CN1515701A - 耐久的溅射金属氧化物镀层 - Google Patents

耐久的溅射金属氧化物镀层 Download PDF

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CN1515701A
CN1515701A CNA031220347A CN03122034A CN1515701A CN 1515701 A CN1515701 A CN 1515701A CN A031220347 A CNA031220347 A CN A031220347A CN 03122034 A CN03122034 A CN 03122034A CN 1515701 A CN1515701 A CN 1515701A
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J・J・芬利
J·J·芬利
筒�
M·阿巴博
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Abstract

本发明公开了一种方法和由该方法制得的产品，其中通过在包含惰性气体和一种活性气体但基本上是非活性的气氛中溅射金属阴极靶而沉积金属薄膜，其中活性气体的浓度足够低，使得溅射是在金属方式下完成的，即薄膜是以金属态沉积的。本发明的金属薄膜比在仅由惰性气体组成的气氛中溅射的金属薄膜硬度要高。本方法及由该方法制得的产品还可包括对该金属薄膜进行热氧化，它比在仅由惰性气体组成的气氛中溅射的金属薄膜的氧化更有效。

Description

耐久的溅射金属氧化物镀层
本申请为分案申请，其母案申请的申请日为1994年11月11日，申请号为94117931.1，名称为“耐久的溅射金属氧化物镀层。”
本发明普通涉及溅射薄膜的技术，特别是用磁控溅射制备耐久的金属氧化物薄膜的技术。
溅射的金属氧化物薄膜在现有技术中是众所周知的。已知道氧化锡、氧化锌、氧化钛和许多其它的金属氧化物是通过相应的金属在氧化气氛例如空气或氧气和惰性气体(如氩气)的混合气体中溅射而沉积的。还知道金属薄膜可以通过在惰性气体(如氩气)中溅射金属来沉积。而且金属薄膜接着通过在一种氧化气氛(如空气)中被加热而热氧化。
许多金属可以沉积为金属薄膜或金属氧化物薄膜，这取决于金属阴极靶是在惰性气氛还是在氧化气氛中溅射的。通常，在惰性气氛中溅射(即以金属方式)要快并且效率更高。得到的镀层是具有金属性质的金属薄膜，即通常有低的透射率、高的反射率和电导性。这样的薄膜通常不是很硬也不耐久，在使用时容易损坏。而介电的金属氧化物薄膜通常具有高的透射率、低的反射率和电绝缘性。然而，因为它们是绝缘的，它们通过溅射而沉积的效率并不高。通过溅射制备很厚的金属氧化物薄膜效率不高，费用大并且不能获得耐久的薄膜。通过在惰性气氛中高效溅射获得的金属薄膜的热氧化来制备很厚的金属氧化物薄膜，其速率本身就受到限制，因为氧不容易透过最初形成的金属氧化物表层。
本发明涉及一种在足够惰性的气氛下溅射金属靶的方法，使得溅射是以金属方式进行的并且沉积的薄膜基本上是金属状态。然而，在气体中还加入了足够的活性气体使得金属薄膜呈非晶态而不是晶态。非晶态的溅射金属薄膜比在只由惰性气体组成的气体中溅射的金属薄膜硬度高并且耐久性好。非晶态的溅射金属薄膜比在只由惰性气体组成的气体中沉积的金属薄膜可以更有效地进行热氧化，结果获得一种晶态的金属氧化物薄膜，这样的晶态金属氧化物薄膜比在氧化气氛中溅射金属沉积的非晶态金属氧化物薄膜具有更高的化学稳定性。
图1图示了使用AIRCO ILS-1600实验室规格的镀膜机以金属方式溅射钛时允许的惰性气体中氧的最大百分含量和以千瓦(Kw)表示的功率的函数关系。
图2图示了使用AIRCO ILS-1600实验室规格的镀膜机以金属方式溅射锆时允许的惰性气体中氧的最大百分含量和功率(以Kw表示)的函数关系。
