TWI554626B - Oxide sputtering target and protective film for optical recording medium - Google Patents
Oxide sputtering target and protective film for optical recording medium Download PDFInfo
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Description
本發明係關於一種為了將使用於Blu-ray Disc(登錄商標)等之光記錄媒體用保護膜成膜之氧化物濺鍍靶以及使用其所製作之光記錄媒體用保護膜。 The present invention relates to an oxide sputtering target for forming a protective film for an optical recording medium used in a Blu-ray Disc (registered trademark) or the like, and a protective film for an optical recording medium produced using the same.
近年來，隨相片及動畫之高畫質化，記錄於光記錄媒體等時數位資訊大增，記錄媒體的高容量需求日益增加，目前市面上已有販售兩層記錄方式，內含50GB容量的Blu-ray Disc(登錄商標：以下簡稱為BD)作為具有高容量記錄的光記錄媒體，為更加提提升今後BD的高容量化，目前記錄層的多層化所達成的高容量化等相關研究相當盛行。 In recent years, with the high image quality of photos and animations, digital information recorded on optical recording media has increased greatly, and the high-capacity demand for recording media has increased. Currently, two-layer recording methods have been sold on the market, which contain 50 GB of capacity. Blu-ray Disc (registered trademark: hereinafter referred to as BD) is an optical recording medium with a high-capacity recording. In order to increase the capacity of BD in the future, the current capacity of the recording layer is increased. Quite prevalent.
於記錄層使用之有機色素構成BD的保護膜用材料方面，以ZnS-SiO2或ITO最廣為人知(參照專利文獻1)，此外、保存度較高的保護膜已知有ZnO系者(參照專利文獻2)。另外，記錄層使用無機物構成BD的保護膜用材料方面，已知有ZnO-Cr2O3也廣為人知(參照專利文獻3)。 ZnS-SiO 2 or ITO is most widely known as a material for a protective film of BD, and ZnO is known (see Patent Document 1), and ZnO is known as a protective film having a high degree of preservation (see Patent). Literature 2). In addition, it is known that ZnO-Cr 2 O 3 is also known as a material for a protective film of BD which is made of an inorganic material (see Patent Document 3).
[專利文獻1]日本特開2009-26378號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2009-26378
[專利文獻2]日本特開2005-228402號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2005-228402
[專利文獻3]日本專利第4612689號公報 [Patent Document 3] Japanese Patent No. 4612689
上述之先前技術尚存有下述課題。 The above prior art still has the following problems.
使用有機色素於記錄層型式的記錄媒體，相較於使用無機物作為記錄層時，因紀錄層變形較大，如專利文獻1段落0058所述，與色素鄰接的保護層需要較低的硬度。為此，過去均採用柔軟度適切的膜之ZnS-SiO2或ITO。然而ZnS-SiO2中，如專利文獻2之段落0004所述，若含有硫磺(S)，則會導致硫磺及反射膜中的金屬反應而降低反射率，有降低保存性的問題。 When the recording medium of the recording layer type is used as the recording layer, the recording layer is largely deformed as compared with the case where the inorganic substance is used as the recording layer. As described in paragraph 0058 of Patent Document 1, the protective layer adjacent to the dye requires a low hardness. For this reason, in the past, ZnS-SiO 2 or ITO having a softness-appropriate film was used. However, in ZnS-SiO 2 , as described in paragraph 0004 of Patent Document 2, if sulfur (S) is contained, the metal in the sulfur and the reflective film reacts to lower the reflectance, and there is a problem that the storage stability is lowered.
另外ITO的問題則是濺鍍時微粒較多，不但會對記錄媒體磁碟造成不良影響，清理製造設備工程浩大，有生產力差之問題。 In addition, the problem of ITO is that there are many particles during sputtering, which not only adversely affects the recording medium disk, but also has a huge problem of cleaning manufacturing equipment and poor productivity.
