GDS for the obtained target plate, the test piece No. ΔNi and ΔMo of 1, 2, 6, 11 were out of the range defined in the present invention. When sputtering film formation was performed using these target plates, many particles were generated on these target plates. Abnormal discharge occurred frequently. When the non-erosion portion was observed after the evaluation, it was confirmed that the deposited Ni—Mo-based oxide was partially peeled and scattered during sputtering as Ni—Mo-based oxide particles.

  For the other test pieces, ΔNi and ΔMo were within the range defined by the present invention. The results of evaluation by sputtering film formation are as follows. In 3, 7, and 8, abnormal discharge hardly occurred twice or less. Further, no abnormal discharge was observed in other test pieces.

  Next, test piece No. 12 to 17, the process when the Ni-Mo target plate was manufactured with the component system as (iv) above, the concentration distribution of Ni and Mo in the target plate, and the abnormal discharge characteristics during sputtering were shown. In either case, the molded body was produced by a dissolution method. As the planarization treatment, both milling and surface grinding were used before the heat treatment. As the heat treatment, test piece No. No. 12 was not performed, and the test piece No. 13 was performed at 500 ° C., and the others were performed at 700 to 1300 ° C. In the finishing process after the heat treatment, polishing was performed with Scotch Bright manufactured by Sumitomo 3M.

  When the concentration distribution of Ni and Mo was measured by GDS for the obtained target plate, the test piece No. The ΔNi and ΔMo of 12, 13 were outside the range defined by the present invention. When sputtering film formation was performed using these target plates, many particles were generated on these target plates. Abnormal discharge occurred frequently. When the non-erosion portion was observed after the evaluation, it was confirmed that the deposited Ni—Mo-based oxide was partially peeled and scattered during sputtering as Ni—Mo-based oxide particles.

  For the other test pieces, ΔNi and ΔMo were within the range defined by the present invention. The results of evaluation by sputtering film formation are as follows. In 14 and 15, abnormal discharge hardly occurred at 2 times or less. Further, no abnormal discharge was observed in other test pieces.

  Next, test piece No. 18 to 22 show the steps when manufacturing the Ni—Mo target plate with the component system as (ii) above, the concentration distribution of Ni and Mo on the target plate, and the abnormal discharge characteristics during sputtering. In either case, the compact was produced by sintering powder produced by atomization with HIP at high temperature and high pressure. As the planarization treatment, both milling and surface grinding were used before the heat treatment. As the heat treatment, test piece No. 18 was not performed, and the others were performed at 700 to 1300 ° C. In the finishing process after the heat treatment, polishing was performed with Scotch Bright manufactured by Sumitomo 3M.

  When the concentration distribution of Ni and Mo was measured by GDS for the obtained target plate, the test piece No. 18 ΔNi and ΔMo were outside the range defined in the present invention. When sputtering film formation was performed using these target plates, many particles were generated on these target plates. Abnormal discharge occurred frequently. When the non-erosion portion was observed after the evaluation, it was confirmed that the deposited Ni—Mo-based oxide was partially peeled and scattered during sputtering as Ni—Mo-based oxide particles.

  For the other test pieces, ΔNi and ΔMo were within the range defined by the present invention. The results of evaluation by sputtering film formation are as follows. In 19 and 20, abnormal discharge hardly occurred twice or less. Further, no abnormal discharge was observed in other test pieces.

  Next, test piece No. 23 to 27 show the steps when the Ni-Mo target plate was manufactured with the component system as (iii) above, the concentration distribution of Ni and Mo in the target plate, and the abnormal discharge characteristics during sputtering. In either case, the compact was produced by sintering powder produced by atomization with HIP at high temperature and high pressure. As the planarization treatment, both milling and surface grinding were used before the heat treatment. As the heat treatment, test piece No. 23 was not performed, and the others were performed at 750 to 1350 ° C. In the finishing process after the heat treatment, emery paper (# 600) polishing was performed.

  When the concentration distribution of Ni and Mo was measured by GDS for the obtained target plate, the test piece No. 23 of ΔNi and ΔMo were out of the range defined in the present invention. When sputtering film formation was performed using these target plates, many particles were generated on these target plates. Abnormal discharge occurred frequently. When the non-erosion portion was observed after the evaluation, it was confirmed that the deposited Ni—Mo-based oxide was partially peeled and scattered during sputtering as Ni—Mo-based oxide particles.

  The etching property and corrosion resistance of the thin film formed by sputtering were at a high level by adding Group VIII Fe to the Ni—Mo system component system.

  For other examples, ΔNi and ΔMo were within the range defined by the present invention. The results of evaluation by sputtering film formation are as follows. In 24 and 25, abnormal discharge hardly occurred twice or less. Further, no abnormal discharge was observed in other test pieces.