图3图示了使用AIRCO ILS-1600实验室规格的镀膜机分别在功率为1Kw、2Kw、3Kw和4Kw下溅射钛时电压与惰性气体中氧的百分含量的函数关系。每条曲线上的峰值是导致溅射方式从金属状态到氧化物状态转变的转变点的氧的含量。
金属如钛、锆、钽、铪、铌、钒和它们的混合物，最好是钛和锆，根据本发明通过在基本上包含惰性气体的但也含少量活性气体，例如氧气和/或氮气，最好是氧气的非活性气氛中溅射金属，可以以基本上非晶的金属状态沉积，其中氧气的含量足够影响金属的沉积使其形成的基本上非晶态而不是晶态，但不够使溅射从金属方式转变为氧化物方式。为达到本发明目的的惰性气氛中氧的合适的含量与阴极工作参数有关，特别是功率和靶的尺寸。
图1和图2分别表示了在AIRCO ILS-1600实验室规格镀膜机上用钛靶和锆靶在不同功率下于氩气氛中溅射时允许的最大氧气含量。当氧气浓度较高时，溅射方式会发生从金属到氧化物的转变。结果会产生非晶的金属氧化物的缓慢沉积。因此，氧气浓度保持足够低以避免沉积金属氧化物。然而，已经发现在低于转变点的情况下，氧气浓度越高，以金属溅射方式沉积的非晶态金属薄膜的硬度越高。
图3表示了使用AIRCO ILS-1600实验室规格镀膜机在功率从1Kw到4Kw时沉积钛薄膜时电压与氧气浓度的函数关系。每条曲线的电压峰值表示溅射方式从金属到氧化物的转变点，并表示使用这种镀膜装置在特定的功率下的最大氧气浓度。最好是在峰值附近工作，即为了获得最大金属硬度，在相对较高的氧气浓度下工作，但又不致于使溅射方式发生从金属溅射方式到氧化物溅射方式的转变。
在含氧但基本上是非活性的气氛中溅射的非晶态金属薄膜的透射率比在纯氩气中溅射的金属薄膜的透射率稍高一些；并且溅射速率大致相同。然而，在含氧但基本上是非活性气氛中溅射的非晶态金属镀膜比在纯氩气中溅射的晶态金属薄膜明显硬度高而且密度小。
这样的金属薄膜的相对硬度是通过在薄膜经研磨后用目测检验并在薄膜损坏的基础上分级而确定的。一种评价金属薄膜的硬度的方法包括用一块研磨垫(abrasive pad)(Scotch-BriteR 98 LightDuty Cleaning Pad from 3M)反复研磨金属薄膜，然后在一块光板上目测检验并把薄膜损坏程度按1到9分级，1代表不明显的损坏而9表示金属薄膜基本上清除了。
在包含惰性气体和10％氧气的基本上非活性的气氛中溅射的非晶态金属钛薄膜的密度是4.0克/立方厘米(g/cm3)，与之相比在纯氩气中溅射金属钛薄膜的密度为4.5g/cm3。非晶态金属钛薄膜的较低的密度加快了它的氧化速率，所以非晶态金属钛薄膜与晶态金属钛薄膜相比可以在较低温度和/或在较短时间内完全氧化。
本发明所制备的硬的、致密的非晶态金属镀层，最好是在100-1500埃的厚度范围内，对钛来说更好是在200-1000埃的厚度范围内，具有足够的耐久性以经受装卸、运输和加工过程，例如热增强、回火和弯曲。最好是进一步通过热氧化处理本发明的非晶态金属薄膜使金属氧化成金属氧化物。本发明的硬的非晶态金属薄膜通过加热可以热氧化为金属氧化物从而制得一种无霾的(haze-free)、致密的、基本上是晶态的金属氧化物镀层，这层镀层具有足够的化学和物理耐久性可以用来作为玻璃基片外露表面的涂层。非晶态金属薄膜最好在空气中加热到至少400℃的温度，更好是在500-700℃，以便能在合理时间内(例如几分钟)完全氧化。本发明通过加热一种非晶态溅射金属膜来制备厚的金属氧化物薄膜的方法与活性溅射同样的薄膜相比是一种生产晶态金属氧化物薄膜的更有效的方法。此外，热氧化的晶态金属氧化物薄膜比活性溅射的基本上是非晶态的金属氧化物薄膜具有更好的化学耐久性。这样的晶态热氧化金属氧化物薄膜可以在很大范围制成不同厚度以获得由干涉作用引起的很大范围内所要求的反射颜色。
二氧化钛镀层的密度是通过测得的镀层厚度和完全氧化的二氧化钛中钛的重量百分含量来确定的。厚度是用一台Tencor P-1Long scan Profiler来测量的，钛的重量百分含量是用X射线荧光分析来测定的。热氧化的晶态钛镀层的密度比活性溅射的非晶态二氧化钛镀层密度要大；热氧化的晶态二氧化钛镀层的密度为4.0克/立方厘米(g/cm3)而非晶态的溅射二氧化钛的密度为3.4g/cm3。热氧化的晶态二氧化钛镀层的密度接近金红石相的二氧化钛(TiO2)的体积密度4.26g/cm3。
