CN1961620B - 金属沉积 - Google Patents
金属沉积 Download PDFInfo
- Publication number
- CN1961620B CN1961620B CN2005800086887A CN200580008688A CN1961620B CN 1961620 B CN1961620 B CN 1961620B CN 2005800086887 A CN2005800086887 A CN 2005800086887A CN 200580008688 A CN200580008688 A CN 200580008688A CN 1961620 B CN1961620 B CN 1961620B
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- ground floor
- layer
- metal
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Images
Classifications
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- 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
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Abstract
用于在激光构图衬底上无电敷镀金属的方法。提供衬底，其上沉积了热成像层和催化层。用激光束曝光时，足够量的辐射在热成像层中被转变成热量，使得相邻的催化层的被曝光区域变得没有活性。然后将激光构图的衬底接触反应溶液，引起金属膜在催化层未曝光的区域上的生长。
Description
技术领域
本发明涉及金属在衬底上的沉积，尤其是金属由金属离子溶液在衬底上的催化反应沉积。
背景技术
无电金属敷镀是许多工业中常用的沉积金属膜的方法，尤其是在印刷电路板的生产中。一般的无电敷镀工艺需要数个步骤。第一步是处理衬底表面为随后敷镀的金属提供良好的粘附性。之后可以进行一系列水浴，使得表面布满催化剂，通常是钯胶体。最后将衬底接触含有金属离子和还原剂的水浴，还原剂在存在催化剂的情况下在衬底表面发生反应形成金属。这一方法在衬底表面上生成均匀薄膜，随后可以用标准光刻和腐蚀技术对其进行构图以形成电路板图形。这些图形的分辨率由所用的光刻技术决定，但是可构图尺寸小于5μm的图形。
在WO04/068389中，描述了使用直写技术进行金属无电敷镀的方法。通过在衬底上优选地用喷墨印刷沉积金属离子反应溶液和还原剂从而用金属材料选择覆盖衬底。对反应进行催化的活化剂的存在辅助了该反应，从而沉积了，例如，细微的金属颗粒或过渡金属的有机盐，例如醋酸钯。活化剂材料当混合到聚合物粘合剂中时可以用溶液沉积技术(例如喷墨印刷)来沉积。从而活化剂材料可以只沉积在需要金属材料的地方，且随后可以通过接触反应溶液生长金属区域。
在US5084299和US4981715中，描述了导电材料在衬底表面上的选择沉积。首先在衬底表面上沉积聚合物层。聚合物与含钯化合物复合，用作无电敷镀金属层的催化剂。照射上层感光聚合物层，随后的显影步骤通过化学湿法腐蚀过程除去未被照射的区域。然后将被照射过的衬底接触无电敷镀水浴形成金属层。
在US5192581中，使用激光在包括保护层的多层衬底上对催化剂层进行构图。所用的工艺与用于上面的专利中的类似，只是多了保护层，用于解决无电敷镀工艺中共有的压片(sheeting)问题。构图或者由消去工艺(例如催化剂颗粒的湿法化学腐蚀或激光辅助湿法化学沉积)来进行。在衬底被激光照射的区域中，催化剂变得不能融解在湿法化学腐蚀水浴中，从而只有在衬底没有被照射到的区域中才会从衬底上除去催化剂层。这一方法使得工艺可以在无需光刻的情况下进行，防止在介电衬底上有害的无电压片，在某些区域中不留意变成具有催化性。
