CN1723496A - 光学信息记录介质及其制造方法 - Google Patents

光学信息记录介质及其制造方法 Download PDF

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CN1723496A
CN1723496A CNA2003801054460A CN200380105446A CN1723496A CN 1723496 A CN1723496 A CN 1723496A CN A2003801054460 A CNA2003801054460 A CN A2003801054460A CN 200380105446 A CN200380105446 A CN 200380105446A CN 1723496 A CN1723496 A CN 1723496A
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dielectric layer
layer
recording medium
optical data
data recording
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CN100378835C (zh
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坂上嘉孝
长田宪一
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Panasonic Holdings Corp
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Matsushita Electric Industrial Co Ltd
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Abstract

本发明提供一种具有氧化钛层的多层记录介质，是在氧化铌、氧化硅或以它们为主成分的第1电介质层上形成氧化钛或以氧化钛为主成分的第2电介质层。这是因为在多层记录介质中，当使用单叶式溅射装置形成氧化钛层时，引氧化钛层的膜厚偏差使得透过率产生较大偏差。另外，在使用单叶式溅射装置时，在装载闭锁室和形成透过率调节层的容器之间至少设置一个用于促进从基板的水和氧气的脱气的容器。

Description

光学信息记录介质及其制造方法
技术领域
本发明涉及使用激光线等光学手段对信息进行高速且高密度记录、再现的光学信息记录介质及其制造方法。
背景技术
利用激光线进行高密度的信息再现或记录的技术是公知的，主要作为光盘而实用化。
光盘可以大致分成再现专用型、追记型、改写型。再现专用型作为光盘(compact disk)或激光盘而实用化，另外，追记型或改写型作为文本文件、数据文件等而实用化。在改写型光盘当中，主要有光磁和相变型。相变光盘利用的是记录层通过激光线的照射在非晶质和晶粒间(或者晶体与不同结构的晶粒间)发生可逆的状态变化。这是因为通过激光照射而使薄膜的折射率或消光系数中的至少一种发生变化而进行记录，透过光或反射光的振幅在该部分发生变化，其结果是检测出到达检测系统的透过光量或反射光量发生变化，从而再现信号。
从使光盘的记录容量增加的观点来看，提出有单面2层的结构(例如特开2001-273634号公报(第8～9页，图1))。
另外，正在进行面向使用蓝紫色激光进行记录再现的2层光学信息记录介质的实用化的研究开发。一直以来，通过使用短波长的激光或数值孔径(NA)大的物镜，可以减小激光的点径，进行更高密度的记录。
