CN1108088C - 用于在电绝缘衬底表面上按结构制造导线的被覆层 - Google Patents

用于在电绝缘衬底表面上按结构制造导线的被覆层 Download PDF

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CN1108088C
CN1108088C CN96191105A CN96191105A CN1108088C CN 1108088 C CN1108088 C CN 1108088C CN 96191105 A CN96191105 A CN 96191105A CN 96191105 A CN96191105 A CN 96191105A CN 1108088 C CN1108088 C CN 1108088C
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约尔格·基克尔海恩
布鲁诺·维特
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Abstract

用来以一定结构形式在电绝缘衬底表面上制造导线，特别是用来制造传感器元件和印刷电路板的被覆层，被覆层由成分为Sn1-(y+z)AyBzO2的掺杂氧化锡层构成，其中A＝Sb或F，B＝In或Al。其特征在于被覆层的掺杂物质锑或氟加铟或铝的含量由0.02≤y+z＜0.11限定，而且掺杂物质之比满足条件1.4＜y/z＜2.2，这样就能用157nm至1064nm的波长范围内的电磁激光辐射进行刻蚀来使被覆层形成结构。这样提供了一种在玻璃或陶瓷衬底上施加的薄的具有高抗化学、机械或热负荷的导电层中，以高分辨率和无浪费地直接构造绝缘通道的经济的方法。

