TW201130992A - A1 based alloy sputtering target - Google Patents

Abstract

The invention provides a technique that reduces the splash, especially for initial splash while taking Al-(Ni, Co)-(La, Nd) based alloy or Al-(Ni,Co)-(La,Nd)-(Cu,Ge) based alloy as sputtering targets. The invention relates to an Al based alloy sputtering target containing at least one selected from A groups consisting of Ni and Co, and at least one selected from B groups consisting of La and Nd. While measuring the crystallized particle diameter of a rolling direction parallel to a face of the rolling direction in the cross-section perpendicular to the rolling surface of the foregoing sputtering target, the average particle diameter is below 500um, and the maximum crystallized particle diameter is below 1500um.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an A1-based alloy sputtering target, and more particularly to an initial stage of sputtering a target when a thin film is formed using a sputtering target. Splashed A1 based alloy sputtering target. The A1 based alloy as the object in the present invention is an A1 based alloy containing at least one selected from Group A (Ni, Co), and at least one selected from Group B (La, Nd), or is further The Al-based alloy containing at least one selected from the group C (Cu, Ge) may also further contain Ti and B. Hereinafter, the former A1 base alloy is referred to as "Al-(Ni, Co) - (La, Nd) alloy", and the latter A1 base alloy is referred to as "Al-(Ni, Co)-(La , Nd) - (Cu, Ge) alloy". [Prior Art] A1 based alloys have low resistivity and are easy to process, and are used in liquid crystal displays (LCD: Liquid Crystal Display), PDP (Plasma Display Panel), and electroluminescent displays (ELD: Electro). Luminescence Display), field emission display (FED: Field Emission Display), MEMS (Micro Electro Mechanical Systems) display, etc. (FPD: Flat Panel Display) 'Touch panel, electronic paper field is widely used It is used for materials such as wiring films, electrode films, reflective electrode films, and the like. For example, an active matrix type liquid crystal display includes a TFT substrate having a thin film transistor as a switching element (TFT: Thin 201130992)

A film transistor, a pixel electrode composed of a conductive oxide film, and a wiring or scanning line including a scanning line or a signal line are electrically connected to the pixel electrode. In the wiring material constituting the scanning line or the signal line, a film of pure A1 or Al-Nd alloy is generally used. However, if these films are directly in contact with the pixel electrode, insulating alumina or the like is formed at the interface, and the contact resistance is formed. Since it is increased, a barrier metal layer made of a high melting point metal such as Mo, Cr, Ti, or W is provided between the wiring material of the above A1 and the pixel electrode to reduce the contact resistance. However, as described above, the method of interposing the barrier metal layer therebetween has a problem that the manufacturing steps are complicated and the production cost is increased. Therefore, in order to provide a technique (direct contact technique) in which a conductive oxide film constituting a pixel electrode can be directly contacted with a wiring material without interposing a barrier metal layer therebetween, it is proposed to use an Al-Ni alloy or further contain Nd. A method of using a thin film of an Al-Ni-rare earth element alloy of a rare earth element such as Y as a wiring material (JP-A No. 2 004-2 1 4606). When an ANNi alloy is used, a conductive Ni-containing precipitate or the like is formed at the interface, and generation of insulating alumina or the like is suppressed, so that the contact resistance can be suppressed to be low. Further, if an A1 - N i - rare earth element alloy is used, the heat resistance is further improved. However, in the formation of an Al-based alloy thin film, a sputtering method using a sputtering target is generally employed. The sputtering method is to form a plasma discharge between a substrate and a sputtering target composed of the same material as the film material, and the gas ionized by the plasma discharge collides with the splash target, and the splash is splashed. A method of forming a thin film by plating atoms of a target and laminating on a substrate. -6- 201130992 Sputtering differs from vacuum evaporation in that it has the advantage of forming a film of the same composition as the sputtering target. In particular, the A1 based alloy thin film formed by the sputtering method can dissolve the alloying element such as Nd which is not dissolved in an equilibrium state, and exhibits excellent performance as a thin film. Therefore, it is an industrially effective film forming method. The development of sputtering targets that have become their raw materials has been promoted. In recent years, in order to cope with the increase in productivity of FPD, etc., the film formation speed at the time of the sputtering step tends to be higher than ever. In order to increase the deposition rate, it is easiest to increase the sputtering power. However, if the sputtering power is increased, sputtering failure such as spatter (fine particles) may occur, and defects such as wiring films may occur. The drawbacks of FPD's yield or operational performance are reduced. For the purpose of preventing the occurrence of spatter, for example, Japanese Patent Laid-Open No. Hei 10-147860, Japanese Patent Application Laid-Open No. Hei No. 10-199830, Japanese Patent Application Laid-Open No. Hei. 2 0 0 1 - 2 7 9 4 3 The method described in the 3rd bulletin. Among them, Japanese Laid-Open Patent Publication No. Hei 10- 1 4 7 8 60, Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. The cause of the occurrence is a fine void in the structure of the