採用無機物於記錄層這類型的記錄媒體，其中所使用的ZnO-Cr2O3因保護膜容易龜裂，若使用於會造成記錄層有較大變形的有機色素類記錄媒體，則可預想其保存性的降低。除此，ZnO-Cr2O3濺鍍靶因阻抗高，無法直流濺鍍，而生產性亦有問題。 In the recording medium of the type in which the inorganic material is used in the recording layer, the ZnO-Cr 2 O 3 used is easily cracked by the protective film, and if it is used in an organic dye recording medium which causes a large deformation of the recording layer, it is expected Reduced preservation. In addition, the ZnO-Cr 2 O 3 sputtering target has high impedance and cannot be DC-sputtered, and productivity is also problematic.
本發明係經詳查上述課題所為者，主要目的為提供一種在光記錄媒體保護膜形成用方面，保存度高，並可成膜柔軟而難以龜裂的膜，同時可以直流濺鍍，微粒也較少的氧化物濺鍍靶，以及用此製作之光記錄媒體用保護膜。 The present invention has been made in consideration of the above-mentioned problems, and the main object of the present invention is to provide a film having a high degree of preservation in the formation of a protective film for an optical recording medium, and which is capable of forming a film which is soft and difficult to be cracked, and can be subjected to DC sputtering and fine particles. There are fewer oxide sputtering targets, and a protective film for optical recording media produced therewith.
本發明者們在進行ZnO-Cr2O3系濺鍍靶研究時，發現藉由在原料中加入Al2O3、Ga2O3之中一種以上，可以直流濺鍍使反射率變化減少，並可成膜為柔軟而難以龜裂的保護膜。 When the ZnO-Cr 2 O 3 -based sputtering target was studied, the inventors found that by adding one or more of Al 2 O 3 and Ga 2 O 3 to the raw material, DC sputtering can reduce the reflectance change. It can form a protective film that is soft and difficult to crack.
因此，本發明係經上述見解所得者，為解決上述課題而採用下述之構成。意即，第1發明之氧化物濺鍍靶，其特徵係以相對於全金屬成分量，含有Al及Ga其中一種以上合計：0.15at%以上、Cr：12at%以上、Al、Ga及Cr合計50at%以下，剩餘部份為Zn及無法避免的雜質。 Therefore, the present invention has been obtained by the above findings, and the following configuration is adopted to solve the above problems. In other words, the oxide sputtering target according to the first aspect of the invention is characterized in that it contains a total of one or more of Al and Ga with respect to the total metal component: 0.15 at% or more, Cr: 12 at% or more, and Al, Ga, and Cr in total. Below 50at%, the remainder is Zn and unavoidable impurities.
這種氧化物濺鍍靶中，由於相對於全金屬成分量，含有Al及Ga之中一種以上之合計：0.15%at以上、Cr；12at%以上、Al,Ga及Cr合計：50at%以下，且剩餘部份為Zn以及無法避免的雜質所組合而成之氧化物，可為比電阻率較低且穩定的直流濺鍍，且可成膜為反射率變化少、具有高度保存性同時柔軟難以龜裂的膜。 In the oxide sputtering target, the total amount of one or more of Al and Ga is 0.15% at least or more, Cr; 12 at% or more, and Al, Ga, and Cr total: 50 at% or less, based on the total metal component amount. The remaining part is an oxide composed of Zn and unavoidable impurities, and can be a DC sputtering with a low specific resistivity and stable, and can be formed into a film with less change in reflectance, high storage stability, and softness. Cracked film.
另外，ZnO中固溶的Al或Ga造成的電荷負擔會降低比電阻率，同時可提高成膜之膜的熱擴散率而減少熱性損壞。 In addition, the charge burden caused by solid solution of Al or Ga in ZnO lowers the specific resistivity, and at the same time, the thermal diffusivity of the film formed film can be increased to reduce thermal damage.
