CN1324481A - 基于薄记录层的光学记录介质 - Google Patents

基于薄记录层的光学记录介质 Download PDF

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CN1324481A
CN1324481A CN99802905A CN99802905A CN1324481A CN 1324481 A CN1324481 A CN 1324481A CN 99802905 A CN99802905 A CN 99802905A CN 99802905 A CN99802905 A CN 99802905A CN 1324481 A CN1324481 A CN 1324481A
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record medium
groove
optical record
substrate
reflectivity
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金成勋
J·W·G·梅伊
G·C·杜贝尔达姆
F·G·H·范威吉克
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Samsung Electronics Co Ltd
Akzo Nobel NV
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Samsung Electronics Co Ltd
Akzo Nobel NV
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Abstract

本发明涉及一种光学记录介质,具有一个带有沟槽的聚碳酸酯基片,一个包括选自Ag、Ta、Ni、Cr、Si,或其合金或其氧化物材料制成的部分反射镜的记录层,一个有机材料制成的缓冲层,一个Au、Al、Ag或其合金制成的厚反射层和一个保护涂层。利用该部分反射镜、该缓冲层和该厚反射层,形成一个Fabry－Perot标准具。通过一个或多个所述部分反射镜、所述缓冲层、所述厚反射层、或所述基片产生的变形而写入信息。该变形改变或破坏了Fabry－Perot,反射率降低。由于利用该变形而写入信息,可以在该缓冲层中使用非液晶高分子材料。寻迹伺服利用了该部分反射镜/基片界面所反射的振幅和/或相位在该沟槽内外的差异。

Description

基于薄记录层的光学记录介质
本发明属于例如光盘(CD)和数字记录带或卡，特别是所谓的WORM介质(一次写入多次读取的光盘或记录带)以及可重写入的CD和记录带的光学记录介质领域。这些类型的介质可以允许消费者写入信息。
在传统的只读CD中，信息存储在该盘上制作的浮雕压纹的凹痕中。根据在规则的凹痕边缘结构的衍射进行读取。各衍射级之间的干涉取决于激光光斑的位置。这产生了用于读取信息的反射调制。传统的只读CD只适合于大规模生产，因为该生产步骤(生产已写盘)是相当复杂的，因此只有在大量生产中才具有成本效率。所以需要可以小批量生产的或者是甚至可以由消费者自己写入的CD和数字记录带或卡。在EP0,353,391中描述的光学记录介质包括一个具有易变形表面的透光基片，以及叠加在该易变形表面上的光吸收层，和叠加在该光吸收层上的光反射层，所述易变形表面因为该光吸收层对写入激光束的吸收所产生的能量而变形，形成可光学读取的凹痕。这种读取也是根据衍射级之间的干涉。在使用读取激光束辐射期间，光穿过光吸收层，并被反射层反射。因为凹痕内的折射率与凹痕外(凸起(land))的折射率不同，因此凹痕内的光路长度与该凸起的光路长度不同。落入该凹痕内的激光和落入该凸起上的光之间相干涉导致衍射。各衍射级之间的干涉取决于该读取光斑的确切位置。用所获得的反射调制读取信息。但是，该光学记录介质的记录层在600-720nm范围之内有强吸收。因此，根据EP0,353,391所制造的盘在650nm处具有低反射率(低于10％)，从而该盘不适合在需要在650nm处具有大于20％反射率的DVD播放器中读取。