  As described above, it was confirmed that the Ni—Mo alloy sputtering target plate of the present invention hardly generated abnormal discharge during sputtering, and that efficient sputtering film formation was possible.

(Example 2)
Ni-Mo series powder was manufactured by the atomizing method. The average particle size of the powder was 6 μm, and the component system is shown in Table 2. An SS400 HIP container (inner dimensions: thickness 55 mm × width 400 mm × length 780 mm) with a thickness of 2.5 mm was prepared and filled with the powder. The inside of the container was evacuated with a rotary pump and an oil diffusion pump, and then heated to 500 ° C. to continue evacuation. After the degree of vacuum reached about 10 ⁻² Pa, the suction port was sealed with care not to cause pinholes to leak. After this. The HIP sintering process was performed at 1000 atm under various temperature and time conditions. The SS400 iron skin was peeled off from the surface of the obtained specimen and planarized with a milling machine. The dimensions at this time were 10 mm thick × 150 mm wide × 600 mm long.

  After the above production, planarization, heat treatment, and finishing were performed to finish the target plate. Table 2 shows details of the manufacturing conditions and evaluation results of each example. Here, the bonding conditions, the Ni and Mo element concentration distribution evaluation of the target plate, and the abnormal discharge evaluation method during sputtering are the same as those performed in the first embodiment.

  Specimen No. 28 to 33, the steps when manufacturing a target plate with Ni and Mo binary system as component system and changing their ratio, concentration distribution of Ni and Mo on the target plate, and abnormal discharge characteristics during sputtering Indicated. In either case, the compact was produced by sintering powder produced by atomization under high temperature and high pressure under HIP conditions of 1100 ° C. × 4 hr. The planarization treatment was performed using both milling and surface grinding before heat treatment. The heat treatment was performed at 1000 ° C. × 1 hr. The finishing process after the heat treatment was polished by Scotch Bright.

  When the Ni and Mo concentration distributions of the obtained target plate were measured by GDS, ΔNi and ΔMo were within the range defined by the present invention. The results of evaluation by sputtering film formation are as follows. In the inventive examples 28 to 33, no abnormal discharge was observed.

  The corrosion resistance of the thin film formed by sputtering was examined. Although it was apt to be slightly corroded in the 28 invention examples, it was a characteristic that the other test pieces were not easily corroded.

  Further, when the etching property of the thin film formed by sputtering was examined, the test piece No. In the 33 invention examples, the etching rate tended to be slightly low, but the etching rate was normal in the other test pieces.

  Specimen No. When a target plate is manufactured in a component system in which Ni, Mo are added to Group VIIa Mn, Group Ib Cu, Group IIb Zn, Group IIIb Al, Group IVb Si This shows the Ni, Mo concentration distribution in the target plate and the abnormal discharge characteristics during sputtering. In either case, the compact was produced by sintering powder produced by atomization under high temperature and high pressure under HIP conditions of 950 ° C. × 8 hours. The planarization treatment was performed using both milling and surface grinding before heat treatment. The heat treatment was performed at 1000 ° C. × 1 hr. The finishing process after the heat treatment was polished by Scotch Bright.

  When the Ni and Mo concentration distributions of the obtained target plate were measured by GDS, ΔNi and ΔMo were within the range defined by the present invention. The results of evaluation by sputtering film formation are as follows. In the inventive examples 34 to 38, no abnormal discharge was observed.

  The corrosion resistance of the thin film formed by sputtering was examined. In Examples 34 to 38, the corrosion resistance did not occur at all. Further, when the etching property of the thin film formed by sputtering was examined, the test piece No. In Examples 34 to 38, the etching rate was normal, and there was no problem in practical use.

  Specimen No. 39 to 44, a process when manufacturing a target plate in which the ratio is changed in a component system in which a group IVa Ti is added to Ni and Mo, a concentration distribution of Ni and Mo in the target plate, and a sputtering time Abnormal discharge characteristics were shown. In either case, the compact was produced by sintering powder produced by atomization under high temperature and high pressure under HIP conditions of 950 ° C. × 8 hours. The planarization treatment was performed using both milling and surface grinding before heat treatment. The heat treatment was performed at 850 ° C. × 2 hr. In the finishing process after the heat treatment, polishing with emery paper (# 600) was performed.

  When the Ni and Mo concentration distributions of the obtained target plate were measured by GDS, ΔNi and ΔMo were within the range defined by the present invention. The results of evaluation by sputtering film formation are as follows. In the inventive examples 39 to 44, no abnormal discharge was observed.

