CN1260273C - 蚀刻终止树脂 - Google Patents

蚀刻终止树脂 Download PDF

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CN1260273C
CN1260273C CNB028209567A CN02820956A CN1260273C CN 1260273 C CN1260273 C CN 1260273C CN B028209567 A CNB028209567 A CN B028209567A CN 02820956 A CN02820956 A CN 02820956A CN 1260273 C CN1260273 C CN 1260273C
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silicone resin
resin
dielectric layer
phsio
free energy
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R·博伊斯维特
S·格里戈拉斯
D·哈
B·哈克尼斯
C·耶克尔
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Abstract

含5-50mol%(PhSiO(3-x)/2(OH)x)单元和50-95mol%(HSiO(3-x)/2(OH)x)的硅氧烷树脂,其中Ph是苯基,且x的值为0、1或2;和其中该固化的硅氧烷树脂的临界表面自由能为30dyn/cm或更高。这些树脂用作临界表面自由能为40dyn/cm或更高的有机介电材料的蚀刻终止层。

Description

蚀刻终止树脂
本发明涉及含5-50mol%(PhSiO(3-x)/2(OH)x)单元和50-95mol%(HSiO(3-x)/2(OH)x)的硅氧烷树脂,其中Ph是苯基,x的值为0、1或2,和其中固化的硅氧烷树脂的临界表面自由能为30dyn/cm或更高。这些树脂用作临界表面自由能为40dyn/cm或更高的有机介电材料的蚀刻终止层。
半导体器件常具有一个或多个构图互连触点(levels)的阵列,所述阵列起电连接形成集成电路(IC)的单个电路元件的作用。互连触点典型地通过绝缘或介电涂层隔开。可通过化学蒸气沉积或通过旋压技术形成涂层。例如,美国专利No.4756977公开了氢倍半硅氧烷树脂用于在电子器件上形成涂层。
形成集成电路的一种方法称为双波纹(dual damascene)。该方法包括施加介电层,将布线图蚀刻成电介质,用布线金属填充图案,和重复该过程,一直到已形成所需数量的触点。
使用具有不同蚀刻特征的至少两种不同材料生产介电层是有益的。实质上,一种介电材料在另一电介质的蚀刻中充当蚀刻终止剂。优选介电层之一是有机材料,而另一层是无机材料,以提高材料之间的蚀刻选择性。任一介电层可充当另一介电层的蚀刻终止剂。在氧基等离子体中,有机电介质往往比无机电介质更快速蚀刻。在氟化碳基等离子体中,无机电介质往往比有机电介质更快蚀刻。无机、有机、无机或有机、无机、有机的夹层结构也用作集成电路的介电层。
AlliedSignal的PCT专利申请No.WO01/18861A1公开了一种微电子器件,它具有基板和位于该基板上的第一介电层材料。第二介电材料层位于第一介电层上,和第一介电材料的附加层位于第二介电层上。有机电介质是含有碳的物质和无机电介质是不含碳的物质。
美国专利No.6218317公开了在介电常数小于3和更优选2.7或更低的聚合物层间介电材料上形成甲基化氧化物型硬掩膜(hardmask)。
当使用两层或多层介电层时,希望上面的物质能充分涂布下面的表面(即润湿表面)。还希望层间具有充足的粘合力。
本发明涉及含5-50mol%(PhSiO(3-x)/2(OH)x)单元和50-95mol%(HSiO(3-x)/2(OH)x)的硅氧烷树脂,其中Ph是苯基,x的值为0、1或2,和其中固化的硅氧烷树脂的临界表面自由能为30dyn/cm或更高。这些树脂用作临界表面自由能为40dyn/cm或更高的有机介电材料的蚀刻终止层。
