[發明所欲解決的問題] [0007] 可是，使用濺鍍靶進行成膜時，有因電荷的集中而發生異常放電(發弧)，因此會無法形成均勻的配線膜。所謂的異常放電，就是與正常的濺鍍時比較下，極端高的電流突然急劇地流動，異常大的放電急劇發生之現象，若發生如此的異常放電，則成為粒子的發生原因，有配線膜的膜厚成為不均勻之虞。因此，宜儘可能地避免成膜時的異常放電。 特別地最近，於半導體裝置、液晶或有機EL面板等的平板顯示器、觸控面板等中，要求配線膜的更高密度化，比以往亦增加，有安定地形成經微細化及薄膜化的配線膜之必要。 [0008] 於專利文獻1記載的濺鍍用銅靶中，記載將再結晶組織的平均結晶粒徑予以微細化，同時減低應變量，但沒有特別言及雜質。例如，當含有硫(S)作為雜質時，由於抑制再結晶的進行，有無法得到均勻的再結晶組織之虞。因此，即使全體的平均結晶粒徑小，應變量低，也當未再結晶區域存在，應變量局部地高之區域存在時，有容易發生異常放電之虞。 [0009] 又，於專利文獻2記載的濺鍍靶之製造方法中，藉由區域熔化法製造純度為99.9995%的熔化鑄錠，抑制雜質量，但是由於完全沒有考慮再結晶行為，亦沒有考慮應變量，故仍然有發生異常放電之虞。又，由於使用區域熔化法，有生產效率大幅降低之問題。 [0010] 本發明係鑒於前述情況而完成者，目的在於提供一種濺鍍靶用銅材料，其可抑制異常放電之發生，安定地進行成膜，同時能以低成本製造。 [解決問題的手段] [0011] 為了解決前述問題，本發明之濺鍍靶用銅材料係以0.001質量%以上0.008質量%以下之範圍內含有由Zr、Ti、Mg、Mn、La、Ca所選出之1種或2種以上的添加元素，Cu的含量與前述添加元素的含量之合計為99.99質量%以上。 [0012] 於此濺鍍靶用銅材料中，以0.001質量%以上0.008質量%以下之範圍內含有由Zr、Ti、Mg、Mn、La、Ca所選出之1種或2種以上的添加元素，Cu的含量與前述添加元素的含量之合計為99.99質量%以上，由於不超出需要地高純度化，可以比較低的成本製造。 又，由於以0.001質量%以上0.008質量%以下之範圍內含有由Zr、Ti、Mg、Mn、La、Ca所選出之1種或2種以上的添加元素，可將S作為與此等添加元素的化合物固定，可抑制因S而阻礙再結晶之進行者。因此，可得到均勻的再結晶組織，可抑制成膜時的異常放電(發弧)之發生。作為前述硫化合物，可舉出ZrS2
、TiS、TiS2
、MgS、MnS、LaS、La2
S3
、CaS等。 [0013] 於本發明之濺鍍靶用銅材料中，S的含量較佳設為0.005質量%以下。此時，由於S的含量被限制在0.005質量%以下，可藉由上述的添加元素而確實地固定S，可得到均勻的再結晶組織，可抑制成膜時的異常放電(發弧)之發生。又，可抑制導電率之降低。 [0014] 又，於本發明之濺鍍靶用銅材料中，於與濺鍍面同一平面內，包含前述添加元素與S的化合物所佔有的面積率較佳為0.4%以下。此時，由於將包含前述添加元素與S的化合物所佔有的面積率抑制在0.4%以下，可抑制再結晶溫度的高溫化，進一步促進再結晶之進行，可更抑制未再結晶區域之生成。又，可確實地抑制因包含添加元素與S的化合物所造成的異常放電之發生。 [0015] 再者，於本發明之濺鍍靶用銅材料中，維氏硬度較佳為80Hv以下。此時，具有均勻的再結晶組織，再者充分地釋放應變，可確實地抑制成膜時的異常放電(發弧)之發生。 [0016] 又，於本發明之濺鍍靶用銅材料中，於與濺鍍面同一平面內的複數地方所測定的維氏硬度之標準偏差較佳為10以下。此時，由於應變被均勻地釋放，而沒有應變量局部地高之區域，可確實地抑制異常放電之發生。 [0017] 再者，本發明之濺鍍靶用銅材料係平均結晶粒徑較佳為100μm以下。此時，由於平均結晶粒徑為100μm以下之比較微細，在濺鍍進行時，於濺鍍面上所發生的凹凸變小，可抑制異常放電之發生。 另一方面，本發明之濺鍍靶具有由前述濺鍍靶用銅材料所構成的靶本體與在前述靶本體之一面上所固定的背板。於此濺鍍靶中，亦可得到前述優異的效果。 [發明效果] [0018] 依照本發明，可提供一種濺鍍靶用銅材料，其可抑制異常放電之發生，安定地進行成膜，同時能以低成本製造。[Problems to be Solved by the Invention] However, when a film is formed by using a sputtering target, abnormal discharge (arcing) occurs due to concentration of electric charges, and thus a uniform wiring film cannot be formed. The so-called abnormal discharge is a phenomenon in which an extremely high current suddenly flows abruptly and an abnormally large discharge suddenly occurs in comparison with a normal sputtering. If such an abnormal discharge occurs, a particle is generated, and a wiring film is formed. The film thickness becomes uneven. Therefore, it is desirable to avoid abnormal discharge at the time of film formation as much as possible. In particular, in a flat panel display such as a semiconductor device, a liquid crystal, or an organic EL panel, a touch panel, or the like, a higher density of the wiring film is required, and the wiring is required to be formed to be finer and thinner. The film is necessary. [0008] In the copper target for sputtering described in Patent Document 1, it is described that the average crystal grain size of the recrystallized structure is miniaturized and the amount of strain is reduced, but impurities are not particularly mentioned. For example, when sulfur (S) is contained as an impurity, since the progress of recrystallization is suppressed, there is a possibility that a uniform recrystallized structure cannot be obtained. Therefore, even if the average crystal grain size of the whole is small, the strain amount is low, and when the non-recrystallized region exists and the region where the strain amount is locally high exists, the abnormal discharge is likely to occur. Further, in the method for producing a sputtering target described in Patent Document 2, a molten ingot having a purity of 99.9995% is produced by a zone melting method to suppress the amount of impurities, but since recrystallization behavior is not considered at all, it is not considered. Due to the variable, there is still a flaw in the abnormal discharge. Moreover, there is a problem that the production efficiency is greatly lowered due to the use of the area melting method. The present invention has been made in view of the above circumstances, and it is an object of the invention to provide a copper material for a sputtering target which can suppress the occurrence of abnormal discharge, stably form a film, and can be manufactured at low cost. [Means for Solving the Problem] In order to solve the above problem, the copper material for a sputtering target of the present invention contains Zr, Ti, Mg, Mn, La, and Ca in a range of 0.001% by mass or more and 0.008% by mass or less. One or two or more kinds of the additive elements are selected, and the total content of Cu and the content of the above-mentioned additive elements is 99.99% by mass or more. [0012] In the copper material for a sputtering target, one or two or more kinds of additive elements