发明内容
本发明的目的在于提供改善的在衬底上从金属离子溶液中沉积金属的方法。
根据本发明第一方面，提供在衬底上形成金属沉积的方法，该方法包括下列步骤：提供具有第一层材料的衬底，通过照射技术可以调整其作为金属从金属离子溶液中沉积的催化剂的活性；使用所述照射技术将第一层构图成有源和无源区域；将所得有源和无源区域图案接触金属离子溶液，金属从其中选择沉积在第一层的有源区域上。
根据本发明另一方面，提供一种混合物，包括用于还原金属离子的催化剂和发色团。
本发明的第一实施方案使用一种衬底，其上沉积了一层热成像层，随后还沉积了催化层。在用激光束照射分层结构时，下层热成像层将来自激光束的辐射转换成热量，使得催化剂被曝光的区域变得没有活性。在随后的敷镀步骤中，将衬底接触金属离子反应溶液和还原剂，促使金属膜在催化剂未曝光区域上的生长，从而使得发生金属层的无电沉积。
本发明的另一实施方案使用一种衬底，在其上用基于溶液的印刷技术(例如喷墨印刷)粗略地构图热成像层顶上的催化层，并使用激光辐射来修整粗略构图的催化剂层以形成更高分辨率的图形。
本发明的另一实施方案使用一种衬底，其上在预先沉积好的催化层上沉积了热成像层。在用激光束照射分层衬底时，热成像层产生足够的热量将催化层的曝光区域转变成非活性催化状态。因此催化剂的曝光区域不会与随后敷镀步骤中所使用的在除去热成像层之后沉积的溶液发生反应。金属层只形成在催化层的未曝光区域上。与下层热成像层类似，也可使用基于溶液的印刷技术(例如，但不局限于喷墨印刷)在上层热成像层的沉积之前对催化剂层进行粗略构图，并用激光辐射修整粗略构图的催化剂层以形成更高分辨率的图形。
本发明的另一实施方案包含在衬底上沉积直接成像催化层，从而无需沉积两个不同的层，即催化材料和热成像层。激光束对直接成像催化层的照射使得曝光区域在随后的显影步骤中不起作用，正如上面所描述的。然后将衬底和激光选择构图直接成像催化层接触反应溶液，金属只生长在未曝光区域上。也可以使用基于溶液的印刷技术——例如，但不局限于喷墨印刷——对直接成像催化剂层进行粗略构图，并用激光辐射修整粗略构图的催化剂层以形成更高分辨率的图形，正如上面所描述的。
附图说明
现在将参考附图(仅作为例子)详细描述本发明的实施方案，其中：
图1示出根据第一实施方案在衬底上进行无电金属敷镀的工艺步骤，该实施方案在催化剂层下方插入了热成像层。
图2示出根据第二实施方案在衬底上进行无电金属敷镀的工艺步骤，该实施方案在催化剂层下方插入了热成像层，催化剂层在沉积后进行了粗略构图。
图3示出根据第三实施方案在衬底上进行无电金属敷镀的工艺步骤，该实施方案在催化剂层上方插入了热成像层。
图4示出使用催化剂层上方的热成像层生长的铜迹线的光学显微照片。
图5示出根据第四实施方案在衬底上进行无电金属敷镀的工艺步骤，该实施方案在催化剂层上方插入了热成像层，催化剂层在沉积后进行了粗略构图。
图6示出根据第五实施方案在衬底上进行无电金属敷镀的工艺步骤，该实施方案使用了可以直接成像的催化剂层。
图7示出衬底上有单层直接成像催化层(DICL)并构图形成隔绝金属区域的工艺。
图8示出使用可以直接成像的催化剂层生长的铜迹线的光学显微照片。
图9示出根据第七实施方案在衬底上进行无电金属敷镀的工艺步骤，该实施方案使用了可以直接成像的催化剂层，该层在沉积后进行了粗略构图。
图10示出根据第八实施方案的工艺，用于通过在激光构图衬底上形成无电敷镀金属制作FET器件。
具体实施方式
参考附图，图1示出本发明第一实施方案。第一实施方案在衬底上沉积一层催化剂层和下层热成像层。被吸收的辐射在热成像层种被转变成热量，使得催化剂层被曝光的区域变得没有活性。这在衬底表面上构图了无电金属层。
