CN1533446A - ZnS－SiO2溅射靶及使用该靶形成了ZnS－SiO2相变化型光盘保护膜的光记录媒体 - Google Patents
ZnS－SiO2溅射靶及使用该靶形成了ZnS－SiO2相变化型光盘保护膜的光记录媒体 Download PDFInfo
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Abstract
本发明涉及一种相对密度为90％以上的ZnS－SiO2溅射靶，其特征在于，使用将1－50摩尔％SiO2系玻璃粉末与其余的ZnS粉末均匀分散、混合的粉末烧结而成，所述的SiO2系玻璃粉末含有总计0.01－20重量％选自金属元素、硼、磷、砷或它们的氧化物的一种以上作为添加剂。通过能够以低成本稳定制造SiO2晶粒小、相对密度90％以上的靶，得到光盘保护膜形成用溅射靶，它能够进一步提高沉积的均匀性和提高生产率，并得到使用该溅射靶形成了ZnS－SiO2相变化型光盘保护膜的光记录媒体。
Description
技术领域
本发明特别涉及有效形成ZnS-SiO2相变化型光盘保护膜的ZnS-SiO2溅射靶，在通过溅射形成膜时它能够减少溅射时产生的微粒(扬尘)和突起物(nodule)，提高高密度产品的生产率且品质变动小，还涉及使用该靶形成了ZnS-SiO2相变化型光盘保护膜的光记录媒体。
背景技术
近年来，开发了不需要磁头就可读/写的高密度可记录光盘技术，该技术迅速引起人们关注。这种光盘分为只读型、一次写入型和可改写型三类。特别是在一次写入型和可改写型光盘中使用的相变化方法引人注目。以下简单说明采用这种相变化光盘进行读/写的基本原理。
相变化光盘是通过照射激光将衬底上的记录薄膜加热升温，使得在该记录薄膜的结构中产生结晶学相变化(无定形晶体)，进行信息的读/写。更具体地，信息的读是通过检测反射率的变化进行的。
上述的相变化是通过缩减至约1～数μm直径的激光束的照射来进行的。此时，例如1μm的激光束以10m/s的线速度通过时，光照射在光盘上确定点的时间是100ns，需要在此时间内进行上述相变化和反射率的检测。
另外，为实现上述结晶学相变化，即无定形与晶体间的相变化，不仅相变化记录层，而且周围的介质保护层和铝合金反射层都将反复受到一次以上的熔融和急冷。
考虑到这些，相变化光盘具有四层结构，其中，例如，用ZnS-SiO2高熔点介质保护层夹住Ge-Sb-Te记录薄膜层的两侧，并进一步设置铝合金反射层。
其中，除要求反射层和保护层具有能够增加无定形部分与结晶部分的吸收并具有大的反射率差的光学功能外，还要求其具有防止记录薄膜的耐湿性或热引起的变形的功能，以及控制记录时的热条件的功能(参照杂志“光学”第26卷1号，9-15页)。
如上所述，高熔点介质保护层必须对加热和冷却引起的重复热应力具有耐性，必须不使这样的热作用影响反射膜或其它区域，并且还要求自身薄、反射率低、并且具有防止变质的强度。从这点上看，介质保护层起着重要的作用。
上述的介质保护层通常是通过溅射法形成。这种溅射法将正电极靶与负电极靶相对，并通过在惰性气氛下在它们的衬底与靶间施加高电压而产生电场。该溅射法利用的基本原理是：此时电离的电子与惰性气体发生碰撞而形成等离子体，该等离子体中的阳离子撞击靶(负电极)表面，将靶构成原子挤出，挤出的原子附着到相对的衬底表面上形成膜。
以往，由于要求上述的保护层在可见光波段具有透过性或耐热性等，因此为形成大约1000至2000的薄膜，使用ZnS-SiO2等形成的陶瓷靶进行溅射。