selected from Zr, Ti, Mg, Mn, La, and Ca are contained in a range of 0.001% by mass or more and 0.008% by mass or less. The total content of Cu and the content of the above-mentioned additive element is 99.99% by mass or more, and since it is not required to be highly purified, it can be produced at a relatively low cost. In addition, since one or two or more kinds of additive elements selected from Zr, Ti, Mg, Mn, La, and Ca are contained in the range of 0.001% by mass or more and 0.008% by mass or less, S may be added as such an additive element. The compound is immobilized to inhibit the progress of recrystallization by S. Therefore, a uniform recrystallized structure can be obtained, and occurrence of abnormal discharge (arcing) at the time of film formation can be suppressed. Examples of the sulfur compound include ZrS 2 , TiS, TiS 2 , MgS, MnS, LaS, La 2 S 3 , and CaS. In the copper material for a sputtering target of the present invention, the content of S is preferably 0.005% by mass or less. In this case, since the content of S is limited to 0.005 mass% or less, S can be surely fixed by the above-mentioned additive element, whereby a uniform recrystallized structure can be obtained, and occurrence of abnormal discharge (arcing) at the time of film formation can be suppressed. . Moreover, the decrease in electrical conductivity can be suppressed. Further, in the copper material for a sputtering target of the present invention, the area ratio of the compound containing the additive element and S in the same plane as the sputtering surface is preferably 0.4% or less. In this case, since the area ratio of the compound containing the additive element and S is suppressed to 0.4% or less, the temperature of the recrystallization temperature can be suppressed, and the progress of recrystallization can be further promoted, and the formation of the non-recrystallized region can be further suppressed. Further, the occurrence of abnormal discharge due to the compound containing the additive element and S can be surely suppressed. Further, in the copper material for a sputtering target of the present invention, the Vickers hardness is preferably 80 Hv or less. At this time, a uniform recrystallized structure is obtained, and the strain is sufficiently released, and the occurrence of abnormal discharge (arcing) at the time of film formation can be surely suppressed. Further, in the copper material for a sputtering target of the present invention, the standard deviation of the Vickers hardness measured in a plurality of places on the same plane as the sputtering surface is preferably 10 or less. At this time, since the strain is uniformly released without the region where the strain amount is locally high, the occurrence of the abnormal discharge can be surely suppressed. Further, the copper material for sputtering target of the present invention preferably has an average crystal grain size of 100 μm or less. In this case, since the average crystal grain size is 100 μm or less, the irregularities occurring on the sputtering surface are reduced, and the occurrence of abnormal discharge can be suppressed. On the other hand, the sputtering target of the present invention has a target body composed of the copper material for a sputtering target and a back plate fixed to one surface of the target body. In the sputtering target, the above excellent effects can also be obtained. [Effect of the Invention] According to the present invention, it is possible to provide a copper material for a sputtering target which can suppress the occurrence of abnormal discharge, stably form a film, and can be manufactured at low cost.
[實施發明的形態] [0020] 以下，說明本發明之一實施形態的濺鍍靶用銅材料。 本實施形態之濺鍍靶用銅材料係在半導體裝置、液晶或有機EL面板等之平板顯示器、觸控面板等中將作為配線膜使用的銅膜在基板上成膜時所用之濺鍍靶的材料。濺鍍靶用銅材料之形狀係沒有限定，但例如可為圓板狀、矩形平板狀、圓筒形狀。 [0021] 本實施形態之濺鍍靶用銅材料之組成係以0.001質量%以上0.008質量%以下之範圍內含有由Zr、Ti、Mg、Mn、La、Ca所選出之1種或2種以上的添加元素，Cu的含量與前述添加元素的含量之合計為99.99質量%以上。又，於本實施形態中，S的含量係設為0.005質量%以下。 [0022] 又，本實施形態之濺鍍靶用銅材料係於與濺鍍面同一平面內，包含前述添加元素(由Zr、Ti、Mg、Mn、La、Ca所選出的1種或2種以上)與S的化合物所佔有的面積率係設為0.4%以下。 再者，本實施形態之濺鍍靶用銅材料係將維氏硬度設為80Hv以下。 還有，本實施形態之濺鍍靶用銅材料係將於與濺鍍面同一平面內的複數地方所測定的維氏硬度之標準偏差設為10以下。 再者，本實施形態之濺鍍靶用銅材料係將平均結晶粒徑設為100mm以下。 [0023] 以下，說明如上述地規定本實施形態之濺鍍靶用銅材料之組成、濺鍍面中的化合物之面積率、維氏硬度、維氏硬度之標準偏差，平均結晶粒徑之理由。 [0024] (由Zr、Ti、Mg、Mn、La、Ca所選出之1種或2種以上的添加元素：0.001質量%以上0.008質量%以下) 上述的添加元素由於是硫化物生成自由能比Cu更低之元素，而可與S(硫)形成化合物，可固定S的全量或大部分。藉此，可促進再結晶。 [0025] 當由Zr、Ti、Mg、Mn、La、Ca所選出之1種或2種以上的添加元素的含量未達0.001質量%時，有無法充分固定銅中的S之虞。另一方面，若由Zr、Ti、Mg、Mn、La、Ca所選出之1種或2種以上的添加元素的含量超過0.008質量%，則包含添加元素與S的化合物之粒子係多數地生成，或化合物之粒子粗大化，有發生因露出濺鍍面的此化合物之粒子所造成的異常放電發生之虞。 [0026] 因此，於本實施形態中，將由Zr、Ti、Mg、Mn、La、Ca所選出之1種或2種以上的添加元素之含量設為0.001質量%以上0.008質量%以下之範圍內。 