一种活性溅射的非晶态的二氧化钛薄膜的折射率为2.3(600nm)，而由在包含氩气和10％氧气的基本上是非活性气氛中溅射的非晶态金属钛薄膜热氧化而形成的晶态二氧化钛薄膜的折射率为2.5(600nm)，接近大块晶体二氧化钛(TiO2)的金红石相的折射率。
在本发明的一个最佳实施方案中，镀膜是在大规格的磁控溅射装置中形成的，这种装置可以对2.54×3.66m的玻璃块进行镀膜。使用商业化生产规模的镀膜机，与小规格的镀膜机相比，允许的活性气体的含量可以很高而不会引起偏离金属溅射方式的转变，特别是如果多个阴极在一个室内同时以高的功率密度溅射的情况。
在下面的实施例中，镀层是小规模沉积的，使用的平板磁控阴极为127mm×432mm的靶。本底压强在10-6Torr量级。镀层是在溅射气压达到4.0×10-3Torr时，再给阴极施加功率而形成的。在每个实施例中，玻璃基板借助传送辊以每分钟3.05米的速度通过靶的下方。透射率是在550nm波长下，使用Dyn-Optic 580D光学监测器在溅射过程中玻璃基板每隔一次通过靶后测定一次而监测的。在镀层沉积完成后，使用Dacific Scientific Spectrogard Color System分光光度计在380nm-720nm波长范围内，测定了其透射率和从玻璃及从镀层两个表面的反射率。
在本发明的大多数实施例中，在含有足够活性气体但基本上是非活性的气氛中(不足以导致溅射从金属方式转变为氧化物方式)溅射沉积比晶态金属薄膜硬度高、密度小的非晶态金属薄膜，在此基础上又在活性气氛中溅射一层薄的非晶态金属氧化物镀层。这层活性溅射的非晶态金属氧化物增加了在包含惰性气体和足够活性气体的基本上是非活性的气氛中(不足以导致溅射方式从金属方式转变为氧化物方式)溅射沉积的非晶态金属薄膜在热氧化过程中的热稳定性。溅射的非晶态金属氧化物层最好包含底层非晶态金属层中同样的金属。这层非晶态金属氧化物层的厚度最好是在40埃-120埃的范围内。
底层非晶态金属层的厚度在热氧化之前最好在200-1000埃的范围内，以在金属氧化物薄膜中产生很宽范围的色品度。在基本上是非活性的气氛中活性气体的含量根据被溅射的金属类型、靶的尺寸和几何形状、阴极的数量和功率水平等可以大不相同。在任何情况下其含量上限应该低于溅射方式从金属方式到氧化物方式的转变点。为了获得非晶态金属薄膜的理想硬度，最好选择接近这个上限但同时还保持溅射是金属方式的位置工作。当溅射钛时氧气含量为2％-30％、优选的氧含量为5％-25％。
从下面对实施例的详细描述中，本发明将得到进一步的理解。
实施例1
一块6mm厚的透明玻璃基板如下述被镀上了一层钛镀层。一个钛阴极靶在含2.5％氧气的氩气中被溅射。本底压强为2×10-6Torr，工作压强为4.0×10-3Torr。功率设置为3.0千瓦(Kw)，电压为381伏(V)，电流是7.8安培，玻璃基板的线速度是每分钟3.05米。溅射一次之后，透射率是19.1％，溅射三次以后透射率为2.0％，溅射四次以后透射率为0。钛薄膜的电阻是41.9欧姆/方块。镀层表面用研磨垫(Scotch-Brite from 3M)擦拭，并将镀层基片置于一块光板上用目测检验。透射率为7级而反射率为5级。
实施例2
一块玻璃基板如实施例1一样被镀膜，只是氩气中的氧气含量为5％，工作电压为385V而电流为7.7A。经过一次镀膜透射率为21.0％，经过三次镀膜透射率为2.6％，经过四次镀膜以后透射率小于1％，钛薄膜电阻为48欧姆/方块。研磨以后镀层表面的透射率为5级而反射率为4级。
实施例3
一块玻璃基板如实施例1和实施例2一样被镀膜，只是氩气中氧气的含量为10％，工作电压为393V，电流为7.6A。经过一次镀膜透射率为26.4％，经过三次镀膜透射率为6.0％，经过四次镀膜透射率为2.0％。钛薄膜的电阻是82欧姆/方块。研磨后镀层表面的透射率和反射率都是2级。