本发明还涉及一种集成电路器件,它具有临界表面自由能为40dyn/cm或更高的有机介电层和由该硅氧烷树脂生产的临界表面自由能为30dyn/cm或更高的苯基化氧化物介电层,其中有机介电层的至少一个表面与苯基化氧化物介电层的表面接触。
本发明涉及含5-50mol%(PhSiO(3-x)/2(OH)x)单元和50-95mol%(HSiO(3-x)/2(OH)x)单元的硅氧烷树脂,基于树脂内含硅单元的总量,其中Ph是苯基,x的值为0、1或2。
硅氧烷树脂含有5-50mol%(PhSiO(3-x)/2(OH)x)单元,或者25-50mol%,或者30-45mol%。硅氧烷树脂内较高量的(PhSiO(3-x)/2(OH)x)导致在苯基化介电层内较高量的碳。这降低了苯基化氧化物介电层与有机介电层之间的蚀刻选择性。另外,在最终膜内较高量的碳有助于降低苯基化氧化物介电层对有机介电层的粘合力。
对于用作与有机介电层结合的介电层中的硅氧烷树脂,希望在固化硅氧烷树脂内的临界表面自由能为30dyn/cm或更高。在硅氧烷树脂内,(PhSiO(3-x)/2(OH)x)每增加1mol%,理论上在固化树脂内临界表面自由能增加0.31dyn/cm。因此,在硅氧烷树脂内较高量的(PhSiO(3-x)/2(OH)x)单元是理想的,然而,发现随着(PhSiO(3-x)/2(OH)x)单元量增加,固化硅氧烷树脂对有机介电层的粘合力降低。优选固化硅氧烷树脂的临界表面自由能范围为35-60dyn/cm,更优选35-45dyn/cm。
对硅氧烷树脂的结构没有特别的限制。硅氧烷树脂可以基本上全部缩合或可以仅仅部分缩合。当硅氧烷树脂部分缩合时,在硅氧烷树脂内小于40mol%的单元应当含有Si-OH基。较高量的这些单元可导致树脂的不稳定性和形成凝胶。典型地,在硅氧烷树脂内6-38mol%的单元含有Si-OH基。
硅氧烷树脂的重均分子量(Mw)在500-400000范围内,和优选在500-100000范围内,或者为700-10000。
本文中有用的硅氧烷树脂可例举,但不限于下述物质:
(PhSiO3/2)a(HSiO3/2)d
(PhSiO3/2)a(PhSiO2/2(OH))b(HSiO3/2)d
(PhSiO3/2)a(PhSiO2/2(OH))b(HSiO3/2)d(HSiO2/2(OH)e
(PhSiO3/2)a(HSiO3/2)d(HSiO2/2(OH)e
(PhSiO3/2)a(PhSiO2/2(OH))b(PhSiO1/2(OH)2)c(HSiO3/2)d
(PhSiO3/2)a(PhSiO2/2(OH))b(PhSiO1/2(OH)2)c(HSiO3/2)d(HSiO2/2(OH)e
其中a>0,b≥0,c≥0,d>0,e≥0,0.05≤a+b+c≤0.5,0.5≤d+e≤0.95和b+c+e≤0.4。
可通过本领域已知的方法生产树脂。例如,如Sakamoto等的美国专利No.5762697中所列出的,可通过水解和缩合苯基三烷氧基和三烷氧基氢硅烷的混合物来生产树脂。或者如Becker等的美国专利No.6281285和Bank等的美国专利No.5010159中所列出的,可通过水解和缩合苯基三氯硅烷和氢三氯硅烷来生产它们。
典型地在溶剂存在下生产硅氧烷树脂。可在硅氧烷树脂的生产中使用不含有可参与反应的官能团的任何合适有机溶剂或硅氧烷溶剂。溶剂的通常用量为40-98重量%,基于溶剂和硅烷反应物的总重量,或者70-90重量%。可以以两相或单相体系进行反应。
有用的有机溶剂可以例举但不限于,饱和脂族化合物,如正戊烷、己烷、正庚烷和异辛烷;脂环族化合物如环戊烷和环己烷;芳族化合物如苯、甲苯、二甲苯、;醚如四氢呋喃、二噁烷、乙二醇二乙醚、乙二醇二甲醚;酮如甲基异丁基酮(MIBK)和环己酮;卤素取代的烷烃如三氯乙烷;卤化芳族化合物如溴苯和氯苯;酯如异丁酸异丁酯和丙酸丙酯。有用的硅氧烷溶剂可例举但不限于,环状硅氧烷如八甲基环四硅氧烷和十甲基环五硅氧烷。可使用单一的溶剂或可使用溶剂的混合物。
