CN1926258A - 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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CN1926258A
CN1926258A CNA2005800062079A CN200580006207A CN1926258A CN 1926258 A CN1926258 A CN 1926258A CN A2005800062079 A CNA2005800062079 A CN A2005800062079A CN 200580006207 A CN200580006207 A CN 200580006207A CN 1926258 A CN1926258 A CN 1926258A
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sputtering target
recording medium
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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，由HfO2以及Y2O3的复合氧化物组成。Y2O3的含量为10～95mol％，余量为HfO2的该溅射靶。以及，以含有10～90mol％的ZrO2为特征的该溅射靶。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，由于它由非硫化物类构成，不容易使相邻的反射层、记录层发生老化，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、记录层发生老化。
背景技术
一直以来，主要是在相变型光信息记录介质的保护层通常使用的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，对重写次数的增加、大容量化、高速记录化有了进一步的强烈要求。
作为光信息记录介质的重写次数等减少的原因，列举其中之一是保护层ZnS-SiO2中的硫成分向被夹在其中的记录层材料的扩散。
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合金作反射层材料，但也将此反射层置于与保护层材料ZnS-SiO2相邻的位置。
因此，这种情况下，由于ZnS-SiO2中硫成分的扩散，也同样成为导致纯Ag或Ag合金反射层材料被腐蚀老化、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，仅用不含硫化物的氧化物的材料替换保护层材料，找出具有与ZnS-SiO2相同或更好的光学特性、非晶态稳定性的材料成为当务之急。
根据上述情况，提出了氧化物类保护层材料、透明导电材料或光学薄膜(参照专利文献1～3)。
但是，专利文献1～3存在包含光学特性以及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、记录层发生老化，由此，本发明的目的在于，大幅度改善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，仅用下文提到的不含硫化物的氧化物的材料替换原来的保护层材料ZnS-SiO2，可以确保与ZnS-SiO2相同的光学特性以及非晶态稳定性，进而可以改善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，由HfO2以及Y2O3的复合氧化物组成。
2)根据1)所述的溅射靶，其特征在于，Y2O3的含量为10～95mol％，余量为HfO2。
3)根据1)或2)所述的溅射靶，其特征在于，还含有10～90mol％的ZrO2。
此外，本发明还提供：
4)根据1)～3)中任一项所述的溅射靶，其特征在于，相对密度在90％以上。
5)使用上述1)～4)中任一项所述的溅射靶，至少形成作为薄膜的光信息记录介质构造的一部分为特征的光信息记录介质及其制造方法。
6)使用上述1)～5)中任一项所述的溅射靶，至少形成作为薄膜的光信息记录介质构造的一部分，且置于与记录层或反射层相邻位置为特征的光信息记录介质及其制造方法。
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，通过仅用不含硫化物的氧化物替换保护层材料ZnS-SiO2，在抑制相邻的反射层、记录层等由于硫的扩散而老化的同时，还具备了与ZnS-SiO2相同或更好的光学特性以及非晶态稳定性，使高速成膜成为可能，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，取得了可以改善光信息记录介质特性的良好效果。
