CN1246244C - 高应变点玻璃

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投票人數:10人

本文揭示了氧化钛-氧化镧硅铝酸盐玻璃系列,以及例如具有涂覆在这种玻璃基底上的多晶硅的电子装置的产品。

所述玻璃的应变点超过780℃,热膨胀系数为20~60×10 -7 /℃ ... CN1246244C-高应变点玻璃 -GooglePatents 高应变点玻璃 DownloadPDF Info Publicationnumber CN1246244C CN1246244C CNB021526605A CN02152660A CN1246244C CN1246244C CN1246244C CN1246244C CNB021526605A CNB021526605A CNB021526605A CN02152660A CN02152660A CN02152660A CN1246244C CN1246244C CN1246244C Authority CN China Priorartkeywords glass strainpoint tio titaniumoxide oxide Priorartdate 2001-11-28 Legalstatus(Thelegalstatusisanassumptionandisnotalegalconclusion.Googlehasnotperformedalegalanalysisandmakesnorepresentationastotheaccuracyofthestatuslisted.) Expired-FeeRelated Applicationnumber CNB021526605A Otherlanguages English(en) Otherversions CN1421412A (zh Inventor B·G·艾特肯 P·L·博克 A·J·G·埃利森 T·E·保尔森 CurrentAssignee(Thelistedassigneesmaybeinaccurate.Googlehasnotperformedalegalanalysisandmakesnorepresentationorwarrantyastotheaccuracyofthelist.) CorningInc OriginalAssignee CorningInc Prioritydate(Theprioritydateisanassumptionandisnotalegalconclusion.Googlehasnotperformedalegalanalysisandmakesnorepresentationastotheaccuracyofthedatelisted.) 2001-11-28 Filingdate 2002-11-28 Publicationdate 2006-03-22 2001-11-28 PrioritytoUS09/997,052 priority Critical 2001-11-28 PrioritytoUS09/997,052 priority patent/US6555232B1/en 2002-11-28 ApplicationfiledbyCorningInc filed Critical CorningInc 2003-06-04 PublicationofCN1421412A publication Critical patent/CN1421412A/zh 2006-03-22 Applicationgranted granted Critical 2006-03-22 PublicationofCN1246244C publication Critical patent/CN1246244C/zh Status Expired-FeeRelated legal-status Critical Current 2022-11-28 Anticipatedexpiration legal-status Critical Links Espacenet GlobalDossier Discuss 239000011521 glass Substances 0.000 title claims abstract description 69 229910021420 polycrystallinesilicon Inorganicmaterials 0.000 claims abstract description 18 239000000758 substrate Substances 0.000 claims abstract description 15 229920005591 polysilicon Polymers 0.000 claims abstract description 8 GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanoxide Chemicalcompound 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[Zr]=O GEIAQOFPUVMAGM-UHFFFAOYSA-N 0.000 claims description 8 229910001845 yogosapphire Inorganicmaterials 0.000 claims description 8 SMYKVLBUSSNXMV-UHFFFAOYSA-J aluminum;tetrahydroxide Chemicalcompound 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[OH-].[OH-].[OH-].[OH-].[Al+3] SMYKVLBUSSNXMV-UHFFFAOYSA-J 0.000 claims description 7 LSYIMYXKHWXNBV-UHFFFAOYSA-N [O-2].[La+3].[Ti+4] Chemicalcompound 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[O-2].[La+3].[Ti+4] LSYIMYXKHWXNBV-UHFFFAOYSA-N 0.000 claims description 6 BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemicalcompound 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[O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 claims description 6 229910001936 tantalumoxide Inorganicmaterials 0.000 claims description 6 229910001929 titaniumoxide Inorganicmaterials 0.000 claims description 6 239000006066 glassbatch Substances 0.000 claims description 5 239000012528 membrane Substances 0.000 claims description 5 230000004580 weightloss Effects 0.000 claims description 5 229910005793 GeO2 Inorganicmaterials 