可在任何温度下进行生产硅氧烷树脂的反应,只要它不引起显著的胶凝或引起硅氧烷树脂的固化即可。典型地,在5℃-150℃的温度范围内进行反应,其中建议采用室温。
形成硅氧烷树脂的时间取决于许多因素,如温度、硅烷反应物的类型与用量,和催化剂(如果存在的话)的用量。典型地,反应时间为几分钟到几小时。本领域的熟练人员能容易地确定完成反应所需的时间。
在反应完成之后,可非必需地除去催化剂。除去催化剂的方法是本领域公知的,和包括中和、汽提或水洗或其结合。催化剂可负面影响硅氧烷树脂、特别地当它为溶液时的储存期,因此建议除去它。
在制造硅氧烷树脂的方法中,在反应完成之后,可在减压下,从硅氧烷树脂溶液中除去挥发物。所述挥发物包括醇副产物、过量的水、催化剂、盐酸(氯代硅烷路线)和溶剂。除去挥发物的方法是本领域已知的,和包括例如蒸馏。
在生产硅氧烷树脂的反应之后,可进行许多非必需的步骤,以获得所需形式的硅氧烷树脂。例如,可通过除去溶剂以固体形式回收硅氧烷树脂。除去溶剂的方法不是关键的,和许多方法是本领域已知的(例如在加热和/或真空下的蒸馏)。一旦以固体形式回收硅氧烷树脂,则可非必需地在同一或另一溶剂中再溶解树脂供特定的用途。或者,若对于最终的产物,如果想要不同于反应中使用的溶剂,则可通过添加第二种溶剂并通过例如蒸馏除去第一种溶剂来进行溶剂交换。另外,可通过除去一些溶剂或通过添加附加量的溶剂来调节溶剂内的树脂浓度。
本发明还涉及形成集成电路器件内的介电材料,其中该介电材料由至少一临界表面自由能为至少40dyn/cm的有机介电层和由本发明的硅氧烷树脂生产的且临界表面自由能为至少30dyn/cm的第二苯基化氧化物介电层组成。
这种“双层”介电材料的益处是一介电层能充当另一层的蚀刻终止层。可通过使用临界表面自由能为至少30dyn/cm的苯基化氧化物无机层和临界表面自由能为至少40dyn/cm的有机电介质,实现良好的表面润湿。藉助良好的表面润湿,人们能实现在另一层上一种物质的基本上均匀涂布。
可通过本领域已知的方法,使用本领域已知的物质,来生产有机介电层。已知合适的有机介电材料是由Dow Chemical Co.制造的SiLKTM。该材料产生临界表面自由能为53dyn/cm的介电层。可使用常规的旋涂技术和设备处理SiLKTM
可使用硅氧烷树脂,通过以下步骤来制备苯基化氧化物介电层:
(I)用含5-50mol%(PhSiO(3-x)/2(OH)x)单元和50-95mol%(HSiO(3-x)/2(OH)x)的硅氧烷树脂(其中Ph是苯基,x的值为0、1或2),涂布半导体基板,和
(II)在足以固化硅氧烷树脂并产生苯基化氧化物介电层的温度下加热涂布的半导体基板,
半导体基板可含有有机介电层,在该有机介电层上形成苯基化氧化物介电层。或者可首先形成苯基化氧化物介电层,然后在该苯基化氧化物介电层上形成有机介电层。
典型地将硅氧烷树脂以溶剂分散液的形式施加到基板上。可使用的溶剂包括将溶解或分散硅树脂形成基本上均匀的液体混合物的任何试剂或试剂的混合物。溶剂典型地是在以上所述的生产硅氧烷树脂的反应中使用的单一溶剂或溶剂的混合物。推荐的溶剂是丙二醇甲醚乙酸酯、环己酮、γ-丁内酯、甲基异丁基酮、甲基丙基酮、和硅氧烷。
不特别限制溶剂的用量,但典型地其存在量为40-99.5重量%,或者60-99.5%,基于硅氧烷树脂和溶剂的重量。
将硅氧烷树脂施加到基板上的具体方法包括但不限于,旋涂、浸涂、喷涂、流涂、筛网印刷和其它。推荐的施加方法是旋涂。
当使用溶剂时,在施加之后从涂布的基板上除去溶剂。可使用除去溶剂的任何合适的手段,如干燥、施加真空和/或施加热(即,例如使涂布的晶片经过热板)。当采用旋涂时,由于旋涂驱走了大多数溶剂,所以使附加的干燥方法减到最小。
在施加到基板上之后,在固化硅氧烷树脂的温度下加热涂布的基板。固化的硅氧烷树脂基本上不溶于在将该硅氧烷树脂施加基板上时可使用的溶剂。典型地,加热涂布的基板到100℃-600℃的范围内,以固化硅氧烷树脂,其中推荐100℃-450℃。
不特别限制在树脂固化过程中所使用的氛围。可用的氛围包括含氧氛围如空气,和惰性氛围,如氮气和氩气。“惰性”是指环境含有小于50ppm和优选小于10ppm的氧气。进行固化和除去步骤的压力不是关键的。典型地在大气压下进行固化,然而低于或高于大气压也可进行。