实施例4
一块玻璃基板如前面的实施例一样被镀膜，只是气体中含15％的氧气，工作电压为432V而电流为6.9A。经过一次镀膜透射率为57.0％，经过三次镀膜透射率为21.0％，经过四次镀膜透射率为13.6％。钛薄膜的电阻为330欧姆/方块。研磨后镀层表面的透射率和反射率都是1级。透射率和电阻的增加表明氧气的浓度已接近以金属方式溅射的最大值，然而薄膜仍然是金属性的，因为它的电阻与二氧化钛的电阻相比仍然很小，二氧化钛的电阻无穷大，即二氧化钛是绝缘材料。
对比实施例A
一块玻璃基板如前述实施例一样被镀膜，只是气体为纯氩气，工作电压为387V而电流为7.85A。经过一次镀膜以后透射率为18.0％，经过三次镀膜以后透射率为1.8％，经过四次镀膜以后透射率为0。薄膜的电阻是24欧姆/方块。研磨后镀层表面的透射率和反射率都是9级。
实施例5
一块4mm厚的浅色玻璃基板(PPG工业公司的SOLEXR玻璃)如下面所述被镀上了钛和二氧化钛镀层。第一层镀层是在含10％氧气的氩气中溅射平面钛阴极而制备的。本底压强为7.0×10-6Torr，工作压强为4.0×10-3Torr，工率设置为3.4千瓦，电压为399伏，电流为8.42安培，玻璃的线速度为每分钟3.05米。经过四次镀膜以后，透射率为1.4％。钛镀层厚度为599埃。在这层以后，又置于50/50的氩气/氧气混合气体中进行活性溅射钛的沉积。功率设置为5.0千瓦，电压为470伏特，电流为10.57安培并且玻璃基板的线速度为每分钟3.05米。经过6次溅射后，最终的透射率为2.0％。活性溅射的二氧化钛镀层厚度为76埃。两层镀层加热4分钟到650℃，制得了厚度为1062埃的单一的均匀二氧化钛镀层。镀层产品的光学性质通过分析列于实施例后面的表中。
实施例6
一块6mm厚的透明玻璃基板通过下述方法镀上一层钛镀层。通过在含10％氧气的氩气混合气中溅射平板钛阴板制得一层镀层。本底压强为5.9×10-6Torr，工作压强为4.0×10-3Torr，功率设置为3.4千瓦，电压为398伏特，电流为8.45安培，玻璃板的线速度为每分钟3.05米。经过六次镀膜后透射率为0。镀层厚度为893埃。镀层然后被加热6.5分钟到637℃制得厚度为1469埃的氧化物镀层。其光学性质列于实施例后的表中。
实施例7
一块6mm厚的透明玻璃基板通过下述方法镀上一层钛镀层。通过在含10％氧气的氩气混合气中溅射平板钛阴极制得一层镀层。本底压强为5.0×10-6Torr，工作压强为4.0×10-3Torr，功率设置为3.4千瓦，电压为398伏特，电流为8.45安培，玻璃基板的线速度为每分钟3.05米。经过5次镀膜后透射率为0.5％。镀层厚度为742埃。镀层然后被加热6.5分钟到637℃，制得厚度为1220埃的氧化物镀层。其光学性质列于实施例后的表中。
实施例8
一块6mm厚的透明玻璃基板通过下述方法镀上一层钛镀层。通过在含10％氧气的氩气混合气中溅射平板钛阴板制得一层镀层。本底压强为3.9×10-6Torr，工作压强为4.0×10-3Torr，功率设置为3.4千瓦，电压为398伏特，电流为8.45安培，玻璃基板的线速度为每分钟3.05米。经过4次镀膜后透射率为1.6％。镀层厚度为599埃。镀层然后被加热6.5分钟到637℃制得厚度为986埃的氧化物镀层。其光学性质列于实施例后的表中。
实施例9
一块6mm厚的透明玻璃基板通过下述方法镀上一层钛镀层。通过在含10％氧气的氩气混合气中溅射平板钛阴极制得一层镀层。本底压强为5.9×10-6Torr，工作压强为4.0×10-3Torr，功率设置为3.4千瓦，电压为398伏特，电流为8.45安培，玻璃基板的线速度为每分钟3.05米。经过3次镀膜透射率为3.9％。镀层厚度为447埃。镀层然后被加热6.5分钟到637℃，制得厚度为735埃的氧化物镀层。其光学性质列于实施例后的表中。
实施例10
