CN1965100B - 溅射靶和光信息记录介质及其制造方法 - Google Patents

溅射靶和光信息记录介质及其制造方法 Download PDF

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CN1965100B
CN1965100B CN2005800183779A CN200580018377A CN1965100B CN 1965100 B CN1965100 B CN 1965100B CN 2005800183779 A CN2005800183779 A CN 2005800183779A CN 200580018377 A CN200580018377 A CN 200580018377A CN 1965100 B CN1965100 B CN 1965100B
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recording medium
optical information
information recording
sputtering target
film
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CN1965100A (zh
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高见英生
矢作政隆
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JX Nippon Mining and Metals Corp
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Abstract

一种溅射靶，其特征在于，含有以Y2O3、Al2O3以及SiO2为主要成分的材料。一种光信息记录介质及其制造方法，其特征在于，使用该溅射靶，形成至少作为薄膜的光信息记录介质结构的一部分，并且于与记录层或反射层相邻设置。本发明涉及一种光信息记录介质用薄膜(特别是用作保护膜)及其制造方法和适用于这些的溅射靶，该光信息记录介质用薄膜的非晶态性稳定，与记录层的密合性、机械特性优良，且透过率高，此外，由于它由非硫化物类构成，不容易使相邻的反射层、记录层发生劣化，由此，本发明的目的在于，提高光信息记录介质的特性及大幅度改善其生产率。