  The corrosion resistance of the thin film formed by sputtering was examined. In Examples 39 to 44, the corrosion resistance did not occur at all. Further, when the etching property of the thin film formed by sputtering was examined, the test piece No. In Examples 39 to 44, the etching rate tended to be fast, and the characteristics were excellent.

  Specimen No. 45 to 47, a process when a target plate is manufactured in a component system in which Group V and Group VIII Fe are added to Ni and Mo, a concentration distribution of Ni and Mo in the target plate, and a sputtering time Abnormal discharge characteristics were shown. In either case, the compact was produced by sintering powder produced by atomization under high temperature and high pressure under HIP conditions of 1180 ° C. × 4 hr. The planarization treatment was performed using both milling and surface grinding before heat treatment. The heat treatment was performed at 950 ° C. × 8 hr. The finishing process after the heat treatment was polished by Scotch Bright.

  When the Ni and Mo concentration distributions of the obtained target plate were measured by GDS, ΔNi and ΔMo were within the range defined by the present invention. The results of evaluation by sputtering film formation are as follows. In the inventive examples of 45 to 47, no abnormal discharge was observed.

  The corrosion resistance of the thin film formed by sputtering was examined. In Examples 45 to 47, the corrosion resistance did not occur at all. Further, when the etching property of the thin film formed by sputtering was examined, the test piece No. In the examples of 45 to 47, the etching rate was fast and the characteristics were excellent.

  Specimen No. 48 to 50, steps when manufacturing a target plate in a component system in which VI, Group Cr, and Group IVa Ti are added to Ni and Mo, Ni and Mo concentration distribution in the target plate, and sputtering Abnormal discharge characteristics were shown. In either case, the compact was produced by sintering powder produced by atomization under high temperature and high pressure under HIP conditions of 1250 ° C. × 3 hours. The planarization treatment was performed using both milling and surface grinding before heat treatment. The heat treatment was performed at 880 ° C. × 6 hr. In the finishing process after the heat treatment, polishing with emery paper (# 600) was performed.

  When the Ni and Mo concentration distributions of the obtained target plate were measured by GDS, ΔNi and ΔMo were within the range defined by the present invention. The results of evaluation by sputtering film formation are as follows. In the 48-50 examples of the present invention, no abnormal discharge was observed.

  The corrosion resistance of the thin film formed by sputtering was examined. It was the outstanding characteristic which corrosion does not occur at all in the examples of 48-50. Further, when the etching property of the thin film formed by sputtering was examined, the test piece No. In the examples of 48 to 50, the etching rate was fast and the characteristics were excellent.

  Specimen No. 51-53, a process when a target plate is manufactured in a component system in which Group Va and Group VIII Fe are added to Ni and Mo, Ni and Mo concentration distribution in the target plate, and sputtering Abnormal discharge characteristics were shown. In either case, the compact was produced by sintering powder produced by atomization under high temperature and high pressure under HIP conditions of 1250 ° C. × 3 hours. The planarization treatment was performed using both milling and surface grinding before heat treatment. The heat treatment was performed at 980 ° C. × 5 hr. The finishing process after the heat treatment was polished by Scotch Bright.

  When the Ni and Mo concentration distributions of the obtained target plate were measured by GDS, ΔNi and ΔMo were within the range defined by the present invention. The results of evaluation by sputtering film formation are as follows. In the inventive examples 51 to 53, no abnormal discharge was observed.

  The corrosion resistance of the thin film formed by sputtering was examined. In Examples 51 to 53, the corrosion resistance did not occur at all. Further, when the etching property of the thin film formed by sputtering was examined, the test piece No. In Examples 51 to 53, the etching rate was fast and the characteristics were excellent.

  Specimen No. 54 to 56, a process when a target plate is manufactured in a component system in which Group IVa Zr and Group VIII Fe are added to Ni and Mo, a concentration distribution of Ni and Mo in the target plate, and a sputtering time Abnormal discharge characteristics were shown. In either case, the compact was produced by sintering powder produced by atomization under high temperature and high pressure under HIP conditions of 1250 ° C. × 3 hours. The planarization treatment was performed using both milling and surface grinding before heat treatment. The heat treatment was performed at 1000 ° C. × 1 hr. The finishing process after the heat treatment was polished by Scotch Bright.

  When the Ni and Mo concentration distributions of the obtained target plate were measured by GDS, ΔNi and ΔMo were within the range defined by the present invention. The results of evaluation by sputtering film formation are as follows. In the inventive examples 54 to 56, no abnormal discharge was observed.

  The corrosion resistance of the thin film formed by sputtering was examined. In Examples 54 to 56, the corrosion resistance did not occur at all. Further, when the etching property of the thin film formed by sputtering was examined, the test piece No. In Examples 54 to 56, the etching rate was fast and the characteristics were excellent.