為了更充分地固定銅中的S，較佳將由Zr、Ti、Mg、Mn、La、Ca所選出之1種或2種以上的添加元素之含量之下限設為0.0015質量%以上，更佳設為0.0020質量%以上。 又，為了因化合物所造成的異常放電之發生，較佳為將由Zr、Ti、Mg、Mn、La、Ca所選出之1種或2種以上的添加元素之含量的上限設為0.0060質量%以下，更佳設為0.0040質量%以下。 [0027] (Cu的含量與添加元素的含量之合計為99.99質量%以上) 以濺鍍將配線膜(高純度銅膜)予以成膜時，為了抑制異常放電(發弧)，較佳為盡量減少雜質。惟，為了高純度化到Cu的含量與添加元素的含量之合計為99.999質量%以上，製造步驟變複雜，製造成本大幅地上升。因此，於本實施形態中，藉由將Cu的含量與添加元素的含量之合計設為99.99質量%以上，而謀求製造成本之減低。又，Cu的含量與添加元素的含量之合計的上限，從製造成本的減低之觀點來看，較佳設為未達99.999質量%。 [0028] (S：0.005質量%以下) S係阻礙銅的再結晶之進行，同時使導電率降低之元素。S的含量超過0.005質量%時，即使添加上述的添加元素時，也無法充分固定S，再結晶變不充分，生成未再結晶區域，有應變量變局部地不均勻之虞。又，有導電率降低之虞。 因此，為了充分進行再結晶，將應變量充分地均勻化，同時確保導電率，較佳為將S的含量限制在0.005質量%以下。S的含量較佳設為0.003質量%以下，更佳設為0.001質量%以下。惟，由於難以使S的含量成為零，故可為0.0003質量%以上。 [0029] (於與濺鍍面同一平面內，包含添加元素與S的化合物所佔有的面積率：0.4%以下) 藉由添加由Zr、Ti、Mg、Mn、La、Ca所選出之1種或2種以上的添加元素，而生成包含添加元素與S的化合物，此化合物的一部分會混入濺鍍靶用銅材料中。當包含此添加元素與S的化合物之粒子數變多時，或當化合物的粒子已粗大化時，有再結晶溫度高溫化而抑制再結晶之虞。又，於成膜時，有由於此化合物的粒子露出濺鍍面而發生異常放電之虞。 因此，於本實施形態中，將包含添加元素與S的化合物所佔有的面積率設為0.4%以下。包含添加元素與S的化合物所佔有的面積率較佳設為0.3%以下，更佳設為0.1%以下。由於難以使前述面積率成為零，故可為0.03%以上。 [0030] (維氏硬度：80Hv以下) 於促進再結晶，充分釋放應變時，維氏硬度變低。若維氏硬度為80Hv以下，則再結晶充分進行，釋放應變。因此，於本實施形態中，將維氏硬度限定在80Hv以下。維氏硬度較佳設為65Hv以下，更佳設為50Hv以下。前述維氏硬度亦可為30Hv以上。 於本實施形態中，將於與濺鍍面同一平面內的複數地方所測定的維氏硬度之平均值設為80Hv以下。所謂的於與濺鍍面同一平面，就是意指將銅材料成形為濺鍍靶後，與所濺鍍的面平行之面，此面視需要可經過研削或研磨或洗淨而成為濺鍍面。 [0031] (於與濺鍍面同一平面內的複數地方所測定的維氏硬度之標準偏差：10以下) 當具有未再結晶區域，應變局部地高之區域存在時，在維氏硬度發生偏差。 若於與濺鍍面同一平面內的複數地方所測定的維氏硬度之標準偏差為10以下，則維氏硬度之參差小，應變局部地高之區域幾乎不存在。 因此，於本實施形態中，將於與濺鍍面同一平面內的複數地方所測定的維氏硬度之標準偏差限定在10以下。於與濺鍍面同一平面內的複數地方所測定的維氏硬度之標準偏差較佳設為5以下，更佳設為3以下。 [0032] 於本實施形態中，上述維氏硬度之測定位置係按照濺鍍靶用銅材料之形狀，如下述地設定。 [0033] 當濺鍍靶用銅材料之濺鍍面為圓形時，如圖1所示地，於圓的中心(1)及通過圓的中心同時互相正交的2條直線上之外周部分(2)、(3)、(4)、(5)的5個地方，測定維氏硬度，算出其平均值及標準偏差。所謂的前述外周部分，例如就是指位於自銅材料的外周緣起5mm內側之點。 [0034] 當濺鍍靶用銅材料之濺鍍面為矩形時，如圖2所示地，於對角線交叉的交點(1)與各對角線上的角部(2)、(3)、(4)、(5)之5個地方，測定維氏硬度，算出其平均值及標準偏差。前述所謂的角部，例如就是指自矩形的頂點起，沿著對角線，位於5mm內側之點。 [0035] 當濺鍍靶用銅材料之濺鍍面為圓筒面時，如圖3A及圖3B所示地，於圍周方向中空出等間隔的3個地方，畫出假想線，於此等3條的假想線上，決定在軸線方向中分隔的3個地方，在此等合計9個地方(A1～A3、B1～B3、C1～C3)，測定維氏硬度，算出其平均值及標準偏差。各假想線上的3個地方，係例如指假想線的中心點與位於自假想線的兩端起10mm內側之點。 [0036] (平均結晶粒徑：100μm以下) 濺鍍速率係當離子1個衝撞靶時，自靶所飛出的原子數之統計上機率值，隨著露出濺鍍面的各結晶的結晶方位而不同。因此，若濺鍍進行，則在濺鍍面上，因濺鍍速率之差異，產生對應於結晶粒的凹凸。 若濺鍍面的平均結晶粒徑超過100mm，則結晶方位的異向性變顯著，故在濺鍍面所產生的凹凸變大，電荷集中於凸部而容易發生異常放電。基於如此的理由，於本實施形態之濺鍍靶用銅材料中，將平均結晶粒徑規定在100mm以下。於本實施形態中，更佳為將平均結晶粒徑設為80mm以下，尤佳設為50mm以下。平均結晶粒徑亦可為5mm以上。 [0037] 接著，參照圖4，說明本實施形態之濺鍍靶用銅材料之製造方法的一例。 [0038] (熔化・鑄造步驟S01) 首先，將銅的純度為99.99質量%以上的銅原料予以熔化，得到銅熔液。其次，於所得之銅熔液中，以成為指定的濃度之方式添加由Zr、Ti、Mg、Mn、La、Ca所選出之1種或2種以上的添加元素，進行成分調製，得到銅合金熔液。 然後，於本實施形態中，使用連續鑄造裝置，製造指定的剖面形狀(例如矩形狀、圓形狀、圓環形狀)之鑄塊。 [0039] (冷軋加工步驟S02) 接著，對於具有指定的剖面形狀之鑄塊，進行冷軋加工。此冷軋加工的加工率較佳設為40.0%以上99.9%以下之範圍內。 [0040] (熱處理步驟S03) 接著，於冷軋加工後實施熱處理。此時的熱處理溫度較佳設為100℃以上600℃以下之範圍內，保持時間較佳設為30分鐘以上300分鐘以下之範圍內。熱處理溫度較佳設為150℃以上400℃以下之範圍內，保持時間較佳設為60分鐘以上180分鐘以下之範圍內。藉由此熱處理步驟S03，再結晶進行，釋放冷軋加工步驟S02中所賦予的應變。 [0041] (機械加工步驟S04) 接著，於熱處理後進行機械加工，去除表面的氧化膜，同時精加工成指定的形狀。 藉由如以上的步驟，製造本實施形態之濺鍍靶用銅材料。於製造濺鍍靶時，藉由將前述銅材料加工成所欲的形狀，在前述銅材料之背面上，按照需要接合由銅等的金屬所構成之背板，而得到濺鍍靶。於銅材料與背板之間，視需要可設置由In或In合金等所構成之接合層。 [0042] 藉由如以上所構成的本實施形態之濺鍍靶用銅材料，以0.001質量%以上0.008質量%以下之範圍內含有由Zr、Ti、Mg、Mn、La、Ca所選出之1種或2種以上的添加元素，Cu的含量與前述添加元素的含量之合計為99.99質量%以上，由於不超出需要地高純度化，可以比較低的成本製造。 又，由於以0.001質量%以上0.008質量%以下之範圍含有由Zr、Ti、Mg、Mn、La、Ca所選出之1種或2種以上的添加元素，可將S作為與此等的添加元素之化合物固定，可抑制因S而阻礙再結晶之進行者。因此，可得到均勻的再結晶組織，可抑制成膜時的異常放電(發弧)之發生。 [0043] 又，於本實施形態中，由於將S的含量限制在0.005質量%以下，可藉由從Zr、Ti、Mg、Mn、La、Ca所選出之1種或2種以上的添加元素，確實地固定S，可得到均勻的再結晶組織，可抑制成膜時的異常放電(發弧)之發生。又，可抑制導電率之降低。 [0044] 再者，於本實施形態中，由於將於與濺鍍面同一平面內包含添加元素與S的化合物所佔有的面積率抑制在0.4%以下，可抑制再結晶溫度之高溫化，進一步促進再結晶，可更抑制未再結晶區域之生成。又，可確實地抑制因包含添加元素與S的化合物所造成的異常放電之發生。 [0045] 再者，於本實施形態中，由於將維氏硬度設為80Hv以下，而具有均勻的再結晶組織，再者充分地釋放應變，可確實地抑制成膜時的異常放電(發弧)之發生。 又，於本實施形態中，由於將於與濺鍍面同一平面內的複數地方所測定的維氏硬度之標準偏差設為10以下，而應變被均勻地釋放，沒有應變量局部地高之區域，可確實地抑制異常放電之發生。 [0046] 再者，於本實施形態中，如圖1至圖3所示地，由於按照濺鍍靶用銅材料之形狀，規定維氏硬度之測定地方，故可恰當地算出於與濺鍍面同一平面內的複數地方所測定的維氏硬度之平均值及標準偏差，可得到具有均勻的應變之濺鍍靶用銅材料。 [0047] 又，於本實施形態中，由於平均結晶粒徑為100μm以下之比較微細，在濺鍍進行時，於濺鍍面上所發生的凹凸變小，可抑制異常放電之發生。 [0048] 再者，於本實施形態中，雖然在熔化・鑄造步驟S01之後實施冷軋加工步驟S02、熱處理步驟S03，但如上述，藉由從Zr、Ti、Mg、Mn、La、Ca所選出之1種或2種以上的添加元素來固定S(硫)，促進再結晶之進行，故可得到均勻的再結晶組織。 [0049] 以上，說明本發明之實施形態，惟本發明不受此所限定，於不脫離本發明的技術思想之範圍內可適宜變更。 於本實施形態中，舉出形成高純度銅膜作為配線膜的濺鍍靶作為例子，進行說明，惟不受此所限定，於其他用途中使用銅膜時亦可適用。 [0050] 關於濺鍍靶用銅材料之製造方法，不受本實施形態所限定，亦可藉由其他的製造方法來製造。例如，於熔化・鑄造步驟後，亦可具有熱軋加工步驟。又，不使用連續鑄造裝置，例如藉由分批式的鑄造裝置，亦可得到鑄塊。 [實施例] [0051] 以下，說明對於前述本實施形態之濺鍍靶用銅材料進行評價的評價試驗之結果。 [0052] 準備純度為99.99質量%以上之銅原料，以成為如表1所示的組成之方式，熔製銅熔液，使用連續鑄造裝置，得到具有50mm´200mm的矩形狀剖面之鑄塊。 對於所得之鑄塊，以表2中所示的加工率實施冷軋。然後，於表2所示的條件下實施熱處理。 然後，進行切削加工，得到成為10mm´130mm´ 140mm的矩形狀之濺鍍靶用銅材料。 [0053] 對於所得之濺鍍靶用銅材料，用以下之程序評價於與濺鍍面同一平面內包含添加元素與S的化合物所佔有的面積率、維氏硬度的平均值與標準偏差、平均結晶粒徑、導電率、異常放電發生次數。表2中顯示評價結果。 [0054] (化合物的面積率) 以SEM-EPMA，實施視野60mm´80mm的面分析，將於同一地方檢測出添加元素M與S之情況視為M-S化合物，藉由「檢測區域(全數)÷觀察區域(60mm´80mm)´100」，算出面積率。 [0055] (維氏硬度) 於濺鍍靶用銅材料之與濺鍍面同一平面內中，在如圖2所示的位置，根據JIS Z 2244，用維氏硬度試驗機測定維氏硬度，算出其平均值及標準偏差。表2中顯示評價結果。 [0056] (平均結晶粒徑) 於濺鍍靶用銅材料之與濺鍍面同一平面中，自圖2所示之位置，採集觀察用試驗片，使用光學顯微鏡進行微組織觀察，根據JIS H 0501：1986(切斷法)，測定結晶粒徑，算出平均結晶粒徑。2中顯示評價結果。 [0057] (成膜條件) 將所得之濺鍍靶用銅材料接合至背板，在以下之條件下形成銅的薄膜。 濺鍍電壓：3000V 極限真空度：5´10-4