Description

溅射靶和光信息记录介质及其制造方法
技术领域
本发明涉及一种光信息记录介质用薄膜(特别是用作保护膜)及其制造方法和适用于这些的溅射靶，该光信息记录介质用溅射膜的非晶态性稳定，与记录层的密合性、机械特性优良，且透过率高，此外，由于它由非硫化物类构成，不容易使相邻的反射层、记录层发生劣化。
背景技术
一直以来，一般主要作为相变型光信息记录介质的保护层使用的ZnS-SiO2，具有优良的光学特性、热特性、与记录层的密合性等特性，使用非常广泛。
然而，今天以Blue-Ray为代表的可重写型DVD，进一步强烈要求重写次数的增加、大容量化、高速记录化。
作为光信息记录介质的重写次数等劣化的原因之一，可以列举：来自ZnS-SiO2的硫成分向被夹在保护层ZnS-SiO2中设置的记录层材料扩散。
此外，为了达到大容量化、高速记录化，使用具有高反射率、高热传导特性的纯Ag或Ag合金作为反射层材料，但也将此反射层与保护层材料ZnS-SiO2相邻设置。
因此，这种情况下，由于来自ZnS-SiO2的硫成分的扩散，也同样是导致纯Ag或Ag合金反射层材料腐蚀劣化、光信息记录介质的反射率等特性变差的主要原因。
为防止硫成分扩散这种情况，也采用在反射层和保护层、记录层和保护层之间设置以氮化物或碳化物为主要成分的中间层的构造。然而，随着层压数的增加，产生生产量下降，成本增加的问题。
为了解决上述问题，在保护层材料中仅用不含硫化物的氧化物来替换材料，找出与ZnS-SiO2具有同等或更佳的光学特性、非晶态稳定性的材料成为当务之急。
从以上问题考虑，提出了氧化物类保护层材料、透明导电材料或者光学薄膜(参照专利文献1～3)。
但是专利文献1～3中包含光学特性和非晶态性差的领域的问题。
专利文献1：特开平01-317167号公报
专利文献2：特开2000-90745号公报
专利文献3：特开2003-166052号公报
发明内容
本发明涉及一种光信息记录介质用薄膜(特别是用作保护膜)及其制造方法和适用于这些的溅射靶，该光信息记录介质用薄膜的非晶态性稳定，与记录层的密合性、机械特性优良，且透过率高，此外，由于它由非硫化物类构成，不容易使相邻的反射层、记录层发生劣化，由此，本发明的目的在于，大幅度改善反复重写特性等光信息记录介质的特性。
为了解决上述课题，本发明人进行了认真的研究，结果发现，用下文提到的不含硫化物的氧化物材料替换原来的保护层材料ZnS-SiO2，可以确保其具有与ZnS-SiO2同等的光学特性以及非晶态稳定性，改善反复重写特性等的光信息记录介质的特性。
本发明以此发现为基础，提供：
1)一种溅射靶，其特征在于，包含Y2O3、Al2O3和SiO2；
2)一种溅射靶，其特征在于，包含Y2O3：10～60mol％、Al2O3：10～40mol％和SiO2：30～80mol％；
3)如上述1)或2)所记载的溅射靶，其特征在于，相对密度为95％以上。
此外，本发明还提供：
4)一种光信息记录介质及其制造方法，其特征在于，使用上述1)～3)中任一项所记载的溅射靶形成薄膜，该薄膜至少形成光信息记录介质结构的一部分；
5)一种光信息记录介质及其制造方法，其特征在于，使用上述1)～3)中任一项所记载的溅射靶形成薄膜，该薄膜至少形成光信息记录介质结构的一部分，并且与记录层或反射层相邻设置。
发明效果
如上所述，本发明能够提供一种光信息记录介质用薄膜(特别是用作保护膜)及其制造方法和适用于这些的溅射靶，该光信息记录介质用薄膜，通过用不含硫化物的氧化物替换以往的保护层材料ZnS-SiO2，在抑制相邻的反射层、记录层等由于硫的扩散而劣化的同时，还具备了与ZnS-SiO2同等或更佳的光学特性以及非晶态稳定性，与记录层的密合性、机械特性优良，且透过率高。
此外，通过使用本材料，取得了可以改善反复重写特性等光信息记录介质特性的良好效果。由于可以提高短波长侧的透过率，特别可以适用于蓝色激光系列的相变型记录介质的保护层材料。
具体实施方式
本发明的溅射靶，包含以Y2O3、Al2O3和SiO2为主要成分的材料。作为玻璃形成氧化物的SiO2使非晶态稳定化。为得到该效果，优选SiO2为30mol％以上。但是，当SiO2超过80mol％时，光学特性(折射率)变差，因此为得到良好的特性，优选将上限设定为80mol％。
添加Al2O3具有降低烧结温度的效果。通过降低烧结温度，能够提高密度，可以稳定的制造。为达到该效果，优选添加Al2O3为10mol％以上。但是，大量添加时，由于非晶态性变差，热传导率过大，因此优选Al2O3为40mol％以下。剩余部分为Y2O3，即Y2O3为10～60mol％。
由此，可使溅射靶的相对密度为95％以上，可以制造稳定的高密度的溅射靶。
另外，本发明使用上述溅射靶能形成薄膜，且使该薄膜至少形成信息记录介质结构的一部分。另外，本发明可以提供使用本发明溅射靶，能形成薄膜，且使该薄膜至少形成光信息记录介质结构的一部分，并且与记录层或反射层相邻设置的光信息记录介质及其制造方法。
这种材料的光学特性及膜的非晶态性稳定，适合作为相变型光记录介质的保护层材料。在成膜中使用高频溅射。
本材料如上所述非晶态性稳定，可以提高透过率，因此适合用作重写速度快的相变记录介质和蓝色激光系列的相变记录介质用保护层材料。
另外，本发明的溅射靶，相对密度可以达到95％以上。密度的提高，具有提高溅射膜的均匀性，而且能够抑制溅射时产生微粒的效果。
使用上述溅射靶，能提供形成薄膜，且使该薄膜至少形成光信息记录介质结构的一部分的光信息记录介质。
而且，使用上述溅射靶，可以制造在形成薄膜，且使该薄膜至少形成光信息记录介质结构的一部分的同时，与记录层或反射层相邻设置的光信息记录介质。
使用本发明的溅射靶形成的薄膜，形成光信息记录介质结构的一部分，与记录层或反射层相邻设置，但如上所述，由于没有使用ZnS，而没有S引起的污染、没有硫成分向被保护层夹住的记录层材料扩散而导致记录层劣化的情况，此效果显著。
而且，为了达到大容量化、高速记录化，在反射层材料中使用具有高反射率、高热传导特性的纯Ag或Ag合金，也没有硫成分向与该相邻的反射层扩散的情况，同样具有消除了引起反射层材料腐蚀劣化、光信息记录介质的反射率等特性变差的原因的优选效果。
本发明的溅射靶可以通过将平均粒径为5μm以下的各构成元素的氧化物粉末常压烧结或高温加压烧结来制造。由此可以得到相对密度为95％以上的溅射靶。
