CN1735711A - 二氧化钛的高速沉积 - Google Patents
二氧化钛的高速沉积 Download PDFInfo
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- CN1735711A CN1735711A CNA2003801084235A CN200380108423A CN1735711A CN 1735711 A CN1735711 A CN 1735711A CN A2003801084235 A CNA2003801084235 A CN A2003801084235A CN 200380108423 A CN200380108423 A CN 200380108423A CN 1735711 A CN1735711 A CN 1735711A
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- titanium oxide
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- plasma
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/44—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating
- C23C16/50—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges
- C23C16/513—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the method of coating using electric discharges using plasma jets
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
- C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
- C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
- C23C16/40—Oxides
- C23C16/405—Oxides of refractory metals or yttrium
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/26—Web or sheet containing structurally defined element or component, the element or component having a specified physical dimension
- Y10T428/263—Coating layer not in excess of 5 mils thick or equivalent
- Y10T428/264—Up to 3 mils
- Y10T428/265—1 mil or less
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31507—Of polycarbonate
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31855—Of addition polymer from unsaturated monomers
Abstract
本发明提供了一种结构，该结构包含一个衬底(12)和沉积在该衬底(12)上的氧化钛层(14)。本发明也提供了一种在衬底(12)上形成氧化钛涂层(14)的方法，该方法包括产生等离子体；往扩展到衬底(12)的等离子体流中提供含钛的第一反应剂和含氧的第二反应剂；以及在衬底(12)上形成氧化钛涂层(14)。
Description
发明背景
本发明主要涉及TiOx(氧化钛)或TiO2(二氧化钛)涂层或薄膜、含有该TiOx涂层的产品、制造这些涂层和产品的方法、以及制造该涂层和产品的设备。
TiO2有着广泛的应用。例如TiO2在玻璃和眼镜应用中作为紫外滤光器，在光学组件(stacle)中作为高折射率材料，以及作为光催化涂层使广告牌和灯具上的有机物降解。TiO2通常采用化学蒸气沉积法(CVD)在高温下沉积。但是，这些CVD技术不能用于低温衬底例如塑料或聚合物上，因为沉积温度将伤害衬底。