可使用任何加热方法固化硅氧烷树脂。例如,可将基板放置在石英管加热炉、对流烘箱、快速热处理机内,或使之置于热板上。在工业上通常使用加热炉来生产在集成电路上的固化树脂膜。
可以以任何顺序生产介电材料层。例如,可在半导体基板上生产有机介电层,此后在其上形成无机介电层。或者,可在半导体基板上生产无机介电层,此后在其上生产有机介电层。另外,可形成夹层结构或多层。例如,可在基板上生产有机介电层,接着生产无机介电层,接着生产另一有机介电层。
提供下述非限制性实施例,以便本领域的熟练人员可更容易地理解本发明。在下述实施例中,Ph表示苯基,Me表示甲基,T表示单元SiO3/2(即TPh=PhSiO3/2)。
基于ASTM D 724的方法,使用接触角测量临界表面自由能(表面能)。
使用螺柱提拉(stud pull)方法测量粘合力。
实施例
实施例1
向乙二醇二甲醚(EGDME)中加入表1中所示用量的相应烷氧基硅烷。搅拌EGDME和烷氧基硅烷的溶液几分钟,之后添加含100ppm硝酸催化剂的去离子水。在室温下剧烈搅拌混合物4天。在搅拌之后添加丙二醇甲醚醋酸酯(PGEMA)。通过旋转蒸发从溶液中除去起始的溶剂(乙二醇二甲醚)、残留的水、醇副产物和残留的硝酸,从而留下在丙二醇甲醚醋酸酯溶液内的树脂产物(10wt%)。
实施例2
在烧瓶反应器内添加如表2所示用量的乙二醇二甲醚(EGDME)、苯基三氯硅烷和三氯硅烷。在维持溶液处于氮气氛围的同时,冷却溶液到10-12℃。以表2所示用量,在另一烧瓶内结合EGDME和水。在表2所示的时间内,将水/EGDME溶液加入到氯代硅烷/EGDME中。在加完之后,使溶液温热到20℃,并搅拌表2所示的时间(增稠时间),以增稠(body)所形成的树脂。将200g丙二醇甲醚醋酸酯(PGMEA)加入到该溶液中。在40℃下使用旋蒸仪,浓缩溶液到约21重量%的树脂含量,以除去EGDME溶剂。然后向树脂中加入30g乙醇,并旋蒸烧瓶内容物,除去乙醇和残留的水和盐酸。然后通过添加PGMEA,将溶液稀释到10重量%的树脂。以PGMEA代替EGDME进行实施例2-2。
表1
  实施例  HSi(OEt)3(g)   PhSi(OMe)3(g)   水(g)   EGDME(g)   分子量Mw(Mn)   SiOH含量(mol%) 目标组成* 实际组成*
  1-1   100.00   40.23   43.82   370.00   1976(951)   15.7 TPh 0.25TH 0.75 TH 0.71TH,OH 0.07TPh 0.13TPh,OH 0.09TPh,(OH)2 0.01
  1-2   55.00   66.38   36.15   380.00   804(601)   38.22 TPh 0.50TH 0.50 TH 0.46TH,OH 0.16TPh 0.13TPh,OH 0.23TPh,(OH)2 0.02
  1-3   130.00   22.41   48.83   356.00   2944(1171)   17.1 TPh 0.125TH 0.875 TH 0.77TH,OH 0.12TPh 0.04TPh,OH 0.05TPh,(OH)2 0.01
  1-4   160.00   4.95   53.94   350.00   9188(2137)   14.3 TPh 0.025TH 0.975 TH 0.86TH,OH 0.14TPh 0.00TPh,OH 0.01
*以摩尔值给出的比例
表2
  实施例No.   PhSiCl3(g)   HSiCl3(g)   EGDME1(g)   EGDME2(g)   水(g)   添加时间,hr   增稠时间,hr 目标组成*   实际组成*
  2-1   40   63   316   80   23   0.75   2.00 TPh 0.25TH 0.75 TPh,OH 0.07TPh 0.23TH 0.72