衬底1覆盖有热成像材料2。衬底材料优选地为，但不局限于：玻璃或聚合物膜。热成像材料能够将吸收的辐射转变成热量。热成像层(TIL)优选地由标准薄膜涂布技术——包括但不局限于：旋涂、浸渍涂布、刮涂、辊涂、狭缝挤压式涂布、或喷涂，喷墨、凹板印刷、胶印或丝网印刷——从溶液中涂布。热成像材料从吸收的辐射(例如，通过透镜5聚焦的聚焦激光束4的形式)中产生热量，或者从光束通过掩模所产生的光图案来产生热量。应当选择热成像层的材料以使热成像层和衬底之间有良好的粘附性。再一个重要的是热成像层不会被随后的催化层沉积步骤所溶解或受其任何形式的影响。下层热成像层的优选材料是混合有红外染料的聚苯乙烯，它可以溶解在非极性溶剂例如二甲苯中。对于使用830nm的红外激光的激光成像来说，合适的染料可以是SDA4554。聚丙烯膜的优选厚度是500nm厚，它在830nm处具有0.15的光学密度。
能够引发无电沉积的催化剂层3优选地从溶液中沉积在热成像层上，并干燥以形成催化层。催化层的特性必须是当它浸在含有金属离子和还原剂的反应溶液中时模板金属膜生长。催化层优选地由标准薄膜涂布技术——包括但不局限于：旋涂、浸渍涂布、刮涂、辊涂、狭缝挤压式涂布、或喷涂，喷墨、凹板印刷、胶印或丝网印刷——从溶液中涂布。催化剂的特性包括热敏特性，从而在温度高温下催化膜不再模板金属层的生长。优选的催化剂材料由Conductive InkjetTechnologies提供，并且在专利公开WO2004068389中作为活化层进行了描述。催化材料由混合有聚合物粘合剂的醋酸钯催化剂组成，从而它可以用可溶液处理的技术来沉积。优选的催化剂配方采用溶解在丙稀乙二醇甲基乙醚与双丙酮醇按大约50∶50混合的混合物中的聚合物粘合剂和醋酸钯。所述催化层的合适材料包括，但不局限于：含有催化物质(金属或金属离子)和至少一种热塑材料的合成物，所述合成物在工艺温度范围内呈现出热转变。
当下层热成像材料暴露在合适波长的辐射中时，会产生热量，促进了催化剂的这些区域中的变化，使得它们变得没有活性。发生这一反应的机制取决于所选的催化剂材料。多层衬底的选择性曝光导致了上层催化层的构图。进行了选择激光构图的上层由交替的活性和非活性催化剂区域构成。通过将红外光的波长选择在830-1064nm，激光将不能被下层半导电层吸收。如果由根据本发明的方法形成的导电结构是形成在多层结构中的电子器件(例如基于共轭聚合物的场效应晶体管器件)的一部分的话，这一点尤其重要。因此，可以避免衬底上的多层堆叠中的下层电活性层的退化。尽管也可以使用位于可见光和紫外谱范围内的其它波长，但是在这样的情形中需要特别小心以使多层的曝光最小化，尤其是在有氧气存在时，以避免像光氧化这样的过程造成的退化。优选的激光工具是832nm红外激光二极管，它具有5微米的光斑尺寸以用于高分辨率构图。所用的流量取决于破坏催化剂层的催化特性所需的温度和热成像层所吸收的辐射总量。优选的流量为1000-2000mJ/cm2。
反应水浴的选择将由所用的催化层材料和需要沉积的金属来决定。某些催化剂层，尤其是由过渡金属有机酸盐(例如醋酸钯)组成的那些可能需要金属离子在反应水浴之前接触还原剂以提高敷镀效率。这优选地通过将多层衬底接触双甲基胺硼烷(DMAB)中来进行。接触还原溶液可以通过例如那些包括将衬底浸入溶液的技术或那些将再生溶液喷墨印刷在衬底表面顶上的技术来实现。通过使催化剂层接触含有所选金属离子和能够将那些离子还原成金属的试剂的反应水浴，将会发生所需金属膜的生长。这也可以作为许多技术的结果而发生，这些技术包括，但不局限于：将衬底浸入溶液和在衬底上喷墨印刷溶液。金属(例如但不局限于：铜、镍、铂、钯、钴和金)可以使用这一技术来沉积。在优选方法中，使用含水反应水浴生长了铜膜，该水浴含有大约9％的硫酸铜(II)、9％的甲醛、4.5％的(2-羟基丙烷)乙二胺、2％的甲醇、4％的氢氧化钠，以及0.05％的氰化钾。铜沉积的速率可通过进一步用水稀释该溶液来调节。从而在DICL层上形成了栅电极。
