CN1383550A - 光记录介质和这种光记录介质的使用 - Google Patents
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Abstract
光记录介质(20)具有底衬(1)和在底衬上提供的层堆叠(2)。具有熔点Tmp的相变记录层(5)被夹在第1电介质层(3)和第2电介质层(7)之间。插入的结晶加速层(4,6)和记录层(5)相接触。还可以有反射层(8)和光覆盖层(9)。结晶加连层(4,6)由双金属合金或半导体组成和具有比记录层(5)的熔点Tmp至少高出250℃的熔点Tmg并且有着同记录层(5)的晶态相类似的晶体结构。
Description
本发明涉及有底衬和在底衬上提供层堆叠的光记录介质，该堆叠包括记录层，结晶加速层和反射层，记录层具有熔点Tmp并能在非晶态和晶态之间变化，它夹在第1和第2电介质层中间，第1电介质层邻近底衬，插入的结晶加速层与记录层接触。
本发明还涉及这种光记录介质的使用。
在本文开头提到的那种类型的光记录介质是从日本专利申请JP-09161316A获悉的。在这种熟悉的介质中，记录层的状态在光记录数据时局部地从晶态改变到非晶态。
依据这种相变原理的光数据存储是有吸引力的，因为它将直接重写和高存储密度的可能性同只读式光数据存储系统的易兼容性结合起来。相变光记录涉及利用聚焦的相当高功率激光束在晶态薄膜内形成亚微米大小的非晶态记录符号。在记录信息期间，该介质相对按所记录的信息加以调制的聚焦激光束移动。由于这样，在相变记录层内发生猝天并且在记录层的曝光区引发非晶态信息位的形成，而在记录层的非曝光区仍保持晶态。用中等功率水平的同一激光加热使之重新晶态化而不熔化其记录层可以擦除已写入的非晶态符号。这种非晶态符号代表数据位，它可以用低功率聚焦激光束，例如经由底衬，读出。相对于晶态记录层非晶态符号的反射率差异产生调制激光束，这种被调制过的激光束借助于探测器基本上将被记录的数字信息转换成调制的光电流。
相变光记录中最重要的要求之一是高数据率，即是说数据能以至少30MB/s的速率写入和从这种介质读出。高数据率要求记录层有高的结晶率，即短结晶时间。为了确保先前被记录的非晶态符号在直接重写时可以晶化，记录层应具备合适的结晶时间以使介质的速度同激光束是相匹配的。假如结晶速度不足以高到使介质的速度同激光束相匹配，则先前记录的，代表旧数据的非晶态符号不可能完全被擦除，即是说，在DOW时需要重新晶化。这样就引发高的噪声水平。在高密度记录和高数据率应用中，例如盘状DVD+RW，DVD-红/兰，特别要求高的结晶速度，此处DVD+RW，是新一代高密数字万能盘的缩写，RW指这种盘的可重写能力，DVR-红/兰代表数字视频记录存储盘，红和兰指所使用的激光波长。对于这类新的光盘，其完全擦除时间(GET)最大不得超过60ns。GET定义为在结晶环境下完全将已写的非晶态符号晶化的擦除脉冲的最小时间间隔，按静态测量。对于DVD+RW，每mm盘的记录密度为4.7GB，需要33MB/s的用户数据比特率，而对DVR-红所说的速率为35MB/s。对于可重写的相变光记录系统，诸如DVR-兰，要求高于50MB/s的用户数据率。
已知的相变型介质包括带有层堆叠的盘状底衬，层堆叠按顺序其组成为，第一电介质层，作为结晶加速层Sb2Te3层，作为成分改正层的Sb层，相变Sb72Te28合金的记录层，第2电介质层和金属反射层。这样一种层堆叠可以视为一种INP’PM结构，此处M表示反射或镜相层，I表示电介质层和P表示相变记录层，而P’表示在第1次记录时和记录层混合的成分改正层。Sb2Te3的结晶加速层N安置在第1电介质层及改正层和记录层之间使之通过激光束在介质中擦除信息期间实现该介质的快速结晶。在已知的记录介质中，N层具有熔点为618℃，比P层的熔点550℃仅高出68℃。已知N层的熔点相当接近P层的熔点，致使在1个或至多几个记录/擦除周期之后引发N层在改正层和记录层P’P中熔化，随后结晶加速层不再存在而它的结晶加速功能也就丧失。
