[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。[Problem to be Solved by the Invention] [0007] However, when a sputtering target is used for film formation, abnormal discharge (arc) occurs due to the concentration of electric charges, and therefore, a uniform wiring film cannot be formed. The so-called abnormal discharge is a phenomenon in which an extremely high current flows suddenly and sharply compared with normal sputtering, and an abnormally large discharge occurs abruptly. If such an abnormal discharge occurs, it becomes the cause of the occurrence of particles, and there is a wiring film. The film thickness may become uneven. Therefore, it is advisable to avoid abnormal discharges during film formation as much as possible. Particularly recently, in flat panel displays such as semiconductor devices, liquid crystal or organic EL panels, touch panels, etc., higher density of wiring films is required, and it is also increasing than before, and stable formation of miniaturized and thinned wiring The necessity of the membrane. [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 refined while reducing the amount of strain, but there is no particular mention of impurities. For example, when sulfur (S) is contained as an impurity, the progress of recrystallization is suppressed, and a uniform recrystallized structure may not be obtained. Therefore, even if the overall average crystal grain size is small and the amount of strain is low, there is a possibility that abnormal discharge is likely to occur when non-recrystallized regions exist and regions where the amount of strain is locally high. [0009] In addition, in the method of manufacturing a sputtering target described in Patent Document 2, a melted ingot with a purity of 99.9995% is produced by the zone melting method to suppress the amount of impurities, but since recrystallization behavior is not considered at all, it is not considered. Strain, so there is still the risk of abnormal discharge. In addition, due to the use of the zone melting method, there is a problem that the production efficiency is greatly reduced. [0010] The present invention was completed in view of the foregoing circumstances, and its object is to provide a copper material for sputtering targets, which can suppress the occurrence of abnormal discharge, stably perform film formation, and can be manufactured at low cost. [Means for Solving the Problem] [0011] In order to solve the aforementioned problems, the copper material for sputtering targets of the present invention contains Zr, Ti, Mg, Mn, La, and Ca in the range of 0.001% by mass to 0.008% by mass. For the selected one or two or more types of additional elements, the total of the content of Cu and the content of the aforementioned additional elements is 99.99% by mass or more. [0012] In this copper material for sputtering targets, one or two or more additional elements selected from Zr, Ti, Mg, Mn, La, and Ca are contained within a range of 0.001% by mass to 0.008% by mass. , The total of the content of Cu and the content of the aforementioned additional elements is 99.99% by mass or more, and since the purity is not higher than necessary, it can be manufactured at a relatively low cost. In addition, since one or two or more types of additional elements selected from Zr, Ti, Mg, Mn, La, and Ca are contained within the range of 0.001% by mass to 0.008% by mass, S can be used as an additional element. The compound is fixed, which can inhibit the progress of recrystallization due to S. Therefore, a uniform recrystallized structure can be obtained, and the occurrence of abnormal discharge (arcing) during film formation can be suppressed. Examples of the sulfur compound include ZrS 2 , TiS, TiS 2 , MgS, MnS, LaS, La 2 S 3 , CaS, and the like. [0013] In the copper material for sputtering targets of the present invention, the content of S is preferably set to 0.005% by mass or less. At this time, since the content of S is limited to 0.005 mass% or less, S can be reliably fixed by the above-mentioned additional elements, a uniform recrystallized structure can be obtained, and the occurrence of abnormal discharge (arcing) during film formation can be suppressed . In addition, the decrease in conductivity can be suppressed. [0014] Furthermore, in the copper material for sputtering target of the present invention, the area ratio occupied by the compound containing the aforementioned additive element and S in the same plane as the sputtering surface is preferably 0.4% or less. At this time, since the area ratio occupied by the compound containing the aforementioned additive element and S is suppressed to 0.4% or less, the increase in the recrystallization temperature can be suppressed, the progress of recrystallization can be further promoted, and the formation of non-recrystallized regions can be further suppressed. In addition, it is possible to reliably suppress the occurrence of abnormal discharge caused by the compound containing the additive element and S. [0015] Furthermore, in the copper material for sputtering target of the present invention, the Vickers hardness is preferably 80 Hv or less. At this time, it has a uniform recrystallized structure, and furthermore, the strain is sufficiently released, and the occurrence of abnormal discharge (arcing) during film formation can be reliably suppressed. [0016] In addition, in the copper material for a sputtering target of the present invention, the standard deviation of the Vickers hardness measured at a plurality of places in the same plane as the sputtering surface is preferably 10 or less. At this time, since the strain is uniformly released and there is no area where the amount of strain is locally high, the occurrence of abnormal discharge can be reliably suppressed. [0017] Furthermore, the average crystal grain size of the copper material for sputtering target of the present invention is preferably 100 μm or less. At this time, since the average crystal grain size is relatively fine at 100 μm or less, the unevenness that occurs on the sputtered surface during sputtering is 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 the sputtering target and a back plate fixed on one surface of the target body. In this sputtering target, the aforementioned excellent effects can also be obtained. [Effects of the Invention] [0018] 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 perform film formation, 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。