参考附图，第二实施方案示于图2中。在这一实施方案中，使用基于溶液的可以进行粗略图形的构图的构图技术(例如喷墨印刷)来沉积催化层3。然后使用热成像步骤修整粗略构图的图形以产生更精细的图案。
第一实施方案的一个优点在于催化层3可以使用更便宜的工业设备来沉积。第二实施方案对于高成本材料来说更为有利，因为这一工艺减小了所沉积的催化材料的总量。另外，由于敷镀工艺过程中累积在膜中的应力，与用于第一实施方案中的一样的连续催化层会更倾向于弯曲变形。在这一情形中，优选粗略构图的催化层，因为当敷镀面积减小时应力不会这么成问题。
第三实施方案示于图3中。这一工艺给出直接沉积在衬底表面上的催化层3。这一步骤之后示热成像层2的沉积。催化层的未曝光区域能够引发无电沉积。
衬底1覆盖有一层催化剂3，后者保留了与上面所描述的催化层相同的特性。然而，该催化层还需要能够很好地粘附在衬底表面上。衬底材料优选地为，但不局限于：玻璃或聚合物膜。催化层优选地由标准薄膜涂布技术——包括但不局限于：旋涂、浸渍涂布、刮涂、辊涂、狭缝挤压式涂布、或喷涂，喷墨、凹板印刷、胶印或丝网印刷——从溶液中涂布。催化剂层的特性必须是它会与金属离子溶液发生反应以引发金属膜的形成。另外，催化剂必须具有热敏特性，从而当温度升高时，催化膜将不再具有作为催化材料的活性。优选的催化剂材料由Conductive Inkjet Technologies提供，并且在专利公开WO2004068389中作为活化层进行了描述。活化材料由混合有聚合物粘合剂的醋酸钯催化剂组成，从而它具有可溶液处理的特性。优选的催化剂配方包括溶解在丙稀乙二醇甲基乙醚与双丙酮醇按大约50∶50混合的混合物中的聚合物粘合剂和醋酸钯。优选的膜厚范围为30nm-1微米。
然后在催化层3上沉积热成像层(TIL)2。如上所述，热成像层材料是能够将从激光束中吸收到的辐射转变成热量的材料。热成像层优选地由标准薄膜涂布技术——包括但不局限于：旋涂、浸渍涂布、刮涂、辊涂、狭缝挤压式涂布、或喷涂，喷墨、凹板印刷、胶印或丝网印刷——从溶液中涂布。必须选择材料和沉积技术以确保下层材料不会受到像下层的溶解这样的因素的任何影响。可用于TIL中的激光染料与催化材料之间的任何相互作用都会妨碍催化作用执行其应有功能。热成像层的合适材料必须能够溶解于可以浇在催化层上的溶剂中，或者催化层可以浇在热成像层上，而不会引入任何问题，例如周围层的溶解。优选的热成像层为与合适的红外激光染料——例如工作在830nm处的SDA4554——混合的聚异丁烯(PIB)。所得溶液能够溶解在极端非极性的溶剂中，例如优选溶剂二甲基环己胺。这一溶剂被选为优选溶剂是因为该溶剂的高沸点，这有助于膜的旋涂。膜的优选厚度为100nm，它在835nm处具有至少0.15的光学密度。
热成像材料从吸收的IR辐射——例如，通过透镜5聚焦的聚焦激光束4的形式——中产生热量，或者从光束通过掩模所产生的光图案来产生热量。产生足够的热量以使上层催化剂对随后的显影步骤无效。与上面一样，这具有使催化层的曝光区域不易形成金属膜的结果。多层衬底的选择曝光导致了下层催化层的构图。被选择性激光构图的下层包括活性和非活性催化剂的交替区域。通过将红外光的波长选择在830-1064nm之间，激光不会被大多数共轭聚合物吸收。因此，可以避免衬底上的多层堆叠中的下层电活性层的退化。尽管也可以使用位于可见光和紫外谱范围内的其它波长，但是在这样的情形中需要特别小心以使多层的曝光最小化，尤其是在有氧气存在时，以避免像光氧化这样的过程造成的退化。优选的激光工具是832nm红外激光二极管，它具有5微米的光斑尺寸以用于高分辨率构图。所用的流量取决于破坏催化剂层的催化特性所需的温度和热成像层所吸收的辐射总量。优选的流量为1000-2000mJ/cm2。