这些材料通过高频溅射(RF)装置、磁控管溅射装置、或对靶材进行特殊处理后使用DC(直流)溅射装置等沉积。
通过将ZnS-SiO2靶的晶粒微细化并且高密度化，可以使靶的溅射面变得均匀且平滑，从而产生减少微粒和突起物以及延长靶寿命的特性。众所周知，这样的结果是提高光盘的生产率。
然而，以往的ZnS-SiO2靶中使用的SiO2具有4N以上的高纯度，以及0.1-20μm的平均粒径，通常是通过在800-1200℃的温度下烧结来制造。但是，在这种温度范围内，SiO2自身不发生变形，也不与ZnS发生反应。
因此，如上制造的ZnS-SiO2靶容易在ZnS和SiO2间形成空隙，当SiO2微细化时，这变得更为显著，并且由于ZnS的致密化也因此受到阻碍，因此存在靶密度将下降的问题。
当靶密度下降时，存在的另一个问题是机械强度也将下降，并且在溅射时产生破裂。鉴于此，提出通过加入10-1000ppm氧化铝(矾土)并提高烧结性，来增加强度(日本专利公开平9-143703)。然而，存在的问题是仅添加氧化铝不能提高靶密度。
因此，以往为实现高密度化，必须使热压等制造条件变为更高温、更高压。但是，例如，通过热压制作时，随温度增加1个工序需要更多的时间，并且随压力增加石墨模保持其强度。从而必须增加外周的径向厚度并且减小负荷面积部分。结果是，存在每个热压批次的生产率将显著减少的问题。
相反，为不使生产率降低，尽管可以增大热压装置以增大石墨模自身，但是这将导致这样的热压装置和石墨模的成本增加。
由于上面的原因，以往不可能以低成本获得ZnS-SiO2相变化型光盘保护膜用的高密度溅射靶。
因此，一般不得不使用低密度靶，但结果是，通过溅射形成膜时将产生微粒(扬尘)和突起物。这导致的问题是沉积的均匀性和品质下降，导致生产率低下。
本发明的公开
本发明的目的是能够以低成本稳定制造晶粒微细的密度90％以上的高密度靶，从而得到可以进一步提高沉积的均匀性和增加生产率的光盘保护膜形成用溅射靶及使用该溅射靶形成了ZnS-SiO2相变化型光盘保护膜的光记录媒体。
为实现上述目的，本发明人进行了广泛细致的研究，结果发现，通过使用在SiO2中加入添加剂的SiO2系玻璃材料，与ZnS之间的空隙可以减小，即使将SiO2微细化也可以容易地实现高密度化，可以在不损害作为保护膜的特性的同时减少溅射时产生的微粒和突起物，也可以提高膜厚的均匀性。
基于上述发现，本发明提供：
1.一种相对密度为90％以上的ZnS-SiO2溅射靶，其特征在于，使用将1-50摩尔％SiO2系玻璃粉末与其余的ZnS粉末均匀分散、混合的粉末烧结而成，所述的SiO2系玻璃粉末含有总计0.01-20重量％选自金属元素、硼、磷、砷或它们的氧化物的一种以上作为添加剂；
2.一种相对密度为90％以上的ZnS-SiO2溅射靶，其特征在于，使用将1-50摩尔％SiO2系玻璃粉末、0.01-30摩尔％SiO2粉末与其余的ZnS粉末均匀分散、混合的粉末烧结而成，所述的SiO2系玻璃粉末含有总计0.01-20重量％选自金属元素、硼、磷、砷或它们的氧化物的一种以上作为添加剂；
3.上述1或2所述的ZnS-SiO2溅射靶，其特征在于，金属元素为锂、钠、镁、铝、钾、钙、钡或铅；
4.上述1-3各项所述的ZnS-SiO2溅射靶，其特征在于，SiO2晶粒的平均粒径为0.1-30μm；和
5.使用上述1-4的各项所述的ZnS-SiO2溅射靶形成了ZnS-SiO2相变化型光盘保护膜的光记录媒体。
附图的简单说明