为了完全擦除非晶态符号，有两个过程发生，即成核和颗粒(结晶)生长。对已知记录介质的调查证实，已知的结晶加速层N只是一种成核促进层。
这种已知介质的缺点是它的结晶加速层只对最多几个记录和擦除周期起作用。对于现代可擦除介质来说这是不够的，它要求至少是上千次的记录和擦除周期的稳定性能。
本发明的目的是提供在本文开始描述的那种类型的光记录介质，它适合于高速可重写光记录，具有最多为60ms的CET值。
本发明的另一个目的是提供在本文开始描述的那种类型的光记录介质，它适合于可重写光记录，具有至少103次记录和擦除周期的稳定性能。
根据本发明的这个目的是通过本文开始描述的光记录介质来实现的，这种光记录介质的特征是结晶加速层，
它包括选自包括双金属合金，半导体元件和半导体合金的组中的一种材料，并且
在比记录层熔点Tmp至少高出250℃的熔点Tmg，和
具有同记录层结晶状态相似的晶体结构。
根据本发明的结晶加速层，以下简记为G，因为记录层的非晶态符号(mark)同G层接触而产生高的记录层结晶速度。它加速结晶生长过程，导致较高的结晶速度。特别是，因为G层的晶体结构类似于，甚至同记录层的结晶态的结构一样，有利于增加非晶态符号的结晶速率。因此，G层的结构对记录层中结晶的生成起到一种很好的颗粒生长初始化或成核层的作用。G层总是邻近热隔离层，此处为第1或第2电介质层，因为在记录层和底衬或反射层之间有G层的堆叠不可能实现所希望的热学特性。
从包括双金属合金，半导体元件和半导体合金的组中的一种材料的G层的一个优点是它具有高的熔点。这就阻止G层在记录层内的熔解并且对大量的记录和擦除周期维持其结晶结构。记录期间，记录层的最高温度约为800℃，它是熔点Tmp为550℃的记录层的Tmp的1.4倍。这可以根据记录期间所存在的激光能量和堆叠的物理特性从温度计算推导出来。G层的熔点温度Tmg必须在这一最高温度之上使之在记录层熔化时G层仍保持结晶状态。
因此，记录层和G层之间的熔点温度差异应为250℃或更大，但是考虑到安全因素，最好为300℃或更大。
可以用作G层的优选材料是PbTe，Ag2Te，CrTe，Ge和Si。
在该记录介质的一种实施方案中，将G层安排在记录层和第2电介质层之间。G层的厚度可以在0.1和10nm之间选择。结晶加速层的热导性一般同金属合金的记录层的热导性接近。但是，这对堆叠的热行为只有小的影响，因为同堆叠中其他层相比，G层的厚度一般是相对小的。这就方便了该种堆叠的热学设计。
在另一种实施方案中，在记录层和第1电介质层之间安排第2G层，使结晶时间进一步降低。因此在记录层的两侧各有一G层。第2G层可以是同其它G层相似或相同的材料。结晶时间的降低是因为现在加速结晶生长过程的结晶层是在两侧对着被记录的非晶态符号。G层的厚度在0.1和10nm之间，最好低于5nm。
在一种特殊实施方案中，在记录层各侧存在的两G层在厚度和成分上基本上是相等的。厚度上相等意味着相互之间在10％以内。厚度的相等性在介质的加工中是有利的。一般而言，该堆叠是通过在真空室内蒸发或溅射积沉的，此时底衬沿具有不同成分靶的一系列站阶梯式移动。在每个站的驻留时间大致相等，而在每站积沉的厚度部分地由沉积过程的接通和断开所决定。结果，相对薄的层的积沉所要求的时间少于在站上提供的时间，而相对厚的层的积沉甚至可以要求具有相同靶的两个邻近站。因此有利于选择用大致相等厚度和成分的两层取代相对厚的一层和相对薄的一层，从而减少了沉积站的数量和一个堆叠的制造时间。
在一种特殊实施方案中，记录层包括Q，In，Sb和Te的合金，其中Q选自由Ag和Ge构成的材料组。
该优选成分包括Qa，Inb，Sbc，Ted(按原子百分比)，其中Q选自由Ag和Ge构成的材料组；
2≤a≤9
0＜b≤6
55≤c≤80
16≤d≤30；a+b+c+d＝100。
在另一种实施方案中，该记录层包括Ge，Sb和Te的复合物。这种复合物的优选成分由如下公式定义
Ge50xSb40-40xTe60-10x(按原子百分比)，其中0.166≤x≤0.444；