在本发明的这一实施方案中，必须在成像之后将TIL剥去。这通过将衬底接触合适的溶剂水浴来完成。对于优选方法，水浴可以包括用于浇注膜的溶剂，即二甲基环己胺。随后的催化剂在化学反应过程中还原以及金属膜生长的步骤与前面描述的那些步骤相同。
第四实施方案示于图5中。这一实施方案与第三实施方案类似。然而，催化层3使用基于溶液的可以进行粗略图形的构图的构图技术来沉积，优选地使用像喷墨印刷这样的技术。然后使用热成像步骤来修整粗略构图的图形以产生更精细的图案。
如上所述，第三实施方案的一个优点在于可以使用更便宜的工业设备来沉积催化层3。然而，当使用高成本材料时第四实施方案更为有利，因为这一工艺减小了所沉积的催化材料的总量。另外，由于敷镀工艺过程中累积在膜中的应力，与用于第三实施方案中的一样的连续催化层会更倾向于弯曲变形。如果弯曲变形是一个问题，那么粗略构图的催化层将是优选的，因为当敷镀面积减小时应力不会这么成问题。
本发明的第五实施方案示于图6中。第五实施方案在衬底上给出单层直接成像催化层(DICL)，从而无需沉积催化材料和热成像层这样两个不同的层。被吸收的辐射被转变成热量从而DICL可以用作构图无电金属层的替代方法。
衬底1覆盖有DICL9。衬底优选地为玻璃或聚合物膜，但不局限于这两种材料。DICL是能够将所吸收的辐射转变成热量但同时又保留催化无电敷镀反应以从反应溶液中形成金属层的能力。必须选择DICL的材料从而这一层和衬底之间具有良好的粘附特性，并且应当选择浇注溶液以确保沉积时对下层不会产生破坏。DICL优选地由标准薄膜涂布技术——包括但不局限于：旋涂、浸渍涂布、刮涂、辊涂、狭缝挤压式涂布、或喷涂，喷墨、凹板印刷、胶印或丝网印刷——从溶液中涂布。优选的DICL是由Conductive Inkjet Technologies提供，并且在专利公开WO2004068389中作为活化层进行了描述的催化剂材料的衍生物。活化层由与聚合物粘合剂混合的醋酸钯催化剂组成，以确保它可溶液处理。如上面所描述的，优选的催化剂配方包括溶解在丙稀乙二醇甲基乙醚与双丙酮醇按50∶50混合的混合物中的聚合物粘合剂和醋酸钯。然后将红外吸收材料(例如碳黑)加入混合物中以吸收红外辐射。优选的膜厚在30nm到1微米之间，在835nm处应当具有至少0.15的光学密度。
DICL从吸收的辐射——例如，通过透镜5聚焦的聚焦激光束4的形式——中产生热量，或者从光束通过掩模所产生的光图案来产生热量。辐射的吸收导致材料的选定区域变得不具有催化剂活性。通过将红外光的波长选择在830-1064nm，激光不会被大多数共轭聚合物吸收。因此，可以避免衬底上的多层堆叠中的下层电活性层的退化。尽管也可以使用位于可见光和紫外谱范围内的其它波长，但是在这样的情形中需要特别小心以使多层的曝光最小化，尤其是在有氧气存在时，以避免像光氧化这样的过程造成的退化。优选的激光工具是832nm红外激光二极管，它具有5微米的光斑尺寸以用于高分辨率构图。所用的流量取决于破坏催化剂层的催化特性所需的温度和热成像层所吸收的辐射总量。优选的流量为1000-2000mJ/cm2。
图7示出根据第六实施方案的工艺，其中在衬底上给出了单层直接成像催化层(DICL)。与上面相同，使用照射技术，吸收的辐射被转换成热量从而DICL可被用于构图催化层14并形成隔离的无电敷镀金属区域15。
随后还原催化剂并生长金属膜的步骤与上面对本发明第一实施方案所描述的相同。图8示出如上所述使用根据本发明的方法在玻璃衬底上生长的20微米铜迹线的光学显微照片。
第七实施方案示于图9中。与第六实施方案相反，直接成像催化层9使用基于溶液的可以进行粗略图形的构图的构图技术(例如喷墨印刷)来沉积。使用热成像步骤修整粗略构图的图形以产生更精细的图案。