Description

用于在电绝缘衬底表面上按结构 制造导线的被覆层
本发明涉及在电绝缘衬表面上用来以一定结构制造导线的，特别是用来制造传感器元件和印刷电路板的被覆层，该被覆层由掺杂的氧化锡层构成，其成分为Sn1-(y+z)AyBzO2，其中A＝Sb或F，B＝In或Al，并涉及被覆层的一种被覆方法，以及对该被覆层进一步加工制成结构化的导线的方法。EP 0 280 362 A2公开了这样的被覆层。
在微型传感器、混合集成电路、显示器件等的芯片和晶片领域，以一定结构制造导线起着主导作用。在这些领域中，一般采用所谓原模(掩模)来形成结构。原模通常由玻璃料作衬底材料而构成。衬底材料上蒸镀一层均匀或不均匀的薄层，通常是蒸镀铬，然后必须以适当要求的形式形成结构。在电子学的许多其他领域，考虑到用作导线网或布线网，使尤其在玻璃衬底上的薄层或复合薄层形成结构很受关注的。这里业已熟知的是，为所要形成结构的厚约0.1μm至0.2μm的金属薄层被覆一层漆，然后用电子束或激光束，或者还经由光学系统，使漆层曝光和显影。然后完成一化学腐蚀工序，除去暴露的金属面。
在印刷电路板制造方面，业已由DE4010244A1得知，在印刷电路板上被覆一层导电漆，然后用激光器将导电漆层加工成走线图。接着对所形成的走线图进行金属化。
EP 0280362A2还公布了全表面的氧化锡被覆层在薄膜加热元件上的应用。其中也叙述了氧化锡用锑和铟的双掺杂，从而使这种膜层能在薄膜加热元件上用于较高的温度。大家知道，特别在较高温度下，氧化锡层与大气(O2，H2O)发生相互作用，这会引起电导率的显著变化。为能使这种氧化锡层在高温下也能用作电性能稳定的透明薄膜加热元件，以等克分子数，即等量地掺入锑和铟。这里特别指出，其量相互不得相差10％以上。而且，膜层具有的锑含量和铟含量各自为4.5mol％。在这种情况下由锑来提高导电率，由铟来稳定晶体缺陷。
本发明的任务在于制成可被覆在玻璃和陶瓷衬底上的薄导电被覆层，被覆层中可以高分辨率直接构成绝缘沟道而无残留物。此外，还给出制备这种被覆层以及对其进一步加工的方法。
根据本发明的一个方面，提供了一种用来以一定结构形式在电绝缘衬底表面上制造导线的被覆层，被覆层由成分为Sn1-(y+z)AyBzO2的掺杂氧化锡层构成，其中A＝Sb或F，B＝In或Al，其特征在于被覆层的掺杂物质锑或氟加铟或铝的含量由0.02≤y+z＜0.11限定，而且掺杂物质之比满足条件1.4＜y/z＜2.2。
根据本发明的另一方面，提供了一种制造上述被覆层的方法，其中被覆层系用气溶胶喷涂法被覆在表面温度为400℃至600℃的衬底上，被覆层的厚度在50nm和500nm之间。
根据本发明的又一方面，提供了一种应用上述被覆层制造具有一定结构的导线的方法，其中用157nm至308nm波长范围内的电磁激光辐射进行刻蚀来使被覆层形成结构。
通过被覆层中掺杂物质锑或氟加铟或铝的含量由极限值0.02＜y+z＜0.11给定，且并通过掺杂物质的比例满足条件1.4＜y/z＜2.2，令人意外地实现的是：这种膜层经用157nm至308nm波长范围内的激光辐射刻蚀，可没有残留物而以高分辨率构成具有绝缘沟道的结构。
此外，该任务由一方法来完成，其特征是：被覆层用气溶胶喷涂法(Aerosol-Spruehpyrolyse-Verfahren)在400℃至600℃的某一温度下淀积于表面温度400℃至600℃的玻璃、陶瓷或半导体硅电绝缘衬底上，厚度在50nm和500nm之间。
用所述波长范围内的电磁激光辐射刻蚀而成的精细导电结构，其特征在于绝缘沟道的垂直和锐边的壁，而且膜层对化学剂以及机械和热负荷有异常良好的稳定性。本发明的被覆层可用于传感器，例如小汽车前窗玻璃的湿度传感器，以及用于微电子电路的导线，这里特别适用于石英玻璃衬底上的高频元件，并且例如与液晶显示层组合用作显示器件。通过特殊的被覆与结构形成工艺，尤其是通过加给氧化锡规定浓度的锑(Sb)和铟(In)，可同时取得高电导率和高抗腐蚀性。在保持规定浓度的情况下，也可用氟代替锑，用铝代替铟。
业已证实，膜层具有Sn0.919Sb0.052In0.029O2的成分特别适宜。诚如所证实，这样一种被覆层特别是具有最佳电导率，此外可用准分子激光器作高分辨率、无残留物和边角锐的刻蚀。这种膜层淀积在玻璃衬底表面，导电性能与金属相近，而且透明，它还具有异常高的抗腐蚀性和机械强度。
被覆层宜在400℃至600℃的温度下用气溶胶喷涂法被覆。被覆层厚度在50nm和500nm之间。膜层随后根据本发明的一优选实施形式用波长为248nm的氟化氪准分子激光器进行刻蚀而形成结构。
本发明的进一步扩充是规定衬底由石英玻璃、玻璃陶瓷、硬玻璃(特别是硼硅硬玻璃)、适当软玻璃、陶瓷(特别是氧化铝陶瓷)或半导体硅构成。
本发明能使氧化锡这种能带隙为3.6eV因而能透可见光的半导体作为能形成精细结构的膜层而例如用于传感器。这里使用了已知的效应，即在氧化锡中掺入适当掺杂物质而能产生对于半导体来说异常高的可自由流动电子密度(将近1021/cm3)。若将这种掺杂氧化锡以薄层形式淀积在玻璃衬底上，这些电绝缘玻璃便取得几乎像金属那样导电的、同时又是透明的敷层。
本发明发现，最好含有5.2mol％锑和2.9mol％铟的氧化锡层能毫无问题地、精确地用准分子激光器形成结构，而且以后电化学和机械性能稳定。业已证明，例如掺等克分子量锑和铟的膜层则不会在用准分子激光器形成结构上有困难。另外，与符合当前技术水平的膜层相比较，现在本发明推出的膜层的电导率和机械粘附性有利地提高了。
全然意想不到的是，本发明采用的被覆层可用准分子激光器作精细结构刻蚀。特别是金属，由于结合能高等等原因，至今不能经济地采用准分子激光器进行无残留物刻蚀。如果考虑激光束与物质的相互作用机理，则激光波长首先在物质内部激发振荡模，从而例如把金属加热到液态或气态聚合状态。最后进行热刻除。这种方法对于形成高分辨率的结构，特别是还由于不可避免地有金属淀积而不能适用。因此，经济地使用准分子激光器的范围至今始终停留在剥蚀聚合物的范围内。与激光辐射产生热效应的情况不同，对于聚合物是抵消分子的结合能而使粒子和分子冷裂解。这涉及的是非热型刻蚀过程。
由于所述原因，以往在掺杂金属氧化物领域完全不能期望得到采用准分子激光器的优点，尤其也不能指望卓有成效地采用准分子激光器来刻蚀本发明采用的氧化锡层。为制造湿度传感器，专利申请人试验可用性能类似的膜层如氮化铬层直接形成结构而终究未获成功。这更加表明，这里采用准分子激光器时由于材料的蒸发，在被刻蚀区内发生沉积。因此，至今未能利用激光支持的材料刻蚀制成能工作的传感器。