sputtering target, by controlling the dispersion state of the compound particles of A1 and the rare earth element in the A1 matrix (Japanese Patent Laid-Open Publication No. Hei No. Hei-1 47860), or A state in which a compound of A1 and a transition element in a matrix of A is controlled to be dispersed (Japanese Patent Laid-Open Publication No. Hei No. Hei No. Hei. Japanese Patent Laid-Open No. 1 1_2 93 4 54) to prevent the occurrence of splashing. In addition, the method disclosed in Japanese Laid-Open Patent Publication No. 2001-27-93 3 is '201130992', in order to reduce the arc discharge (abnormal discharge) as a cause of splashing, after performing the fine machining after adjusting the hardness of the sputtering surface, Thereby, the occurrence of surface defects accompanying machining is suppressed. On the other hand, Japanese Laid-Open Patent Publication No. Hei 9-23 5666 discloses a technique for preventing the occurrence of spatter, which is carried out by rolling at a processing rate of 75% or less in a temperature range of 300 to 450 °C. The ingot in which Ai is the main body is in the form of a plate. Then, the heat treatment at 550 ° C or lower is performed at a temperature exceeding the rolling, and the side of the rolled surface is turned into a sputtering surface, whereby the obtained A1 - T i - W is obtained. The sputtering target of the alloy or the like has a Vickers hardness of 25 or less. [Explanation] [Problems to be Solved by the Invention] As described above, various techniques for reducing the occurrence of spatter and improving the sputtering failure have been proposed. However, further improvements are required. In particular, in the initial stage of the initial stage of the sputtering, the yield of the FPD is lowered, which causes a serious problem. However, the above-mentioned Japanese Patent Laid-Open No. Hei-47860, Japanese Patent Publication No. Hei 10-199830, and Japanese Special The splash prevention technique of Japanese Laid-Open Patent Publication No. Hei. In particular, it is useful as a wiring material which can be used in the above-described direct contact technique among the bismuth-based alloys, that is, as a wiring material which can directly contact the conductive oxide film constituting the pixel electrode, and is preferably used for peeling. The photoresist (resin) cleaning solution (representatively an amine-containing organic stripper) formed in the photolithography step is also excellent in corrosion resistance (resistance to peeling liquid corrosion - 8 to 201130992), and further Al-(Ni,Co)-(La,Nd)-based alloy or Al-(Ni,Co)-(La,Nd) for forming a wiring material which can be used as a direct contact with a semiconductor layer of a thin film transistor In the A1-based alloy sputtering target of the (Cu, Ge)-based alloy, it is desirable to provide a technique capable of effectively preventing the occurrence of initial splash even by the conventional melt casting method. The present invention has been made in view of the above circumstances, and an object thereof is to provide a technique of using an Al-(Ni,Co)-(La,Nd)-based alloy or Al-(Ni,Co)-(La,Nd). When the -(Cu,Ge)-based alloy is used as a sputtering target, splashing, particularly initial splashing, can be reduced. [Means for Solving the Problem] The present invention includes the following aspects. (1) an A1 based alloy sputtering target comprising an A1 based alloy containing at least one selected from the group consisting of Ni and c〇 and at least one selected from the group consisting of La and Nd The sputtering target is characterized in that, in the cross section perpendicular to the rolling surface of the sputtering target, the crystal grain size in the rolling direction of the surface parallel to the direction of the rolling direction is 500 μηι or less. And the maximum crystal grain size is ΐ5〇〇μηι or less. (2) The bismuth-based alloy sputtering target according to (1), wherein the total content of the a group is 原子·〇5 atom% or more and 2.5 atom% or less, and the total content of the b group is 0.1 atom% or more. , 1 atom% or less. (3) The bismuth-based alloy sputtering according to (1) or (2), which further contains at least one selected from the group consisting of Cu and Ge. (4) The A1 based alloy sputtering target according to (3), wherein the total content of the group c-9 - 201130992 is 0.1 atom% or more and 1 atom% or less. (5) The A1 based alloy beach plating target according to any one of (1) to (4) further comprising Ti and B. (6) The A1 based alloy sputtering target according to (5), wherein the Ti content is 0.0002 atom% or more and 0.012 atom% or less, and the B content is 0.0002 atom% or more '0.012 atom% or less. (7) The A1 base alloy sputtering target according to (1), (2), (5) or (6), wherein only Ni is selected from the group A, and only Nd is selected from the group B. (8) The A1 base alloy sputtering target according to (1), (2), (5) or (6), wherein only Ni is selected from the group A, and only La is selected from the group B. (9) The A1 based alloy sputtering target according to (3), (4), (5) or (6), wherein only Ni is selected from the group A, and only Nd is selected from the group B, Only Ge is selected from the aforementioned C group. The A1 based alloy sputtering target according to any one of (1) to (9), which has a Vickers hardness Hv of 26 or more. (1 1 ) A ruthenium-based alloy film obtained by using the sputtering target according to any one of (1) to (1 〇), which is directly connected to a transparent conductive film. (12) The ruthenium-based alloy film according to (1), which comprises at least one selected from the group consisting of Ni and Co, and selected from the group B composed of La and Nd. At least one selected from the group consisting of (5) and Ge, and at least one selected from the group consisting of Ti and B;