[Mode for Carrying Out 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 the sputtering target of this embodiment is a sputtering target used when a copper film used as a wiring film is formed on a substrate in a flat panel display such as a semiconductor device, a liquid crystal or organic EL panel, a touch panel, etc. material. The shape of the copper material for the sputtering target is not limited, but it may be, for example, a circular plate shape, a rectangular flat plate shape, or a cylindrical shape. [0021] The composition of the copper material for the sputtering target of this embodiment contains one or two or more selected from Zr, Ti, Mg, Mn, La, and Ca within the range of 0.001% by mass to 0.008% by mass. The sum of the content of Cu and the content of the aforementioned additional elements is 99.99% by mass or more. Moreover, in this embodiment, the content of S is set to 0.005% by mass or less. [0022] In addition, the copper material for the sputtering target of this embodiment is in the same plane as the sputtering surface, and contains the aforementioned additional elements (one or two selected from Zr, Ti, Mg, Mn, La, and Ca) Above) The area ratio occupied by the compound with S is set to 0.4% or less. In addition, the copper material for a sputtering target of this embodiment has a Vickers hardness of 80 Hv or less. In addition, the copper material for a sputtering target of this embodiment sets the standard deviation of the Vickers hardness measured at a plurality of places in the same plane as the sputtering surface to 10 or less. In addition, the copper material for sputtering targets of this embodiment has an average crystal grain size of 100 mm or less. [0023] Hereinafter, the reason for defining the composition of the copper material for the sputtering target of the present embodiment, the area ratio of the compound in the sputtering surface, the standard deviation of the Vickers hardness and the Vickers hardness, and the average crystal grain size of the sputtering target as described above . [0024] (One or more additional 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 additional elements are due to the free energy ratio of sulfide formation Elements with lower Cu can form compounds with S (sulfur), which can fix the whole or most of S. Thereby, recrystallization can be promoted. [0025] When the content of one or more additional elements selected from Zr, Ti, Mg, Mn, La, and Ca is less than 0.001% by mass, there is a possibility that S in copper cannot be sufficiently fixed. On the other hand, if the content of one or two or more additional elements selected from Zr, Ti, Mg, Mn, La, and Ca exceeds 0.008% by mass, the particles containing the compound of the additional element and S are formed in large numbers , Or the particles of the compound become coarser, and there is a risk of abnormal discharge caused by the particles of the compound exposed on the sputtering surface. [0026] Therefore, in this embodiment, the content of one or more of the additional elements selected from Zr, Ti, Mg, Mn, La, and Ca is set within the range of 0.001% by mass to 0.008% by mass. . In order to more fully fix the S in copper, it is preferable to set the lower limit of the content of one or more of the additional elements selected from Zr, Ti, Mg, Mn, La, and Ca to 0.0015 mass% or more, and it is more preferable to set It is 0.0020% by mass or more. In addition, for the occurrence of abnormal discharge caused by the compound, it is preferable to set the upper limit of the content of one or more of the additional elements selected from Zr, Ti, Mg, Mn, La, and Ca to 0.0060 mass% or less , More preferably 0.0040 mass% or less. [0027] (The sum of the content of Cu and the content of additional elements is 99.99% by mass or more) When the wiring film (high-purity copper film) is formed by sputtering, in order to suppress abnormal discharge (arcing), it is preferable to try as much as possible Reduce impurities. However, in order to achieve high purity so that the total of the content of Cu and the content of additional elements is 99.999% by mass or more, the manufacturing steps are complicated, and the manufacturing cost is greatly increased. Therefore, in this embodiment, by setting the total of the content of Cu and the content of additional elements to 99.99% by mass or more, the manufacturing cost is reduced. In addition, the upper limit of the total of the content of Cu and the content of additional elements is preferably less than 99.999% by mass from the viewpoint of reduction in manufacturing cost. [0028] (S: 0.005 mass% or less) S is an element that hinders the progress of recrystallization of copper and at the same time reduces electrical conductivity. When the S content exceeds 0.005% by mass, even when the above-mentioned additional elements are added, S cannot be sufficiently