一块6mm厚的透明玻璃基板通过下述方法镀上一层钛镀层。通过在含10％氧气的氩气混合气中溅射平板钛阴板制得一层镀层。本底压强为5.2×10-6Torr，工作压强为4.0×10-3Torr，功率设置为3.4千瓦，电压为398伏特，电流为8.45安培，玻璃基板的线速度为每分钟3.05米。经过2次镀膜后透射率为8.9％。镀层厚度为301埃。镀层然后被加热6.5分钟到637℃制得厚度为495埃的氧化物镀层。其光学性质列于实施例后的表中。
实施例11
一块4mm厚的浅色玻璃基板(PPG工业公司的SOLEXR玻璃)通过下述方法镀上一层钛镀层。通过在含10％氧气的氩气混合气中溅射平板钛阴极制得一层镀层。本底压强为7.0×10-3Torr，工作压强为4.0×10-3Torr，功率设置为3.4千瓦，电压为400伏特，电流为8.4安培，玻璃基板的线速度为每分钟3.05米。经过4次镀膜透射率为1.5％。镀层厚度为599埃。镀层然后被加热4分钟到650℃，制得厚度为986埃的氧化物镀层。其光学性质列于实施例后的表中。                               表
  实施例             透射率*                          反射率*
         薄膜面             玻璃面
    #567891011       Y      x      y74.46  .3102  .364665.71  .3444  .337382.90  .3451  .379279.31  .2968  .337460.37  .2897  .302256.63  .3205  .337472.15  .2925  .3398   Y      x      y12.25  .3038  .215230.43  .2418  .318213.23  .2056  .183317.33  .3733  .307236.54  .3574  .391440.09  .2985  .320517.51  .3794  .3165     Y      x       y10.34  .3032   .228628.94  .2412   .320912.82  .2074   .188416.37  .3679   .310534.31  .3502   .392237.76  .2940   .322414.73  .3652   .3264
★C.I.E.色度座标(1931 2度观察器，照明剂D-65)
上述给出的实施例用来说明本发明。其它的金属例如锆、钽、钒、铪和铌也可以在含有活性气体但基本上还是非活性的气氛中溅射。其它活性气体例如氮气也可以用来代替氧气或作为氧气的补充。活性气体的含量保持足够低使得溅射方式基本上是金属性的，并且沉积的金属基本上是金属性的。为了获得金属薄膜的最优硬度，活性气体在惰性气体中的含量最好高一些但仍然维持一种基本上是非活性的气氛，即以金属方式溅射。当活性气体是氧气时，最小含量应足够形成非晶态金属的沉积，通常至少约为2％，而且为了使热氧化以较高速率进行，应优选较高的含量，至少大约10％。金属性薄膜的热氧化可以在足够氧化金属而又不破坏薄膜的完整性的温度范围内进行。典型地，选择至少400℃的温度以便在合理时间里(例如几分钟)完全氧化金属。薄膜的厚度可以在很大范围里变化以便获得要求的性质，特别是在反射中的干涉颜色效果。本发明的范围在下面的权利要求书中得到定义。

Claims (31)

1.一种镀膜产品，包括：
基板；
金属阴极靶溅射膜，该膜是在包含惰性气体和活性气体的气氛中，由金属阴极靶溅射形成的，所述金属阴极靶中的金属具有活性气体转变点，其中在溅射过程中活性气体的浓度低于活性气体转变点，从而使金属靶以金属方式溅射，沉积形成具有非晶态结构的金属膜，所述膜定义为非晶态金属膜；以及
位于非晶态金属膜上的金属氧化物膜。
2.权利要求1的产品，其中金属阴极靶的金属选自钛、锆、钽、铪、铌、钒及其混合物。
3.权利要求2的产品，其中金属阴极靶的金属选自钛和锆。
4.权利要求3的产品，其中金属阴极靶的金属为钛。
5.权利要求1的产品，其中金属膜的厚度范围为100-1500埃。