具体实施方式
本发明的溅射靶由HfO2及Y2O3的复合氧化物组成。特别是，其中Y2O3的含量为10～95mol％，余量为HfO2。因为当Y2O3的含量不足10mol％或超过95mol％时，有欠缺非晶态稳定性的问题。
此外，可以进一步添加10～90mol％的ZrO2。ZrO2具有热传导性高的特性。为了有效的利用此特性，添加附加的ZrO2时，优选为10～90mol％。因为，ZrO2若不足10mol％则没有添加效果，而超过90mol％会产生欠缺非晶态稳定性的问题，所以添加时优选上述范围。
这种材料的光学特性及膜的非晶态性稳定，适合作相变型光记录介质的保护层材料。成膜时使用高频溅射靶。
如上所述，本材料的非晶态性稳定，能够使透过率提高，因此适合用作重写速度快的相变记录介质或蓝激光系列的相变记录介质用保护层材料。
而且，本发明的溅射靶，相对密度可以达到90％以上。密度的增加，具有提高溅射膜的均匀性，而且能够抑制溅射时产生颗粒的效果。
使用上述溅射靶，能提供至少形成作为薄膜的光信息记录介质构造的一部分的光信息记录介质。而且，使用上述溅射靶，能制造至少形成作为薄膜的光信息记录介质构造的一部分，且置于与记录层或反射层相邻位置的光信息记录介质。
进而，使用本发明的溅射靶形成的薄膜，形成光信息记录介质构造的一部分，置于与记录层或反射层相邻的位置，但如上所述，由于没有使用ZnS，而没有S的污染、没有硫成分向被夹在保护层中的记录层材料扩散而导致记录层老化的情况，此效果显著。
而且，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合金作反射层材料，同样，也没有硫成分向此相邻反射层的扩散，清除了引起反射层材料腐蚀老化、光信息记录介质的反射率等特性变差的原因，此效果优良。
本发明的溅射靶可以通过常压烧结或高温加压烧结平均粒径为5μm以下的各构成元素的氧化物粉末制造。这样能得到相对密度为90％以上的溅射靶。这种情况下，烧结前，优选在800～1400℃下煅烧以氧化铪及氧化钇为主要成分的氧化物粉末。该煅烧后，粉碎至3μm以下，作为烧结用的原料。
而且，通过使用本发明的溅射靶，有如下显著的效果，即，可以提高生产率、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。
本发明的溅射靶随着密度的增加，有如下显著的效果，可以使细孔减少、晶粒细小化、靶的溅射面变得均匀而且平滑，因此减少了溅射时的颗粒或结核，而且靶的寿命延长，质量偏差小、提高了批量生产性。
实施例
下面以实施例以及比较例为基础进行说明。当然，本实施例只是一例，本发明并不受此例的任何限制。也就是说，本发明只受权利要求范围的限制，也包含本发明的实施例以外的各种变形。
(实施例1-6)
将相当于4N的5μm以下的Y2O3粉，以及相当于3N的平均粒径5μm以下的ZrO2粉和HfO2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，达到平均粒径为1μm后，添加粘合剂，用喷雾干燥器制粒。再将此制粒粉冷压成形，在1300℃～1600℃下、氧气环境中常压烧结，最终将此烧结材料机械加工成靶的形状。此靶的成分组成如表1所示。
表1
  例   组成  透过率405nm(％)   折射率405nm   非晶态性
  实施1   HfO2-20mol％Y2O3   98   2.1   1.1
  实施2   HfO2-40mol％Y2O3   96   2.1   1.0
  实施3   HfO2-60mol％Y2O3   97   2.0   1.1
  实施4   HfO2-80mol％Y2O3   97   1.9   1.0
  实施5   ZrO2-10mol％HfO2-20mol％Y2O3   97   2.1   1.1
  实施6   ZrO2-30mol％HfO2-40mol％Y2O3   97   2.0   1.0
  比较1   HfO2   95   2.1   1.9
  比较2   ZrO2   97   2.1   2.3
  比较3   Y2O3   93   1.9   2.5
  比较4   ZrO2-5mol％Y2O3   97   2.0   2.1
  比较5   HfO2-5mol％Y2O3   95   2.1   1.8
  比较6   ZnS-SiO2(20mol％)   80   2.3   1.1
非晶态性是以相对于经退火(600℃、氩气环境、30min)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。
使用上述最终加工得到的直径大小为6英寸的靶进行溅射。以RF溅射方式、1000W溅射能、0.5Pa氩气压为溅射条件，以1500为目标膜厚成膜。