用通常的物理蒸气沉积(PVD)技术例如溅射和电子束蒸发法，已能将TiO2沉积在低温衬底例如一些塑料上。但是这些PVD技术的缺点是处理的速度非常低、通常是10-100埃/分钟。此外，这些TiO2涂层往往具有高的拉伸应力，因而限制了它们在需要厚的沉积层、多层叠合以及在薄的膜上沉积的应用，在此情况下应力将引起衬底翘曲。另外，这些涂层往往比较粗糙，在紫外光范围内每单位厚度的吸收性(A/t)低，其中A是吸收性，而t是厚度)。
近来，研究人员试图解决上述问题，方法是在有偏流或没有偏流的等离子体增强的化学蒸气沉积(PECVD)反应器中进行TiO2沉积。但是，这些PECVD方法并未克服经典PVD方法的局限性，仍然产生低速的高应力的TiO2涂层，其在紫外光范围内的(A/t)仍低。
发明概述
根据本发明的一个方面，提供了一种结构，包含：衬底；及沉积在衬底上的氧化钛层，其中氧化钛层用性能表征，其中该性能至少是下列性能中的一种：在光波长为330nm下每单位厚度的吸收性大于4/μm；在光波长为330nm下每单位厚度的吸收性大于4/μm，在65℃下该结构浸于蒸馏水中3天之后该吸收性降低不大于5％；以及在65℃下该结构浸于蒸馏水中3天之后雾度增加小于1％。
根据本发明的另一方面，提供了在衬底上形成氧化钛涂层的方法，该方法包括：用扩张热等离子体发生器产生等离子体流；往扩展到衬底的等离子体流中，提供含钛的第一反应剂和含氧的第二反应剂；及在衬底上形成氧化钛涂层。
根据本发明的又一方面，提供了形成氧化钛薄膜的设备，包括：含TiCl4的第一反应剂源；含水蒸气的第二反应剂源；等离子体流发生器；及衬底固定器。
附图简述
图1是根据本发明一个示例性实施方案涂有TiO2层的衬底的侧截面图。
图2是用于制造根据本发明一个示例性实施方案涂有TiO2层的衬底的设备侧截面图。
优选实施方案的详细描述
本发明已实现了扩张热等离子体(ETP)方法能在低温下沉积TiO2的同时维持高的沉积速度，并仍能提供高质量的具有良好透明度、折射率、紫外吸收性、气体/湿气屏障性和水解稳定性的涂层。
有TiO2 涂层的结构
图1说明一种结合有本发明一个实施方案的改进的TiOx涂层的结构10。该TiOx涂层可含有化学计量的TiO2涂料或非化学计量的TiOx涂料，式中x不等于2。该结构包括衬底12及沉积在衬底上的TiOx层14。结构10根据不同应用可任选包括沉积在衬底12和TiOx层14之间的中间层16。中间层16的作用可以作为衬底12与TiOx层14之间的粘合层以促进这些层之间的粘合，或者用来减少衬底12与上面的层(包括TiOx层14)之间的应力。中间层16可含有次层，其中一个次层的作用是降低衬底12与TiOx层14之间的应力，而另一次层的作用是促进衬底12与TiOx层14之间的粘合。或者，该中间层16可以同时提供粘合层的作用和减少应力的作用。结构10在TiOx层14上还可任选包括耐磨层18，以便保护TiOx层14不受到磨擦。该结构还可在TiO2层14和耐磨层18(如果有的话)之间包括红外反射层或导电层。该结构10可任选包括在层18上面的抗反射层。或者，该应力释放/减少层和TiOx层14可以重复多次以形成多层叠合物，它比单层TiOx屏障涂层具有优越的屏障功能。
衬底10可以是低温衬底。在这一应用中的低温衬底是指在稍高于150℃的温度下就可能被破坏的衬底。该衬底10也可以是高温衬底。在这一应用中的高温衬底是指不希望在稍高于250℃的温度下就被破坏的衬底。
该衬底可以包含例如聚合物树脂。例如，该衬底可以包含聚碳酸酯。适合形成衬底的聚碳酸酯在本技术领域是公知的。
芳族碳酸酯聚合物可以用本领域公知的方法来制备，例如在此作为参考文献引用的U.S.3,161,615；3,220,973；3,312,659；3,312,660；3,313,777；3,666,614；3,989,672；4,200,681；4,842,941；及4,210,699所述。
该衬底也可包含聚酯碳酸酯，该聚酯碳酸酯可由碳酸酯前体、二元酚和二羧酸或其形成酯的衍生物进行反应来制备。聚酯碳酸酯的例子被描述在例如美国专利4,454,275；5,510,448；4,194,038及5,463,013之中，这些专利在该全部作为参考文献引用。