然而，诚如意外地表明的那样，一脉冲准分子激光器很适用于经济地直接刻蚀现在研制成的被覆在玻璃或陶瓷衬底上并具本发明所述成份的特殊被覆层。这能在玻璃片或陶瓷片上被覆的薄氧化锡层的微米级区域内形成分辨率特别高的无残留物结构。这种被覆层采用准分子激光器直接形成结构或者是在应用设置在光路中的掩模的情况下来完成，掩模的透激光辐射的区域形状和结构与应刻蚀的膜层区域对应；或者用一聚焦的激光束来完成。
下面根据一示例详述本发明。
本发明采用的被覆层按照气溶胶喷涂法被覆在衬底上。这时利用市售喷雾装置使喷射液气动雾化成气溶胶。工作气体采用干燥氮气。气溶胶粒滴的平均直径在数微米范围内。用XY传动装置使喷嘴在10cm至15cm的距离上垂直于水平放置在扁平炉上的玻璃衬底移动。玻片在用一种已知的玻璃清洁剂预先清洁后进行被覆。该衬底在一炉中加热到表面温度约为550℃。这一温度特别适宜，因为被覆成的膜层的比电导率一般随温度上升而明显增大。
本发明的喷射液按下述制备：在100cm3醋酸正丁酯中首先溶解20cm3氯化锡SnCl4。随后溶解2.10g氯化锑SbCl3及1.14g氯化铟InCl作为掺杂物质。
被覆时，溶剂中含有的氯化物在赤热衬底表面上主要利用热解转换成具有本发明成分Sn0.919Sb0.052In0.029O2氧化物薄膜。这时所得氧化锡膜厚为140nm至400nm。
一硼硅玻璃板被覆了厚度为140nm的掺杂氧化锡层。该层的表面电阻为93Ω。该层的其他特征为：-晶体结构：            多晶，锡面(金红石结构)-平均可见光透射率：    ＞85％-折射指数：            1.95±0.03-目视光学质量：        透明，无散射，没有条纹和点块陷-显微                  200倍下无裂纹-附着：                抗胶带和橡皮擦拭-化学稳定性：          不溶于水、稀释的酸或碱(特别是HNO3，
                   H2SO4，HCl；NaOH，KOH)，在盐的水溶液
                   (NaCl，KCl)中不腐蚀，对市售玻璃清洁剂稳
                   定，较难在含水NaCl/KOH中电解腐蚀，在根
                   据DIN的盐雾试验中稳定。-稳定的表面电阻：      空气中至少至400℃稳定，用水润湿时未发现
                   变化-表面电阻的温度系数：  3×104K-1(以20℃为基准)-显微硬度              对硬玻璃未测得增高(在软玻璃上测得明显较
                   高的硬度)
这里叙述的硼硅酸盐衬底上的氧化锡层用准分子激光系统形成结构，以制造润湿传感器，这里是制造小汽车擦拭-洗涤传感器。
采用激光器的结构形成工艺的首要特征在于采用一准分子激光器并与掩模投影相结合。所采用的激光系统具有以下技术参数：激光器类型：           KrF准分子激光器波长：                 248nm脉冲宽度：             3至25ns最大脉冲能量：         460mJ平均功率：             70W脉冲峰值功率：         ＞18MW重复频率：             200Hz发散度：               2×3mrad光束截面：             (7-10)×20mm2能量稳定度：          ±4％
另一种方法是采用准分子激光器与一聚焦装置相组合。这种设备技术具有很灵活地形成结构的优点。原则上掩模投影技术和聚焦加工均能用准分子激光器实现。这些技术是已知的。以上所述也适用于可能采用的反射镜偏转系统。
本发明利用准分子激光器对氧化锡层的材料刻蚀已发展得毫无问题。特别是意外地丝毫没有看到在绝缘沟道中有被蒸发的膜层材料沉积，因此能产生极精细的结构而不需要任何修整。在绝缘沟道以内附带刻蚀掉深度达20nm的衬底材料。氧化锡材料内的绝缘沟道具有的特征是几乎垂直的壁和尖锐的可视边(Sichtkanten)。本发明的膜层的表面电阻约为50Ω至150Ω。
制成的小汽车擦拭-洗涤传感器很灵敏，足以探测局部蒙上的雾珠。此外，试验显示了对干摩擦的良好耐磨强度、对市售玻璃清洁剂和汽车洗涤剂的充裕稳定性以及在汽车工业规定的盐雾试验、环境负荷试验和电镀试验中的足够耐用度。
经补充测定，被覆在硼硅玻璃上的、厚度为140nm的氧化锡层，其电阻率只有微小的增长。目前把这一点归因于多晶膜层结构的晶粒尺寸随层厚增大而有些增大。因此，对厚度为360nm的一膜层测得表面电阻为30Ω，而不是预期的36Ω。
鉴于小汽车前窗玻璃的复合玻璃板是在钠石灰玻璃(软玻璃)的基础上制造这一事实，本发明还特别有在软玻璃衬底上制成上述传感器的任务。软玻璃衬底上的传感器的实现将在下面作为本发明的另一实施例进行叙述。该场合下仅是被覆工艺需要加以调整，所以只叙述被覆时衬底特有的差别。
与硬玻璃相比，其中一点是软玻璃具有高得多的碱金属氧化物含量，尤其是Na2O含量。大家都知道，从450℃以上的温度开始，钠作为小离子大量向软玻璃表面扩散。如果这时在本发明的500℃至550℃表面温度下进行氧化锡被覆，便形成一含钠的中间层，该中间层由于钠与氧化锡中自由电子相结合的性质而具有高电阻率。因此，在低被覆速率时形成含钠的氧化锡层，这会在层厚在100nm范围内时使表面电阻在MΩ范围内。分光光度测量证实存在这样的转移层。
但是，例如在被覆时间为7min时选择约52nm/min的高被覆速率，便得到厚360nm、表面电阻(128±6)Ω的低阻膜层。这一被覆是在500℃被覆温度下完成。用这一膜层能做出很有效地工作的小汽车前窗玻璃板用传感器。为避免温度变形造成的应力使敷膜中的玻璃板破裂，在玻璃厂浮法玻璃生产的冷却阶段立即进行膜层被覆是有优点的。这样就能避免成问题的软玻璃加热。
原则上本发明的使用范围决非局限于湿度传感器，也可能用于制作电子电路的导线。也许还有可能用铜、金、铂等导体材料对本发明的氧化锡层进行电镀或还原法镀膜。对于电子电路的导线，作这样的加厚来降低导线电阻会是有利的。本发明的n型电导氧化锡层与这些金属构成电阻极小的欧姆接触。此外，这里使用介电损耗很小的石英玻璃作衬底用来制造高频电路的导线结构也是适宜的。本发明的氧化锡层一般与这里所述的所有衬底构成很稳固的复合体，因为在各自的表面上实现了稳定的化学接合。
本发明的另一适宜的扩展是在软玻璃和硬玻璃上制造显示用的结构。这时，形成结构的氧化锡用作液晶薄膜(LCD)的透明电极结构。另外，还可能应用于其他静电控制的显示器件中。最后，也可能把所述形成结构的氧化锡层用作形成结构的加热元件。除湿度传感器外，其他的传感器应用例如还有微结构气体传感器。在这些气体传感器上，为实现对某些气体的选择性，必须对各个气室作不同的加热。