0.000 claims description 4 229910004140 HfO Inorganicmaterials 0.000 claims description 4 229910006404 SnO2 Inorganicmaterials 0.000 claims description 4 ODINCKMPIJJUCX-UHFFFAOYSA-N calciummonoxide Chemicalcompound 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[Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims 6 CPLXHLVBOLITMK-UHFFFAOYSA-N magnesiumoxide Chemicalcompound 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[Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims 6 XLOMVQKBTHCTTD-UHFFFAOYSA-N zincmonoxide Chemicalcompound 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[Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims 6 QVQLCTNNEUAWMS-UHFFFAOYSA-N bariumoxide Inorganicmaterials 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[Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 claims 3 IATRAKWUXMZMIY-UHFFFAOYSA-N strontiumoxide Inorganicmaterials 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[O-2].[Sr+2] IATRAKWUXMZMIY-UHFFFAOYSA-N 0.000 claims 3 LIVNPJMFVYWSIS-UHFFFAOYSA-N siliconmonoxide Inorganicmaterials 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[Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 claims 2 239000011248 coatingagent Substances 0.000 abstract description 4 238000000576 coatingmethod Methods 0.000 abstract description 4 MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemicalcompound 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[O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 abstract description 3 239000005354 aluminosilicateglass Substances 0.000 abstract 1 239000005357 flatglass Substances 0.000 description 7 238000000137 annealing Methods 0.000 description 6 239000002241 glass-ceramic Chemicalclass 0.000 description 6 XUIMIQQOPSSXEZ-UHFFFAOYSA-N silicon Chemicalcompound 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[O-2].[O-2].[Ti+4].[O-2].[O-2].[La+3] NDAAUCVGRWUFRI-UHFFFAOYSA-N 0.000 description 1 NLHHRLWOUZZQLW-UHFFFAOYSA-N acrylonitrile Chemicalcompound 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[O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1 229910052712 strontium Inorganicmaterials 0.000 description 1 230000002522 swelling Effects 0.000 description 1 229910052715 tantalum Inorganicmaterials 0.000 description 1 Classifications C—CHEMISTRY;METALLURGY C03—GLASS;MINERALORSLAGWOOL C03C—CHEMICALCOMPOSITIONOFGLASSES,GLAZESORVITREOUSENAMELS;SURFACETREATMENTOFGLASS;SURFACETREATMENTOFFIBRESORFILAMENTSMADEFROMGLASS,MINERALSORSLAGS;JOININGGLASSTOGLASSOROTHERMATERIALS C03C3/00—Glasscompositions C03C3/04—Glasscompositionscontainingsilica C03C3/076—Glasscompositionscontainingsilicawith40%to90%silica,byweight C03C3/083—Glasscompositionscontainingsilicawith40%to90%silica,byweightcontainingaluminiumoxideoranironcompound C—CHEMISTRY;METALLURGY C03—GLASS;MINERALORSLAGWOOL C03C—CHEMICALCOMPOSITIONOFGLASSES,GLAZESORVITREOUSENAMELS;SURFACETREATMENTOFGLASS;SURFACETREATMENTOFFIBRESORFILAMENTSMADEFROMGLASS,MINERALSORSLAGS;JOININGGLASSTOGLASSOROTHERMATERIALS C03C3/00—Glasscompositions C03C3/04—Glasscompositionscontainingsilica C03C3/076—Glasscompositionscontainingsilicawith40%to90%silica,byweight C03C3/095—Glasscompositionscontainingsilicawith40%to90%silica,byweightcontainingrareearths Abstract 本文揭示了氧化钛-氧化镧硅铝酸盐玻璃系列,以及例如具有涂覆在这种玻璃基底上的多晶硅的电子装置的产品。