將上述Al及Ga中一種以上之合計含有量設定為0.15at%以上的理由為，係因若不滿0.15at%，則直流濺鍍會不穩定，容易產生膜的龜裂。另外將上述Cr之含有量設定為12at%以上的理由為，係因若不滿12at%，則膜的 硬度(後述的壓印硬度)會高達800mgf/μm2以上，導致變硬。將Al、Ga及Cr之合計量設定為50at%以下的理由為，係因若超過15at%，則直流濺鍍就會不穩定，導致異常放電發生頻率增加。 The reason why the total content of one or more of Al and Ga is set to 0.15 at% or more is that if it is less than 0.15 at%, DC sputtering is unstable, and cracking of the film is likely to occur. In addition, the reason why the content of Cr is 12 at% or more is that the hardness of the film (imprint hardness to be described later) is as high as 800 mgf/μm 2 or more, resulting in hardening. The reason why the total amount of Al, Ga, and Cr is set to 50 at% or less is that if it exceeds 15 at%, DC sputtering is unstable, and the frequency of abnormal discharge increases.
亦即，若加到原料中的Al2O3、Ga2O3、Cr2O3過多，會產生大量ZnO及複合氧化物，則濺鍍靶的比電阻就會提高。 That is, if too much Al 2 O 3 , Ga 2 O 3 , or Cr 2 O 3 is added to the raw material, a large amount of ZnO and a composite oxide are generated, and the specific resistance of the sputtering target is improved.
第2發明之光記錄媒體用保護膜為相對於全金屬成分量含有Al及Ga中一種以上之合計：0.15%at以上、Cr：12at%以上、Al、Ga及Cr合計：50at%以下，且剩餘部份為Zn以及無法避免的雜質之成分組成之氧化物。 The protective film for an optical recording medium according to the second aspect of the invention contains a total of one or more of Al and Ga with respect to the total metal component: 0.15% at or more, Cr: 12 at% or more, and a total of Al, Ga, and Cr: 50 at% or less. The remainder is an oxide of the composition of Zn and unavoidable impurities.
第3發明的光記錄媒體用保護膜係使用第1發明之氧化物濺鍍靶濺鍍成膜者。 The protective film for an optical recording medium according to the third aspect of the invention is the one obtained by sputtering the oxide sputtering target of the first invention.
亦即，此光記錄媒體用保護膜係反射率變化小，保存度高，同時具有柔軟而不易龜裂之特性，並適合用於使用有機色素紀錄層之BD的保護膜。 In other words, the protective film for an optical recording medium has a small change in reflectance, a high degree of preservation, and is soft and not easily cracked, and is suitable for use as a protective film of BD using an organic dye recording layer.
本發明具有下列效果。 The present invention has the following effects.
亦即，根據本發明之氧化物濺鍍靶為相對於全金屬成分量含有Al及Ga中一種以上之合計：0.15%at以上、Cr：12at%以上、Al、Ga及Cr合計：含有50at%以下，且剩餘部份為Zn以及無法避免的雜質所成成分組成之氧化物，因此可以穩定直流濺鍍，並能夠成膜為保存度高且柔 軟而不易龜裂之膜。 That is, the oxide sputtering target according to the present invention contains a total of one or more of Al and Ga with respect to the total metal component: 0.15% at or more, Cr: 12 at% or more, and a total of Al, Ga, and Cr: 50 at%. The following, and the remaining part is an oxide composed of Zn and unavoidable impurities, so that DC sputtering can be stabilized, and the film can be formed into a high degree of preservation and softness. Soft and not cracked film.
因此以本發明的氧化物濺鍍靶所成膜的光記錄媒體用保護膜，適合作為使用有機色素記錄層之BD用的介電體保護膜。 Therefore, the protective film for an optical recording medium formed by the oxide sputtering target of the present invention is suitable as a dielectric protective film for BD using an organic dye recording layer.