fixed, recrystallization becomes insufficient, and non-recrystallized regions are formed, and there is a possibility that the amount of strain becomes locally uneven. In addition, there is a possibility that the conductivity may decrease. Therefore, in order to fully recrystallize and sufficiently homogenize the amount of strain while ensuring electrical conductivity, it is preferable to limit the content of S to 0.005% by mass or less. The content of S is preferably set to 0.003% by mass or less, and more preferably set to 0.001% by mass or less. However, since it is difficult to make the S content zero, it may be 0.0003 mass% or more. [0029] (In the same plane as the sputtering surface, the area ratio of the compound containing the added element and S: 0.4% or less) By adding one selected from Zr, Ti, Mg, Mn, La, and Ca Or two or more kinds of additive elements, and a compound containing the additive element and S is generated, and a part of this compound is mixed into the copper material for the sputtering target. When the number of particles of the compound containing this additive element and S increases, or when the particles of the compound are already coarsened, the recrystallization temperature may increase and the recrystallization may be suppressed. In addition, during film formation, there is a possibility that abnormal discharge may occur due to the exposure of the particles of this compound to the sputtering surface. Therefore, in this embodiment, the area ratio occupied by the compound containing the additive element and S is set to 0.4% or less. The area ratio occupied by the compound containing the additive element and S is preferably set to 0.3% or less, more preferably set to 0.1% or less. Since it is difficult to make the aforementioned area ratio zero, it may be 0.03% or more. [0030] (Vickers hardness: 80 Hv or less) When recrystallization is promoted and strain is sufficiently relieved, the Vickers hardness becomes low. If the Vickers hardness is 80 Hv or less, recrystallization proceeds sufficiently and strain is released. Therefore, in this embodiment, the Vickers hardness is limited to 80 Hv or less. The Vickers hardness is preferably 65 Hv or less, more preferably 50 Hv or less. The aforementioned Vickers hardness may be 30 Hv or more. In this embodiment, the average value of the Vickers hardness measured at a plurality of places in the same plane as the sputtering surface is set to 80 Hv or less. The so-called “Y” and the sputtering surface are in the same plane, which means that after the copper material is formed into a sputtering target, it is parallel to the sputtered surface. This surface can be ground or polished or cleaned to become the sputtering surface if necessary. . [0031] (Standard deviation of Vickers hardness measured at a plurality of places in the same plane as the sputtering surface: 10 or less) When there is a non-recrystallized region and a region where the strain is locally high, deviation occurs in the Vickers hardness . If the standard deviation of the Vickers hardness measured at a plurality of places in the same plane as the sputtering surface is 10 or less, the variation of the Vickers hardness is small, and there is almost no area where the strain is locally high. Therefore, in this embodiment, the standard deviation of the Vickers hardness measured at 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 at a plurality of places in the same plane as the sputtering surface is preferably set to 5 or less, more preferably 3 or less. [0032] In this embodiment, the measurement position of the above-mentioned Vickers hardness is set as follows in accordance with the shape of the copper material for the sputtering target. [0033] When the sputtering surface of the copper material for the sputtering target is circular, as shown in FIG. 1, the outer peripheral portion is on the center of the circle (1) and the two straight lines passing through the center of the circle at the same time orthogonal to each other. Measure the Vickers hardness at 5 places (2), (3), (4), and (5), and calculate the average value and standard deviation. The aforementioned outer peripheral portion refers to, for example, a point located 5 mm inside from the outer peripheral edge of the copper material. [0034] When the sputtering surface of the copper material for the sputtering target is rectangular, as shown in FIG. 2, at the intersection point (1) where the diagonal lines cross and the corners (2), (3) on each diagonal line , (4), (5) 5 places, measure the Vickers hardness, calculate the average value and standard deviation. The aforementioned corners refer to, for example, the points located on the inner side of 5 mm along the diagonal from the apex of the rectangle. [0035] When the sputtering surface of the copper material for the sputtering target is a cylindrical surface, as shown in FIG. 3A and FIG. 3B, three imaginary lines are drawn at equal intervals in the peripheral direction. Wait for 3 imaginary lines, determine 3 places separated in the axial direction, and measure the Vickers hardness at 9 places in total (A1～A3, B1～B3, C1～C3), and calculate the average value and standard deviation. The three places on each imaginary line refer to, for example, the center point of the imaginary line and the point located 10 mm inside from both ends of the imaginary line. [0036] (Average crystal grain size: 100 μm or less) The sputtering rate is a statistical probability value of the number of atoms flying out of the target when one ion hits the target, and the crystal orientation of each crystal on the sputtering surface is exposed. But different. Therefore, if sputtering