该衬底还可以包含热塑性或热固性材料。适用热塑材料的例子包括聚乙烯、聚丙烯、聚苯乙烯、聚醋酸乙烯酯、聚乙烯醇、聚乙烯醇缩乙醛、聚甲基丙烯酸酯、聚丙烯酸类、聚醚、聚酯、聚碳酸酯、纤维素树脂、聚丙烯腈、聚酰胺、聚酰亚胺、聚氯乙烯、含氟树脂及聚砜。适用热固材料的例子包括环氧树脂及尿素三聚氰胺树脂。
本技术领域也公知的丙烯酸类聚合物是用以形成衬底的另一种材料。丙烯酸类聚合物可由单体例如丙烯酸甲酯、丙烯酸、甲基丙烯酸、甲基丙烯酸甲酯、甲基丙烯酸丁酯、甲基丙烯酸环己酯等等制得。取代的丙烯酸酯和甲基丙烯酸酯如丙烯酸羟乙酯、丙烯酸羟丁酯、丙烯酸2-乙基己酯、及丙烯酸正丁酯也可使用。
聚酯也可用来形成衬底。聚酯在本技术领域是公知的，可通过有机多元羧酸(例如邻苯二甲酸、六氢邻苯二甲酸、己二酸、马来酸、对苯二甲酸、间苯二甲酸、癸二酸、十二双酸等等)或它们的酸酐，与含有伯羟基或仲羟基的有机多元醇(如乙二醇、丁二醇、新戊二醇及环己烷二甲醇)发生聚酯反应而制得。
聚氨酯是另一类能用于形成衬底的材料。聚氨酯在本技术领域是公知的，由多异氰酸酯与多元醇反应而制得。有用的多异氰酸酯的例子包括六亚甲基二异氰酸酯、甲苯二异氰酸酯、MDI、异佛尔酮二异氰酸酯和缩二脲，以及这些二异氰酸酯的三异氰脲酸酯。有用的多元醇的例子包括低分子量脂族多元醇、聚酯多元醇、聚醚多元醇、脂肪醇等等。
能够用以形成衬底的其他材料的例子包括丙烯腈-丁二烯-苯乙烯、玻璃、VALOX(聚邻苯二甲酸丁二醇酯，Ceneral Electric Co.)，XENOY(LEXAN与VALOX的掺混物，General Electric Co.)等等。该衬底通常含有透亮的聚合物材料如PC、PPC、PES、PEI或丙烯类聚合物。
可以用通常方式来形成衬底，例如用注塑、挤出、冷成形、真空成形、吹塑、压塑、压铸、热成形、溶剂浇铸等等。制品或产品可以是任何形状，不必是商业上的精制品，即可以是片材或薄膜，这种片或膜可以切割或做成各种大小或用机械加工成形为精制品。这些衬底可以是透明的或不透明的。该衬底可以是刚性的或柔性的。
该衬底可以是例如运输工具的窗，如车窗、卡车窗、摩托车窗、拖拉机窗或飞机窗。该衬底也可以包括眼镜镜片、光学多层叠合物(stack)、显示屏，或显示屏的元件如电视屏、LCD屏、计算机显示器、等离子体显示屏或计算机显示器的强光保护屏(glare guand)。
该衬底优选是聚合物衬底，通常是一种低温衬底。
TiO2层优选用下面更详细讨论的扩张热等离子体法(ETP)制造。ETP法例如等离子体电弧沉积和几种进行ETP的体系，都是公知的，例如在U.S.6,420,032中作了描述，该专利这里作为参考文献引用。TiOx层14具有紫外吸收性能，其厚度典型地为10～10,000nm。
中间层在衬底12与顶层之间可以起释放应力的作用。例如，由于不同的热膨胀系数、不同的展延性、和不同的弹性模量，衬底12与放在上面的这些层之间可产生应力。优选的是，中间层含有一种材料，其热膨胀系数、展延性、和弹性模量介于衬底和放在上面的这些层的相应值之间。合适中间层材料的一个例子是等离子聚合的有机硅，如在申请号为09/271654，题目为“多层制品及用等离子体电弧沉积法制造该制品的方法”的申请中所描述的，其在此作为参考文献引用。
耐磨层18防止TiOx层14在使用过程中被刮伤。耐磨层18可含有任何耐刮或耐磨材料及对紫外线稳定的材料。例如耐磨层18可含有如在美国申请序号09/271654中所描述的等离子体聚合的有机硅材料。该有机层材料可含有例如八甲基环四硅氧烷(D4)、四甲基二硅氧烷(TMDSO)、六甲基二硅氧烷(HMDSO)或其他有机硅，如在上面申请中描述过的。这些有机硅的单体在电弧等离子体法沉积设备中被氧化、沉积及聚合，形成含有例如氧化的D4、TMDSO或HMDSO的耐磨层。该耐磨层可以称为SiOx层。但是，SiOx层也可含有氢和碳原子，在这一情况下，它通常称为SiOxCyHz。适合用作耐磨材料的化合物和材料包括例如二氧化硅和氧化铝。
沉积体系
形成TiOx层14的体系优选是在U.S.6,420,032中描述过的ETP体系。图2解释了形成本发明实施方案的TiOx层14的合适体系100的例子。图2的体系与U.S.6,420,032的图4体系相似。但是，图中仅示出两条反应剂供应管线，而该体系可以具有多于两个反应剂供应管线，其他合适ETP体系公开在标题为“采用多级扩张热等离子体发生器进行大面积化学蒸气沉积的设备”的U.S.6,397,776中，以及序号为09/683148，09/683149及10/064888的美国专利申请中，这些在该均作为参考文献引用。后面公开的这两篇解释了各个特征，例如多个注射环、一个环绕若干个电弧的环、和/或可调节从阴极到阳极的距离。它们在一些应用中可能是优选的。