以下，說明本發明之氧化物濺鍍靶及光記錄媒體用保護膜其中一實施型態。 Hereinafter, one embodiment of the oxide sputtering target and the protective film for an optical recording medium of the present invention will be described.
本實施型態之氧化物濺鍍靶係例如為製作層積於以BD有機色素形成之記錄層上之介電體保護膜的濺鍍靶，其設定為：相對於全金屬成分量，含有Al及Ga之中一種以上之合計：0.15at%以上、Cr：12at%以上、Al、Ga及Cr合計：50at%以下，剩餘為Zn及無法避免的雜質所成之成分組成。 The oxide sputtering target of the present embodiment is, for example, a sputtering target for forming a dielectric protective film laminated on a recording layer formed of a BD organic dye, and is set to contain Al with respect to the total metal component amount. And a total of one or more of Ga: 0.15 at% or more, Cr: 12 at% or more, and a total of Al, Ga, and Cr: 50 at% or less, and the remaining composition of Zn and unavoidable impurities.
此外，為進行直流(DC)濺鍍，濺鍍靶的比電阻以1Ω‧cm以下為佳。為了穩定進行濺鍍，最好是0.1Ω‧cm以下，更佳為0.01Ω‧cm以下。 Further, in order to perform direct current (DC) sputtering, the specific resistance of the sputtering target is preferably 1 Ω‧cm or less. In order to stably perform sputtering, it is preferably 0.1 Ω ‧ cm or less, more preferably 0.01 Ω ‧ cm or less.
又，使用本實施型態之氧化物濺鍍靶藉由濺鍍所成膜之光記錄媒體用保護膜，係與上述濺鍍靶相同，係由相對於全金屬成分量含有Al及Ga中一種以上之合計：0.15at%以上、Cr：12at%以上、Al、Ga及Cr合計：50at%以下，且剩餘部份為Zn及無法避免的雜質所成之成分組成之氧化物。 Further, the protective film for an optical recording medium formed by sputtering using the oxide sputtering target of the present embodiment is the same as the above-described sputtering target, and contains one of Al and Ga with respect to the total metal component amount. The total of the above is 0.15 at% or more, Cr: 12 at% or more, Al, Ga, and Cr total: 50 at% or less, and the remainder is an oxide composed of Zn and an unavoidable impurity.
若針對本實施型態之製造氧化物濺鍍靶的方法之一例 詳述的話，首先秤量氧化鋅，氧化鉻，與氧化鋁及氧化鉀中至少一種之各原料粉末使呈既定之比率。 An example of a method of manufacturing an oxide sputtering target according to the present embodiment In detail, first, zinc oxide, chromium oxide, and each of the raw material powders of at least one of alumina and potassium oxide are weighed to a predetermined ratio.
將秤量後的原料粉末及其3倍量(重量比)的氧化鋯球(直徑5mm)置入塑料罐，以粉碎裝置進行濕式混合18小時。此時溶劑方面，例如可使用酒精。其次將所得的混合粉末乾燥後，例如以篩孔500μm篩網過篩，以1000-1400℃，更佳為在1150-1300℃溫度下乾燥2-9小時，於150-400kgf/cm2壓力下，以真空或惰性氣體的環境下進行熱壓，形成濺鍍靶。 The weighed raw material powder and its three times (by weight) zirconia balls (diameter: 5 mm) were placed in a plastic can, and wet-mixed by a pulverizing apparatus for 18 hours. At this time, for the solvent, for example, alcohol can be used. Next, the obtained mixed powder is dried, for example, sieved through a 500 μm sieve, and dried at 1000-1400 ° C, more preferably at a temperature of 1150-1300 ° C for 2-9 hours, under a pressure of 150-400 kgf/cm 2 . It is hot pressed in a vacuum or an inert gas to form a sputtering target.