Pa 濺鍍氣體：Ar，0.4Pa 於前述成膜條件下進行1小時的濺鍍，對於異常放電之發生次數，以附屬於濺鍍電源裝置的發弧計數器，自動地計測其次數。2中顯示評價結果。 [0058][0059][0060] 於未添加由Zr、Ti、Me、Mn、La、Ca所選出之1種或2種以上的添加元素之比較例1中，維氏硬度的標準偏差大，異常放電發生次數比較多。推測此係因為因S妨礙再結晶之進行，未再結晶區域存在，應變局部地高之區域存在。 於超過0.008質量%添加有由Zr、Ti、Me、Mn、La、Ca所選出之1種或2種以上的添加元素之比較例2中，化合物的面積率高，異常放電發生次數比較多。又，導電率亦變低。 於Cu的含量與前述添加元素的含量之合計未達99.99質量%之比較例3中，維氏硬度高，標準偏差亦大。又，平均結晶粒徑亦大，異常放電之發生次數變多。推測此係因為再結晶不充分、應變高。 [0061] 相對於其，若為於以0.001質量%以上0.008質量%以下之範圍內含有由Zr、Ti、Mg、Mn、La、Ca所選出之1種或2種以上的添加元素，Cu的含量與前述添加元素的含量之合計為99.99質量%以上之本發明例1-23，則異常放電之發生次數少。推測此係因為促進再結晶，均勻地釋放應變。 由以上確認，藉由本發明之濺鍍靶用銅材料，抑制異常放電之發生，可安定地成膜。[Embodiment of the Invention] [0020] Hereinafter, a copper material for a sputtering target according to an embodiment of the present invention will be described. The copper material for a sputtering target of the present embodiment is a sputtering target used for forming a copper film used as a wiring film on a substrate in a flat panel display such as a semiconductor device, a liquid crystal or an organic EL panel, or a touch panel. material. The shape of the copper material for the sputtering target is not limited, but may be, for example, a disk shape, a rectangular plate shape, or a cylindrical shape. [0021] The composition of the copper material for a sputtering target of the present embodiment contains one or more selected from the group consisting of Zr, Ti, Mg, Mn, La, and Ca in a range of 0.001% by mass or more and 0.008% by mass or less. The additive element has a total content of Cu and a content of the aforementioned additive element of 99.99% by mass or more. Further, in the present embodiment, the content of S is set to 0.005% by mass or less. Further, the copper material for a sputtering target of the present embodiment is contained in the same plane as the sputtering surface, and includes the above-mentioned additive element (one or two selected from Zr, Ti, Mg, Mn, La, and Ca). The area ratio occupied by the compound of the above) and S is set to 0.4% or less. In addition, the copper material for a sputtering target of the present embodiment has a Vickers hardness of 80 Hv or less. Further, the copper material for the sputtering target of the present embodiment has a standard deviation of Vickers hardness measured at a plurality of places in the same plane as the sputtering surface, and is 10 or less. In addition, the copper material for a sputtering target of the present embodiment has an average crystal grain size of 100 mm or less. [0023] Hereinafter, the composition of the copper material for sputtering target of the present embodiment, the area ratio of the compound in the sputtering surface, the standard deviation of Vickers hardness and Vickers hardness, and the reason of the average crystal grain size are defined as described above. . (1 or 2 or more types of additive elements selected from Zr, Ti, Mg, Mn, La, and Ca: 0.001% by mass or more and 0.008% by mass or less) The above-mentioned additive element is a sulfide-forming free energy ratio The lower element of Cu forms a compound with S (sulfur) and can fix the full or majority of S. Thereby, recrystallization can be promoted. When the content of one or two or more kinds of additive elements selected from Zr, Ti, Mg, Mn, La, and Ca is less than 0.001% by mass, S in the copper may not be sufficiently fixed. On the other hand, when the content of one or two or more kinds of additive elements selected from Zr, Ti, Mg, Mn, La, and Ca is more than 0.008% by mass, the particles containing the compound of the additive element and S are mostly produced. Or the particles of the compound are coarsened, and abnormal discharge due to particles of the compound exposed on the sputtering surface may occur. Therefore, in the present embodiment, the content of one or two or more kinds of additive elements selected from Zr, Ti, Mg, Mn, La, and Ca is in the range of 0.001% by mass to 0.008% by mass. . In order to more sufficiently fix S in the copper, the lower limit of the content of one or two or more kinds of additive elements selected from Zr, Ti, Mg, Mn, La, and Ca is preferably 0.0015% by mass or more, and more preferably It is 0.0020% by mass or more. In addition, the upper limit of the content of one or two or more kinds of additive elements selected from Zr, Ti, Mg, Mn, La, and Ca is preferably 0.0060% by mass or less for the occurrence of abnormal discharge due to the compound. More preferably, it is set to 0.0040% by mass or less. (The total content of Cu and the content of the additive element is 99.99% by mass or more) When a wiring film (high-purity copper film) is