  2-2   42   81   PGMEA304   PGMEA615   30   2   0.75 TPh 0.25TH 0.75 TPh,OH 0.08TPh 0.17TH 0.75
  2-3   81   52   617   121   30   1   1.5 TPh 0.50TH 0.50 TPh,(OH)2 0.07TPh,OH 0.25TPh 0.22TH 0.46
  2-4   61   69   612   120   30   1.5   3.5 TPh 0.36TH 0.54 TPh,(OH)2 0.02TPh,OH 0.135TPh 0.2TH 0.64
  2-5   54   74   613   120   30   1.5   3.5 TPh 0.32TH 0.68 TPh,(OH)2 0.04TPh,OH 0.14TPh 0.16TH 0.67
对比例1
以表3所示的用量结合浓盐酸(37%,在水中)、辛基硫酸钠和甲苯(1)。在20℃下,在1200rpm下搅拌溶液,混合两相。以表3所示的用量向另一烧瓶内添加甲苯(2)、三氯硅烷和甲基三氯硅烷。在维持剧烈搅拌的同时,在4小时内合并氯代硅烷和甲苯的混合物。在20℃下,增稠所得树脂最少4小时。然后终止搅拌,并使相分离。除去浓盐酸相并弃置。用1L份去离子水8次洗涤有机相。继续洗涤直到达到pH为4。将有机相转移到烧瓶内,并使用旋蒸仪浓缩到30重量%的树脂。将甲苯加入到树脂溶液中,以降低树脂浓度到20重量%。然后以总溶液重量的10重量%的用量,向该溶液中加入乙醇。采用旋蒸仪,再次浓缩树脂到30重量%,以除去乙醇和任何残留的水和盐酸。用甲苯稀释溶液到20重量%的树脂。
通过添加乙腈到甲苯/树脂溶液内来分馏树脂,从而纯化树脂。典型地,通过添加乙腈,可分离三种树脂馏分:当达到溶液/乙腈比为0.65时,沉淀高分子量馏分,当比例为0.13时,沉淀中间馏分(该物质的40-45%),以及含低分子量物质的最终溶液。使用中间馏分评价目的物和通过3D光散射GPC测量的平均分子量为40000。
将这些物质以7.5-10wt%的固体浓度溶解在环己酮中,用于薄膜研究。
对比例2
采用与实施例1相同的步骤制备树脂,所不同的是使用Me(OMe)3替代Ph(OMe)3。反应物和所产生的树脂的用量见表4。
表3
实施例No. MeSiCl3(g) HSiCl3(g) HCl(g) OSS* 甲苯1 甲苯2 目标组成*
  C1-1   149   406   1422   10   3910   700 TMe 0.25TH 0.75
  C1-2   299   271   1422   10   3910   700 TMe 0.50TH 0.50
**OSS=辛基硫酸钠
表4
实施例NO. HSi(OEt)3(g) MeSi(OMe)3(g) 水(g) EGDME(g) 目标组成*
C2-1  30.42  40.23  13.82  100.00  TMe 0.25TH 0.75
C2-2  20.21  16.9  13.92  100  TMe 0.50TH 0.50
实施例4
在PGMEA中稀释来自实施例1和2的样品到1-3wt%的浓度,过滤并旋涂在硅片上。选择旋涂速度在2000-5000RPM范围内,以实现在250埃范围内的初旋(as-spun)厚度。在快速热处理机内,在250℃下,在氮气氛围中加热涂布的晶片2分钟,产生苯基化氧化物涂层。结果见表4。
采用与如上所述相同的步骤,在第一层上生产第二苯基化氧化物层。表1给出了膜质量(膜上膜)的结果。
表5
实施例材料 膜质量(硅片) 250℃固化的表面能 Dk 粘合力 膜质量(膜上膜)
1-1 没有反润湿(dewets) 34  3.06  43.9 反润湿
1-2 小孔 41 3.01 13.4 小孔
1-3 没有反润湿 31 3.04 65.3 反润湿
1-4 没有反润湿 31 3.09 59.8 反润湿
2-1 没有反润湿 37.1 47.3 没有反润湿
2-2 没有反润湿 40.1 3.32 43.9 没有反润湿
2-3 没有反润湿 40.8 3.10 4.4 没有反润湿