基於上述實施型態而實際製作氧化物濺鍍靶之實施例，說明進行評鑑之結果。 An embodiment in which an oxide sputtering target is actually produced based on the above embodiment will be described, and the results of the evaluation will be described.
秤量氧化鋅(化學式：ZnO、D50=1μm)、氧化鉻(化學式：Cr2O3，D50=0.4μm)、與氧化鋁(化學式：Al2O3，D50=0.2μm)及氧化鎵(化學式：Ga2O3，D50=1.7μm)中至少一種之各原料粉末以成表1所示既定比例。 Weighing zinc oxide (chemical formula: ZnO, D 50 =1 μm), chromium oxide (chemical formula: Cr 2 O 3 , D 50 = 0.4 μm), and alumina (chemical formula: Al 2 O 3 , D 50 = 0.2 μm) and oxidation Each of the raw material powders of at least one of gallium (chemical formula: Ga 2 O 3 , D 50 = 1.7 μm) was set to a predetermined ratio shown in Table 1.
將秤量後的原料粉末及其3倍量(重量比)的氧化鋯球(直徑5mm)置入塑料罐，以粉碎裝置採濕式混合18小時。且，此時的溶劑為使用酒精。其次將所得的混合粉末乾燥後，以篩孔500μm篩網過篩，以篩孔1250℃ 3小時、350kgf/cm2之壓力下於真空中進行熱壓，製作實施例 1-7之濺鍍靶。將靶尺寸調整為直徑125mm×厚度5mm。 The weighed raw material powder and its three times (by weight) zirconia balls (diameter: 5 mm) were placed in a plastic can and mixed by a pulverizing apparatus for 18 hours. Moreover, the solvent at this time is alcohol. Next, the obtained mixed powder was dried, sieved through a 500 μm sieve, and hot pressed in a vacuum at a pressure of 1,350 ° C for 3 hours and a pressure of 350 kgf / cm 2 to prepare a sputtering target of Example 1-7. . The target size was adjusted to a diameter of 125 mm x a thickness of 5 mm.
且，比較例方面，不含有Al2O3及Ga2O3(比較例1)，及使本發明之成分組成比例為設定範圍外者(比較例2、3)，也以表1所示組成同樣地製作濺鍍靶。更準備以往之ZnS-SiO2(比較例4)及ITO(比較例5)的濺鍍靶。ZnS-SiO2為三菱材料製的ZSSO靶(20mol% SiO2)，ITO為三菱材料製的ITO靶(10wt%Sn O2) Further, in the comparative example, Al 2 O 3 and Ga 2 O 3 (Comparative Example 1) were not contained, and those having a composition ratio of the present invention outside the set range (Comparative Examples 2 and 3) were also shown in Table 1. The composition was prepared in the same manner as the sputtering target. Further, conventional sputtering targets of ZnS-SiO 2 (Comparative Example 4) and ITO (Comparative Example 5) were prepared. ZnS-SiO 2 is a ZSSO target (20 mol% SiO 2 ) made of Mitsubishi Materials, and ITO is an ITO target (10 wt% Sn O 2 ) made of Mitsubishi Materials.
使用此等實施例及比較例之濺鍍靶，以下述成膜條件成膜實施例1~7及比較例1~5之光記錄媒體用保護膜。濺鍍靶之金屬組成表示於表2，光記錄媒體用保護膜之金屬組成表示於表3。 Using the sputtering targets of the examples and the comparative examples, the protective films for optical recording media of Examples 1 to 7 and Comparative Examples 1 to 5 were formed under the following film formation conditions. The metal composition of the sputtering target is shown in Table 2, and the metal composition of the protective film for an optical recording medium is shown in Table 3.