图1是根据实施例1得到的靶表面的显微镜照片；图2是根据实施例2得到的靶表面的显微镜照片；图3是比较例1得到的靶表面的显微镜照片。
实施本发明的最佳方式
本发明使用含有总量为0.01-20重量％选自金属元素、硼、磷、砷或它们的氧化物的一种以上作为添加剂的SiO2系玻璃粉末。作为前述的金属元素，特别优选使用锂、钠、镁、铝、钾、钙、钡或铅。如上所述，本发明的显著特征是使用SiO2系玻璃材料。
添加剂的添加量小于0.01重量％时添加剂无效果，并且添加量超过20重量％时膜特性将大大变化所以不优选，总量设定为0.01-20重量％。
通过将1-50摩尔％含有上述添加元素的SiO2系玻璃粉末及其余的ZnS粉末均匀分散、混合，然后通过热压等烧结，来制造靶。
在前述的SiO2系玻璃粉末中加入0.01-30重量％SiO2粉末，将其与其余的ZnS粉末均匀分散、混合，并通过热压等烧结也是可以的。通过加入SiO2粉末，可以根据使用目的减少前述金属元素的添加量，并且即使SiO2成分量大也可以高密度化。另外，希望各添加材料的纯度高，例如使用纯度99.99重量％以上的材料，但添加材料不必限于该范围。
由此可以得到ZnS与SiO2间的空隙少、相对密度90％以上的ZnS-SiO2相变化型光盘保护膜形成用溅射靶。
另外，通过仅添加前述材料，就可以将ZnS-SiO2靶晶粒微细化和高密度化，并且因此产生了显著的效果：靶的溅射面可以做得均匀、光滑，可以减少溅射时的微粒和突起物，并且可以延长靶寿命。结果，形成了ZnS-SiO2相变化型光盘保护膜的光记录媒体的生产率将提高，可以得到品质优良的材料。
通过使SiO2晶粒的平均粒径为0.1-30μm，也可以进一步改善上述特性。
实施例和比较例
以下参考实施例和比较例说明本发明。这些实施例仅是举例，因此本发明无论如何不受限制。即，本发明仅通过专利权利要求范围来限制，包括本发明的实施例以外的各种变形。
(实施例1)
使用成分组成为SiO2-0.5重量％Na2O的SiO2系玻璃粉末，以对ZnS为20摩尔％的比例与ZnS均匀混合。
将该混合粉末填充到石墨模中，在下面条件下进行热压：Ar气氛、压力150kg/cm2、温度1000℃。
这样得到的靶的相对密度为99％。该靶表面的显微镜照片如图1所示。
图1中的黑色球形部分表示SiO2，SiO2晶粒的平均粒径为5μm以下，并且几乎不能辨认ZnS与SiO2的表面间的空隙。结果，得到了ZnS-SiO2相变化型光盘保护膜形成用高密度溅射靶。
(实施例2)
使用成分组成为SiO2-0.5重量％B2O3的SiO2系玻璃粉末，以对ZnS为20摩尔％的比例与ZnS均匀混合。
将该混合粉末填充到石墨模中，在下面条件下进行热压：Ar气氛、压力150kg/cm2、温度1000℃。这样得到的靶的相对密度为97％。结果，得到了ZnS-SiO2相变化型光盘保护膜形成用高密度溅射靶。其显微镜照片如图2所示。
图2中的黑色球形部分表示SiO2，SiO2晶粒的平均粒径为10μm以下，很明显ZnS与SiO2间的空隙极少。
(比较例1)
将纯度为99.99重量％以上的SiO2粉末以对ZnS为20摩尔％的比例与ZnS均匀混合。
将该混合粉末填充到石墨模中，在下面条件下进行热压：Ar气氛、压力150kg/cm2、温度1000℃。这样得到的靶的相对密度为94％。结果，得到了密度比本发明的实施例差的ZnS-SiO2相变化型光盘保护膜形成用溅射靶。