The Ti content is 0.0004 atom% or more and 0,008 atom% or less, and the B content is -10-201130992, and the amount is 0.0004 atom% or more, and 〇.〇〇8 atom% or less. As described above, in the preferred embodiment of the present invention, the A1 based alloy film contains at least one selected from the group A (Ni, Co) and at least one selected from the group b (La, Nd). At least one selected from the group C (Cu, Ge), and Ti and B; the Ti content is 0.0004 atom% or more, 0.008 atom% or less, and the 8 content is 0.0004 atom% or more and 0.008 atom% or less. The peeling resistance of the peeling liquid is further improved. [Effect of the Invention] According to the present invention, an Al-(Ni,Co)-(La,Nd)-based alloy or an Al-(Ni,Co)-(La,Nd)-(Cu,Ge)-based alloy is used as a sputtering target. When the crystal grain size (average crystal grain size and maximum crystal grain size) in the rolling direction in the surface parallel to the rolling direction is appropriately controlled, the occurrence of spatter, particularly the occurrence of initial splash, is suppressed, and splashing is caused. Poor plating can be effectively suppressed. Further, the A1 based alloy film obtained by using the sputtering target of the present invention is useful as an A1 alloy film for a display device which is in direct contact with a transparent conductive film, in particular, the above-mentioned Al-(Ni,Co)-( A1 alloy film obtained by sputtering target with specific Ti and B in La, Nd) alloy or Al-(Ni,Co) -(La, Nd) -(Cu, Ge) alloy, resisting stripping corrosion Extremely excellent. The inventors of the present invention have made an intensive effort to provide an A1-based alloy splash target which can reduce splashing occurring during sputtering film formation, particularly in the initial stage of sputtering deposition. In particular, in the present invention, from the viewpoint of providing the following technique from -11 to 201130992, the technique is even in the case of the above-mentioned A1-(Ni,c〇)_(La) which can be used for the direct contact technique. Al-(Ni,Co)-(La,Nd) alloy sputtering target for film formation of Nd) alloy or Al-(Ni,Co)-(La,Nd)-(Cu,Ge) alloy Or Al-(Ni, Co) - (La, Nd) - (Cu, Ge) alloy sprinkled leather for the object, the sputter target may further contain Ti and B (hereinafter referred to as "short" and abbreviated as " In the case of the A1 based alloy sputtering target", the sputtering target can be produced by the conventional melt casting method, and the occurrence of spatter can be effectively prevented. As a result, it was found that (I) in the above-mentioned A1 based alloy spatter target, the crystal grain size in the rolling direction in the surface parallel to the rolling direction in the cross section perpendicular to the rolling surface is appropriately controlled (average The crystal grain size and the maximum crystal grain size) are effectively suppressed by the occurrence of spatter: (II) it is preferable to increase the Vickers hardness (Hv) to 26 Hv or more, whereby the occurrence of spatter is remarkably lowered, and the completion is completed. The invention has been made. In the present specification, "the occurrence of the initial splash prevention can be prevented (reduced)" means that the average 値 of the splash generated when the sputtering is performed under the conditions (the sputtering time of 8 1 second) described in the examples below is 9 ～20 cells/cm 2 (evaluation standard Δ of the examples) is preferably 8 cm 2 or less (evaluation standard 实施 of the examples). As described above, in the present invention, the sputtering time is set to 81 seconds, and the splash in the initial stage of the sputtering film formation is evaluated. This point is the same as the above-mentioned Japanese Patent Laid-Open No. 10-1478, which does not evaluate the occurrence of the splash in the initial stage. The technique of the Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. -12- 201130992 First, 'Al-(Ni,Co)-(La, Nd)-based alloy or Al-(Ni,Co)-(La,Nd)-(Cu,Ge)-based alloy as the object of the present invention Be explained. First, the A1-based sputtering target of the present invention contains at least one selected from Group A (Ni, Co) and at least one selected from Group B (La, Nd). Among them, the group A (Ni, Co) is an element effective for lowering the contact resistance of the A1-based alloy film and the pixel electrode directly in contact with the A1 alloy film. In addition, it is also effective for controlling the crystal grain size for preventing the occurrence of spatter. Ni and Co constituting the group A can be used alone or in combination. The preferred one is Ni. The total content of the group A is preferably from 0.05 to 2.5 atom%. The reason why the total content is 0.05 atom% or more is to more effectively exhibit the effect of lowering the contact resistance, and it is preferably 〇 7 atom% or more, more preferably 〇 1 atom% or more. On the other hand, if the total content of the group A is too large, the electrical resistivity of the Al-based alloy film is improved, and therefore it is preferably 2.5 atom% or less. More preferably, it is 1.5 atomic%, more preferably 1.3 atomic% or less, and even more preferably 1.1 atomic% or less. In addition, the B group (La, Nd) improves the heat resistance of the A1 based alloy film formed by using the A1 based alloy sputtering target to prevent the hillock formed on the surface of the A1 based alloy film (Hi丨丨0). Ck ) is a valid element. La and Nd constituting the B group may be used alone or in combination. The total content of group B is preferably 〇. 1~〗 atom%. The reason why the total content is 〇·1 atom% or more is to improve the heat resistance more effectively. That is, the prevention effect of the hillock is preferably 0. 2 atom% or more and more preferably -13- 201130992 〇·3 atom% or more. On the other hand, when the total content of the B group is too large, the electrical resistivity of the A1 based alloy film is improved, so that it is preferably 1 atom% or less. More preferably, it is 0.8 atomic% or less, and further preferably 〇.6 atom% or less. The Al-based alloy used in the present invention contains at least one selected from Group A (Ni, Co) and at least one selected from Group B (La, Nd), the remainder being A1 and inevitable impurities. The unavoidable impurities are elements which are inevitably mixed in the production process and the like, and examples thereof include Fe, Si, C, 0, and N, and the content thereof is preferably 0.05 atom% or less per element. The above Al-based alloy may further contain at least one selected from the group C (Cu, Ge). The group C (Cu, Ge) is an effective element for improving the corrosion resistance of the A1-based alloy film formed using the A1 based alloy sputtering target. Cu and Ge constituting the C group may be used singly or in combination, and the total content of the 〇C group may be preferably 0.1 to 1 atom%. The reason why the total content is 0.1 atom% or more is to more effectively exhibit the effect of improving the corrosion resistance, and is preferably 0.2 atom% or more, more preferably 0.3 atom% or more. On the other hand, when the total content of the group C is too large, the electrical resistivity of the A1-based alloy film is improved, so that it is preferably 1 atom% or less. More preferably, it is 8 atom% or less, and more preferably 〇 6 atom% or less. Preferred examples of the A1 based alloy used in the present invention include Al-Ni-Nd alloy, Al-Ni-La alloy, Al-Ni-Nd-Ge alloy, and Al-Ni-La-Cu alloy. , Al-Co-La-Ge alloy, Al-Co-Nd-Ge alloy, and the like. -14- 201130992 The above A1 base alloy may further contain Ti and B. They are elements which contribute to the refinement of crystal grains, and are broadened by the range (permissible range) of the conditions of addition of Ti and B. However, if the amount is excessively added, the electrical resistivity of the A1 based alloy film is improved. The preferred content of Ti and B is Ti: 0.00 0 2 atom% or more, 〇·〇1 2 atom% or less, B: 0 · 0 0 0 2 atom% or more, 0.012 atom% or less, more preferably Ti: 0.0004 Atom% or more, 0.00 6 atom% or less, B: 0.00 0 4 atom% or more, 〇. 〇〇6 atom% or less. In addition, the content of Ti and B is preferably 0.0004 atom% or more and 0.008 atom% or less, more preferably 0.001 atom% or more, from the viewpoint of providing an A 1 -based alloy film which is excellent in corrosion resistance to the peeling liquid. 0.006 atomic % or less. When Ti and B are added, a generally used method can be used, and a representative one can be added to the melt as an Al-Ti-B refiner. The composition of Al-Ti-B described above is as long as the desired Al-based alloy sputtering can be obtained.