progresses, unevenness corresponding to crystal grains is generated on the sputtered surface due to the difference in sputtering rate. If the average crystal grain size of the sputtered surface exceeds 100 mm, the anisotropy of the crystal orientation becomes significant, so the unevenness generated on the sputtered surface becomes larger, and the electric charge is concentrated on the convex portions, and abnormal discharge is likely to occur. For this reason, in the copper material for sputtering targets of this embodiment, the average crystal grain size is specified to be 100 mm or less. In this 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, referring to FIG. 4, an example of a method of manufacturing a copper material for a sputtering target of this embodiment will be described. [0038] (Melting/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. Next, add one or two or more elements selected from Zr, Ti, Mg, Mn, La, and Ca to the obtained copper melt in a specified concentration to prepare the composition to obtain a copper alloy Melt. Then, in this embodiment, a continuous casting device is used to manufacture an ingot having a predetermined cross-sectional shape (for example, a rectangular shape, a circular shape, and an annular shape). [0039] (Cold rolling step S02) Next, cold rolling is performed on the ingot having a predetermined cross-sectional shape. The working rate of this cold rolling is preferably set to be in the range of 40.0% or more and 99.9% or less. [0040] (Heat treatment step S03) Next, heat treatment is performed after cold rolling. The heat treatment temperature at this time is preferably within a range of 100°C or more and 600°C or less, and the holding time is preferably within a range of 30 minutes or more and 300 minutes or less. The heat treatment temperature is preferably set to be within the range of 150°C or more and 400°C or less, and the holding time is preferably set to be within the range of 60 minutes or more and 180 minutes or less. With this heat treatment step S03, recrystallization proceeds, and the strain imparted in the cold rolling step S02 is released. [0041] (Machining Step S04) Next, after the heat treatment, machining is performed to remove the oxide film on the surface, and at the same time, it is finished into a specified shape. Through the above steps, the copper material for sputtering target of this embodiment is manufactured. When manufacturing the sputtering target, the copper material is processed into a desired shape, and a backing plate made of metal such as copper is bonded to the back surface of the copper material as necessary to obtain the sputtering target. Between the copper material and the back plate, if necessary, a bonding layer made of In or In alloy can be provided. [0042] The copper material for the sputtering target of the present embodiment constructed as described above contains 1 selected from Zr, Ti, Mg, Mn, La, and Ca in a range of 0.001 mass% to 0.008 mass %. One or two or more kinds of additional elements, the total of the content of Cu and the content of the aforementioned additional elements is 99.99% by mass or more, and the purity is not more than necessary and can be manufactured at a relatively low cost. In addition, since one or two or more additional elements selected from Zr, Ti, Mg, Mn, La, and Ca are contained within the range of 0.001% by mass to 0.008% by mass, S can be used as an additional element. The compound fixation can inhibit the progress of recrystallization due to S. Therefore, a uniform recrystallized structure can be obtained, and the occurrence of abnormal discharge (arcing) during film formation can be suppressed. [0043] In addition, in this embodiment, since the content of S is limited to 0.005 mass% or less, one or two or more additional elements selected from Zr, Ti, Mg, Mn, La, and Ca can be used , S is surely fixed, a uniform recrystallized structure can be obtained, and the occurrence of abnormal discharge (arcing) during film formation can be suppressed. In addition, the decrease in conductivity can be suppressed. [0044] Furthermore, in this embodiment, since 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, the increase in the recrystallization temperature can be suppressed, and further Promotes recrystallization and can suppress the formation of non-recrystallized regions. In addition, it is possible to reliably suppress the occurrence of abnormal discharge caused by the compound containing the additive element and S. [0045] Furthermore, in the present embodiment, since the Vickers hardness is set to 80 Hv or less, it has a uniform recrystallized structure, and furthermore, the strain is sufficiently relieved, and abnormal discharge (arcing) during film formation can be reliably suppressed. ) Happened. In addition, in this embodiment, since the standard deviation of the Vickers hardness measured at multiple places in the same plane as the sputtering surface is set to 10 or less, the strain is uniformly released, and there is no area where the amount of strain is locally high. , Can reliably suppress the occurrence of abnormal discharge. [0046] Furthermore, in this embodiment, as shown in FIGS. 1 to 3, since the Vickers hardness measurement location is specified according to the shape of the copper material for the sputtering target, it can be appropriately calculated as The average value and standard deviation of the Vickers hardness measured at multiple places in the same plane can be used to obtain a copper material for sputtering targets with uniform strain. [0047] Furthermore, in this embodiment, since the average crystal grain size is relatively fine with a size of 