所述玻璃的应变点超过780℃,热膨胀系数为20~60×10-7/℃,杨氏模量大于12mpsi,并且在化学方面持久耐用。

Description 高应变点玻璃 本申请要求提交于2001年11月28,Bruce G.Aitken等人的美国专利申请No.09/997,052的优先权,其内容在此引用作为参考。

技术领域 本发明涉及以高应变点、低热膨胀系数和能够用常规方法生产平板玻璃为特征的(TiO2,Ta2O5)-La2O3-Al2O3-SiO2玻璃。

背景技术 电子装置用玻璃基底,其使用和加工温度不能超过约600~650℃的温度。

至于更高的温度,唯一可用的透明材料是熔凝硅石或玻璃陶瓷类的材料。

这些材料制造困难,因此很昂贵。

熔凝硅石能提供高的应变点(通常>1000℃)和优良的热稳定性。

但是,它很难生产和制造。

同时它具有的低膨胀系数(CTE)(5×10-7/℃)与一些电子材料如硅不相容。

透明的尖晶石玻璃陶瓷也可以提供高应变点(通常>900℃),并提供能和硅(25-40×10-7/℃)相适应的较好膨胀性。

但是,将这些材料陶瓷化会增加它们的成本。

它们的前体玻璃在其液相线温度流动性很大。

这对形成精确的平板玻璃和其它玻璃制品是一个挑战。

因此就需要(1)具有高应变点(>780℃),(2)制成后不需要昂贵的热处理,(3)可以在大于103泊的粘度下成形,(4)可以在常规的熔制装置中熔制的玻璃。

而且,此玻璃必须对可见光透明,并具有化学耐久性。

对于制造种种玻璃制品,如在高温下具有稳定性的平板型显示器、光电池、以及管材和光纤应用就需要上述这些性质。

平板型显示器使用对可见光波长和紫外线必须透明的平板玻璃。

也需要此平板玻璃应能适于在其表面上形成硅层。

最初,所用的硅层是无定形硅(a-Si)。

制造这种装置要求温度不超过350℃。

很容易得到在这些条件下使用的合适玻璃。

涂层材料从a-Si到poly-Si(多晶硅)的发展对使用的玻璃基底是个很大的挑战。

poly-Si涂层需要更高的加工温度为600~1000℃。

一种可取用的基底材料是熔凝硅石。

这种材料具有约为1000℃的高应变点和优良的热稳定性。

但是,它的CTE低,明显低于poly-Si。

而且,这种材料的加工能力受到限制,并且很昂贵。

另一潜在的候选材料是透明的尖晶石玻璃陶瓷。

这种材料具有所需高于780℃的高应变点。

它们在CTE方面也能很好地和poly-Si配合。

但是,其额外要进行的陶瓷化过程会显著增加其生产成本。

也许更重要的是这些玻璃陶瓷的前体玻璃在其液相线温度流动性很大。

这对形成精确的平板玻璃是个严峻的挑战。

由Corning Incorporated可得的型号为1737和2000的玻璃,可以用于大约600~650℃的某些较低温度用途。

这种玻璃是含有二价金属氧化物混合物并且基本不含碱金属氧化物的硅铝酸盐玻璃。

即使是这种玻璃也必须进行特定的热处理,以避免poly-Si沉积在其上面发生的收缩或压缩。

制造高质量poly-Si薄膜时需要在800~900℃范围内的温度下进行热退火。

这种在较高温度的退火可以缩短退火时间。

也可以使涂层与基底的界面具有优良的均匀性,并获得更加稳定的装置性能时间稳定性。

除了上述的熔融玻璃和玻璃陶瓷基底以外,尚不存在其它合适的基底材料。

发明内容 本发明的主要目的是提供一种具有适于在其表面形成poly-Si涂层的性能的玻璃。

本发明另一目的是提供一种具有足够高的应变点,使其能在800~900℃下加工的玻璃。

本发明再一目的是提供一种能用生产平板玻璃的常规步骤进行熔制和成形并能为高质量poly-Si膜应用提供基底的玻璃。

本发明再一目的是提供一种电子装置,具体是包括用常规步骤生产的平板玻璃基底和在其表面具有高质量poly-Si薄膜的平面显示器。

本发明另一目的是提供一种主要包含(TiO2和/或Ta2O5)、La2O3、Al2O3,并选择性包含选自Y2O3、ZrO2、HfO2、SnO2、GeO2、Ga2O3、Sb2O3、B2O3和/或P2O5氧化物的新型玻璃系列。

本发明一方面涉及应变点超过780℃,热膨胀系数为20~60×10-7/℃,杨氏模量大于12mpsi,在BHF(缓冲HF)中重量损失小于1mg/cm2的氧化钛-氧化镧-硅铝酸盐玻璃系列。

氧化钛,或相者氧化钽同样是能降低玻璃的CTE、使之和poly-Si相容的必要组分。

这些氧化物也起熔剂的作用,锐化粘度曲线并提高应变点。

本发明还涉及一种在透明玻璃基底上具有多晶硅薄膜的电子装置,所述基底是应变点超过780℃,热膨胀系数为20~60×10-7/℃,杨氏模量大于8.28×104MPa(12mpsi),在BHF中重量损失小于1mg/cm2的氧化钛-氧化镧-硅铝酸盐玻璃。