The target is not particularly limited, but for example, human 1-5 mass% 1-1 mass% B, eight 1-5 mass%, ^-0.2 mass% B, or the like can be used. These commercially available products can be used. Next, the crystal grain size of the A1-based alloy sputtering target of the present invention will be described. In the present invention, in the cross section perpendicular to the rolling surface of the A1-based alloy sputtering target, the crystal grain size in the rolling direction of the surface parallel to the rolling direction is 'average crystal grain size is 5 0 0 μηη. Hereinafter, the maximum crystal grain size is equal to or less than 1 500 ηηι. Thereby, the occurrence of spatter can be effectively prevented. The above crystal grain size is measured by the intercept (i n t e r c e p t ) method. The specific measurement procedure is as follows. -15- 201130992 First, 'cut the above-mentioned sputtering target' to make the measurement surface of the A1-based alloy sputtering target (the surface parallel to the rolling direction among the sections perpendicular to the rolling surface) with respect to the thickness t of the above-mentioned sputtering target , for a range of 1/2 xt) exposed. Next, in order to smooth the measurement surface, honing with a sandpaper or honing with a diamond honing paste, etc., using Barker's solution (volume ratio of HBF4 (tetrafluoroboric acid) to water by a ratio of 1:30 The mixed aqueous solution was subjected to electrolytic etching, and the structure was observed by a polarizing microscope. Specifically, when the magnification of the tissue is 50 times, the two fields of view are taken at the total of three positions of the surface layer side, the l/4xt portion, and the l/2xt portion in the thickness direction of the sputtering target (1). The field of view is 1 300 μηιι Width 1 8 00 μηι), and a tissue image is obtained. In each of the tissue images thus obtained, a plurality of (5 to 10) total lengths are randomly drawn in a direction parallel to the rolling direction, which corresponds to a specific length (L 1 μm, which is specific to the examples described later) A line with a length L1 of 1 8 00 μιη). Then, the number of crystal grains (Ν1) traversing straight in each tissue image is counted, and the length of the straight line on the image (L 1 μιηη) is divided by the number of crystal grains (Ν1). L 1 /Ν 1 ). The same operation was carried out for all measurement fields. The average of these was taken as the average crystal grain size (μιη). Further, in the entire measurement field of view, the maximum 値 of the length of the straight line traversing in each measurement image is the maximum crystal grain size (μιη). The smaller the average crystal grain size and the maximum crystal grain size of the ruthenium-based alloy sputtering target thus measured, the better. The occurrence of spatter is further reduced. A preferred average crystal grain size is 200 μm or less, and a preferred maximum crystal grain size is 800 μm or less. More preferably, the average crystal grain size is 15 μm or less, and more preferably the maximum crystal grain size is 500 μm or less. -16- 201130992 The lower limit of the average crystal grain size and the maximum crystal grain size is not particularly limited, and is mainly determined by the relationship with the production method. Hereinafter, in the present invention, the melt casting method is employed for the purpose of manufacturing cost, reduction in manufacturing steps, improvement in yield, and the like. The melt casting method is a method of producing an ingot from an A1 alloy melt, which is widely used in the production of a sputtering target. According to a preferred method of refining the crystal grains by the melt casting method employed in the present invention, the lower limit of the average crystal grain size is approximately 1 Ομτη to 3 0 μηη, and the lower limit of the maximum crystal grain size is approximately 70 μm to 120 μm. Further, in order to make the crystal grain size finer, when the bismuth-based alloy sputtering target is produced by the melt casting method, for example, the rolling start temperature is minimized, or the total reduction ratio is increased as much as possible, or the first pass pressure is increased as much as possible. The average crystal grain size and the maximum crystal grain size can be further refined by the lower ratio, etc. However, the current equipment has a flaw in which it cannot be directly used, and is not practical. In addition, as a method of producing a sputtering target, for example, a spray forming method may be mentioned, and if the spray molding method is employed, crystal grains may be made finer, for example, an average crystal grain may be obtained. The crystal grains having a diameter of several μηη grade. Here, in the spray molding method, a high-pressure inert gas is sprayed on the Α1 alloy melt stream in a chamber in an inert gas atmosphere, and the particles are rapidly cooled to a semi-molten state, a semi-solidified state, and a solid phase state. A method of obtaining a semi-finished product (preform) of a specific shape. However, when the grain refining means used in the melt casting method of the present invention is used, it is possible to obtain a splash suppressing effect which is substantially the same as that in the case of the spray molding method, which is confirmed by an experiment. -17- 201130992 Further, the A1-based alloy sputtering target of the present invention preferably has a Vickers hardness of 26 HV or more. This is because, according to the results of the study by the inventors of the present invention, it is found that an A(Ni,Co)-(La,Nd)-based alloy or Al-(Ni,Co)-(La,Nd)-(Cu,Ge) is used. When the alloy is used as a sputtering target, if the hardness of the sputtering target is low, initial splashing tends to occur. Although the reason is not clear, it can be estimated as follows. In other words, if the hardness of the sputtering target is low, the microscopic smoothness of the machined surface of the machine for milling or lathe used for manufacturing the sputtering target is deteriorated, in other words, due to complicated deformation of the surface of the material. It becomes rough, so dirt such as cutting oil used for machining enters the surface of the sputtering target and remains. Even if the surface cleaning is performed in the subsequent step, it is difficult to completely remove such dirt. As described above, the dirt remaining on the surface of the shovel target is considered to be the starting point of the initial splash at the time of sputtering. In order to prevent such dirt from remaining on the surface of the sputtering target, it is preferable to improve the workability (knife sharpness) during machining so that the surface of the raw material is not rough. Therefore, in the present invention, it is preferable to increase the hardness of the sputtering target. The Vickers hardness of the A1-based alloy sputtering target of the present invention is preferably as high as possible from the viewpoint of preventing occurrence of spatter, for example, 35 Hv or more, more preferably 40 Hv or more, still more preferably 45 Hv or more. Further, the upper limit of the Vickers hardness is not particularly limited. However, if it is too high, it is necessary to increase the rolling ratio of the cold rolling for hardness adjustment, and it is difficult to carry out the rolling. Therefore, it is preferably 160 Hv or less. More preferably, it is 140 HV or less, and even more preferably 120 Hv or less. The A1 based alloy sputtering target of the present invention has been described above. -18- 201130992 Next, a method for manufacturing the above-described A1-based alloy sputtering target will be described. As described above, the A1-based alloy sputtering target is produced by the melt casting method in the present invention. Particularly in the present invention, in order to produce an A1-based splash target capable of appropriately controlling the crystal grain size, in the step of melt casting-(heating if necessary)-hot roll-annealing, the hot rolling conditions are appropriately controlled. (for example, rolling start temperature, rolling end temperature, maximum pass rate of one pass, total reduction ratio, etc.), soaking conditions (soaking temperature, soaking time, etc.), annealing conditions (annealing temperature, annealing time, etc.) At least one of them is better. After the above steps, cold rolling-annealing (second rolling-> annealing step) may also be performed. Further, in the present invention, in order to appropriately control the Vickers hardness of the preferred Al-based alloy sputtering target, the hardness is adjusted by performing the cold rolling rate control or the like in the second rolling-annealing step described above. good. Strictly speaking, the crystal grain size refining means or the hardness adjusting means which can be applied depending on the type of the A1 based alloy differs. Therefore, for example, the above-mentioned means may be used alone or in combination, etc., depending on the type of the Al-based alloy. Means can be. Hereinafter, each step will be described in detail with respect to the preferred method used in the present invention. (Molten Casting) The melt casting step is not particularly limited, and a step generally used in the production of a sputtering target can be suitably employed. For example, as a casting method, DC (semi-continuous) casting and continuous casting of a thin plate (two-roll type, belt continuous casting type, Proppez type, block type continuous casting type, etc.) can be cited. - 201130992