100 μm or less, the unevenness that occurs on the sputtering surface during sputtering is reduced, and the occurrence of abnormal discharge can be suppressed. [0048] Furthermore, in this embodiment, although the cold rolling step S02 and the heat treatment step S03 are performed after the melting/casting step S01, as described above, it is obtained from Zr, Ti, Mg, Mn, La, and Ca. One or two or more selected additional elements fix S (sulfur) and promote the progress of recrystallization, so a uniform recrystallized structure can be obtained. [0049] The embodiments of the present invention are described above, but the present invention is not limited thereto, and can be appropriately changed without departing from the technical idea of the present invention. In this embodiment, a sputtering target for forming a high-purity copper film as a wiring film is given as an example for description, but it is not limited to this, and it is also applicable when a copper film is used in other applications. [0050] The method of manufacturing the copper material for the sputtering target is not limited by this embodiment, and may be manufactured by other manufacturing methods. For example, after the melting and casting steps, there may be a hot rolling processing step. In addition, without using a continuous casting device, for example, a batch-type casting device can be used to obtain an ingot. [Example] [0051] Hereinafter, the results of an evaluation test for evaluating the copper material for a sputtering target of the present embodiment described above will be described. [0052] A copper raw material with a purity of 99.99% by mass or more was prepared, and the copper melt was melted so as to have the composition shown in Table 1, and a continuous casting device was used to obtain an ingot with a rectangular cross-section of 50 mm × 200 mm. For the obtained ingot, cold rolling was performed at the working rate shown in Table 2. Then, heat treatment was performed under the conditions shown in Table 2. After that, cutting is performed to obtain a rectangular copper material for sputtering target of 10mm´130mm´140mm. [0053] For the obtained copper material for sputtering target, the area ratio of the compound containing the additive element and S in the same plane as the sputtering surface was evaluated by the following procedure, the average value and standard deviation of Vickers hardness, and the average Crystal size, conductivity, and number of abnormal discharges. Table 2 shows the evaluation results. [0054] (Area ratio of compound) SEM-EPMA is used to perform surface analysis with a field of view of 60mm´80mm, and the case where the added elements M and S are detected at the same place is regarded as an MS compound, and the "detection area (total) ÷ Observe the area (60mm´80mm)´100" and calculate the area ratio. [0055] (Vickers hardness) In the same plane as the sputtering surface of the copper material for the sputtering target, the Vickers hardness was measured with a Vickers hardness tester in accordance with JIS Z 2244 at the position shown in FIG. 2, Calculate the average and standard deviation. Table 2 shows the evaluation results. [0056] (Average crystal grain size) In the same plane as the sputtering surface of the copper material for the sputtering target, a test piece for observation was collected from the position shown in FIG. 2, and the microstructure was observed using an optical microscope, according to JIS H 0501: 1986 (cutting method), the crystal grain size is measured, and the average crystal grain size is calculated. The evaluation result is shown in 2. [0057] (Film formation conditions) The obtained copper material for sputtering targets was joined to the back plate, 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 aforementioned film forming conditions. The number of occurrences of abnormal discharges is attached to the sputtering power supply device The arc counter automatically counts the number of times. The evaluation result is shown in 2. [0058] [0059] [0060] In Comparative Example 1 in which one or more additional 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 S hinders the progress of recrystallization, unrecrystallized regions exist, and regions with locally high strains exist. In Comparative Example 2 in which one or two or more additional elements selected from Zr, Ti, Me, Mn, La, and Ca are added in excess of 0.008% by mass, the area ratio of the compound is high, and the number of occurrences of abnormal discharge is relatively high. In addition, the conductivity also becomes low. In Comparative Example 3 in which the total of the content of Cu and the content of the aforementioned additional elements was less than 99.99% by mass, the Vickers hardness was high and the standard deviation was also large. In addition, the average crystal grain size is also large, and the number of occurrences of abnormal discharge increases. It is presumed that this system is due to insufficient recrystallization and high strain. [0061] On the other hand, if one or two or more additional elements selected from Zr, Ti, Mg, Mn, La, and Ca are contained within a range of 0.001% by mass to 0.008% by mass, Cu In Example 1-23 of the present invention in which the total content of the content and the content of the aforementioned additive elements is 99.99% by mass or more, the occurrence of abnormal discharge is small. It is presumed that this system promotes recrystallization and uniformly releases strain. From the above, it was confirmed that the copper material for sputtering target of the present invention suppresses the occurrence of abnormal discharge and can form a stable film.