如上所述，在第一实施方案中，DICL能够用更便宜的工业设备来沉积。然而，在需要使用高成本材料时就可以看到第七实施方案的优点，因为这一工艺减小了所沉积的催化材料的总量。此外，如上所述，由于敷镀工艺过程中膜中所累积的应力，连续催化膜(如第一方面中所见的)会更倾向于弯曲变形。在连续催化膜的弯曲变形是一个问题的情形中，粗略构图的催化层将是优选的，因为当敷镀面积减小时应力不会这么成问题。
上面所述的构图催化层的技术可用于电子开关器件中源、漏或栅电极的形成，也可用于电路元件(例如互连、母线、天线和其它零件)的形成。另外，上述技术可用于制作电子电路中的像素电极和像素电容。催化剂层利用热过程的转变在考虑用共轭聚合物技术制作的电子器件时尤其有利，在这样的器件中，半导电层对高能辐射和过度溶剂显影步骤常常很敏感。另外，催化材料可以沉积在衬底(例如电路板)的大面积上。通过使用如上所述的热成像技术，催化层的一些区域变得没有活性，从而避免了短路并形成隔离的接触区域。这一工艺可用来制作与精细图形(例如接触点或其它电路元件)的接触。这样一种工艺的另一好处在于不需要高分辨率的零件，因为与它们的接触点的连接可以使用上面的工艺来进行数字化实现。
然后可以将半导体层(顶栅结构情形)或介电层(底栅结构情形)直接沉积在无电沉积的金属区域的顶上。这些附加的层可优选地由标准薄膜涂布技术——包括但不局限于：旋涂、浸渍涂布、刮涂、辊涂、狭缝挤压式涂布、或喷涂，喷墨、凹板印刷、胶印或丝网印刷——从溶液中涂布。在顶栅结构情形中，随后可以将栅电极沉积在半导体层顶上。这需要仔细调节下层的溶剂以避免半导电层的分解或膨胀(见WO01/47093)。
实例：采用镀铜栅的顶栅FET的形成：
根据第八实施方案用于通过在激光构图衬底上形成无电敷镀金属制作FET器件的方法示于图10中。导电材料沉积在衬底1上并进行构图以形成源和漏电极11。衬底可以是玻璃或聚合物膜，但是优选地使用塑性衬底，例如聚对苯二甲酸乙二脂(PET)，聚萘二酸乙二醇脂(PEN)。导电聚合物(例如PEDOT)或金属材料(例如金或银)的构图导电层11由溶液加工技术——包括但不局限于：旋涂、浸渍涂布、刮涂、辊涂、狭缝挤压式涂布、或喷涂，喷墨、凹板印刷、胶印或丝网印刷——或蒸发，以及光刻技术来沉积。
一旦导电层构图形成了源和漏电极，随后就可以将一层半导电材料12沉积在衬底和已构图电极上。半导电层可含有如下材料，但不局限于这些材料：多方基胺、聚芴或聚噻吩衍生物。很多印刷技术都可用于沉积半导电材料，包括，但不局限于：喷墨印刷、软光刻印刷(J.A.Rogers et al.，App.Phys.Lett.75，1010(1999)；S.Brittain et al.，Physics World May 1998，p.31)、丝网印刷(Z.Bao，et al.，Chem.Mat.9，12999(1997))，以及光刻构图(见WO99/10939)、胶印、刮涂或浸渍涂布、帘幕式涂布、新月式涂布、喷涂，或挤压涂布。
然后将一层栅介电材料13沉积到分层结构上。像聚异丁烯或聚乙烯基苯酚这样的材料可以用作介电材料，但是优选地使用聚甲基异丁烯酸盐(PMMA)和聚苯乙烯。介电材料可以以连续层的形式沉积，所用的技术可以是，但不局限于：喷涂或刮涂。然而，优选地使用喷涂技术。
随后在介电层上通过溶液加工技术——例如但不局限于：旋涂、浸渍涂布、刮涂、辊涂、狭缝挤压式涂布、或喷涂，喷墨、凹板印刷、胶印或丝网印刷——或蒸发，以及光刻技术来沉积直接成像催化层(DICL)。DICL包括能够将吸收的辐射转变成热量的导电材料，沉积在分层衬底14上并进行构图。在该层中加入红外吸收材料(例如碳黑)作为吸收红外辐射的催化剂。优选的膜厚在30nm到1微米之间，在835nm处应当具有至少0.15的光学密度。优选的催化剂配方具有溶解在丙稀乙二醇甲基乙醚与双丙酮醇按大约50∶50混合的混合物中的聚合物粘合剂和醋酸钯。