具体实施方式 本发明是基于我们对氧化钛-氧化镧硅铝酸盐玻璃系列的发现。

这些玻璃具有独特的性能,尤其是适合生产在玻璃表面具有多晶硅薄膜的电子装置的性能。

更具体地说,这些玻璃具有超过780℃的应变点和20~60×10-7/℃,更好是20~40×10-7/℃的热膨胀系数。

所述玻璃还具有大于8.28×104MPa(12mpsi)的杨氏模量,且在化学方面尤其在缓冲HF(BHF)中耐久性很好。

其中的氧化钛可以部分或全部用氧化钽代替,对CTE或应变点没有任何有害的影响。

所述缓冲HF试验测定将玻璃样品浸入缓冲氢氟酸溶液中5分钟后的重量损失(mg/cm2)并观察其外观。

所述溶液由1体积的50重量%HF和10体积的40重量%氟化铵(NH4F)配成。

溶液在试验中保持30℃。

正如前面所指出的,在市面上是有用常规方法熔制并在其表面沉积多晶硅薄膜的玻璃供应。

为此需要对玻璃进行特殊处理,且该操作必须在不低于650℃的温度下进行。

具有含高质量多晶硅薄膜的玻璃基底的装置,其有效生产需要在800~900℃的温度下进行薄膜的热退火。

但是,常规方法生产的玻璃并不能经受此退火温度。

本发明就提供了这种玻璃。

本发明的玻璃属于氧化钛-氧化镧-硅铝酸盐(TiO2-La2O3-Al2O3-SiO2)玻璃系列。

它的特征是具有很高的应变点(大于780℃),并且具有与硅(25~40×10-7/℃)相当接近的CTE。

如上所述,氧化钛可以部分或全部用氧化钽代替,而对CTE或应变点没有有害的影响。

广泛地说,本发明玻璃的组成具有落在如下的范围内,这是以玻璃批料中氧化物的摩尔%表示。

SiO240~90%         TiO20~20%Al2O35~35%          Ta2O50~10%La2O32~30%          (TiO2+Ta2O5) 0.5~20%RO              0~10%其中,R为Mg、Ca、Sr、Ba和/或Zn。

在SiO2为40~60%的范围时,氧化镧可以部分或全部用氧化钇代替,能降低密度和CTE,同时保持甚至提高其应变点。

其它和本发明玻璃相容的组分包括ZrO2、HfO2、SnO2、GeO2和/或Ga2O3。

还可以加入至多为10摩尔%的这些每种氧化物和/或至多3摩尔%的Sb2O3、WO3、B2O3和/或P2O5,而不会使应变点降低到780℃以下。

若超过上述含量,玻璃要么变得不稳定,要么其性能不如本发明的玻璃组合物。

这些玻璃具有如下的特征性能:应变点                 >780℃CTE                    20~60×10-7/℃杨氏模量               >8.28×104MPaBHF中的耐久性          <1mg/cm2优选的实施方式具有如下范围内的组成,这也是以玻璃批料中氧化物的摩尔%表示:SiO270~84%Al2O36~18%La2O32~15%Ta2O50~8%TiO20~8%(TiO2+Ta2O5)      0.5~10%RO                    <3%在一优选实施例中,TiO2+Ta2O5的摩尔%为1-8%。

这些优选的玻璃的特征性能为:应变点               840~900℃CTE                  20~40×10-7/℃杨氏模量             8.78×104MPaBHF中的耐久性        ~0.5mg/cm2重量损失在约为1650℃的温度熔制4.54千克(101b.)在所述优选组成内的坩埚料,时间不到20小时,获得了良好澄清的透明单相玻璃。