作为在单面多层记录介质中要求的磁盘特性，邻近用于对信息进行记录再现的激光的入射侧的信息层，具有高透过率。在2层光学信息记录介质的情况下，使用透过邻近激光入射侧的信息层的激光，进行深部侧的信息层的记录再现。为此，记录深部侧的信息使所必需的激光功率，应该是用面前侧的层的透过率去除深部侧的信息层为单层情况下的记录功率而得到的功率。即，在是2层的情况下，有必要使用于记录再现的激光功率较大。为此，特别是面前侧的层需要有高透过率(例如50％)。目前进行研究的技术是，从激光的入射侧来看，在按顺序至少具备记录层、反射层的信息层中，研究靠近反射层的与激光入射侧相反一侧而设置由电介质构成的透过率调节层，进而研究了通过使上述透过率调节层与反射层的折射率、消光系数最佳化而实现高透过率的技术(例如，特愿2002-591524号)。
当利用溅射在光盘上形成记录层、反射层、电介质层、透过率调节层等时，从其批量生产的观点来看，多使用单叶式溅射装置。使用图3说明单叶式溅射装置。关于该装置的构造，借助装载闭锁室11而被投入到真空容器内(主要容器18)的成膜前磁盘基板9，被运送至用于形成第1层的成膜室(此时为成膜室12)并进行成膜，接着被运送至用于形成第2层的成膜室(此时为成膜室13)并进行成膜，重复进行，在形成需要的层之后，再次通过装载闭锁室11取出成膜后磁盘10。磁盘基板9继续借助装载闭锁室11而一个接一个投进去。使用该单叶式溅射装置，可以制造大量的光磁记录介质或DVD-RAM等。
本发明人等在进行单面多层记录介质的研究时，首先致力于2层光学信息记录介质的研发。为了提高入射侧的信息层的透过率，通过设置氧化钛层作为透过率调节层的结构(图2)进行研究，确保透过率为50％以上。不过，在该结构的单面多层记录介质的批量生产研究中，明确了以下的问题。
使用单叶式溅射装置进行了批量生产，但已知当使用氧化钛层作为透过率调节层时，在对样品进行多张成膜的情况下，在透过率或反射率中产生较大的偏差。详细研究的结果发现这是因为氧化钛膜厚的偏差较大造成的。即，通过实验已经明确光学特性对透过率调节层的膜厚的要求非常苛刻，但氧化钛的成膜速度或光学性质(折射率、消光系数)对成膜气氛中的氧气量非常敏感，微量的氧气量变动都会造成成膜速度变得不稳定(当氧气大量存在时，成膜速度减少)，这对磁盘反射率或透过率等带来较大的影响。在本研究中，氧气(或水)作为成为问题的成膜速度的不稳定性的原因，预测其使吸附于树脂基板上的物质在成膜时脱气而造成影响。不过，氧化钛在进行本研究的激光波长处的光学性质是最好的(折射率大，透光性大)。为此，在解决上述问题的基础上，必须进行具有使用了氧化钛的结构的磁盘研发。
发明内容
因此，本发明的第1目的在于，提供一种将均匀的氧化钛膜作为信息层的构成要素的光学信息记录介质。
另外，本发明的第2目的在于，提供将氧化钛膜用作透过率调节层且具有高透过率的单面多层结构的光学信息记录介质及其制造方法。
为了解决上述问题，因有吸附于树脂基板上的物质在成膜时脱气而造成影响的观点，从而潜心研究的结果发现，在形成氧化钛层之前，在基板侧形成折射率与氧化钛层或基板相近的且氧气的存在不会对成膜速度造成影响的电介质层，并在其上形成氧化钛层，此时可以形成实际上均匀的氧化钛层。
因此，本发明提供一种光学信息记录介质，其特征在于，包括：在基板上形成的且通过上述激光照射在非晶质相和晶体相之间产生可用光学检测的可逆变化的记录层，在上述记录层和基板之间形成的折射率与氧化钛层或基板接近的且氧气的存在也不会对形成的膜厚造成实质影响的第1电介质层，在上述记录层和第1电介质层之间形成的且作为主成分含有氧化钛的第2电介质层。