(Homogeneous heat as needed) After the ingot is cast in the A1 based alloy ingot as described above, hot rolling is performed, but it is also possible to perform soaking as needed. In order to control the crystal grain size, it is preferred to control the soaking temperature to approximately 300 to 600 ° C and to control the soaking time to approximately 1 to 8 hours. (Hot Rolling) After the above soaking is performed as needed, hot rolling is performed. In order to control the crystal grain size, the hot rolling start temperature is controlled to be approximately 200 to 500 ° C, and the hot rolling end temperature is controlled to approximately 50 to 300 ° C to control the maximum reduction ratio of 1 pass. It is about 2 to 25%, and it is preferable to control the total reduction ratio to approximately 60 to 9.5 %. Specifically, for example, when manufacturing an Al-Ni-Nd-Ge alloy sputtering target, regarding hot rolling, a rolling start temperature: 200 to 400 ° C, a rolling end temperature: 50 to 200 ° C, 1 way. The second maximum reduction ratio: 3 to 25%, and the total reduction ratio: 70 to 95% is preferred. (annealing) Annealing was performed after hot rolling as described above. In order to control the crystal grain size ' to control the annealing temperature to approximately 260 to 450 ° C, it is preferred to control the annealing time to approximately 1 to 1 hr. -20- 201130992 (Cold-rolling annealing if necessary) The crystal grain size of the A1-based alloy sputtering target can be controlled by the above method, but thereafter, cold rolling-annealing (second cold rolling, further) can be performed. annealing). In order to control the crystal grain size, the cold rolling conditions are not particularly limited, but it is preferable to control the annealing conditions. It is recommended to control the annealing temperature to approximately 1 50 to 250 ° C, and to control the annealing time to approximately 1 to 5 hours. about. Further, in order to control the hardness of the above-mentioned Al-based alloy sputtering target, it is preferable to control the cold rolling ratio to approximately 15 to 30%. In the present invention, an A1 based alloy film obtained by using the above A1 based sputtering target is also included. Such an Al-based alloy film has the same composition as that of the sputtering target, and has a low specific resistance, and can directly suppress the contact resistance even when it is directly connected to the transparent conductive film (the conductive oxide film constituting the pixel electrode). It is suitable for use as a wiring film for display devices for direct contact. In particular, the Al-based alloy film containing Ti and B is extremely excellent in corrosion resistance to the peeling liquid as confirmed by the examples described later. In the manufacturing step of the TFT substrate, although a large amount of wet processing is performed, if a metal which is more expensive than A1 is contained as an alloying element, the problem of electrolytic corrosion appears and the corrosion resistance is deteriorated. For example, in the cleaning step of stripping the photoresist (resin) formed in the photolithography step, the organic stripping liquid containing an amine is continuously washed with water. However, if an amine is mixed with water, it becomes an alkaline solution, so that A1 is corroded in a short time. However, the A1 alloy film is subjected to a heat history before the peeling and cleaning step, and the A1 type precipitate containing an alloy element during the heat history is formed in the A1 matrix. Since the potential difference between the precipitate of the A1 system and the A1 matrix is large, there is a problem in that, in the peeling cleaning step - 21 to 201130992, the above-mentioned electrolytic corrosion occurs at the moment when the amine which is a component of the organic stripping liquid comes into contact with water. In the electrochemical aspect, A1 is ionized and eluted to form pit-like pitting (black spots). When a black dot occurs, the transparent pixel electrode (ITO film) becomes discontinuous, and it is considered to be a defect in the visual inspection, which may cause a decrease in yield. As shown in the examples below, the corrosion resistance of the peeling was changed by adding Ti and B. In order to secure desired characteristics, the content of Ti and B is preferably 0.0004 atom% or more and 0.008 atom% or less, and more preferably 〇·〇〇1 atom% or more and 0.006 atom% or less by adding The reason why the Ti and B change the corrosion resistance (corrosion density) of the peeling liquid is not known, but it is presumed to be, for example, the following structures (1) to (3). (1) The starting point of corrosion in the stripping liquid washing step is a metal compound of the Al-A group. In the temperature region where the intermetallic compound is deposited, by adding an appropriate amount of Ti and B, the crystal grain growth of the Al alloy film occurs simultaneously, and therefore the precipitation point (three-dimensional point of the grain boundary) of the intermetallic compound which is the starting point of the corrosion is present in a large amount. Since the corrosion starting point is dispersed, it is estimated that the peeling resistance of the peeling liquid is improved. On the other hand, when the amount of addition of Ti and B is insufficient, crystal grain growth does not occur before the precipitation of the intermetallic compound, and the precipitation point does not increase, and it is estimated that the peeling resistance of the peeling liquid is not improved. On the other hand, if the amount of addition of Ti and B is excessive, the crystal grain growth of the A1 alloy film is suppressed, and the above-mentioned precipitation point does not increase, and the peeling resistance of the peeling liquid is not expected to be improved. (2) When the amount of Ti and the amount of B in the above preferred range are added, Ti and B (especially Ti) are not precipitated in the heat history during the manufacturing process of the display device, and -22-201130992 is considered to be in the A1 alloy film. The possibility of solid solution is high. In this case, the effect of improving the corrosion resistance of the substrate is improved. The corrosion resistance of the intermetallic compound is lowered, and the corrosion resistance of the peeling liquid is estimated to be improved. (3) Alternatively, an oxide containing Ti and B is formed in the oxide film formed on the surface of the A1 alloy film, and the latency is prolonged in the peeling liquid washing step until the peeling liquid comes into contact with the substrate and the intermetallic compound. It is also considered to cause an increase in the corrosion resistance of the peeling resistant liquid. Although it is a useful method to add Ti and B as described above for the improvement of the corrosion resistance of the stripping liquid, the total content of the group A (Ni, Co) and the total content of the group B (La, Nd) may be used. The ratio (group A/group B) is controlled to exceed 0.1 and be 7 or less. The smaller the ratio, the better, for example, preferably 1. 〇 or less, more preferably 0.4 or less. [Embodiment] [Examples] Hereinafter, the present invention will be specifically described by way of examples, but the present invention is not limited by the following examples, and may be appropriately modified and implemented within the scope of the above-described embodiments. All are included in the technical scope of the present invention. (Example 1) Each of the A1 base alloys shown in Table 1 was prepared, and an ingot having a thickness of 100 mm was subjected to ingot casting by a DC casting method, and then hot rolled and annealed under the conditions described in Table 1 to prepare a roll. Rolling plate. For reference, the thickness of the produced rolled sheet -23-201130992 is shown in Table 1. Here, the A1 based alloy containing Ti and B is produced by adding it to the melt in the form of α1·_5 mass % Ti -1 mass % B of the refining agent. For example, when the A1 base alloy of No. 2 in Table 1 (Ti: 〇.〇〇〇5 atom%, B: 0.0005 atom%) is produced, the mass of the entire A1 based alloy is 〇.02% by mass. When the above-mentioned fine refining agent was added, on the other hand, when the A1 base alloy (Ti: 0.0046 atom%, B: 0.0051 atom%) of Νο·3 in Table 1 was produced, the mass of the entire Al-based alloy was 0.2% by mass. The above refining agent is added in proportion. Cold rolling and annealing were further carried out (2 hours at 200 ° C). Here, in the case of Nos. 1 to 3, 5 to 9, and 11 to 25, the cold rolling ratio at the time of cold rolling was 22%, and the other conditions of Nos. 4 and 10 were such that the cold rolling ratio was 5%. Next, machining (circular press working and lathe machining) was performed to produce a disk-shaped A1-based alloy sputtering target (size: diameter: 101.6 mm x 5.0 mm). The crystal grain size (average crystal grain size and maximum crystal grain size) in the rolling direction of each of the sputtering targets produced as described above was measured by the above method. Further, the Vickers hardness of each of the above-described sputtering targets ( Hv) was measured using a Vickers hardness tester (AVK-G2 manufactured by Akashi Seisakusho Co., Ltd.). Next, using the respective sputtering targets described above, the number of spatters (initial splashes) which occurred when sputtering was performed under the following conditions was measured. First, for the Si wafer substrate (dimensions: diameter 100.0 mm X thickness 0.50 mm), DC magnetron sputtering was performed using a sputtering device of "sputtering system 1^511-5 4 2 S" manufactured by Shimadzu Corporation. . The sputtering conditions are as follows -24- 201130992. Back pressure: 3.0xl0'6Torr or less