该记录层具有厚度5至35nm；
这种成分存在于在三角形的Ge-Sb-Te成分图上连接GeTe和Sb2Te3的线的部分线段上，并且包括理想配比复合物Ge2Sb2Te5(x＝4/9)，GeSb2Te4(x＝2/7)和GeSb4Te7(x＝1/6)。特别是，这些三元理想配比复合物是优选的，因为这些材料在结晶期间不要求分离而结晶迅速。
第1和第2电介质层最好用ZnS和SiO2的混合物，例如(ZnS)80(SiO2)20，制做。该层也可以用SiO2，TiO2，Ta2O5，ZnS，AIN和/或Si3N4制做。激光穿过它进入堆叠的电介质层最好具有厚度70至(70+λ/2n)nm，其中n为第1电介质层的折射率，λ是读/写激光束的波长。假如总厚度小于70nm，其周期能力明显降低。该周期能力用在大量DOW周期，例如103之后，光反差M0的相对改变加以测量。光反差M0定义为|RC-RA|RC，其中RC和RA分别为结晶态的记录材料的反射率和非晶态记录材料的反射率。定义周期能力的另一种方法是同介质的颤动增加相关。颤动是记录符号形状畸变的一种量度，它用信息信号上升和下降边沿的时间漂移加以测量。在至少103DOW周期期间这种介质颤动应当处于恒定的低水平。
如上面所提到的，第1电介质层的厚度最好小于(70+λ/2n)nm。更大的厚度不会进一步增大周期能力，而制造更为昂贵。假如，例如波长等于630nm，折射率为1.5，则该厚度范围从70nm延伸至280nm。
最接近反射层的电介质层具有10至40nm的厚度。邻近反射层的该电介质层的厚度最好大于或等于15nm。厚度较薄将导致该记录层冷却速率的增大，结果使写功率出现不希望的增大。该厚度最好小于40nm。厚度较大将使记录层和反射层之间的热学接触减少过多，导致记录层过低的冷却速率而使记录性能变坏。
反射层可以包括金属像AL，Ti，Au，Ni，Cu，Ag和Cr以及这些材料的合金。反射层最好具有厚度60至120nm。
反射层和电介质层一般都是用真空积沉或溅射提供的。
光学上，在堆叠上可以有当作复盖层的最外层，它保护下面的各层免受环境的侵蚀。该复盖层，例如，用紫外(UV)光处理过的聚(甲基)丙烯酸盐制做。
另一种实方案的特征是在底衬和第1电介质层之间存在有反射层。在堆叠的顶部有复盖层，它在光学上对激光是透明的并且有允许光记录进入它下面的记录层的信息和用聚焦激光束从记录层读出信息的表面。因此在这种实施方案中，光记录介质的写入和读出是穿过复盖层进行的。这种方法用在上面提到过的新型DVR盘内。DVR盘的复盖层厚度大约为100μm。这种复盖层允许在光盘记录机内使用具有高数值孔径的读/写透镜，这一点对于高密记录和读出是必要的。因为激光通过复盖层进入介质，所以有必要调整堆叠各层的厚度以便优化记录区和非记录区之间的最佳光接触。
上面提到的高速记录一词应理解为，在本文中意味着相对于至少7.2m/s的激光束而言介质的线速度，根据压缩盘标准它是6倍于该速度。因此使用根据本发明的光记录介质是有益的，因为结晶速率快得足以允许至少有这种记录速度。其重要的参数是CET(ns为单位)，上面已经定义。CET同结晶速率成反比。
信息介质的底衬对激光波长一般是透明的，并且，例如，是用聚碳酸酯，聚甲烯甲基丙烯酸盐(PMMA)，非晶态聚烯烃或玻璃制做。在一种典型的实例中，底衬是盘状的，直径为120mm，而厚度对低、中和高信息密度应用分别为1.2mm，0.6mm或0.1mm。
或者，底衬可以是合成树脂弹性带，例如，用聚脂膜制做。这种有层堆叠积沉在其上面的弹性带叫做光带，可适合用于光带记录机，例如依据快速旋转的多角形的光带记录机。在这种设备中反射激光束横过光带表面平移扫描。
记录层侧面的盘状底衬的表面最好装备有可被光扫描的伺服轨道。这种伺服轨道通常是由一种螺旋状的纹构成，并且是在注模或压制期间用模型在底衬内形成的。这种纹也可以用复制工艺在合成树脂层，例如，UV光处理过的丙烯酸盐层内形成，它是分别在底衬上提供的。在高密记录中，这种纹具有，例如，0.5-0.8μm的槽，而槽的宽度约为槽的一半。