上述第1电介质层优选至少将氧化铌或氧化硅作为主成分而成的电介质层，可以利用氧化铌或氧化硅形成，作为主成分含有它们(这里所说的主成分是指51mol％以上)，剩下的可以由从氧化钛、ZrO2、ZnO、Ta2O5、SiO2、Al2O3、Bi2O3、Ti-N、Zr-N、Nb-N、Ta-N、Si-N、Ge-N、Cr-N、Al-N、Ge-Si-N、Ge-Cr-N和ZnS中选择的至少一个而形成。
另外，氧化钛层可以只由氧化钛形成，还可以将氧化钛作为主成分，且由从ZrO2、ZnO、氧化铌、Ta2O5、SiO2、Al2O3、Bi2O3、Ti-N、Zr-N、Nb-N、Ta-N、Si-N、Ge-N、Cr-N、Al-N、Ge-Si-N、Ge-Cr-N和ZnS中选择的至少一个而形成。这里所说的主成分是指51mol％以上。
本发明的光学信息记录介质，具备含有记录层的信息层，其中，所述的记录层在上述激光的照射下会在非晶质相和晶体相之间产生可用光学检测的可逆变化，上述的信息层可以应用于至少由2层构成的情况。此时，上述第1电介质层和第2电介质层与实施例一样，被用作透过率调节层。即，从激光的入射侧来看，第1信息层最好是如下所示的构造，即从上述记录层向基板侧具备透过率调节层，该透过率调节层是在作为主成分至少含有氧化铌或氧化硅的第1透过率调节层的上面层叠作为主成分至少含有氧化钛的第2透过率调节层的结构。
在上述单面多层光学信息记录介质中，最好在第2透过率调节层和记录层之间设置反射层，使两者的折射率、消光系数最佳化，从而实现高透过率(参照特愿2002-591524号)。其中，作为反射层，可以使用将Ag、Au、Al等金属元素作为主成分的材料。另外，也可以通过层叠折射率不同的2种以上的保护层来代替金属反射层，得到与反透过层相同的光学特性。
另外，上述作为主成分至少含有氧化钛的第2透过率调节层是含有氧化钛为51％以上的层，可以只用氧化钛来形成，但与上述一样，可以将氧化钛作为主成分，并由从ZrO2、ZnO、氧化铌、Ta2O5、SiO2、Al2O3、Bi2O3、Ti-N、Zr-N、Nb-N、Ta-N、Si-N、Ge-N、Cr-N、Al-N、Ge-Si-N、Ge-Cr-N和ZnS中选择的至少一个而形成。其中，第1透过率调节层可以是能够阻断氧气影响的膜厚，大约10nm左右已足够，但第2透过率调节层需要以如上所述的与反射膜的关系来实现高透过率，所以优选其膜厚在10～40nm的范围内。
另外，为了解决上述问题，本发明中的光学信息记录介质的制造方法包括：在基板上形成氧化铌、氧化硅或将它们作为主成分的第1电介质层的步骤，在形成第1电介质层之后形成氧化钛或以氧化钛为主成分的第2电介质层的步骤，在形成第2电介质层之后形成通过激光的照射而在非晶质相和晶体相之间产生可用光学检测的可逆变化的记录层的步骤。
通过单叶式溅射装置，形成氧化铌、氧化硅或将它们作为主成分的第1电介质层，和氧化钛或以氧化钛为主成分的第2电介质层；上述基板是从用于出入溅射装置的真空容器内的装载闭锁室被按顺序运送至形成各层的各容器内，在形成第1和第2电介质层的情况下，在形成第1和第2电介质层之前，优选对上述基板进行水和氧气的脱气。
为此，优选在装载闭锁室和形成电介质层的成膜室之间至少经由1个容器，其中，所述的容器用于促进从基板的水和氧气的脱气。
通过本发明的光学信息记录介质及其制造方法，可以形成均匀的氧化钛层。然后，在将氧化钛层用作透过率调节层的情况下，可以使其膜厚稳定化，从而可以提供批量生产性出色的单面多层光学信息记录介质。
附图说明
图1是表示用于本发明的实施方式的光盘的结构图。
图2是表示用于本发明的实施方式的光盘的结构图。
图3是表示作为光盘的制造装置的单叶式溅射装置的结构图。
图4是表示使本实施方式的透过率调节层2层化的情况和未2层化的情况的磁盘的透过率偏差的图。
图5是表示基于本实施方式的透过率调节层材料的成膜速度依赖于氧气添加量特性的图。