Ar pressure: 2_25xl (T3T〇rr

Ar gas flow rate: 30sccm, laser plating power: 8iiw Distance between poles: 5 1 . 6 m m Substrate temperature: room temperature Sputtering time: 8 1 second Thus, a sputtering target is used to form 6 films. Therefore, the sputtering is performed for 8 1 (seconds) xl6 (sheet) = 1296 seconds. Then, the position coordinates, the size (average particle diameter), and the number of particles confirmed on the surface of the film were measured using a particle counter (manufactured by 株式会社股份有限公司: Wafer Surface Inspection Apparatus WM-3). Here, a size of 3 μηι or more is regarded as a pellet. Thereafter, the surface of the film was observed by optical microscopy (magnification: 1 〇〇〇), and the shape of the hemisphere was regarded as a splash, and the number of spatters per unit area was measured. Specifically, the step of performing the sputtering on the one thin film is continuously performed while replacing the S i wafer substrate, and the above steps are performed in the same manner for the 16 films, and the average number of spatters is referred to as "initial splash". The number of occurrences." In the present embodiment, the number of occurrences of the initial splash obtained as described above is 8 pieces/cm2 or less, and the evaluation is 〇, and those of 9 to 20 pieces/cm2 are evaluated as 8%, and those of 2 1 pieces/cm2 or more are evaluated as X. In the present embodiment, '〇 or △ was evaluated as acceptable (the effect of reducing the initial splash). The results of these tests are recorded in Table 1. -25- 201130992

Plate thickness after manufacture (mm) σ> CM 2 05 eg eg CO £ So s 00 g CO 5 S3 CO CNJ CO CO Organization* Characteristics 1__ 〇〇〇< 〇〇〇O 〇<1 〇〇〇0 〇 〇〇〇XXXXXXX CO (D ri* ΙΛ 00 00 卜卜 (O 00 卜 oo 卜 00 CM CO CM CO CNJ m CSJ CM CvJ CSJ CM m 5 00 CO 03⁄4 CO CO CM in CO 05 CO 00 CO 00 CO R eg CSJ oo CO in co § s (•D CO 00 CO oo CO § CO CO in CO (O CO eo OO CO maximum crystal size (μ m) 5 CO σ> CNj <£> — CO inch 03⁄4 2 卜CO Bu CVJ m CO m CQ CO 00 00 o (O 00 00 CO Cvj 00 CNJ u〇CO t— ΙΛ CO 00 00 <·〇CO inch CM (M CO in CSJ CO 2 卜 in σ* &lt ; & r r- (D < D § in fl§] g in CO 00 CM CO 2 CO — CS3 CO 2 00 in 兮eg r- CNJ but r- CO CO N CM C'J 00 CO CO oo os in 00 N ΙΛ LO CO o 〇0 g CO s 03⁄4 CS3 Manufacturing condition Annealing time (hr) CM CM CVJ CM CvJ CM CM iD CSJ CM CSJ CSJ CSJ CNJ CNi 兮CNJ CO Tj* lie o 〇s CO o § o § o CO s CO o § s 兮〇^rs CO 〇§ s CO s CO o CO g CO o in CO ο CO g CO o CO gg CO g inch o § s lg g κο CO in (O oo o in ς〇un 1/3 00 (O 00 in 00 o ir> 00 00 ίβ 00 § Ι Ω CO LO {〇in g in s § LO (O oss 1 pass maximum reduction rate (%) 1—^ to 2 (〇in 00 <£> O C>3 2 00 eg o 2 1 in co ΙΗβ CM m CO 寸 K ΙΟ 00 σ> (D CSJ § § CNJ iD σ> In 00 (O to LO but co to CO s inch C>3 co 00 00 r—s Oi CNJ CM CSJ Rolling start temperature CC) g 03 s CO s CN3 s CO s CO s CM g CNJ 5 CO g CM s CO § CM CO s CvJ g CO s CM o CO s CSJ g CO g CO smo inch ss inch o ΙΩ g CvJ 1 1 1 i 兮1 1 1 1 ) 1 1 1 1 1 1 1 1 1 1 1 I 1 1 1 II g 1 1 1 1 om J 1 1 1 1 1 ] 1 1 1 1 1 1 1 1 1 1 1 1 1 Composition (unit is atomic %) • The remaining part A1 and the inevitable impurities) CO 1 soosoo 1 1 1 1 soo in oo 1 1 1 1 1 1 soo 1 soosoo 1 go ό 1 1 1 1 1 soo (O soo 1 1 1 1 soo (Ό 〇o 1 1 1 1 1 1 ΙΛ ooo I in oposoo 1 LO soo 1 1 1 1 gosogogoooso 1 1 1 1 1 1 1 1 sos o' sosooo Go 1 1 1 1 1 1 1 1 1 1 1 soso 1 I 1 I 1 1 1 g 〇l 1 soso § osogooo 1 1 \ 1 \ \ \ \ ° o ° o \ 1 odgo . 1 1 1 so 1 •3 I 1 1 I 1 1 irt c〇o ΙΛ CO 〇1ft CO 〇ΙΛ CO osososo another o 1 1 soso 1 1 so in CO o ° o 1 ° o 1 1 1 1 1 1 1 1 1 1 1 1 1 1 oooooooo 1 1 1 1 1 odooodoooooooo csi s C) sdsosos o' ooo CM' 〇§ o 1 1 1 1 soooso § oo I 1 _〇fH CSJ CO in (O 00 σ > o rH CNJ CO in !2 卜 — 00 2 s CNJ CNJ CO Cv3 守 CNJ 1Λ CM -26- 201130992 Table 1 can be examined as follows. First, N 〇 · 4 and 10 are examples of the alloy composition and the crystal grain size (average crystal grain size and maximum crystal grain size) in the rolling direction, which are examples of the requirements of the present invention, and the number of initial splashes is suppressed to 20 Below /cm2, the effect of reducing the initial splash is confirmed. Further, No. 1 to 3, 5 to 9, and 1 1 to 18 are examples in which the cold rolling ratio at the time of the second rolling is appropriately controlled, and the Vickers hardness satisfies the present invention in addition to the alloy composition and the crystal grain size. The preferred element. Therefore, the number of occurrences of the initial splash is further suppressed to 8 or less, and the effect of the initial splash is further reduced. On the other hand, in the following examples which do not satisfy any of the requirements of the present invention, the occurrence of initial splash cannot be effectively prevented. Specifically, first, No. 19 is an example in which the amount of Ni is small, and both the average crystal grain diameter and the maximum crystal grain size become large, and the number of initial splashes rises.