在PCT/EP9605373中公开了基于Fabry-Perot标准具原理的光学记录介质。该光学记录介质包括带槽的基片，一个部分反射镜，一个含有高分子材料的缓冲层，和一个反射镜。已经发现，在非常特殊的条件下，不需要高分子材料，并可使用非常薄的缓冲层，因此所得到的光学记录介质可以更容易的制造，也更加便宜。
本发明的光学记录介质包括以下层：
a)一个聚碳酸酯基片，带有在未写入状态下其深度dgu为170-270nm的沟槽(1)，其上叠加有
b)一个记录层，包括：其材料选自Ag,Ta,V,Ni,Cr,Si，其合金和其氧化物的部分反射镜(2)，在没有沟槽的基片部分它在770-790nm的透射率在40％-85％之间，其上叠加有一个缓冲层(3)，该层含有在未写入状态下在770-790nm处其固体状态下所测得的折射率nbu为1.45-3.0，消光系数kbu为0-0.2的有机材料，凸起处的厚度db为10-70nm，沟槽图象(groove image)处的深度di是深度dgu的40％-90％，其上叠加有Au,Al,Ag或其合金的厚反射层(4)，共同形成Fabry-Perot标准具，其中该凸起部分在770-790nm的反射处于高反射状态，其上叠加有
c)保护涂层(5)。
利用该部分反射镜形成一个Fabry-Perot标准具。通过一个或多个所述部分反射镜、所述缓冲层、所述厚反射层、或所述基片的变形可以写入信息。该变形作用改变或破坏了Fabry-Perot标准具，并且使反射率下降。因为利用变形作用而进行写入，可以在该缓冲层中使用非液晶高分子材料。利用能够导致将在下文中进一步说明的衍射的该部分反射镜/基片界面所反射的振幅和/或相位在该沟槽内外的差异而实现寻迹(将写入激光限制在沟槽内)。
为了方便起见，使用CD一词表示本发明的所有光学记录介质。
本发明的光学记录介质优选处于Fabry-Perot的高反射状态，当激光读取光斑位于该沟槽之上时，在未写入状态的反射率高于50％，而当该激光读取光斑位于该凸起之上时，反射率大于60％，因为传统的CD播放器在写入状态下需要来自于沟槽的大约20％的背景反射用于寻迹，而CD标准需要60％的写入反差。已经发现，在部分反射镜材料满足上述的复折射率要求的情况下，可以根据该CD标准制造CD。但如果CD播放器变得可以需要更小的背景反射，就可以采用低于50％的反射率。对于高密度记录介质来讲，优选在未写入状态的反射率为20％以上。在写入时，Fabry-Perot会因为一个或多个所述部分反射镜、所述缓冲层、所述厚反射层、或所述基片的变形而失调或被破坏，导致未写入状态的反射率降低了至少40％。
在已知的只读CD中，所记录的信息被存储在螺旋形轨迹中，在该轨迹，低反射率的区域(已写入沟槽区域)和背景反射率高于65％的区域(未写入沟槽区域)相交错。对于传统的CD，凹痕的长度在0.9-3.3μm之间以0.3μm为间隔发生变化。在最长的凹痕中(产生11T信号)，反射率必须降低至未写入状态的反射率的40％以下。传统CD播放器中的读取激光的波长为780-830nm，一般为780±10nm。因此，为了与只读CD兼容，当使用CD播放器的传统读取激光时，本发明的CD的未写入状态的反射率应当为65％，而在最长的凹痕中反射率应当低于未写入状态反射率的40％。
本发明提供记录后可与标准CD兼容、并可由数字式通用盘播放器(DVDP)播放的可记录的CD(CD-R)。