图6是表示使用了用于在本实施方式的透过率调节层成膜前对基板进行脱气的容器的情况和未使用的情况的磁盘的透过率偏差的图。
具体实施方式
(实施例1)
下面，使用附图说明本发明。
使用图2对用于本实施例的磁盘的结构进行说明。本发明人等正在进行单面多层信息记录介质的研发，但在本实施例中，在基板上只形成作为激光入射侧的最上层的第1信息层，并研究其特性稳定性。
基板1是由聚碳酸酯、PMMA等树脂板、玻璃板等形成。
在基板1上的基板侧设置未图示的第2信息层，在其上设置第1信息层。第1信息层至少具有反射层4，电介质层5、7，记录层6，透过率调节层3。
电介质层5、7的材料，可以使用将Al、Si、Ta、Mo、W、Zr等的氧化物，ZnS等硫化物，Al、B、Ge、Si、Ti、Zr等的氮化物，Pb、Mg、La等的氟化物作为主成分的材料。在本实施方式中，使用ZnS-20mol％SiO2作为电介质层7，使用GeN作为电介质层5。
记录层6的材料可以使用将Te、In、Se等作为主成分的相变材料。作为众所周知的相变材料的主成分，可以举出TeGeSb、TeGeSn、TeGeSnAu、SbSe、SbTe、SbSeTe、In-Te、In-Se、In-Se-Tl、InSbInSbSe、GeSbTeAg等。目前，作为通过相变光盘而商品化的材料或者被广泛进行研究的材料系，是GeSbTe系、AgGeSbTe系。在本实施例中，主要使用GeSbTe系的材料。，
反射层4可以使用将Ag、Au、Al等金属元素作为主成分的材料。另外，通过层叠折射率不同的2种以上的保护层来代替金属反射层，可以得到与反透过层同样的光学特性。
在本实施例中，使用将Ag作为主成分的金属反射层。
关于透过率调节层3，在进行信息记录的激光波长处的折射率较大的一侧可以增高透过率。在本实施例中，使用激光波长为405nm的材料。作为在该波长处折射率较高的材料，可以举出氧化钛或氧化铌等(折射率分别为2.7和2.5)。
另外，也优选在记录层6和电介质层5以及7之间，以提高记录层的结晶能力并确保良好的记录删去的循环特性为目的而设置C或氮化物界面层。氮化物界面层的主材料是含有Ge、Cr、Si、Al、Te但中的至少1个元素的材料。
作为保护层、记录层、反射层、氮化物界面层、透过率调节层等各层的形成方法，通常可以适合使用电子束蒸镀法、溅射法、离子镀法、CVD法、激光溅射法等。在本实施方式中，使用溅射法。
详细说明在本实施方式中使用的磁盘的构造。作为磁盘构造的一个例子，通过使用了表面被间距为0.3μm且沟深为20nm的凹凸形状的引导沟覆盖的直径为120mm、厚度为1.1mm的聚碳酸酯的基板，采用磁控溅射法在其上按顺序形成作为透过率调节层3的氧化钛、Ag反射层、GeN、Ge22Sb25Te53(at％)、Zns-20mol％SiO2，从而形成第1信息层。接着，通过旋涂法形成厚0.1mm的透光层。
首先，显示对将透过率调节层2层化情况下的透过率偏差的改善效果进行研究的结果。
作为参比，只用1层氧化钛层形成透过率调节层3。关于该磁盘的制作方法，是在厚1.1mm的聚碳酸酯基板上，使用单叶式溅射装置按顺序形成20nm的作为透过率调节层3的氧化钛、10nm的Ag反射层、15nm的GeN、7nm的Ge22Sb25Te53(at％)、40nm的Zns-20mol％SiO2，制作同一结构的磁盘100个。
接着，在将如图1所示的本发明的透过率调节层2层化的情况下，即使用了作为透过率调节层2的氧化铌和作为透过率调节层3的氧化钛的情况下的磁盘的制作方法，是在厚1.1mm的聚碳酸酯基板上，使用单叶式溅射装置按顺序形成10nm的作为透过率调节层2的氧化铌、10nm的作为透过率调节层3的氧化钛、10nm的Ag反射层、15nm的GeN、7nm的Ge22Sb25Te53(at％)、40nm的Zns-20mol％SiO2，制作同一结构的磁盘100个。