利用短波激光，例如波长为675nm或更短(红或兰)的激光，可以实现高密记录和擦除。
可以用蒸汽积沉或合适靶的溅射而适用相变记录层和G层。因此积沉的记录层是非晶态的并显示出低的反射率。为了制成有高反射率的合适的记录层，必须首先将这一层结晶，通常将这一过程叫做初始化。为此目的，可以将记录层在炉内加热至刚好超出，例如，Ge-In-Sb-Te或Ge-Sb-Te复合物的结晶温度，如200℃。对于高温可能引起损伤的合成树脂底衬，诸如聚碳酸脂，可以选择用足够功率的激光束加热。这一点是可以做到的，例如，在一种记录机内，此时可用激光束扫描移动的记录层。因此，非晶态层被加热到使该层结晶所要求的温度，而不会使底衬遭受不利的热负荷。
如有必要，还可以在堆叠内插入另外的光学透明的金属层M’，因而形成所谓的MIRIM结构，此处R表示包括根据本发明的记录层和至少一结晶加速层的层堆叠。虽然这种结构变得更为复杂，但是该附加的金属层增大了该记录层的冷却率以及其光反差M0。
参照附图将对本发明的光记录介质的实施方案加以描述。
在附图中：
图1示出该光记录介质的第1实施方案的原理剖面图。
图2示出第2种实施方案的如图1那样的视图。
图3示出第3种实施方案的如图2那样的视图。
图1中，光记录介质20有底衬1和在底衬上提供的堆叠2。底底1可以用，例如，1片塑料，如聚碳酸脂，或玻璃制做。图1中，堆叠2包括相变记录层5，它具有熔点Tmp并能在非晶态和晶态之间变化，该记录层夹在第1电介质层3和第2电介质层7之间，第1电介质层3邻近底衬1。在这种实施方案中，第1电介质层3和第2电介质层7是用材料(ZnS)80(SiO2)20制做的并且分别具有厚度125nm和20nm。结晶加速层6，简记为G层，是被插入的，和记录层5接触并包括Q，In，Sb和Te的合金，其中Q选自由Ag和Ge组成的材料组。在堆叠2顶部有反射层8。反射层8是一层100nm的Al或铝合金，如AlCr或AlTi。结晶加速层6包括双金属合金或半导体元件或半导体合金，并具有比记录层5的熔点Tmp高出250℃的熔点Tmg。这些材料的晶体结构同记录层5的结晶状态相似。在这种实施方案中，记录层5是用Ge6.2In3.2Sb71.1Te19.6制做，其厚度为12nm。所示的实施方案具有可用有机材料，如UV处理过的树脂制做的复盖层9。波长为λ＝405nm的聚焦激光束穿过底衬1进入介质。该激光束在图形上用图1中的箭头10表示。
在这种实施方案中，当使用PbTe作为G层时，它的厚度为3nm，已经对CET进行测量，它等于40ns，短到足以允许高速记录。当没有G层存在时，可以获得48ns的CET值。其他可作为G层的优选材料是Ag2Te，CrTe，Ge或Si。PbTe，Ag2Te，CrTe，Ge和Si的熔点Tmg分别为914，960，1292，936和1414℃。对该介质的写功率为相当低，在辐射束和介质之间的相对速度为7.2m/s时，介质入射表面的功率为9mw。RA和RC分别测量为4.3％和23％。
周期能力是用颤动(jitter)已经增大到时钟时间TC的12％的一组重写周期加以测量的。该颤动是信息信号的上升和下降边沿同从该信息信号恢复的数据时钟之间的差异的标准偏差。作为一个实例，对用所谓的EFM码在1.2m/s的CD速度和230ns的时钟时间写入的标准CD格式，其颤动应低于28ns。在介质的退化变得明显，例如，其颤动已增至时钟时间的12％之前，重写周期的数大于103。从介质读出模式的颤动作为重写周期的函数没有表现出大的突增。
在写期间，Ge6.2In3.2Sb71.1Te19.6的记录层5被加热至大约750℃的温度，远高出其约为550℃的熔点温度。在读出期间，该温度低于包括PbTe的G-层6的熔点温度。因此，用作邻近记录层5的G层的材料的高熔点温度导致该记录层周期能力的增大。
在JP-09161316A的专利申请中，Sb2Te3的结晶加速层N，具有熔点温度618℃，被加热至它的熔点温度之上，使层中的原子变成移动。这些原子则可以熔入记录层内。记录层的特性受外来原子注入的影响，导致记录介质的退化。