˙電源：脈衝DC500W(一部分為高頻(RF)濺鍍) ̇ Power supply: pulse DC500W (part of high frequency (RF) sputtering)
˙全壓：0.4Pa ̇ full pressure: 0.4Pa
˙濺鍍氣體：Ar=47.5sccm、O2：2.5sccm(只有比較例4為Ar=50sccm、O2：0sccm) ̇ sputtering gas: Ar = 47.5 sccm, O 2 : 2.5 sccm (only Comparative Example 4 is Ar = 50 sccm, O 2 : 0 sccm)
˙濺鍍基板(TS)距離：70mm ̇ Sputtered substrate (TS) distance: 70mm
針對各實施例、比較例之濺鍍靶，求得其密度比、比電阻、異常放電次數、微粒量、膜壓印硬度、膜的龜裂及反射率之變化。 With respect to the sputtering targets of the respective examples and comparative examples, changes in density ratio, specific resistance, abnormal discharge number, particle amount, film imprint hardness, film crack and reflectance were obtained.
密度比是將燒結體以既定尺寸進行機械加工後，測定重量求得其體密度，以此為理論密度相除算出。且，理論密度乃基於原料重量而以下述的公式求得。 The density ratio is obtained by dividing the sintered body by a predetermined size and measuring the weight to obtain the bulk density, thereby dividing the theoretical density. Further, the theoretical density is obtained by the following formula based on the weight of the raw material.
濺鍍靶之比電阻測定是採用三菱化學製阻抗測定器GP來測定。 The specific resistance of the sputtering target was measured by using Mitsubishi Chemical's impedance measuring instrument GP.
於聚碳酸酯上濺鍍Ag98.1Nd1.0Cu00.9合金，採用專利文獻1所述成膜下述色素之基板，且以上述條件將各實施例及比較例之保護膜以14nm厚度成膜。之後靜置於80℃、85%之恆溫恆濕器中100小時，測定其前後反射率變化。且，反射率之測定為採用紫外可視分光光度計(日本分光股份有限公司製V-550)。並求出對波長405nm之光的反射率。 Ag 98.1 Nd 1.0 Cu 00.9 alloy was sputtered on the polycarbonate, and a substrate of the following dye was formed by the method described in Patent Document 1, and the protective films of the respective Examples and Comparative Examples were formed into a film having a thickness of 14 nm under the above conditions. Thereafter, it was allowed to stand in a constant temperature and humidity apparatus at 80 ° C and 85% for 100 hours, and the change in reflectance before and after was measured. Further, the reflectance was measured by using an ultraviolet visible spectrophotometer (V-550, manufactured by JASCO Corporation). The reflectance of light having a wavelength of 405 nm was obtained.
色素：成膜於上述基板的色素係使以下列結構式所示之配位體A及二價的Ni所成之含金偶氮色素A、配位體B及二價的Co所成之含金偶氮色素B，以70：30重量%之比混合，並使以八氟戊醇(OFP)稀釋成1.0重量%之混合溶液，以旋轉塗佈方式成膜。另外，旋轉塗佈係將上述混合溶液於基板中央附近環狀塗佈1.5g，將基板以1200rpm 旋轉7秒，讓色素延伸後，再以9200rpm使其旋轉3秒將色素甩乾以進行塗佈。且，藉由塗佈後將基板保持於80℃環境下1小時，蒸發除去溶劑OFP。 Pigment: a dye-formed film formed on the substrate, comprising a gold-containing azo dye A, a ligand B, and a divalent Co formed by the ligand A and the divalent Ni represented by the following structural formula. The gold azo dye B was mixed at a ratio of 70:30% by weight, and a mixed solution of octafluoropentanol (OFP) diluted to 1.0% by weight was added to form a film by spin coating. Further, in the spin coating, the mixed solution was applied in a ring shape of 1.5 g near the center of the substrate, and the substrate was 1200 rpm. After rotating for 7 seconds, the pigment was allowed to spread, and then the dye was dried at 9200 rpm for 3 seconds to dry the dye for coating. Further, the substrate was kept at 80 ° C for 1 hour after coating, and the solvent OFP was removed by evaporation.