No. 20 is an example produced at a temperature higher than the upper limit (400 ° C) of the hot rolling start temperature recommended when using an Al-Ni-Nd-Ge alloy, and the average crystal grain size and the maximum crystal grain size are two. Both of them become larger, and the number of initial splashes increases. N0.21 is an example in which the total reduction ratio at the time of hot rolling is lower than the lower limit (60%) recommended by the present invention, and both the average crystal grain size and the maximum crystal grain diameter become large, and the initial splash The number of occurrences has risen.

No. 22 is an example produced at a temperature at which the hot rolling start temperature is higher than the upper limit (5 〇〇 ° C ) recommended by the present invention, and the average crystal grain size and the maximum -27-201130992 crystal grain size are changed. Large, the number of occurrences of initial splashes increased.

No. 23 is an example in which the maximum reduction ratio of one pass at the time of hot rolling is lower than the lower limit (2 %) recommended by the present invention, and both the average crystal grain size and the maximum crystal grain size become large. The number of occurrences of initial splashes increased.

No. 24 is an example in which the hot rolling start temperature is higher than the upper limit (5 〇 (TC)) recommended by the present invention, and both the average crystal grain size and the maximum crystal grain size become large, and the initial splash is The number of occurrences has increased.

No. 2 5 is an example in which the maximum reduction ratio of one pass at the time of hot rolling is lower than the lower limit (2%) recommended by the present invention, the maximum crystal grain size is increased, and the number of initial splashes is increased. . For reference, in the first (a) to (c) drawings, optical microscopes showing crystal grain sizes in the rolling direction in Nos. 3 and 4 (the above are the examples) and No. 20 (comparative examples) are shown. photo. As shown in these photographs, in No. 3 (Fig. 1 (a)) and 4 (Fig. 1 (b)), the average crystal grain size and the maximum crystal grain size in the rolling direction are controlled to be small, On the other hand, in No. 20 (Fig. 1 (c)), the crystal grain size in the rolling direction extends very long. (Example 2) In this example, the characteristics of the Al-based alloy film obtained by using the A1-based alloy sputtering target were evaluated. Specifically, the various A1 based alloys (the remaining portion: A1 and unavoidable impurities) described in Table 2 were prepared, and a sputtering target was produced by the method described in the above Example 1. Here, the hot rolling and annealing conditions are as described in Table 2, and the cold rolling and annealing conditions of -28-201130992 are as follows. The results of measuring the crystal grain size (average crystal grain size and maximum crystal grain size), the Vickers hardness, and the number of initial splashes in the rolling direction of the sputtering target obtained as described above were measured in the same manner as in the above-described Example 1.倂 is recorded in Table 2. Further, No. 1 and No. 4 of Table 2 correspond to No. 2 and No. 3 of Table 1 above. The sputtering target obtained as described above was used by DC magnetron sputtering [substrate = glass substrate (Eagle 2000, manufactured by Corning), atmosphere gas = argon gas, pressure = 2 mTorr, substrate temperature = 25 ° C ( Room temperature)] Various A1 alloy films (film thickness = 300 nm) were formed. The content of each of the alloying elements of Ni, Ge, and Nd of each of the A1 alloy films obtained as described above was determined by ICP emission analysis (inductively coupled plasma luminescence analysis). The results are shown in Table 2, which is consistent with the composition of the sputtering target for forming the A1 alloy film. Further, the content of Ti and B as a very small amount of the additive element in the A1 alloy film is a glass substrate of 4 inches. Five A1 alloy films (about 100 mg) were formed in a film thickness of 100 °rn, and analyzed by the following methods. The amount of Ti was calculated by ICP emission analysis. The amount of B is calculated in accordance with the amount of addition by ICP emission analysis or distillation to separate a curcumin absorption spectrophotometry. Using the A1 alloy film formed as described above, the resistivity of the A1 alloy film itself after heat treatment and the contact resistance with ITO when the A1 alloy film was directly connected to the transparent pixel electrode were measured by the method described below (hereinafter, a brief description) It is "contact resistance") and is resistant to peeling liquid. -29- 201130992 (1) The resistivity of the A1 alloy film itself after heat treatment is a line and space pattern of ΙΟμηι width for the above A1 alloy film, and 51: /min in an inert gas atmosphere. The heating rate was increased at a heating rate, and the heat treatment was performed at 270 ° C for 30 minutes or at 30 ° C for 30 minutes, and then the specific resistance was measured by a four-terminal method. (2) Contact resistance with the transparent pixel electrode The contact resistance when the alloy film is in direct contact with the transparent pixel electrode is by sputtering a transparent pixel electrode (ITO, adding 1 〇 atom% of tin oxide to indium oxide) under the following conditions The obtained indium tin oxide was used to produce the Kelvin pattern (contact hole size: ΙΟμιη square) shown in Fig. 2, and the 4-terminal measurement was performed (the current was flowed through the ΙΤΟ-Α1 alloy film, and the ΙΤΟ-Α1 alloy was measured by other terminals. The method of voltage reduction). Specifically, the current I and the monitored voltage V are passed between 1 and 12 in Fig. 2, whereby the contact resistance R of the contact portion C is determined to be [R = (V, -V2) / 12]. Then, the quality of the contact resistance is judged by the following criteria. Moreover, the contact resistance of the pure A1 alloy film is 1 5,000 Ω ° (film formation conditions of the transparent pixel electrode) • Atmosphere gas = gas. Pressure = 0.8 mTorr • Substrate temperature = 25 ° C (room temperature) (3) Stripping resistance Corrosion -30- 201130992 Observe the black spots (correctly pit corrosion density) generated after the stripping solution is cleaned. This black spot is generated around the precipitate with the precipitate as a base point as described above. Specifically, the sample obtained by the above-mentioned heat treatment (3 2 0. (3:10 minutes) was used, and the amine-based resist stripper (TOK106) manufactured by Tokyo Chemical Industry Co., Ltd. was used. The immersion liquid solution of =10.5 was immersed for 1 minute) - (immersed in a stripping solution aqueous solution adjusted to ρ Η = 9.5 for 5 minutes) - (washed with pure water) - > (dry). The optical microscope was observed at a magnification of 1,000 times (about 8600 μm 2 ), and the sample after washing was subjected to image analysis to measure the black dot density (number/ΙΟΟμιη2). (Criteria for evaluation) 〇: 4.0 or less /1 ΟΟμιη2 X: more than 4·0 /1 ΟΟμηι2 These results are not shown in Table 3. Table 2 and Table 3 correspond to each 〇. For example, the characteristics of No. 1 in Table 2 are No. 1 in Table 3.示》 -31 - 201130992 [s谳] After manufacture · (mm) 00 fH 21 00 o Surgery 1 飞溅 initial splash / cm2 CO in in CO (D CO 1 5 σ> CO σ> CO § § Oi CO 00 CO Maximum crystal size (μπΟ CO 〇> CsJ CO 甘 c a 00 00 inch (Ο 00 00 04 - average crystal grain size (μ m) CNJ σ> § LO but s in destruction condition C<3 CM CQ Ν OJ CM CM η o CO s CO nest CO s CO § CO ono廿gs 00 00 — (〇CO 00 CM o S in 00 CO 00 iO 00 CO in 00 00 1 pass maximum reduction ratio (%) CO 7 eg <〇<O 00 CO but r-^ 5 σ> CO inch CO but rolling start temperature (V) s rs o CO s eg § eg s CO s CO o CN3 rice S $ 1 1 1 1 1 1 1 SgM G Welcome letter t: 1 1 1 1 1 1 1 Composition ( The unit is atomic %, the remaining part A1 and the inevitable impurities) QQ soo 2 oonoosoo in opo 1 oso ό 2 oosod (DS oosoo 1 a d Q) asosogososososo c3 1 1 1 1 1 1 1 2 so § o 8 d § ddsdso J3 1 1 1 1 1 1 1 1 1 1 1 1 1 l Lack ooo 〇ododoooood 1 cq CO inch ΙΛ t— -32- 201130992