本发明的光学记录介质包括带槽的基片(1)。通过该基片对该介质进行读取。因此，对于用来读取和写入的激光来讲，该基片应当是透光的。在传统的CD播放器中，使用波长为780nm的激光。聚碳酸酯基片因为其价格便宜和易于加工而被优选使用。另外，聚碳酸酯基片的性质也符合CD标准。聚碳酸酯容易受到涂布缓冲层材料所使用的几乎所有常规溶剂的化学侵蚀。本发明的CD对于这个问题有两种解决办法：第一，部分反射镜会保护该基片免受化学侵蚀。第二，因为将非液晶材料用于缓冲层，给溶剂的选择可带来极大的自由。所以，可以使用相对温和的溶剂。因此，在本发明的CD中，可以使用聚碳酸酯作为基片。对于DVD-R，该基片对于波长为610-700nm，或更低波长的光必须是透明的。
如上所述，本发明的CD使用带槽的基片。所述沟槽是压制在基片上的螺旋形轨迹。该轨迹在读写期间被用来控制激光光斑位置。由于该部分反射镜具有高折射率，因此可以利用该部分反射镜/基片界面所反射的振幅和/或相位在该沟槽内外的差异而进行寻迹。
该沟槽的宽度和深度决定了寻迹。通常使用的轨迹宽度为0.1-1.2μm。该轨迹的深度是一个重要的参数，必须根据缓冲层和部分反射镜的厚度来选择，在未写入状态下，在170-270nm之间。已经发现，这样的沟槽深度连同在凸起处为10-70nm，优选为15-40nm的缓冲层厚度，以及连同选自Ag,Ta,Ni,Cr,Si，其合金和其氧化物的部分反射镜，可在保持反射性质的同时，形成最佳的寻迹反差。这样的缓冲层厚度显著比在先有技术中披露的厚度小。因此，优选该沟槽图象(该沟槽深度与该缓冲层厚度之和减去该缓冲层在未写入状态下在该沟槽处的最小厚度；见图1)是该沟槽深度dgu的40-90％。该缓冲层在写入状态下的折射率nbw和消光系数kbw优选小于该缓冲层在未写入状态下的折射率nbu和消光系数kbu。当nbu和kbu分别在1.8-2.2和0-0.05之间时，可以得到极好的结果。如果该沟槽写入部分的深度dgw小于该沟槽未写入状态下的深度dgu，也是优选的。
为了减少由于在空气/基片界面的反射而导致的激光损耗，可以对该基片没有覆盖薄反射层的那一侧提供抗反射结构。
对于部分反射镜(2)，可以采用Ag,Ta,V,Ni,Cr,Si，其合金和其氧化物，只要能将该层做得足够薄，从而可以部分透过激光即可。相应于在该基片没有沟槽的部分在770-790nm透射率为40-90％时，其一般处于0.3-5.0nm的范围之间。各种材料的复折射率已经在固体光学常数手册(Handbook of Optical Constant of Solids)，扁1和2,ed.Palik,Acc.Press(1985)中列出。薄金属膜呈现出一种类似轧制(reduced)金属的性质，本领域的普通技术人员可以很容易的选择一种合适的材料。优选的，可以选择例如银和钽，其合金和其氧化物的材料。
通常金属折射率的虚部高。这意味着假设nk的乘积也是高的，当它们用于透明环境中(例如聚碳酸酯)时是高反射的和吸收的。每μm的吸收α可以表示为-2πnk/λ(λ单位为μm)。因此，在用激光写入时，该激光被Fabry-Perot系统反射(寻迹)，并被该金属部分反射镜吸收。所吸收的激光转化为热量，并且一个或多个所述部分反射镜、所述缓冲层、所述厚反射层、或所述基片产生变形。
非吸收性材料例如银，或其合金，或者硅、氮化硅、硅-锗、二氧化硅、SiO、SiO-锗等一般其折射率具有一个高的部分(实部或虚部)。这意味着该材料是反射的，但几乎不吸收。当用激光在有这种部分反射镜的CD上写入时，该激光被Fabry-Perot系统反射，但是该激光的吸收主要发生在缓冲层。因此，当在本发明的CD中采用非金属部分反射镜时，优选使用高吸收性缓冲层。特别优选的是硅-锗合金，氮化硅，和硅，因为它们的折射率的虚部低。可以采用该领域的各种传统常规方法将该部分反射镜施加在该基片上，例如真空沉积、电子束沉积和溅射。