6.权利要求5的产品，其中金属膜的厚度范围为200-700埃。
7.权利要求1的产品，其中活性气体选自氧气、氮气及其混合物。
8.权利要求7的产品，其中活性气体为氧气。
9.权利要求7的产品，其中惰性气体为氩气。
10.权利要求1的产品，其中惰性气体为氩气。
11.权利要求10的产品，其中活性气体为氧气。
12.权利要求11的产品，其中所述基板为玻璃，所述金属膜中的金属为钛。
13.权利要求11的产品，其中所述气氛包含氩气和至多30％氧气。
14.权利要求13的产品，其中所述气氛包含2-15％氧气。
15.权利要求1的产品，其中所述基板是玻璃。
16.权利要求1的产品，其中所述金属膜是被热氧化。
17.权利要求16的产品，其中所述金属膜被加热到至少400℃。
18.权利要求16的产品，其中所述金属氧化物膜在对非晶态金属膜进行热氧化之前沉积在非晶态金属膜上。
19.权利要求18的产品，其中沉积在所述金属膜上的金属氧化物膜的厚度范围为40-120埃。
20.权利要求18的产品，其中所述基板是玻璃，各层膜中的金属为钛，热氧化的非晶态金属膜的密度为4g/cm3，并且热氧化的非晶态金属膜的折射指数为2.5。
21.权利要求18的产品，其中各层膜中的金属分别独立地选自钛、锆、钽、铪、铌、钒及其混合物。
22.权利要求21的产品，其中各层膜中的金属分别独立地选自钛和锆。
23.一种镀膜制品，包括玻璃基板、第一钛氧化物膜及沉积在第一钛氧化物膜上的第二钛氧化物膜，其中所述第一钛氧化膜是热氧化非晶态的溅射钛金属膜形成的，而非晶态的溅射钛金属膜是由钛金属阴极靶在包含氩气和氧气的气氛中沉积得到的，所述气氛中氧气的含量低于钛金属阴极靶的活性转变点。
24.权利要求1的产品，其中所述金属氧化物膜含有与底层非晶态金属层相同的金属。
25.权利要求1的产品，其中所述金属氧化物膜含有活性溅射的非晶态金属氧化物，从而增强非晶态金属膜的热稳定性。
26.权利要求1的产品，其中所述金属氧化物膜的厚度为40-120埃。
27.权利要求1的产品，其中非晶态金属层要比在纯氩中溅射形成的晶态金属膜更硬并且密度更低，而较低的密度加快了氧化速率，从而使非晶态金属膜与晶态金属膜相比可以在较低温度下或较短时间内完全氧化。
28.一种镀膜产品，包括：
基板；
金属氧化物膜，该膜由基本非晶态的金属膜氧化形成，而所述基本非晶态的金属膜是在包含惰性气体和活性气体的气氛中，由金属阴极靶溅射形成的，所述金属阴极靶中的金属具有活性气体转变点，其中在溅射过程中活性气体的浓度低于活性气体转变点，从而使金属靶以金属方式溅射，沉积形成具有非晶态结构的金属膜。
29.权利要求27的产品，其中所述氧化通过热氧化进行。
30.权利要求27的产品，其中所述热氧化的非晶态金属膜含有晶态金属氧化物。
31.权利要求30的产品，其中所述热氧化的非晶态金属膜为具有晶态结构的钛氧化物膜，其密度高于3.4g/cm3。
CNB031220347A 1993-11-12 1994-11-11 耐久的溅射金属氧化物镀层 Expired - Lifetime CN1239736C (zh)

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US20070196695A1 (en) 2007-08-23
CN1112461C (zh) 2003-06-25
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EP0657562B1 (en) 2001-09-12
CN1105712A (zh) 1995-07-26
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EP0657562A3 (en) 1996-01-10
US6346174B1 (en) 2002-02-12
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