体系100包括等离子体发生室110和沉积室111。沉积室111包括固定在控温支撑122上的衬底120。衬底120可以是透明玻璃或聚合物衬底，涂有中间层16，如图1所示。沉积室111也可包括供放入或取出衬底120的门(未示出)，和供连接到泵的出口123。支撑122可以位于沉积室111的空间中的任何位置。衬底120的位置可以是与等离子体发生器的阳极119的相距为10-50cm，通常为约25.5cm。
沉积室111还任选包括可收缩挡板124。该挡板例如可用把手125或计算机控制的定位器来定位。该挡板124还可包括环状小孔以控制从等离子体发生室110向衬底120发出的等离子体直径。沉积室111还可任选的包括邻接于室壁的磁体或磁场产生线圈(未示出)以指引等离子体流的方向。
沉积室111还可包括任选的喷嘴118。喷嘴118对沉积在衬底120上的反应剂的注入、离子化和反应提供良好的控制。喷嘴118使材料例如TiOx层在衬底120上产生沉积，并减少甚至防止在衬底120上产生粉末状反应剂沉积。优选的是，喷嘴118如果采用的话，是呈锥形，扩张角为约40度，长度约为10-80cm，优选为约16cm。但是，喷嘴118也可具有可变的截面，例如圆锥-圆筒-圆锥形，或圆锥-圆筒形。此外，喷嘴118的扩张角可以不是40度，长度可以不是16cm。喷嘴也可以全部没有。
沉积室111还包括至少一条反应剂供应管线。反应剂供应管线的数目可以例如是两条或多条。例如，沉积室111可含有第一反应剂供应管线112和第二反应剂供应管线114，以便使TiOx层的薄膜沉积在衬底120上。供应管线112和114优选与喷嘴118相连，并通过该喷嘴将反应剂供入等离子体流中。沉积室111通常包括真空泵(未示出)将使沉积室111抽成真空。
等离子体发生室110包括至少一个阴极113。等离子气体供应管线117及阳极119。等离子体发生室110典型地包括三个阴极113。阴极113可以包括例如钨或掺杂钨的钍尖状物。使用钍能使尖状物温度维持在低于钨的熔点，因而避免等离子体被钨原子污染。
等离子体发生室110通常包括至少一条等离子气体供应管线117。等离子体发生室110还可包括邻接载气供应管线117的供应吹扫气体的管线，以便在送入等离子气体之前将吹扫气体送至室110和111。
为了在等离子体发生室110形成等离子体，通过等离子气体供应管线117送入等离子气体。该等离子气体含有惰性气体(如氩气或氦气)或反应性气体(如氮气、氨气、二氧化碳气或氢气或它们的混合物)。如果需要有多于一种等离子气体，那么可通过多个供应管线送入多种气体。优选的是，为进行TiOx沉积，该等离子气体含有氩气。将在等离子体发生室110中的等离子气体维持在比沉积室111更高的压力之下，而该气体被泵连续抽空。然后在阴极113与阳极119之间施以电弧电压以便在等离子体产生室110中产生等离子体。随后，由于室110与111之间的压力差，等离子体通过阳极119的小孔，扩展进入沉积室111。通过供应管线112和114把反应剂供入等离子体中。
形成TiOx 涂层的方法
现在描述本发明实施方案在衬底上形成TiOx涂层的方法。该衬底可包括例如在聚碳酸酯上形成了中间层的聚碳酸酯低温衬底。在图2的体系100的沉积室111中提供衬底。使用从等离子气体供应管线117送入的等离子气体，产生等离子体。
然后通过供应管线将第一和第二反应剂送入到等离子体中。第一反应剂含有钛而第二反应剂含有氧，优选的是，第一反应剂含有TiCl4而第二反应剂含有水蒸气。第一和第二反应剂反应，在衬底上形成TiOx薄膜。
对含TiCl4的第一反应剂及含水的第二反应剂来说，沉积的优选范围为10～1000nm，更优选为200～600nm，优选的反应剂流速范围TiCl4为0.1～1slm，水为0.4～4slm。优选的电能范围为20～3000W直流电，1～100安培，20～30伏。在大于1微米/分钟的速度下能沉积高质量的TiOx薄膜。
实施例
将聚碳酸酯做成一个衬底。在该聚碳酸酯上直接形成TiOx层。在聚碳酸酯上的全部沉积物包括一个V-D4层，该层是在20安培、1.65lpm Ar和0.03lpmV-D4以2.3cm/秒通过Etp扫描下沉积的。第一反应剂是TiCl4。第二反应剂是水蒸气，氩被用作等离子气体。室压力为45mT(毫乇)。沉积参数示于表1中。表1中的全部实施例都是ETP沉积，实施例6除外。