该缓冲层中的染料能使写入激光转化为热量，由此使一个或多个所述部分反射镜、所述缓冲层、所述厚反射层、或所述基片产生变形。如果使用金属部分反射镜，该染料层的厚度可以减小，因为该部分反射镜也可以吸收该激光和通过Fabry-Perot标准具改善该光学信号的振幅。因此，本发明的盘更加不依赖于波长。由此合适的染料必须在所使用的激光的波长范围内吸收。对于根据CD标准的、用780nm的激光写入的CD，使用在780-850nm的范围内吸收的近红外吸收染料。实例例如蒽醌染料：IR-750,ex Nippon Kayaku Co.Ltd，方形(squarilium)染料：NK-2772,ex Nippon Kankohshikiso Kenkyusho Co.Ltd，双-[3-(7-异丙基-1-甲基)-甘菊环-4-基-2-乙基-丙酸正丁酯]方形酸染料(EP0,310,080，实施例16)，在EP0,310,080中描述的染料，和邻二羟环戊烯三酮(croconium)染料：ST 172,ex Syntec,ST9/3,exSyntec,ST9/1,ex Syntec，酞菁染料：铜(Ⅱ)-1,4,8,11,15,18,22,25-辛基丁氧基-29H,31H-酞菁，锌-1,4,8,11,15,18,22,25-辛基丁氧基-29H,31H-酞菁，ex Aldrich。优选的染料是花青染料，例如L-04,S-04，或其混合物，和选自Victoria蓝、Luxol Fast蓝，和孔雀石绿草酸盐(Malachite Green Oxalate)或其混合物的染料。L-04,S-04和单氧淬灭剂IRG-022的混合物也是优选的。
该缓冲层可以含有至多接近100％重量比的染料。但是，优选用量至多为60％重量比。该缓冲层也可以含有稳定剂和/或1O2-淬灭剂(例如Perkacit)以改善该层的稳定性。为了涂布该缓冲层，将高分子材料和任选的染料和其它添加剂优选溶解在合适的溶剂中并进行旋涂。也可以采用其它涂布厚度精确的传统涂布方法。
如上所述，该缓冲层的吸收系数连同该部分反射镜的光学参数影响Fabry-Perot的反射和吸收。该吸收系数是由染料在该缓冲层中的浓度和其消光系数确定。这可以被用来确定本发明的符合CD标准的CD的参数。
厚反射层是金、铝、银或其合金的金属层，通过例如化学真空沉积或溅射的方法叠加在缓冲层上。该厚层应当对激光不透明。对于传统的CD其透光率优选为0-5％。优选银或其合金。
保护层(5)可以是具有高抗冲性的任何树脂。通常使用采用旋涂方法、随后利用UV辐射固化的UV固化树脂。其它适合作为保护涂层的材料是环氧树脂、丙烯酸树脂、硅酮硬质涂层树脂(silicone hard coatresins)和聚氨酯树脂。该保护涂层的厚度并不重要，通常在3-30μm之间，优选在5-15μm之间。
本发明还涉及一种制造本发明的光学记录介质的方法。该方法包括以下步骤：●在带有沟槽的基片上施加部分反射镜，●在所述部分反射镜上施加缓冲层，●在所述缓冲层上施加厚保护层。
如上所述，该部分反射镜和厚反射层可以通过例如真空沉积、电子束沉积或溅射而施加。该缓冲层也可以通过例如旋涂而施加。
该制造方法很容易成为连续工艺。通过在传统的生产线中插入施加部分反射镜的装置和施加缓冲层的装置，制造传统的只读CD的设备可以很容易的改为制造本发明的光学记录介质的设备。本发明还涉及一种连续制造本发明的光学记录介质的设备，包括：●传递带有沟槽的基片的装置，●在所述基片上施加部分反射镜的装置，●在所述部分反射镜上施加缓冲层的装置，● 在所述缓冲层上施加厚保护层的装置。
下面参考以下的实施例对本发明作进一步的说明。
实施例1
按照如PCT/EP9605373所披露的标准工序的方法，制备包括如下聚碳酸酯基片、部分反射镜、缓冲层、厚反射层和保护涂层的CD-R：
基片：聚碳酸酯；沟槽深度190nm，沟槽宽度(FWHM)350nm，轨迹间距1.6μm.