[Table 3] No. Wiring resistance (Μ Ω·αη) Contact resistance with ΠΌ (Ω) Corrosion resistance 2702⁄4 320t: Black dot density 7 (one / lOOumi judgment 1 3.7 3.4 65 2.7 〇 2 3.7 3.4 70 0 __ Ο -^- 3 3.7 3.4 70 0.1 Ο 4 3.7 3.4 65 0.4 〇5 3.9 3.5 120 0 _ 〇6 3.7 3.4 60 4.1 X 7 3.7 3.5 80 4.9 ^X The results of Tables 2 and 3 can be examined as follows. The A1 based alloy sputtering target described in Table 2 satisfies the invention. The A1 based alloy film obtained by using such a spatter target is as shown in Table 3 & The contact resistance of ITO is also suppressed to be low. 'It is useful as a wiring film for direct contact with IT 0.>> As shown in No. 1 to 5 of Table 2, the amount of Ti and the amount of B are controlled within a preferred range, and no addition is made. Ti and B in Table 2, N〇.6, or No. 7 in Table 2, which does not contain a preferred amount of Ti and B, are known to have excellent corrosion resistance to the peeling liquid. As the contents of Ti and B increase, it is visible. Corrosion resistance of the peeling-resistant liquid tends to increase. In addition, Νο·5 of Table 2 is the ratio of the total content of the group A (Ni, Co) to the total content of the group B (La, Nd) (A /B group = 0.10 / 0.27 and 0.37) In order to satisfy the more preferable range (〇·4 or less) of the present invention, the black dot density can be suppressed. The present application will be described in detail with reference to a specific embodiment. However, various changes and modifications may be made without departing from the spirit and scope of the invention, which is known to those skilled in the art. -33- 201130992 This application is based on the application dated October 23, 2009 (patent application 2009-244414 ), July 15, 2010 application (patent application 2 0 1 0 - 1 6 1 0 0 2), the contents of which are cited. [Simplified illustration] [Figure 1] 1 (a) ~ (c) The figure is an optical micrograph of the crystal grain size of s1 (a), 4 (1 (b), and ν 〇). [Fig. 2] Fig. 2 is a view showing a Kelvin diagram 3 in which the contact resistance between the film and the transparent pixel electrode is used in the second embodiment. Japanese Patent Application No. 1 is hereby incorporated by reference to the entire disclosure of N 〇 · 3 (20 (1) in the measurement of A1 alloy (TEG pattern) -34-

Claims (1)

201130992 VII. Patent application scope: 1. A type A1 alloy splashing target, which contains: at least one selected from group A consisting of Ni and Co, and group B composed of La and Nd Selecting at least one of the A1 based alloy sputtering targets, and measuring the crystal grain size in the rolling direction of the surface parallel to the rolling direction in the cross section perpendicular to the rolling surface of the sputtering target, The crystal grain size is 500 μm or less, and the maximum crystal grain size is 1 500 μm or less. 2. The bismuth-based alloy sputtering target according to the first aspect of the invention, wherein the total content of the ruthenium group is 0.05 atom% or more and 2.5 atom% or less and the total content of the group B is 0.1 atom% or more. 1 atom% or less. 3. The A1 based alloy sputtering target according to the first aspect of the invention, which further comprises at least one selected from the group consisting of Cu and Ge. 4. The A1-based alloy sputtering target as described in claim 3, wherein the total content of the group C is 0.1% by atom or more and 1% by atom or less. 5. The A1 based alloy sputter 祀 as described in claim 1 further contains Ti and B. 6. The A1 based alloy sputtering target as described in claim 5, wherein the Ti content is 0_00 〇 2 atom% or more 〇. 〇 12 atom% or less, and the B 衅 is 0.0002 atom% or more and 0.012 atom% or less. The aluminum-based alloy sputtering target according to the first aspect of the invention, wherein only Ni is selected from the group A, and only Nd is selected from the group b. 8. The A-based alloy sputtering target according to the first aspect of the invention, wherein only Ni is selected from the group A, and only La is selected from the group b. 9. The a bismuth-based alloy sputtering target according to the third aspect of the invention, wherein only Ni is selected from the group A, and only Nd is selected from the group B, and only Ge is selected from the group C. 1A. The A-based alloy sputtering target according to the first aspect of the invention, which has a Vickers hardness H v of 26 or more. A bismuth-based alloy film obtained by using a sputtering target according to any one of the above-mentioned items of the first aspect of the invention, which is directly connected to a transparent conductive film. The A1 base alloy film according to the item n of the patent application, which contains: at least one selected from the group consisting of Ni and Co, and the group B composed of La and Nd The at least one selected from the group consisting of at least one species, and the group consisting of Ge and the butyl group and B, Τι content is 〇.〇0〇4 atom% or more and 0.008 atom% or less, and the B content is 0.0004 atom. % or more 〇〇. 〇〇 8 atom% or less. -36-