作为另一实施例，采用Ar ETP，以异丙醇钛作为第一反应剂，以水蒸气作为第二反应剂而形成TiOx层。沉积条件示于表1中。
作为又一实施例，采用Ar ETP，以乙醇钛作为第一反应剂，以水蒸气作为第二反应剂。沉积条件示于表1中。
表1
| # | 来源 | lpm | Arlpm | Oxlpm | H2Olpm | Amp | 吸收性 | 厚度(nm) | 雾度 | A/t(/μm) | 变化AWS(％) |
| 1 | TiCl4 | 0.2 | 1.65 | 0.8 | 80 | 1.1 | 186 | 0.6 | 5.9 | 0 | |
| 2 | 异丙醇盐 | 0.4 | 1.65 | 2.0 | 80 | 0.74 | 300 | 19 | 2.5 | 20 | |
| 3 | 异丙醇盐 | 0.3 | 2.0 | 6.0 | 70 | 0.30 | 80 | 0.5 | 3.76 | NA | |
| 4 | 异丙醇盐 | 0.3 | 2 | 2.5 | 80 | 0.89 | 558 | 1.5 | 1.6 | 5 | |
| 5 | 乙醇盐 | 0.3 | 2 | 2.5 | 90 | 0.75 | 500 | 2.2 | 1.5 | NA | |
| 6 | 异丙醇盐* | * | * | * | * | 0.78 | 506 | 11 | 1.5 | 分层 | |
| 7 | TiCl4 | 0.6 | 5 | 2.4 | 90 | 1.65 | 319 | 0.8 | 5.2 | 0 |
在室压力为45mT下制备1至7的样品，除样品6之外，其他样品的沉积时间为～7秒。样品6是对比用的PECVD，使用100sccm的N2O，5sccm的TiPT，在100mT压力和200W电力下沉积14分钟。在水浸湿处理下该PECVD膜分层。
表1列出了源气体TiCl4、异丙醇钛及乙醇钛的流速，氩气(Ar)、氧气(Ox)、水(H2O)的流速。表1也列出了电流(Amp)、吸收性(Abs)、厚度(nm)、雾度以及每单位厚度的吸收性(A/t)。
为进行水浸湿处理，将样品在65℃下浸没在蒸馏水中3天，并测定分层面积的大小和吸收性能的变化。变化A WS(％)这栏表示，在水浸湿处理后在320nm处吸收的变化百分数。正如从表1能看到的，仅仅用源气体TiCl4形成的薄膜在水浸湿处理后不改变吸收性。
采用异丙醇盐形成的样品，与采用TiCl4形成的那些样品相比是相对雾化了并且吸收性较低，除非氧气流速(对异丙醇盐形成的薄膜而言)相对于水流速(对TiCl4形成的薄膜而言)有实质性的提高。在水流速较低时，TiCl4形成的膜的吸收性能和厚度也更好。如从表1可看到的，TiCl4形成的膜的性能相对于乙醇盐形成的膜，也提高了。
表2显示许多用TiCl4形成的氧化钛薄膜的样品，其中该氧化钛簿膜是多层簿膜包装物的一部分，并且多层包装物是经过水浸渍处理的。
表2
| # | 温度 | Arlpm | H2Olpm | 安培 | 分层面积％ | 变化AWS％ |
| 8 | 75 | 1.65 | 1.8 | 80 | 30 | 60 |
| 9 | 100 | 1.65 | 1.8 | 80 | 35 | 40 |
| 10 | 120 | 1.65 | 1.8 | 80 | 35 | 5 |
| 11 | 130 | 1.65 | 1.8 | 80 | 30 | 0 |
| 12 | 120 | 2 | 1.8 | 80 | 10 | 2 |
| 13 | 120 | 3 | 1.8 | 80 | 5 | 0 |
| 14 | 120 | 3 | 0.8 | 80 | 0 | 0 |
| 15 | PECVD | 50％ |
在表2中，全部样品均按下述制备，表中另有指出的除外。将聚碳酸酯衬底在IPA中清洗，漂洗，在80℃下干燥过夜。全部的沉积和腐蚀均在45mT的压力下在下列条件下用ETP进行。把样品预热至不同温度以获得表2中所示的沉积温度(Tlmp)。在沉积参数20A、1.65lpm Ar，0.03lpm V-D4之下沉积中间层。将该中间层在40A、1.65lpmAr、0.3lpm氧气中腐蚀。在80A、0.2lpm TiCl4、使用不同量的Ar和水沉淀氧化钛。该氧化钛层在40A、1.65lpm Ar、0.3lpm氧气中腐蚀。然后沉积出含有5个耐磨层的耐磨层，条件是，在层1～5中分别使用氧气0.2，0.4，0.6和0.8lpm。将这些样品在65℃下浸在蒸馏水中3天，并测量分层面积大小和吸收性能的改变。一些样品被水浸湿处理时显示许多圆形缺陷，在扫描电子显微镜(SEM)分析中可以看到。正如从表2中所示的，在较高Ar流速下制备的样品，分层最少。