初始化各100个的这些磁盘(对于相变光盘，通常由于在刚刚成膜后的记录层为非晶质状态，所以使用激光等进行晶体化的工序)，测定结晶状态下的透过率。
使用分光测定装置，评价实际上和用于在这些磁盘中记录并再现信息的激光波长相同的405nm处的透过率，研究其偏差。其结果如图4所示。
由图4可知，当作为参比的透过率调节层为1层时，即当使用氧化钛作为透过率调节层3时，透过率有p-p5％的偏差。当透过率也偏移p-p5％时，在是单面多层介质的情况下，从激光入射侧来看，到达深部侧的层的激光量只以透过率偏差分量发生变动。进而对深部侧的层的反射率的影响达到透过率的2次方，所以对深部侧的层的信号特性的有较大影响。
另一方面，如同本发明，当将透过率调节层2层化时，即当使用氧化铌作为透过率调节层2且使用氧化钛作为透过率调节层3时，可以将透过率的偏差改善至p-p2.5％。
这2个透过率的偏差的差可以用透过率调节层的膜厚的偏差的差进行说明。在这里，显示了对氧化钛和氧化铌的溅射速度的氧气量依赖性进行研究的结果。对于两种材料，都和在本实施方式中使用的成膜条件相同，使用可以DC放电的溅射靶，以各种比例混合Ar气和O2气以使溅射功率为2kW，溅射气压力为0.3Pa，比较其溅射速度。其结果如图5所示。
由图5可知，氧化钛的溅射速度的O2依赖性大于氧化铌，通过稍微的O2添加量的增加可以大大变动溅射速度。
因此，100个基板的吸湿释状态不同，在溅射速度的O2依赖性大的氧化钛中，受其影响较大而使膜厚发生变动。另一方面，在O2依赖性小的氧化铌中，与氧化钛相比，其影响较小，膜厚变动也小。
在实际上不向氧化钛、氧化铌中添加氧气的状态下，消光系数不是0，即膜具有吸收能力。膜吸收减少透过第1信息层的光的量，在制成多层介质的情况下，从激光入射侧来看，到达深部侧的层的激光减少，所以不优选。为此，有必要添加O2以使消光系数为0。当考虑到消光系数时，有必要向氧化钛、氧化铌中添加氧气2％以上，在此次的研究中添加2％的氧气。
由上述可知，氧化铌的溅射速度的O2依赖性小于氧化钛。不过，氧化铌的折射率比氧化钛稍小，稍微降低作为透过率调节层的功能的透过率。但是，溅射速度的变动成为磁盘特性的较大偏差，当然希望使用溅射速度的O2依赖性较小的氧化铌使透过率调节层为2层而抑制磁盘特性的偏差。
其中，在本实施例中，说明作为透过率调节层2、3的氧化铌、氧化钛的情况，但即使在透过率调节层3是由作为主成分的氧化钛，和含有从ZrO2、ZnO、氧化铌、Ta2O5、SiO2、Al2O3、Bi2O3、Ti-N、Zr-N、Nb-N、Ta-N、Si-N、Ge-N、Cr-N、Al-N、Ge-Si-N、Ge-Cr-N和ZnS中选择的至少一个的材料而形成的情况下，也可以得到同样的结果(这里所说的主成分是指51mol％以上)。
其中，在本实施例中，即使在透过率调节层2是由作为主成分的氧化铌，和含有从氧化钛、ZrO2、ZnO、Ta2O5、SiO2、Al2O3、Bi2O3、Ti-N、Zr-N、Nb-N、Ta-N、Si-N、Ge-N、Cr-N、Al-N、Ge-Si-N、Ge-Cr-N和ZnS中选择的至少一个的材料而形成的情况下，也可以得到同样的结果(这里所说的主成分是指51mol％以上)。
(实施例2)
当将基板从用于出入溅射装置的真空容器内的装载闭锁室，按顺序运送至形成透过率调节层3、反射层4、记录层6各层的各容器内，形成透过率调节层3时，在装载闭锁室和形成透过率调节层的容器之间，设置至少一个用于对上述基板进行真空吸引的容器，并该情况进行说明。