部分反射镜：银，无沟槽部分在780nm处透射率为80％。
缓冲层：Luxol Fast蓝MBSN/L-04/PerkacitNDBC的混合物(3.6％的固体；比例为47.6/45.6/6.77)。在780nm处nbu=1.94,kbu=0.007。层厚度为60nm(在凸起部分)，沟槽图象为沟槽深度的60％。
厚反射层：银，厚度为100nm。
保护涂层：交联的含有环氧的聚丙烯酸酯，厚度为5-10μm。
对所形成的CD采用780nm的激光束利用测定设备进行测定。在1.2m/秒，720KHz和8mw的记录条件下使用0.7mw的读取能量，所记录的3T信号的信噪比(CNR)为55dB，在凸起处的反射率为77％，反射率(Rtop)为70％。该盘在商业性的光盘播放器中可反复播放。抖动值大大低于35ns。该盘在650nm处利用紫外光谱仪(Shimadzu MPC-3100)所测的反射率为40％(图2)。所记录的音乐可以在Panasonic DVD-A3000播放器上播放。
实施例2
制备一种如实施例1的CD，具有：
部分反射镜：钽，无沟槽部分在780nm处透射率为80％。
缓冲层：Luxol Fast蓝MBSN/L-04/IRG 022的混合物(比例为33/60/7)，固体含量为3.2重量％，在凸起部分的涂敷厚度为60nm，沟槽图象为沟槽深度的60％。对所形成的CD采用波长为780nm的聚焦激光束利用测定设备进行测定，分析在采用波长同样为780nm的写入激光束的商业记录器上以1.2m/s的2倍和4倍的速度记录的区域。所测得的反射率(Rtop)为70％，在2倍的写入速度下观察到的最佳写入能量为11mW。该CD盘可在商业性的光盘记录器/播放器中记录和再次播放。该盘在650nm处的反射率为37％，并且所记录的盘可由DVDP播放。
实施例3
制备一种如实施例2的CD，具有：
缓冲层：Luxol Fast蓝MBSN/L-04/IRG 022的混合物(比例为48/45/7)，其固体含量为3.2重量％，在凸起部分的涂敷厚度为60nm，沟槽图象为沟槽深度的60％。
按照如实施例2的方法对所得到的CD进行测定，测得反射率(Rtop)为65％。其它参数，包括但并不限于凸起-和凹痕-抖动值，在2倍的写入速度下很满足Orange Book Ⅱ(版本2.9)的要求。该盘可在商业性的光盘记录器/播放器中记录和再次播放。该盘在650nm处的反射率为42％，并且所记录的盘可由DVDP播放。
实施例4
制备一种如实施例3的CD，具有：
基片：聚碳酸酯；沟槽深度230nm，沟槽宽度(FWHM)450nm，轨迹间距1.6μm。
部分反射镜：如同实施例3中的银，在上述基片上形成60％的透射率。
按照如实施例3的方法对所得到的CD进行测定，测得反射率(Rtop)为65％，以及2倍的写入速度最佳能量为11mW，串话低于20％(OrangeBook要求低于50％)。其它相关参数也满足Orange Book的要求。该盘可在商业性的光盘记录器/播放器中记录和再次播放。该盘在650nm处的反射率为40％，并且所记录的盘可由DVDP播放。
实施例5
制备一种如实施例3的CD，具有：
基片：如同实施例4所述，其轨迹间距1.5μm。
按照如实施例4的方法对所得到的CD进行测定，所测的结果大致与之相同，只是抖动值略有改进(2-5ns)。
实施例6
制备一种如实施例5的CD，具有：
缓冲层：一种洗涤过的纯化Victoria蓝B/L-04/IRG 022的混合物(比例为30/60/10)的固体含量为3.2％的溶液，如实施例2所述，并按照实施例2的方法进行涂敷。
按照如实施例5的方法对所得到的CD进行测定，测定结果显示，使用商业化的CD记录器，在2倍和4倍的写入速度下得到已记录区域的凸起-和凹痕-抖动值都低于35ns。所得到的凹痕-和凸起-长度偏差都处于Orange BookⅡ的特定范围之内，对于3T-11T的凹痕-和凸起-标记长度差异(分别是60ns-90ns)显示出比Orange Book差异允许值(分别是150ns和130ns)更为平坦的特性。该盘可在商业性的光盘记录器/播放器中记录和再次播放。