此外，用TiCl4和水形成的薄膜中氧化钛层密度高的程度和孔隙度低的程度，足以使氧气和水蒸气渗透通过涂聚碳酸酯膜的衬底的速度在室温下在100％O2中明显低于10cc/m2/日。
正如从表1和表2能看到的，氧化钛薄膜本身(表1)和结合有氧化钛薄膜的多层包装物，在使用TiCl4和水作为反应剂气体的情况下，在进行水浸渍处理时，均显示良好的分层性和小的吸收性变化。
尽管已参考具体的实施方案对本发明作了详细的描述，但本领域技术人员应该明白，各种不偏离本发明的构思和范围的改变和改进都是可以做的。因此，本发明的范围不应受上述所举出的任一实施方案的限制，而应当根据所附权利要求和它们的等同物来确定。
Claims (10)
1.一种结构，包含：
衬底(12)；和
沉积在衬底(12)上的氧化钛层(14)，其中氧化钛层(14)用性能表征，其中该性能至少是下列性能中的一种：在光波长为330nm下每单位厚度的吸收性大于4/μm；在光波长为330nm下每单位厚度的吸收性大于4/μm，在65℃下该结构在蒸馏水中浸3天之后该吸收性降低不大于5％；以及该结构在65℃下浸于蒸馏水中3天之后雾度增加小于1％。
2.权利要求1的结构，还包含：
在氧化钛层(14)之上形成交替的中间层(16)和氧化钛层(14)的重叠层。
3.权利要求1的结构，其中该衬底(12)含有聚合物。
4.权利要求1的结构，其中氧化钛层(14)是用扩张热等离子体技术沉积的。
5.权利要求1的结构，其中衬底(12)是聚碳酸酯，在室温下在100％O2中氧气通过聚碳酸酯膜的渗透速度小于10cc/m2/日。
6.权利要求1的结构，其中在该结构于65℃下浸于蒸馏水中3天之后氧化钛层(14)的雾度的增加小于1％。
7.在衬底(12)上形成氧化钛涂层(14)的方法，该方法包括：
用扩张热等离子体发生器产生等离子体流；
往扩展到衬底的等离子体流中，提供含钛的第一反应剂和含氧的第二反应剂；及
在衬底(12)上形成氧化钛涂层(14)。
8.权利要求7的方法，其中第一反应剂含有TiCl4，而第二反应剂含有水蒸气。
9.权利要求7的方法，其中氧化钛层(14)在光波长330nm下每单位厚度的吸收性大于4/μm，在65℃下该结构浸于蒸馏水中3天之后该吸收性降低不大于5％。
10.形成氧化钛膜(14)的设备，它包括
含TiCl4的第一反应剂源；
含水蒸气的第二反应剂源；
等离子体流发生器；及
衬底固定器。
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| US10/248,152 | 2002-12-20 | ||
| US10/248,152 US6890656B2 (en) | 2002-12-20 | 2002-12-20 | High rate deposition of titanium dioxide |
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| EP (1) | EP1579026A1 (zh) |
| JP (1) | JP2006511714A (zh) |
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| CN105296965A (zh) * | 2004-03-09 | 2016-02-03 | 埃克阿泰克有限责任公司 | 膨胀式热等离子沉积系统 |
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| US20040121164A1 (en) | 2004-06-24 |
| EP1579026A1 (en) | 2005-09-28 |
| US6890656B2 (en) | 2005-05-10 |
| JP2006511714A (ja) | 2006-04-06 |
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