formed by sputtering, in order to suppress abnormal discharge (arcing), it is preferable to try to suppress abnormal discharge (arcing) Reduce impurities. However, in order to increase the purity to a total of the content of Cu and the content of the additive element to be 99.999 mass% or more, the production steps are complicated, and the production cost is greatly increased. Therefore, in the present embodiment, the total of the content of Cu and the content of the additive element is set to be 99.99% by mass or more, thereby reducing the manufacturing cost. In addition, the upper limit of the total content of Cu and the content of the additive element is preferably less than 99.999 mass% from the viewpoint of reduction in production cost. (S: 0.005 mass% or less) S is an element which inhibits the progress of recrystallization of copper and lowers the electrical conductivity. When the content of S is more than 0.005 mass%, even when the above-mentioned additive element is added, S cannot be sufficiently fixed, and recrystallization is insufficient, and a non-recrystallized region is formed, and the strain is locally uneven. In addition, there is a decrease in electrical conductivity. Therefore, in order to sufficiently recrystallize, the strain amount is sufficiently uniform and the conductivity is ensured, and it is preferable to limit the content of S to 0.005 mass% or less. The content of S is preferably 0.003% by mass or less, and more preferably 0.001% by mass or less. However, since it is difficult to make the content of S zero, it can be 0.0003 mass% or more. [0029] (area ratio of the compound containing the additive element and S in the same plane as the sputter surface: 0.4% or less) by adding one selected from Zr, Ti, Mg, Mn, La, and Ca Or two or more types of addition elements, and a compound containing an additive element and S is produced, and a part of this compound is mixed in the copper material for sputtering targets. When the number of particles of the compound containing the additive element and S is increased, or when the particles of the compound are coarsened, the recrystallization temperature is increased to suppress recrystallization. Further, at the time of film formation, there is a possibility that abnormal discharge occurs due to the particles of the compound being exposed to the sputtering surface. Therefore, in the present embodiment, the area ratio occupied by the compound containing the additive element and S is set to 0.4% or less. The area ratio of the compound containing the additive element and S is preferably 0.3% or less, more preferably 0.1% or less. Since it is difficult to make the aforementioned area ratio zero, it can be 0.03% or more. (Vickers hardness: 80 Hv or less) When the recrystallization is promoted and the strain is sufficiently released, the Vickers hardness is lowered. When the Vickers hardness is 80 Hv or less, recrystallization is sufficiently performed, and strain is released. Therefore, in the present embodiment, the Vickers hardness is limited to 80 Hv or less. The Vickers hardness is preferably set to 65 Hv or less, more preferably 50 Hv or less. The aforementioned Vickers hardness may be 30 Hv or more. In the present embodiment, the average value of the Vickers hardness measured in a plurality of places on the same plane as the sputtering surface is 80 Hv or less. The so-called plane on the same plane as the sputter surface means that the copper material is formed into a sputter target and is parallel to the surface to be sputtered. This surface can be ground, polished or washed as needed to become a sputtered surface. . [0031] (Standard deviation of Vickers hardness measured in a plurality of places in the same plane as the sputter surface: 10 or less) When there is a region where the re-recrystallized region is locally high in strain, the Vickers hardness is deviated . When the standard deviation of the Vickers hardness measured in a plurality of places in the same plane as the sputtering surface is 10 or less, the variation in Vickers hardness is small, and the region where the strain is locally high hardly exists. Therefore, in the present embodiment, the standard deviation of the Vickers hardness measured in a plurality of places in the same plane as the sputtering surface is limited to 10 or less. The standard deviation of the Vickers hardness measured in a plurality of places in the same plane as the sputtering surface is preferably 5 or less, more preferably 3 or less. In the present embodiment, the measurement position of the Vickers hardness is set in accordance with the shape of the copper material for the sputtering target as