磁盘的结构与作为实施例1的参比的且只使用氧化钛作为透过率调节层的磁盘相同。
使用单叶式溅射装置进行上述研究。此时，研究如下所示情况下的磁盘透过率偏差，即从装载闭锁室被运送的基板立即将氧化钛成膜的情况，和设置用于从基板脱气的容器的情况。在此次的研究中，磁盘成膜间歇设为10秒，所以在脱气用容器内的基板脱气时间为7秒。
使用分光测定装置，评价实际上和用于在这些磁盘中记录并再现信息的激光波长相同的405nm处的透过率，研究其偏差。其结果如图6所示。
由图6可知，在没有用于从基板脱气的容器的情况下，透过率有p-p5％的偏差。
另一方面，在如同本发明使用用于脱气的容器的情况下，透过率的偏差改善至p-p2％。
偏差得到改善的原因在于，通过脱气用容器使对氧化钛的溅射速度造成较大影响的O2产生脱气，所以在投入到装载闭锁室之前就吸附在基板上的O2(水)量的偏差减小。
如上述，在有脱气用容器的成膜方法中，可以实现磁盘特性的偏差较小的光学信息记录介质。
其中，在本实施例中，说明作为透过率调节层3的氧化钛的情况，但即使在透过率调节层3是由作为主成分的氧化钛，和含有从ZrO2、ZnO、氧化铌、Ta2O5、SiO2、Al2O3、Bi2O3、Ti-N、Zr-N、Nb-N、Ta-N、Si-N、Ge-N、Cr-N、Al-N、Ge-Si-N、Ge-Cr-N和ZnS中选择的至少一个的材料而形成的情况下，也可以得到同样的结果(这里所说的主成分是指51mol％以上)。
工业上的可利用性
如同以上说明，通过本发明的光学信息记录介质及其制造方法，可以改善初始化工序中的光盘批量生产时的生产效率。

Claims (11)

1、一种光学信息记录介质，其特征在于，包括：
在基板上形成的且通过上述激光照射在非晶质相和晶体相之间产生可用光学检测的可逆变化的记录层，
在上述记录层和基板之间形成的以氧化铌或氧化硅为主成分的第1电介质层，和
在上述记录层和第1电介质层之间形成的且以氧化钛为主成分的第2电介质层。
2、如权利要求1所述的光学信息记录介质，其特征在于，
所述第2电介质层含有氧化钛51％以上。
3、如权利要求1所述的光学信息记录介质，其特征在于，
所述第2电介质层的膜厚在10～40nm的范围内。
4、如权利要求1所述的光学信息记录介质，其特征在于，
在上述基板的与上述记录层相反的一侧上具备第2记录层。
5、如权利要求1所述的光学信息记录介质，其特征在于，
在第2电介质层和上述记录层之间具有反射层。
6、一种光学信息记录介质的制造方法，其特征在于，包括：
形成以氧化铌或氧化硅为主成分的第1电介质层的步骤，
在形成上述第1电介质层之后形成以氧化钛为主成分的第2电介质层的步骤，和
在形成上述第2电介质层之后形成通过激光的照射而在非晶质相和晶体相之间产生可用光学检测的可逆变化的记录层的步骤。
7、如权利要求6所述的光学信息记录介质的制造方法，其特征在于，
所述第2电介质层含有氧化钛51％以上。
8、如权利要求6所述的光学信息记录介质的制造方法，其特征在于，
所述第2透过率调节层的膜厚在10～40nm的范围内。
9、如权利要求6所述的光学信息记录介质的制造方法，其特征在于，
在基板上形成所述第1电介质层、所述第2电介质层、所述记录层，在形成所述第1电介质层或第2电介质层之前，从上述基板进行水和氧气的脱气。
10、如权利要求6所述的光学信息记录介质的制造方法，其特征在于，
还包括形成通过激光的照射而在非晶质相和晶体相之间产生可用光学检测的可逆变化的第2记录层的步骤。
11、如权利要求6所述的光学信息记录介质的制造方法，其特征在于，
包括在所述第2电介质层和所述记录层之间形成反射层的步骤。
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