2-4 没有反润湿 37 3.35 60.6 没有反润湿
2-5 没有反润湿 35.5 3.38 59.1 没有反润湿
对比例3
在PGMEA中稀释来自对比例1和2的样品到1-3wt%的浓度,过滤并旋涂在硅片上。选择旋涂速度在2000-5000RPM范围内,以实现在250埃范围内的初旋厚度。在快速热处理机内,在250℃下,在氮气氛围中加热涂布的晶片2分钟,产生甲基化氧化物涂层。结果见表6。
表6
  目标组成   实施例No.   固化温度(℃/2分钟热板)   表面能(dyn/cm)   膜质量
  TMe 0.25TH 0.75   C2-1   100   25.5   反润湿
  TMe 0.25TH 0.75   C2-1   150   29.5   反润湿
  TMe 0.50TH 0.50   C2-2   150   29.9   反润湿
  TMe 0.50TH 0.50   C2-2   250   26   反润湿
  TMe 0.25TH 0.75   C1-1   250   24.9   反润湿
  TMe 0.25TH 0.75   C1-1   350   25.9   反润湿
  TMe 0.50TH 0.50   C1-2   250   27.3   反润湿

Claims (5)

1.硅氧烷树脂,包括5-50mol%(PhSiO(3-x)/2(OH)x)单元和50-95mol%(HSiO(3-x)/2(OH)x)单元,基于树脂内含硅单元的总量,其中Ph是苯基,且x的值为0、1或2,和其中硅氧烷树脂的重均分子量为500-400000。
2.一种溶液,包括:
(I)硅氧烷树脂,该硅氧烷树脂包括5-50mol%(PhSiO(3-x)/2(OH)x)单元和50-95mol%(HSiO(3-x)/2(OH)x)单元,基于树脂内含硅单元的总量,其中Ph是苯基,且x的值为0、1或2,和其中硅氧烷树脂的重均分子量为500-400000;
(II)40-99.5wt%溶剂,基于(I)和(II)的总重量。
3.苯基化氧化物电介质,其由权利要求1的硅氧烷树脂形成且其临界表面自由能为至少30dyn/cm。
4.生产苯基化氧化物电介质的方法,该方法包括;
(I)将硅氧烷树脂施加到基板上,其中所述硅氧烷树脂包含5-50mol%(PhSiO(3-x)/2(OH)x)单元和50-95mol%(HSiO(3-x)/2(OH)x)单元,基于树脂内含硅单元的总量,其中Ph是苯基,且x的值为0、1或2,和其中硅氧烷树脂的重均分子量为500-400000;
(II)加热涂布的基板到100℃-450℃的温度范围内,以固化所述硅氧烷树脂,其中所述苯基化氧化物电介质的临界表面自由能为至少30dyn/cm。
5.集成电路,包括介电材料,其中该介电材料包括:
(a)至少一临界表面自由能为至少40dyn/cm的有机介电层,和
(b)至少一临界表面自由能为至少30dyn/cm的苯基化氧化物介电层,其由权利要求1的硅氧烷树脂形成。
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DE60239555D1 (de) 2011-05-05
ATE502974T1 (de) 2011-04-15
US20040186223A1 (en) 2004-09-23
JP4413612B2 (ja) 2010-02-10
US20030096090A1 (en) 2003-05-22
JP2005507015A (ja) 2005-03-10
EP1442071B1 (en) 2011-03-23
TW574104B (en) 2004-02-01
CN1575310A (zh) 2005-02-02
EP1442071A1 (en) 2004-08-04
KR20050018629A (ko) 2005-02-23
US6924346B2 (en) 2005-08-02
KR100898158B1 (ko) 2009-05-19

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