在图2和图3中，相应的参考号标记如图1中的同样的层。
图2中，在记录层5和第1电介质层3之间安排与结晶加速层6相类似的第2结晶加速层4。现在在邻近记录层5的两侧都有G层4，6。G层6用PbTe制做，具有厚度1.5nm。第2G层4在厚度和成分上基本上与G-层6相等。记录层5的厚度为10nm。而且，堆叠2的特性与图1中的相同。CET的测量值为36ns。在这一实施方案中，其CET值小于仅有一层G层的实施方案中的CET。RA和RC的测量值分别为4.6％和22％。
图3中，在底衬1和第1电介质层3之间有反射层8。在这种实施方案中，激光10穿过厚度为100μm的复盖层进入堆叠2。该复盖层的厚度均匀，因而在读写激光束通过所说的复盖层9时，改善了在其下面的记录层的光学读写性能。例如，100μm的复盖层9被用于新型的半径为60mm的数字视频记录(DVR)盘。这种盘通过这一复盖层9录入和读出，因此复盖层必须具备良好的光学质量。复盖层9在半径直到58.5mm之前，其厚度最好为100+/-3μm。该复盖层9用UV处理过的树脂制做。电介质层3和7的厚度分别为20nm和125nm并用跟图1中相同的介质材料制做。G层4，6用跟图2中相同的材料制做，两者的厚度均为1.5nm。记录层5的厚度为10nm。对于没有特别提到的特性，可参考对图1的描述。
最好对所有的实施方案，堆叠2侧面上的盘状底衬1的表面装备有可被光扫描的伺服轨道。这种伺服轨道常用螺旋状纹构成并且是在注模或压制期间用模型在底衬内形成的。这种纹也可以用复制工艺在，例如，UV处理过的丙烯酸酯层的合成树脂层内形成，它是在底衬1上分别提供的。在高密记录中，这种纹具有，例如，0.5-0.8μm的槽和大约一半槽的宽度。
在图3的记录介质的修改方案中，记录介质5包括Ge，Sb和Te的合金，例如Ge2Sb2Te5。
应当注意，上面提到的实施方案并非展示对本发明的限制，本领域的技术人员将能够设计许多不同的实施方案而不会偏离在附录权利要求中规定的范围。在权利要求中，不应当将括号中间的参考符号作为对权利要求的限制。其字“包括”不应排除与权利要求中所列举的那些元件和方法不同的元件和方法的存在。在元件之前的字“一种”不应排除众多的这类元件。事实上，在相互不同依据的 中所引用的某些措施并非表明不可以将这些措施加以结合而得益。
根据本发明，提供一种光记录介质，它适合于高速记录，例如，具有可能的数据率高于50MB/s，并且可适合于直接重写至少103次。
Claims (9)
1.一种具有底衬(1)和在其上面提供的层堆叠(2)的光记录介质(20)，该堆叠包括记录层(5)，结晶加速层(4，6)和反射层(8)，记录层具有熔点Tmp并能在非晶态和晶态之间变化，夹在第1电介质层(3)和第2电介质层(7)之间，第1电介质层(3)邻近底衬(1)，结晶加速层(4，6)是插入并与记录层(5)相接触，其特征是结晶加速层(4，6)
包括选自包括双金属合金，半导体元件和半导体合金的一组中的一种材料，并且
具有比记录层(5)的熔点Tmp至少高出250℃的熔点Tmg和
具有与记录层(5)的结晶状态相似的晶体结构。
2.如权利要求1的光记录介质(20)，其特征是结晶加速层(4，6)包括选自包括PbTe，Ag2Te，CrTe，Ge和Si的一组中的一种材料。
3.如权利要求1或2任一项的光记录介质(20)，其特征是结晶加速层(6)放置在记录层(5)和第2电介质层(7)之间。
4.如权利要求3的光记录介质(20)，其特征是同结晶加速层(6)相似的第2结晶加速层(4)放置在记录层(5)和第1电介质层(3)之间。
5.如权利要求4的光记录介质(20)，其特征是第2结晶加速层(4)在厚度上和成分上基本同结晶加速层(6)相等。
6.如权利要求1的光记录介质(20)，其特征是记录层(5)包括Q，In，Sb和Te的合金，其中Q选自Ag和Te的组中的一种材料。
7.如权利要求1的光记录介质(20)，其特征是记录层(5)包括Ge，Sb和Te的合金。