Claims (9)

1.用来以一定结构形式在电绝缘衬底表面上制造导线的被覆层，被覆层由成分为Sn1-(y+z)AyBzO2的掺杂氧化锡层构成，其中A＝Sb或F，B＝In或Al，其特征在于被覆层的掺杂物质锑或氟加铟或铝的含量由0.02≤y+z＜0.11限定，而且掺杂物质之比满足条件1.4＜y/z＜2.2。
2.权利要求1的所述的被覆层，其特征在于被覆层成分为
                   Sn0.919Sb0.052In0.029O2。
3.权利要求1或2所述的被覆层，其特征在于被覆层厚度在50nm和500nm之间。
4.权利要求1所述的被覆层，其特征在于衬底由石英玻璃、玻璃陶瓷、硬玻璃、软玻璃、氧化铝陶瓷或半导体硅构成。
5.权利要求4所述的被覆层，其特征在于，所述硬玻璃是硼硅硬玻璃。
6.权利要求1的被覆层的制造方法，其特征在于被覆层系用气溶胶喷涂法被覆在表面温度为400℃至600℃的衬底上，被覆层的厚度在50nm和500nm之间。
7.权利要求6所述的方法，其特征在于被覆层系在衬底制造的冷却阶段被覆到衬底上。
8.应用权利要求1至4任一项所述被覆层制造具有一定结构的导线的方法，其特征在于用157nm至308nm波长范围内的电磁激光辐射进行刻蚀来使被覆层形成结构。
9.权利要求8所述的方法，其特征在于用波长为248nm的氟化氪进行刻蚀来使被覆层形成结构。
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US5397920A (en) * 1994-03-24 1995-03-14 Minnesota Mining And Manufacturing Company Light transmissive, electrically-conductive, oxide film and methods of production

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DE19535068A1 (de) 1997-03-27
EP0793903A1 (de) 1997-09-10
KR970707707A (ko) 1997-12-01
WO1997011589A1 (de) 1997-03-27
ATE164483T1 (de) 1998-04-15
JP2931413B2 (ja) 1999-08-09
CN1165609A (zh) 1997-11-19
DE19535068C2 (de) 1997-08-21
KR100268122B1 (ko) 2000-10-16
DK0793903T3 (da) 1998-11-30
JPH10501104A (ja) 1998-01-27
DE59600129D1 (de) 1998-04-30
EP0793903B1 (de) 1998-03-25
US5955179A (en) 1999-09-21
ES2116817T3 (es) 1998-07-16

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