直接成像催化层对辐射的吸收导致该层的选定区域变得不具有催化剂活性。使用具有5微米光斑尺寸的832nm红外激光二极管作为红外光源以实现高分辨率构图。激光的优选流量为1000-2000mJ/cm2。
为了形成FET器件的栅电极14，将衬底暴露于金属离子和还原剂的反应溶液，促使了金属膜在催化层的上述未曝光区域上的生长。随后这使得能够进行金属层的无电沉积。通过使催化剂层暴露于含有所选金属离子和能够将这些离子还原成金属的反应水浴，将发生所需金属膜的生长。这又可作为许多技术的结果，这些技术包括但不局限于将衬底浸入溶液和将溶液喷墨印刷到衬底上的方法。使用这一技术能够沉积金属，例如，但不局限于：铜、镍、铂、钯、钴和金。在优选方法中，使用含水反应水浴生长了铜膜，该水浴含有大约9％的硫酸铜(II)、9％的甲醛、4.5％的(2-羟基丙烷)乙二胺、2％的甲醇、4％的氢氧化钠，以及0.05％的氰化钾。铜沉积的速率可通过进一步用水稀释该溶液来调节。
可用做半导电层的可能材料包括任何可溶液处理的共轭聚合物或寡聚物材料，它们具有适当的超过10-3cm2/Vs，优选地超过10-2cm2/Vs的场效应迁移率。可能适用的材料已经在下面的例子中评论过：H.E.Katz，J.Mater.Chem.7，369(1997)，或Z.Bao，AdvancedMaterials 12，227(2000)。其它的可能包括具有增溶侧链的小共轭分子(J.G.Laquindanum，et al.，J.Am.Chem.Soc.120，664(1998))、从溶液中自组织形成的半导电有机-无机混合材料(C.R.Kagan，et al.，Science 286，946(1999))，或溶液沉积的无机半导体，例如CdSe纳米颗粒(B.A.Ridley，et al.，Science 286，746(1999))。
如上所述制作的器件(例如TFT)可以是更复杂的器件或电路的一部分，其中一个或多个这样的器件可以互相或与其它器件集成。应用的实施例包括用于显示器或存储器件的逻辑电路和有源矩阵电路，或用户定义的栅阵列电路。如上所述的构图工艺也可用于构图其它电路零件，例如，但不局限于：互连、电阻和电容。
利用上述方法，在沉积催化剂材料之前无需在衬底上有预定图案。这具有减少所需工艺步骤的数量的好处。另外，相对于先有技术中所进行的工艺来说另一优点在于在无电敷镀工艺过程中，金属膜将仅生长在没有接触热成像激光的区域上。这通过仅在需要的地方生长金属减少了材料成本，且无需化学腐蚀或显影步骤来在辐射照射之后除去部分催化剂层。最后，上述方法无需将导电区域喷墨印刷到分层衬底上(见WO02/095805)。
此外，使用红外辐射来构图催化剂层的热成像技术的使用具有特定优点，如下所述。电活性或共轭聚合物通常对红外光不如对UV光敏感，从而可以减小任何这样的下层的退化。另外，利用红外热成像工艺，对于活化/钝化来说需要辐射阈值水平，因此在暴露在阳光下时无需考虑催化剂层材料的退化或意外钝化/活化，而这在如果，例如，UV光敏材料用作催化剂层的话就需要考虑。
在本发明中依然可以利用到喷墨印刷的所有优点，它还克服了基于溶液的印刷技术的低分辨率和相对较低的可实现的精度的问题。这对于需要窄线宽结构(例如线宽小于10-20微米的互连)的应用来说尤其重要。
本发明并不局限于前述实施例。本发明的方面包括此处所描述的概念的所有新颖性和创造性方面，以及此处所描述的特征的所有新颖性和创造性组合。
因此申请人分开公开此处所描述的每个单独特征以及两个或更多个这种特征的任意组合，只要这样的特征或组合能够根据本说明书作为一个整体按照本领域的技术人员的公共常识来实现，无论这样的特征或特征组合是否解决了此处所公开的任何问题，并且并不局限于权利要求的范围。申请人指出本发明的方面可包括任何这样的单独特征或特征组合。考虑到前面的描述，显然对于本领域技术人员来说，只要不超出本发明的范围，可以作出各种调整。