follows. [0033] When the sputtering surface of the copper material for the sputtering target is circular, as shown in FIG. 1, the outer circumference portion of the two straight lines orthogonal to each other at the center (1) of the circle and the center of the circle The Vickers hardness was measured at five places (2), (3), (4), and (5), and the average value and standard deviation were calculated. The aforementioned outer peripheral portion means, for example, a point located inside of 5 mm from the outer periphery of the copper material. [0034] When the sputtering surface of the copper material for sputtering target is rectangular, as shown in FIG. 2, the intersection (1) intersecting the diagonal lines and the corner portions (2), (3) on each diagonal line In five places (4) and (5), the Vickers hardness was measured, and the average value and standard deviation were calculated. The aforementioned corner portion is, for example, a point located on the inner side of 5 mm along the diagonal from the apex of the rectangle. [0035] When the sputtering surface of the sputtering target copper material is a cylindrical surface, as shown in FIG. 3A and FIG. 3B, imaginary lines are drawn in three places at equal intervals in the circumferential direction. On the imaginary line of the three lines, three places separated in the axial direction are determined. In these nine places (A1 to A3, B1 to B3, and C1 to C3), the Vickers hardness is measured, and the average value and standard are calculated. deviation. The three places on each imaginary line are, for example, the center point of the imaginary line and the point located 10 mm inside from the both ends of the imaginary line. (Average crystal grain size: 100 μm or less) The sputtering rate is a statistical probability value of the number of atoms flying from the target when one ion collides with the target, and the crystal orientation of each crystal which is exposed on the sputtering surface And different. Therefore, when the sputtering is performed, irregularities corresponding to the crystal grains are generated on the sputtering surface due to the difference in the sputtering rate. When the average crystal grain size of the sputtering surface exceeds 100 mm, the anisotropy of the crystal orientation becomes remarkable, so that the unevenness generated on the sputtering surface is increased, and electric charges are concentrated on the convex portion, and abnormal discharge is likely to occur. For this reason, in the copper material for sputtering targets of the present embodiment, the average crystal grain size is set to 100 mm or less. In the present embodiment, the average crystal grain size is more preferably 80 mm or less, and particularly preferably 50 mm or less. The average crystal grain size may also be 5 mm or more. [0037] Next, an example of a method of producing a copper material for a sputtering target according to the present embodiment will be described with reference to FIG. 4. [Smelting/Casting Step S01] First, a copper raw material having a copper purity of 99.99% by mass or more is melted to obtain a copper melt. Then, one or two or more kinds of additive elements selected from Zr, Ti, Mg, Mn, La, and Ca are added to the obtained copper melt to prepare a composition, thereby obtaining a copper alloy. Melt. Then, in the present embodiment, an ingot having a predetermined cross-sectional shape (for example, a rectangular shape, a circular shape, or a circular ring shape) is produced using a continuous casting apparatus. [Cold Rolling Processing Step S02] Next, the ingot having the specified cross-sectional shape is subjected to cold rolling. The processing rate of this cold rolling processing is preferably in the range of 40.0% or more and 99.9% or less. [Heat Treatment Step S03] Next, heat treatment is performed after the cold rolling process. The heat treatment temperature at this time is preferably in the range of 100 ° C to 600 ° C, and the holding time is preferably in the range of 30 minutes or more and 300 minutes or less. The heat treatment temperature is preferably in the range of from 150 ° C to 400 ° C, and the holding time is preferably in the range of from 60 minutes to 180 minutes. By this heat treatment step S03, recrystallization proceeds, and the strain imparted in the cold rolling processing step S02 is released. [Machining Step S04] Next, after the heat treatment, machining is performed to remove the oxide film on the surface and finish it into a predetermined shape. The copper material for a sputtering target of the present embodiment is produced by the above steps. When the sputtering target is produced, the copper material