La2O3必须以上述的量加入,制得该熔体;且La2O3加上TiO2+Ta2O5(若有的话)的总量不能大于AL2O3的含量。

为了使应变点最大和CTE最小,必须存在TiO2和/或Ta2O5。

更适宜的是,La2O3对于TiO2+Ta2O5的含量之比要在1~4之间。

含TiO2玻璃的UV限的位置,由向组合物加入As2O3或CeO2来控制。

此氧化物可以减缓Ti+4较少变成Ti+3。

它们还会促进澄清作用,如同采用氯化物如AlCl3、AlF3和/或AlBr3代替要熔制的玻璃批料中的氧化物一样。

下表1中列出以氧化物的摩尔%表示的几种组合物,用来说明本发明。

表中也列出对生产的玻璃测得的特征性能。

表1 上述应变点稍微低于熔凝硅石或尖晶石玻璃陶瓷的应变点。

但是,它们均显著高于有供应的用常规方法熔制的玻璃,且对于其所用的用途已经足够了。

应变点虽然稍低,但是能使用常规的熔制和加工步骤,还有其它有益的性能,如与多晶硅相容的热膨胀和在玻璃液相线温度粘度合适,这些优点已可对其大大弥补。

例如,具有表1中实施例7组成的玻璃,除了应变点为882℃,CTE为22.7×10-7/℃外,还具有7000泊的液相线粘度。

已经观察到La2O3对TiO2的高比例可以提供下拉成形玻璃板过程中的玻璃稳定性。

例如,表1中实施例4的玻璃可以拉制成尺寸精确的厚壁玻璃管。

此拉制操作是在高于150℃,但低于玻璃液相线温度的温度进行的。

这种玻璃的管和棒也已在商业化的拉伸塔中拉制形成了高强度的纤维。

Claims(12) 1.一种应变点超过780℃,0~300℃的热膨胀系数为20~60×10-7/℃,杨氏模量大于12mpsi,在BHF中重量损失小于1mg/cm2的氧化钛-氧化镧-硅铝酸盐玻璃系列,其中氧化钛可以部分或全部用氧化钽代替,其中,以玻璃批料中氧化物的摩尔%表示的基本组成为40~90%SiO2、5~35%Al2O3、2~30%La2O3和0.5~20%(TiO2+Ta2O5)。

2.权利要求1所述的玻璃系列,其特征在于它还包含0~10%的ZrO2、HfO2、SnO2、GeO2和/或Ga2O3。

3.权利要求1所述的玻璃系列,其特征在于它还包含0~3%的Sb2O3、WO3、B2O3和/或P2O5。

4.权利要求1所述的玻璃系列,其特征在于它还包含0~10%的MgO、CaO、SrO、BaO和/或ZnO中的一种或多种。

5.权利要求1所述的玻璃系列,其特征在于它的基本组分为70~84%SiO2、6~18%Al2O3、2~15%La2O3和1~8%(TiO2+Ta2O5)。

6.权利要求5所述的玻璃系列,其特征在于它还含有含量小于3%的RO,其中RO为MgO、CaO、SrO、BaO和/或ZnO中的一种或多种。

7.权利要求5所述的玻璃系列,其特征在于它的应变点在840~900℃范围内,热膨胀系数在20~40×10-7/℃范围内。

8.一种含有在透明玻璃基底上的多晶硅薄膜的电子装置,所述基底是应变点超过780℃,热膨胀系数为20~60×10-7/℃、杨氏模量大于12mpsi,在BHF中重量损失小于1mg/cm2的氧化钛-氧化镧-硅铝酸盐玻璃,其中所述氧化钛可以部分或全部用氧化钽代替,其中所述基底玻璃以玻璃批料中氧化物的摩尔%表示的基本组成为40~90%SiO2、5~35%Al2O3、2~30%La2O3和0.5~20%(TiO2+Ta2O5)。

9.权利要求8所述的电子装置,其特征在于所述玻璃还含有0~10%的ZrO2、HfO2、SnO2、GeO2和/或Ga2O3。

10.权利要求8所述的电子装置,其特征在于所述玻璃还含有0~3%的Sb2O3、WO3、B2O3和/或P2O5。

11.权利要求8所述的电子装置,其特征在于所述基底玻璃还含有0~10%的MgO、CaO、SrO、BaO和/或ZnO中的一种或多种。

12.权利要求8所述的电子装置,其中所述基底玻璃的基本组分为70~84%SiO2、6~18%Al2O3、2~15%La2O3和1~8%(TiO2+Ta2O5)的氧化钛-氧化镧-硅铝酸盐玻璃,且它具有840~900℃范围的应变点和20~40×10-7/℃范围的热膨胀系数,所述氧化钛可以部分或全部用氧化钽代替。

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