上述條件中，基板係採康寧公司製1737玻璃，使膜厚為500nm進行成膜，使壓印加重為35mgf，以超微小壓印硬度試驗機(Elionix公司製ENT-1100a)進行測定。另將基板設置於27℃之裝置內，經過1小時以上後開始測定。將10點測定之平均值作為測定值。 In the above conditions, the substrate was a 1737 glass manufactured by Celtic Co., Ltd., and a film thickness of 500 nm was formed to form a film, and the embossing weight was 35 mgf, and the measurement was carried out by a micro-imprint hardness tester (ENT-1100a manufactured by Elionix Co., Ltd.). Further, the substrate was placed in a device at 27 ° C, and measurement was started after 1 hour or more. The average value of the 10-point measurement was taken as the measured value.
上述條件中，於厚度0.1mm之PET膜上以100nm膜 厚成膜，將膜彎折10次後，用顯微鏡以倍率1000倍觀察膜表面有無龜裂。 Among the above conditions, a 100 nm film is formed on a PET film having a thickness of 0.1 mm. After thick film formation, the film was bent 10 times, and the surface of the film was observed by a microscope at a magnification of 1000 times for cracking.
上述條件中，進行12小時濺鍍，並計測異常放電的次數。之後打開濺鍍反應室，確認反應室內的微粒。 Among the above conditions, sputtering was performed for 12 hours, and the number of abnormal discharges was measured. Then, the sputtering reaction chamber was opened to confirm the particles in the reaction chamber.
將此等評鑑結果顯示於表4。 The results of these evaluations are shown in Table 4.
由此等結果可知，本發明的實施例均為比電阻0.1Ω‧cm以下，異常放電次數非常少，且微粒量也很少。相對於此，比較例1、4則比電阻高為可測定範圍外，並無法直流濺鍍。又，比較例2顯示異常放電次數多，比較例5則是微粒量很多。此外，本發明之實施例及比較例均為密度90%以上者。 As a result of the above, it is understood that the examples of the present invention have a specific resistance of 0.1 Ω ‧ cm or less, the number of abnormal discharges is extremely small, and the amount of fine particles is also small. On the other hand, in Comparative Examples 1 and 4, the specific resistance was higher than the measurable range, and DC sputtering was not possible. Further, in Comparative Example 2, the number of abnormal discharges was large, and in Comparative Example 5, the amount of fine particles was large. Further, the examples and comparative examples of the present invention are all those having a density of 90% or more.
其次，表示保護膜柔軟度的壓印硬度，比較例1，3乃超過800mgf/μm2，且此等比較例1、3發現膜龜裂。 相對於此等，本發明實施例均在800mgf/μm2以下，與比較例1，3相較可取得較柔軟的膜，且並未發生龜裂。又作為ITO膜之比較例5係產生龜裂。 Next, the imprint hardness indicating the softness of the protective film was compared with Comparative Examples 1 and 3 to exceed 800 mgf/μm 2 , and the film cracks were found in Comparative Examples 1 and 3. In contrast, in the examples of the present invention, each of the examples of the present invention was 800 mgf/μm 2 or less, and a softer film was obtained as compared with Comparative Examples 1 and 3, and cracking did not occur. Further, in Comparative Example 5 which is an ITO film, cracks were generated.
再者，反射率變化方面，ZnS-SiO2的比較例4呈現較大變化，相對地本發明之實施例均為變化率1.0%以下，可確認其高保存性。 Further, in the change in reflectance, Comparative Example 4 of ZnS-SiO 2 exhibited a large change, and in the examples of the present invention, the rate of change was 1.0% or less, and the high storage stability was confirmed.
本實施例之保護膜為常溫下非晶質。 The protective film of this embodiment is amorphous at normal temperature.