  Specimen No. 57 to 59, a process when a target plate is manufactured in a component system in which Group IVa Hf and Group VIII Fe are added to Ni and Mo, a concentration distribution of Ni and Mo in the target plate, and a sputtering time Abnormal discharge characteristics were shown. In either case, the compact was produced by sintering powder produced by atomization under high temperature and high pressure under HIP conditions of 1250 ° C. × 3 hours. The planarization treatment was performed using both milling and surface grinding before heat treatment. The heat treatment was performed at 1100 ° C. × 0.5 hr. In the finishing process after the heat treatment, polishing with emery paper (# 600) was performed.

  When the Ni and Mo concentration distributions of the obtained target plate were measured by GDS, ΔNi and ΔMo were within the range defined by the present invention. The results of evaluation by sputtering film formation are as follows. In the inventive examples 57 to 59, no abnormal discharge was observed.

  The corrosion resistance of the thin film formed by sputtering was examined. In Examples 57 to 59, the corrosion resistance did not occur at all. Further, when the etching property of the thin film formed by sputtering was examined, the test piece No. In Examples 57 to 59, the etching rate was fast and the characteristics were excellent.

  Specimen No. 60 to 62, a process when a target plate is manufactured in a component system in which Va, Nb, and Group VIII Fe are added to Ni and Mo, a concentration distribution of Ni and Mo in the target plate, and a sputtering time Abnormal discharge characteristics were shown. In either case, the molded body was produced by sintering powder produced by atomization under high temperature and high pressure under HIP conditions of 1280 ° C. × 3 hr. The planarization treatment was performed using both milling and surface grinding before heat treatment. The heat treatment was performed at 1200 ° C. × 1 hr. In the finishing process after the heat treatment, polishing with emery paper (# 600) was performed.

  When the Ni and Mo concentration distributions of the obtained target plate were measured by GDS, ΔNi and ΔMo were within the range defined by the present invention. The results of evaluation by sputtering film formation are as follows. In the inventive examples 60 to 62, no abnormal discharge was observed. The corrosion resistance of the thin film formed by sputtering was examined. In Examples 60 to 62, the corrosion resistance did not occur at all. Further, when the etching property of the thin film formed by sputtering was examined, the test piece No. In the examples of 60 to 62, the etching rate was fast and the characteristics were excellent.

  As described above, it was confirmed that the Ni—Mo alloy sputtering target plate of the present invention hardly generated abnormal discharge during sputtering, and that efficient sputtering film formation was possible.

It is a figure explaining the erosion part and non-erosion part of a sputtering target board surface.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Ni-Mo type alloy sputtering target board 2 Non-erosion part 3 Erosion part 4 Ni-Mo oxide 5 End part of Ni-Mo oxide

Claims (5)

A sputtering target plate of a Ni-Mo alloy composed of Ni, Mo and unavoidable impurity elements,
The Ni concentration and the Mo concentration at a position of 10 μm in the thickness direction from the surface of the surface of the sputtering target plate are Ni (10) and Mo (10) in mass%, respectively, and the Ni at a position of 100 μm from the surface in the thickness direction. A Ni—Mo-based sputtering target plate characterized by satisfying the relationship of the following formula, with Ni and M concentration being 100% by mass and Mo (100), respectively.
−2.0 ≦ ΔNi ≦ 0.2
−0.2 ≦ ΔMo ≦ 2.0
and,
−0.2 ≦ ΔNi + ΔMo ≦ 0.2
Here, ΔNi = Ni (10) −Ni (100)
ΔMo = Mo (10) −Mo (100)   The Ni-Mo based alloy sputtering target plate according to claim 1, wherein the Ni concentration is 20 mass% or more and the Mo concentration is 10 mass% or more. In addition, one or more metal elements other than Ni in Group IVa, Va, Group VIIa, Group VIII, Group Ib, Group IIb, Group IIIb, and Group IVb of the periodic table are summed in an average concentration of 0. The sputtering target plate of the Ni-Mo type alloy according to claim 2, wherein the sputtering target plate has 2 mass% to 15 mass%. Among the Group IVa, Va, Group VIIa, Group VIII, Group Ib, Group IIb, Group IIIb, and Group IVb, one or more metal elements other than Ni are Ti, V, Fe 2 , Ta 3 , Zr, The sputtering target plate of a Ni-Mo alloy according to claim 3, wherein the sputtering target plate is one or more metal elements of Hf and Hf. In the sputtering target board as described in any one of Claims 1-4,
The Ni-Mo type alloy sputtering target board characterized by satisfy | filling the relationship of following Formula.
−0.2 ≦ ΔNi ≦ 0.2
−0.2 ≦ ΔMo ≦ 0.2