is processed into a desired shape, and a backing plate made of a metal such as copper is bonded to the back surface of the copper material as needed to obtain a sputtering target. A bonding layer made of In or In alloy or the like may be provided between the copper material and the back sheet as needed. [0042] The copper material for a sputtering target of the present embodiment, which is configured as described above, contains 1 selected from Zr, Ti, Mg, Mn, La, and Ca in a range of 0.001% by mass or more and 0.008% by mass or less. The total amount of the content of Cu and the content of the above-mentioned additive element is 99.99% by mass or more, and it can be produced at a relatively low cost because it is not required to be highly purified. In addition, since one or two or more kinds of additive elements selected from Zr, Ti, Mg, Mn, La, and Ca are contained in the range of 0.001% by mass or more and 0.008% by mass or less, S can be added as such an additive element. The compound is immobilized, and it is possible to suppress the progress of recrystallization by S. Therefore, a uniform recrystallized structure can be obtained, and occurrence of abnormal discharge (arcing) at the time of film formation can be suppressed. In the present embodiment, the content of S is limited to 0.005 mass% or less, and one or two or more additive elements selected from Zr, Ti, Mg, Mn, La, and Ca may be used. When S is surely fixed, a uniform recrystallized structure can be obtained, and occurrence of abnormal discharge (arcing) at the time of film formation can be suppressed. Moreover, the decrease in electrical conductivity can be suppressed. Further, in the present embodiment, the area ratio occupied by the compound containing the additive element and S in the same plane as the sputtering surface is suppressed to 0.4% or less, thereby suppressing the increase in the temperature of the recrystallization temperature, and further Promoting recrystallization can further inhibit the formation of non-recrystallized regions. Further, the occurrence of abnormal discharge due to the compound containing the additive element and S can be surely suppressed. Further, in the present embodiment, since the Vickers hardness is 80 Hv or less, the uniform recrystallized structure is obtained, and the strain is sufficiently released, and the abnormal discharge at the time of film formation can be surely suppressed (arcing) ) happened. Further, in the present embodiment, the standard deviation of the Vickers hardness measured in a plurality of places on the same plane as the sputtering surface is 10 or less, and the strain is uniformly released, and there is no region where the strain amount is locally high. It can surely suppress the occurrence of abnormal discharge. Further, in the present embodiment, as shown in FIGS. 1 to 3, since the measurement position of the Vickers hardness is specified in accordance with the shape of the copper material for the sputtering target, the sputtering and sputtering can be appropriately calculated. The average value and standard deviation of the Vickers hardness measured in a plurality of places in the same plane can be obtained as a copper material for a sputtering target having uniform strain. Further, in the present embodiment, since the average crystal grain size is 100 μm or less, the unevenness generated on the sputtering surface is reduced during the sputtering, and the occurrence of abnormal discharge can be suppressed. [0048] In the present embodiment, the cold rolling processing step S02 and the heat treatment step S03 are performed after the melting/casting step S01, but as described above, by Zr, Ti, Mg, Mn, La, and Ca. One or two or more kinds of additive elements are selected to fix S (sulfur) to promote recrystallization, so that a uniform recrystallized structure can be obtained. The embodiments of the present invention are described above, but the present invention is not limited thereto, and can be appropriately modified without departing from the scope of the technical idea of the present invention. In the present embodiment, a sputtering target in which a high-purity copper film is formed as a wiring film will be described as an example. However, the present invention is not limited thereto, and may be applied to a copper film used for other applications. [0050] The method for producing the copper material for a sputtering target is not limited to the embodiment, and may be produced by another manufacturing method. For example, after the melting and casting steps, a hot rolling processing step may be provided. Further, the ingot can be obtained without using a continuous casting