其次針對本發明具代表性之實施例3的濺鍍靶進行X線繞射(XRD)測定，其結果如圖1所示。由此結果可得知，歸屬於ZnO繞射高峰及歸屬於作為Cr2O3及ZnO複合氧化物之ZnCr2O4的繞射高峰被檢出，可確認ZnO及ZnCr2O4之存在。 Next, X-ray diffraction (XRD) measurement was performed on the sputtering target of the representative example 3 of the present invention, and the results are shown in Fig. 1. From this result, it was found that the diffraction peak attributed to ZnO diffraction and the ZnCr 2 O 4 attributed to Cr 2 O 3 and the ZnO composite oxide were detected, and the presence of ZnO and ZnCr 2 O 4 was confirmed.
就實施例3的濺鍍靶，係以EPMA(電場放出型電子線探針)觀察表示反射電子像(CP)及各元素之組成分佈的元素分佈像。上述反射電子像及元素分佈像如圖2所示。 In the sputtering target of Example 3, an element distribution image indicating a reflected electron image (CP) and a composition distribution of each element was observed by EPMA (Electrical Field Release Type Electron Line Probe). The above reflected electron image and element distribution are shown in Fig. 2.
上述EPMA所示元素分佈像本來是彩色像，但因記載有轉變成黑白像，故濃淡較淡的部分(較白的部份)表示既定元素之濃度較高部份。 The element distribution shown in the above EPMA is originally a color image, but since it is described as being converted into a black-and-white image, the lighter and lighter portion (the whiter portion) indicates the higher concentration of the predetermined element.
從這些畫像可得知，實施例3的濺鍍靶是由ZnO及ZnCr2O4之相形成，Al均勻分散於ZnCr2O4中。 As can be seen from these images, the sputtering target of Example 3 was formed of a phase of ZnO and ZnCr 2 O 4 , and Al was uniformly dispersed in ZnCr 2 O 4 .
欲將本發明運用為濺鍍靶時，以表面粗度5.0μm以下較佳為1.0μm以下，粒徑20μm以下，較佳為10μm以下，金屬系雜質濃度0.1原子%以下較佳為0.05原子%以下，抗折強度50MPa以上較佳為100MPa以上。上述的 實施例均符合所述條件。 When the present invention is applied as a sputtering target, the surface roughness is 5.0 μm or less, preferably 1.0 μm or less, the particle diameter is 20 μm or less, preferably 10 μm or less, and the metal-based impurity concentration is 0.1 atom% or less, preferably 0.05 atom%. Hereinafter, the bending strength of 50 MPa or more is preferably 100 MPa or more. abovementioned The examples all met the stated conditions.
此外，本發明之技術範圍不受限於上述實施型態及實施例，只要在未偏離本發明主旨範圍內，可加上各種變更。 In addition, the technical scope of the present invention is not limited to the above-described embodiments and examples, and various modifications can be added without departing from the spirit and scope of the invention.
例如，在上述實施型態及實施例中雖然是以加壓燒結進行熱壓，但也可以採用其他如HIP法等方法(熱間等方加壓燒結法)。 For example, in the above-described embodiment and examples, although hot pressing is performed by pressure sintering, other methods such as HIP method (heat-to-equal pressure sintering method) may be employed.
[圖1]表示本發明之氧化物濺鍍靶及光記錄媒體用保護膜之實施例中，氧化物濺鍍靶之X線繞射(XRD)之結果。 Fig. 1 shows the results of X-ray diffraction (XRD) of an oxide sputtering target in an embodiment of the oxide sputtering target and the protective film for an optical recording medium of the present invention.
[圖2]本發明之氧化物濺鍍靶及光記錄媒體用保護膜實施例中，以EPMA測定氧化物濺鍍靶之剖面組織時，各元素之元素分佈像。 [Fig. 2] In the examples of the protective film for an oxide sputtering target and an optical recording medium of the present invention, when the cross-sectional structure of the oxide sputtering target is measured by EPMA, the element distribution image of each element is shown.
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