该靶的显微镜照片如图3所示。与上面同样，图3中的黑色球形部分表示SiO2，确认ZnS与SiO2的表面间有许多空隙。
发明效果
通过使用本发明的在SiO2中加入添加剂的SiO2系玻璃材料，可以减少与ZnS间的空隙，即使将SiO2微细化也容易高密度化。因此，得到了优良的效果：可以得到在不损害作为保护膜的特性的同时，能够抑制溅射时产生的微粒(扬尘)和突起物，提高沉积的均匀性和提高生产率的光盘保护膜形成用溅射靶，及使用该溅射靶形成了ZnS-SiO2相变化型光盘保护膜的光记录媒体。
(按照条约第19条的修改)
1.一种相对密度为90％以上的ZnS-SiO2溅射靶，其特征在于，使用将1-50摩尔％SiO2系玻璃粉末与其余的ZnS粉末均匀分散、混合的粉末烧结而成，所述的SiO2系玻璃粉末含有总计0.01-20重量％选自硼、磷、砷、金属元素、或它们的氧化物的一种以上作为添加剂，所述的金属元素由锂、钠、镁、铝、钾、钙、钡组成。
2.一种相对密度为90％以上的ZnS-SiO2溅射靶，其特征在于，使用将1-50摩尔％SiO2系玻璃粉末、0.01-30摩尔％SiO2粉末与其余的ZnS粉末均匀分散、混合的粉末烧结而成，所述的SiO2系玻璃粉末含有总计0.01-20重量％选自硼、磷、砷、金属元素、或它们的氧化物的一种以上作为添加剂，所述的金属元素由锂、钠、镁、铝、钾、钙、钡组成。
3.(删除)
4.权利要求1或2所述的ZnS-SiO2溅射靶，其特征在于，SiO2晶粒的平均粒径为0.1-30μm。
5.使用权利要求1、2或4各项所述的ZnS-SiO2溅射靶形成了ZnS-SiO2相变化型光盘保护膜的光记录媒体。
Claims (5)
1.一种相对密度为90％以上的ZnS-SiO2溅射靶，其特征在于，使用将1-50摩尔％SiO2系玻璃粉末与其余的ZnS粉末均匀分散、混合的粉末烧结而成，所述的SiO2系玻璃粉末含有总计0.01-20重量％选自金属元素、硼、磷、砷或它们的氧化物的一种以上作为添加剂。
2.一种相对密度为90％以上的ZnS-SiO2溅射靶，其特征在于，使用将1-50摩尔％SiO2系玻璃粉末、0.01-30摩尔％SiO2粉末与其余的ZnS粉末均匀分散、混合的粉末烧结而成，所述的SiO2系玻璃粉末含有总计0.01-20重量％选自金属元素、硼、磷、砷或它们的氧化物的一种以上作为添加剂。
3.权利要求1或2所述的ZnS-SiO2溅射靶，其特征在于，金属元素为锂、钠、镁、铝、钾、钙或钡。
4.权利要求1-3各项所述的ZnS-SiO2溅射靶，其特征在于，SiO2晶粒的平均粒径为0.1-30μm。
5.使用权利要求1-4的各项所述的ZnS-SiO2溅射靶形成了ZnS-SiO2相变化型光盘保护膜的光记录媒体。
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| JP2002358699A (ja) * | 2001-06-01 | 2002-12-13 | Nikko Materials Co Ltd | 相変化型光ディスク保護膜形成用スパッタリングターゲット及び該ターゲットを使用して相変化型光ディスク保護膜を形成した光記録媒体 |
| JP5019343B2 (ja) * | 2004-01-27 | 2012-09-05 | Ｊｘ日鉱日石金属株式会社 | スパッタリングターゲット用ＺｎＳ粉末及びスパッタリングターゲット |
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