8.如权利要求1的光记录介质(20)，其特征是在底衬(1)和第1电介质层(3)之间有反射层(8)。
9.记录介质(20)的使用，其中该介质是在前面权利要求的任意一项中要求保护的，其特征是相对于激光束(10)其介质的线速度至少是7.2m/s。
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| EP (1) | EP1279170A1 (zh) |
| JP (1) | JP2003532248A (zh) |
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| CN (1) | CN1218310C (zh) |
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| MX (1) | MXPA01013105A (zh) |
| RU (1) | RU2002101129A (zh) |
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| CN100339900C (zh) * | 2003-10-30 | 2007-09-26 | 株式会社神户制钢所 | 光信息记录用铝合金反射膜及其形成用靶材、记录介质 |
| CN100388372C (zh) * | 2002-12-30 | 2008-05-14 | 皇家飞利浦电子股份有限公司 | 可重写式光学记录载体 |
| CN101156203B (zh) * | 2005-04-07 | 2010-09-15 | 三菱化学媒体股份有限公司 | 光记录介质 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100388372C (zh) * | 2002-12-30 | 2008-05-14 | 皇家飞利浦电子股份有限公司 | 可重写式光学记录载体 |
| CN1322504C (zh) * | 2003-07-10 | 2007-06-20 | 株式会社理光 | 光记录介质及其制造方法 |
| CN100339900C (zh) * | 2003-10-30 | 2007-09-26 | 株式会社神户制钢所 | 光信息记录用铝合金反射膜及其形成用靶材、记录介质 |
| CN101156203B (zh) * | 2005-04-07 | 2010-09-15 | 三菱化学媒体股份有限公司 | 光记录介质 |
Also Published As
| Publication number | Publication date |
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| KR100770768B1 (ko) | 2007-10-26 |
| RU2002101129A (ru) | 2003-09-27 |
| US6670013B2 (en) | 2003-12-30 |
| WO2001082297A1 (en) | 2001-11-01 |
| EP1279170A1 (en) | 2003-01-29 |
| TWI232446B (en) | 2005-05-11 |
| CA2377619A1 (en) | 2001-11-01 |
| KR20020026187A (ko) | 2002-04-06 |
| CN1218310C (zh) | 2005-09-07 |
| JP2003532248A (ja) | 2003-10-28 |
| US20010033991A1 (en) | 2001-10-25 |
| MXPA01013105A (es) | 2002-06-04 |
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