在这种情况下，烧结前，优选在1000～1400℃下煅烧以氧化钇为主要成分的氧化物粉末。该煅烧后，粉碎至3μm以下，得到烧结用的原料。
本发明具有特别添加Al2O3这一特征。如上述，通过添加Al2O3，得到可以降低烧结温度的优异效果。
Y2O3-SiO2这两种成分虽然光学特性和非晶态性等良好，但根据情况如果没有上升到1700℃的高温，就不能充分提高密度，有难以稳定制造的问题。在本发明中，烧结温度可以降低为1600℃以下，可以取得满足高密度且光学特性和非晶态性等的显著效果。
而且，通过使用本发明的溅射靶，有如下显著的效果，即，生产率提高，能够得到质量优良的材料，能稳定地以低成本制造具有光盘保护膜的光记录介质。
本发明的溅射靶密度的增加，有如下显著的效果：可以减少孔隙，使晶粒变得微细，使靶的溅射面变得均匀而且平滑，因此可以减少溅射时的颗粒和结核，而且靶的寿命延长，质量偏差小、提高了批量生产性。
实施例
下面基于实施例以及比较例进行说明。当然，本实施例只是一例，本发明并不受此例的任何限制。亦即，本发明只受权利要求范围的限制，本发明也包含实施例以外的各种变形。
(实施例1-4)
准备相当于4N的5μm以下的SiO2粉、Y2O3粉以及Al2O3粉，按表1所示的组成调合，用湿法混合、干燥后，在1100℃下煅烧。然后，将此煅烧粉湿法细粉碎到平均粒径为1μm左右后，添加粘合剂，用喷雾干燥器制粒。再将此制粒粉冷压成形，氧气环境(流动)中、在1200～1600℃下常压烧结，最终将此烧结材料机械加工成靶的形状。
实施例1～4的烧结温度分别为1400℃、1550℃、1250℃、1400℃。另外，只要烧结温度在上述的温度范围，就可几乎同等地进行烧结。
表1
 例   组成Y2O3∶Al2O3∶SiO2   T/P密度   透过率405nm(％)   折射率405nm   非晶态性※1
 实施例1   35∶20∶45   98   95   1.8   ○
 实施例2   45∶20∶35   96   96   1.9   ○
实施例3 15∶20∶65 99 96 1.7 ○
 实施例4   20∶35∶45   96   96   1.8   ○
 比较例1   20∶65∶15   97   93   1.8   ×
 比较例2   5∶5∶90   94   98   1.5   ○
 比较例3   85∶5∶10   75   98   2.1   △
 比较例4   ZnS-20molSiO2   80   80   2.3   ○
非晶态性是以相对于经退火(600℃、氩气环境、30分钟)处理的成膜样品在XRD测定中2θ＝20-60°范围内的未成膜玻璃基板的最大峰强度比表示。并且，○为1.0-1.5，△为1.5-2.0，×为2.0以上。
使用上述终加工得到的直径为6英寸的靶进行溅射。在RF溅射方式、溅射功率1000W、氩气压0.5Pa的溅射条件下，以
Figure GSB00000129889500071
目标膜厚成膜。
成膜样品的透过率(波长405nm)％、折射率(波长405nm)、非晶态性(以相对于经退火处理(600℃×30分钟、氩气环境)的成膜样品在XRD(Cu-Kα、40kV、30mA)测定中2θ＝20-60°范围内的未成膜玻璃基板的最大峰强度比表示)的测定结果等一并表示于表1。
以上结果表明，实施例1-4的溅射靶，相对密度都达到95％以上、能够稳定的进行RF溅射。
溅射膜的透过率达到95～96％(405nm)、折射率为1.7～1.9，而且看不到特定的结晶峰，具有稳定的非晶态性(1.0～1.5)。
并且，本实施例的靶由于没有使用ZnS，不会发生因为硫的扩散、污染而导致光信息记录介质的特性变差的情况。此外，与下述的比较例相比，成膜样品的透过率、折射率、非晶态的稳定性均显示出良好的数值。
(比较例1-4)
如表1所示，准备与本发明的条件不同的原料粉的成分和组成比的材料，特别是比较例4中的ZnS原料粉，将烧结温度设定为1500～1800℃，其他在与实施例相同的条件下制作靶，并用此靶形成溅射膜。比较例1～4的烧结温度分别设定为1650℃、1550℃、1750℃、1000℃(通过热压)。
其结果同样如表1所示。
脱离本发明组成比的比较例的成分、组成，例如在比较例1中，Al2O3过多为60mol％，结果是非晶态性变差。
在比较例2中，由于Y2O3和Al2O3少，而另一方面SiO2多，因此不均衡，折射率比基准还低。
在比较例3中，一方面Y2O3过多，另一方面SiO2少，因此不均衡，结果是密度没有充分提高，溅射性变差。
在比较例4中，虽然折射率高、密度也高，但是含有较多的ZnS，是有硫污染风险的材料。并且，透过率也差。
产业实用性
使用本发明的溅射靶形成的薄膜，形成光信息记录介质结构的一部分，由于没有使用ZnS，故具有不会由于硫成分向记录层材料扩散而导致记录层劣化的显著效果。而且，相邻的反射层使用具有高反射率、高热传导特性的纯Ag或Ag合金时，也没有硫成分向该反射层的扩散，具有消除了引起反射层腐蚀劣化、特性变差的原因的优良效果。
此外，由于非晶态性稳定化的同时赋予靶导电性，可以在较低温度下烧结而能够稳定制造。并且，由此可以达到相对密度为95％以上的高密度化，可以稳定进行RF溅射成膜。而且，容易控制溅射、提高溅射效率的效果十分显著，减少了溅射成膜时颗粒(起尘)和结核的产生，质量偏差小、提高了批量生产性，能稳定地以低成本制造具有光盘保护膜的光记录介质。

Claims (6)

1.一种溅射靶，其特征在于，包含Y2O3：10～60mol％、Al2O3：10～40mol％以及SiO2：30～80mol％。
2.如权利要求1所述的溅射靶，其特征在于，相对密度为95％以上。
3.一种光信息记录介质，其特征在于，使用权利要求1或2所述的溅射靶形成薄膜，该薄膜至少形成光信息记录介质结构的一部分。
4.如权利要求3所述的光信息记录介质，其特征在于，所述光信息记录介质结构的一部分与记录层或反射层相邻设置。
5.一种光信息记录介质的制造方法，其特征在于，使用权利要求1或2所述的溅射靶形成薄膜，该薄膜至少形成光信息记录介质结构的一部分。
6.如权利要求5所述的光信息记录介质的制造方法，其特征在于，所述光信息记录介质结构的一部分与记录层或反射层相邻设置。
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