apparatus, for example, by a batch type casting apparatus. [Examples] [0051] Hereinafter, the results of an evaluation test for evaluating the copper material for a sputtering target of the present embodiment will be described. A copper raw material having a purity of 99.99% by mass or more was prepared, and a copper melt was melted so as to have a composition as shown in Table 1, and a continuous casting apparatus was used to obtain an ingot having a rectangular cross section of 50 mm ́200 mm. For the obtained ingot, cold rolling was performed at the processing rate shown in Table 2. Then, heat treatment was carried out under the conditions shown in Table 2. Then, cutting was performed to obtain a rectangular copper material for a sputtering target of 10 mm ́130 mm ́ 140 mm. [0053] The obtained copper material for the sputtering target was evaluated by the following procedure for the area ratio and the standard deviation and the average deviation of the Vickers hardness in the area ratio of the compound containing the additive element and S in the same plane as the sputtering surface. Crystal grain size, electrical conductivity, and number of abnormal discharges. The evaluation results are shown in Table 2. (area ratio of compound) The surface analysis of 60 mm ́80 mm of the field of view was carried out by SEM-EPMA, and the addition of elements M and S was detected in the same place as the MS compound, by "detection area (all)" Observe the area (60mm ́80mm) ́100" and calculate the area ratio. (Vickers hardness) In the same plane as the sputter surface of the sputtering target copper material, the Vickers hardness is measured by a Vickers hardness tester according to JIS Z 2244 at a position as shown in FIG. 2 . Calculate the average and standard deviation. The evaluation results are shown in Table 2. (Average crystal grain size) In the same plane as the sputtering surface of the copper material for sputtering target, a test piece for observation was taken from the position shown in FIG. 2, and microscopic observation was performed using an optical microscope, according to JIS H 0501: 1986 (cutting method), the crystal grain size was measured, and the average crystal grain size was calculated. The evaluation results are shown in 2. (Film Formation Conditions) The obtained sputtering target copper material was bonded to a back sheet, and a copper thin film was formed under the following conditions. Sputtering voltage: 3000V Ultimate vacuum: 5 ́10 -4 Pa Sputtering gas: Ar, 0.4Pa Sputtering for 1 hour under the above film forming conditions, for the number of occurrences of abnormal discharge, attached to the sputtering power supply device The arc counter automatically measures the number of times. The evaluation results are shown in 2. [0058] [0059] In Comparative Example 1 in which one or two or more kinds of additive elements selected from Zr, Ti, Me, Mn, La, and Ca were not added, the standard deviation of Vickers hardness was large, and the number of abnormal discharges was relatively large. . It is presumed that this is because the S does not interfere with the progress of recrystallization, the non-recrystallized region exists, and the region where the strain is locally high exists. In Comparative Example 2 in which one or two or more kinds of additive elements selected from Zr, Ti, Me, Mn, La, and Ca were added in an amount of more than 0.008% by mass, the area ratio of the compound was high, and the number of occurrences of abnormal discharge was relatively large. Also, the electrical conductivity is also low. In Comparative Example 3 in which the total content of Cu and the content of the aforementioned additive elements were less than 99.99% by mass, the Vickers hardness was high and the standard deviation was large. Further, the average crystal grain size is also large, and the number of occurrences of abnormal discharge increases. It is presumed that this is because the recrystallization is insufficient and the strain is high. In the range of 0.001% by mass or more and 0.008% by mass or less, one or two or more kinds of additive elements selected from Zr, Ti, Mg, Mn, La, and Ca are contained, Cu In the case of the inventive example 1-23 in which the total content of the additive element and the content of the additive element was 99.99% by mass or more, the number of occurrences of abnormal discharge was small. It is speculated that this is because the recrystallization is promoted and the strain is released uniformly. From the above, it was confirmed that the copper material for a sputtering target of the present invention suppresses the occurrence of abnormal discharge and can form a film stably.