实施例7
制备一种如实施例6的CD，具有：
基片：如同实施例6所述，但是沟槽深度为260nm。
缓冲层：如实施例6所述，但是改进旋涂顺序。
按照上述实施例的方法对所得到的CD进行测定。
比较实施例1(EP0,353,391的实施例1)
将0.65gNK3219的10ml双丙酮醇的涂布溶液旋涂在预先带有沟槽的聚碳酸酯基片上。该预先沟槽的几何尺寸如下：深度80nm，半宽度600nm，轨迹间距1600nm。该盘可由CD-R记录器(Yamaha 400TX)记录，并在CD播放器(Philips CDP MKⅡ)上播放，但是不能在DVDP上回放。该盘在650nm处利用UV光谱仪所测得的反射率低于12％(图2)。

Claims (9)

1．一种光学记录介质，包括如下各层：
a)一个聚碳酸酯基片，带有在未写入状态下其深度dgu为170-270nm的沟槽(1)，其上叠加有
b)一个记录层，包括：其材料选自Ag,Ta,V,Ni,Cr,Si，其合金和其氧化物的部分反射镜(2)，在没有沟槽的基片处它在770-790nm的透射率在40％-90％之间，其上叠加有一个缓冲层(3)，含有在未写入状态下在770-790nm处其固体状态下所测得的折射率nbu为1.45-3.0，消光系数kbu为0-0.3的有机材料，其凸起处的厚度db为10-70nm，该层沟槽图象的深度di是深度dgu的40％-90％，其上叠加有Au,Al,Ag或其合金的厚反射层(4)，它们共同形成Fabry-Perot标准具，其中该凸起部分在770-790nm的反射处于高反射状态，其上叠加有
c)保护涂层(5)。
2．如权利要求1的光学记录介质，其中在写入状态下的折射率nbw和消光系数kbw分别小于nbu和kbu。
3．如权利要求1或2的光学记录介质，其中该沟槽写入部分的深度dgw小于该沟槽未写入状态下的深度dgu。
4．如权利要求1-3中任何一项的光学记录介质，其中dgu为180-240nm。
5．如权利要求1-4中任何一项的光学记录介质，其中在650nm处的反射率高于30％，而在780nm处的反射率高于60％。
6．如权利要求1-5中任何一项的光学记录介质，其中该部分反射镜选自Ag,Ta，其氧化物和其合金。
7．如权利要求1-6中任何一项的光学记录介质，其中该有机材料的折射率nbu为1.8-2.2。
8．如权利要求1-7中任何一项的光学记录介质，其中Kbu为0-0.05。
9．如权利要求1-8中任何一项的光学记录介质，其中厚度db为15-40nm。
CN99802905A 1998-02-13 1999-02-03 基于薄记录层的光学记录介质 Pending CN1324481A (zh)

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KR100316772B1 (ko) * 1998-04-09 2002-01-16 윤종용 광기록 매체
WO2003060894A1 (en) * 2002-01-18 2003-07-24 Koninklijke Philips Electronics N.V. Optical data storage medium and use of such medium
US7132338B2 (en) * 2003-10-10 2006-11-07 Applied Materials, Inc. Methods to fabricate MOSFET devices using selective deposition process

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EP0777224B1 (en) * 1995-12-01 2002-07-03 Samsung Electronics Co., Ltd. Optical recording medium and method
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