成膜样品的透过率(波长633nm)％、折射率(波长633nm)、非晶态性(以相对于经退火(600℃×30min、氩气环境)处理的成膜样品在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，总结如表1所示。
以上结果表明，实施例1-6的溅射靶，相对密度都达到90％以上、能够进行稳定的RF溅射。
而且，溅射膜的透过率达到96～98％(405μm)、折射率为1.9～2.1，而且看不到特定的结晶峰，具有稳定的非晶态性(1.0～1.1)。
另外，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。而且，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1-6)
如表1所示，准备具有与本发明的条件不同的原料粉成分和组成比的材料，特别是比较例6中的ZnS原料粉，在与实施例相同的条件下制作靶，并用此靶形成溅射膜。
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，由于完全不含Y氧化物，导致非晶态性为1.9这样差的结果。
在比较例2中，同样由于不含Y氧化物，导致非晶态性为2.3这样差的结果。
在比较例3中，由于是单独的Y氧化物，同样导致非晶态性为2.5这样差的结果。
对于比较例4，它由Zr氧化物和Y氧化物组合，但Y氧化物的含量比基准量少，同样导致了非晶态性为2.1这样差的结果。
对于比较例5，它由Hf氧化物和Y氧化物组合，但Y氧化物的含量比基准量少，同样导致了非晶态性为1.8这样差的结果。
此外，特别是比较例6，ZnS含量较多，透过率低于80％，而且是有硫污染危险的材料。
工业实用性
使用本发明的溅射靶形成的薄膜，形成光信息记录介质构造的一部分，由于没有使用ZnS，故而没有硫成分向记录层材料扩散而导致记录层老化的情况，效果显著。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，清除了引起反射层材料腐蚀老化、特性变差的原因，效果优良。
此外，由于非晶态性稳定化的同时付与靶导电性、相对密度达90％以上的高密度化，可以进行稳定的RF溅射成膜。而且简化溅射操作、提高溅射效率的效果十分显著。此外，还有如下显著的效果：可以减少溅射成膜时颗粒(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。
权利要求书
(按照条约第19条的修改)
1.用于形成光信息记录介质薄膜的溅射靶，其特征在于，由HfO2以及Y2O3的复合氧化物组成。
2.根据权利要求1所述的用于形成光信息记录介质薄膜的溅射靶，其特征在于，Y2O3的含量为10～95mol％，余量为HfO2。
3.根据权利要求1或2所述的用于形成光信息记录介质薄膜的溅射靶，其特征在于，还含有10～90mol％的ZrO2。
4.根据权利要求1～3中任一项所述的用于形成光信息记录介质薄膜的溅射靶，其特征在于，相对密度在90％以上。
5.光信息记录介质，其特征在于，在光信息记录介质构造的至少一部分，具有通过溅射形成的由HfO2以及Y2O3的复合氧化物组成的薄膜。
6.根据权利要求5所述的光信息记录介质，其特征在于，Y2O3的含量为10～95mol％，余量为HfO2。
7.根据权利要求5或6所述的光信息记录介质，其特征在于，还含有10～90mol％的ZrO2。
8.根据权利要求5～7中任一项所述的光信息记录介质，其特征在于，所述薄膜置于与记录层或反射层相邻的位置。
9.使用权利要求1～4中任一项所述的靶，通过溅射，至少在光信息记录介质构造的一部分形成薄膜为特征的光信息记录介质的制造方法。
10.根据权利要求9所述的光信息记录介质的制造方法，其特征在于，所述薄膜与记录层或反射层相邻而形成。

Claims (6)

1.一种溅射靶，其特征在于，由HfO2以及Y2O3的复合氧化物组成。
2.根据权利要求1所述的溅射靶，其特征在于，Y2O3的含量为10～95mol％，余量为HfO2。
3.根据权利要求1或2所述的溅射靶，其特征在于，还含有10～90mol％的ZrO2。
4.根据权利要求1～3中任一项所述的溅射靶，其特征在于，相对密度在90％以上。
5.使用权利要求1～4中任一项所述的溅射靶，至少形成作为薄膜的光信息记录介质构造的一部分为特征的光信息记录介质及其制造方法。
6.使用权利要求1～5中任一项所述的溅射靶，至少形成作为薄膜的光信息记录介质构造的一部分，且置于与记录层或反射层相邻位置为特征的光信息记录介质及其制造方法。
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