Claims (24)
1.一种在衬底上形成金属沉积的方法，该方法包括下列步骤：提供具有催化剂材料的第一层的衬底，催化剂材料用于从金属离子的溶液中沉积金属，催化剂材料可通过加热来非活性化；使用辐射技术来选择性加热所述第一层的选定区域以将第一层构图成活性区域和非活性区域；将所得的活性区域和非活性区域的图案暴露于金属离子溶液，由此金属被从中选择性沉积在所述第一层的所述活性区域上。
2.根据权利要求1的方法，其中所述辐射技术形成所述第一层的通过非活性区域而与其它环绕的具有催化活性的区域隔离的活性区域。
3.根据权利要求1的方法，其中在所述第一层之下提供热成像层以辅助所述第一层的所述选定区域的选择性加热。
4.根据权利要求1的方法，其中在所述第一层之上提供热成像层以辅助所述第一层的所述选定区域的选择性加热；并包含进一步的在将所述第一层构图成非活性区域和活性区域的步骤之后除去所述热成像层的步骤。
5.根据权利要求1的方法，其中辐射为红外波长的辐射。
6.根据权利要求1的方法，包括将所述第一层选择性沉积在所述衬底相应于要沉积金属的那些位置的选定位置上的步骤。
7.根据权利要求1的方法，包括：在衬底的选定位置上选择性沉积所述第一层作为第一层地带；使用所述辐射技术将每个第一层地带构图成活性区域和非活性区域；将所得的活性区域和非活性区域图案暴露于金属离子溶液，由此金属被从中选择性沉积在所述第一层地带的活性区域上。
8.根据权利要求7的方法，其中所述第一层地带由喷墨印刷来沉积。
9.根据权利要求1-8中任何一个的方法，其中在所述衬底上形成的金属沉积是电子器件的至少一个金属元件。
10.根据权利要求9的方法，其中所述电子器件形成电气器件的零件。
11.根据权利要求1-8中任何一个的方法，其中所述第一层包括一种合成物，该合成物包括用于金属离子的还原的催化剂和发色团。
12.根据权利要求11的方法，其中所述发色团为吸收红外辐射的化学部分。
13.根据权利要求11的方法，其中所述发色团为碳黑。
14.根据权利要求1至8中任何一个的方法，其中金属从金属离子溶液中的沉积为一种无电敷镀技术。
15.根据权利要求1至8中任何一个的方法，其中所述催化剂材料由混合有聚合物粘合剂的醋酸钯催化剂组成。
16.根据权利要求1至8中任何一个的方法，其中催化剂材料的所述第一层为直接成像催化层，催化剂配方采用溶解在丙稀乙二醇甲基乙醚与双丙酮醇按50∶50混合的混合物中的聚合物粘合剂和醋酸钯。
17.根据权利要求3的方法，其中在所述第一层之下提供的热成像层的材料是混合有红外染料的聚苯乙烯。
18.根据权利要求4的方法，其中在所述第一层之上提供的热成像层的材料是与红外激光染料混合的聚异丁烯。
19.一种金属化衬底，根据权利要求1-8中任何一个的方法制作。
20.一种电子器件，包括根据权利要求19的金属化衬底。
21.一种制作电气或电子电路的方法，包括由根据权利要求1至8中任何一个的方法形成其至少一个金属元件的步骤。
22.一种逻辑电路，由根据权利要求21的方法制作。
23.一种显示器或存储器件，包括由根据权利要求21的方法制作的有源矩阵电路。
24.一种互连阵列，由根据权利要求21的方法制作。
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| PCT/GB2005/000458 WO2005079126A2 (en) | 2004-02-10 | 2005-02-10 | Metal deposition |
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| US7927454B2 (en) | 2007-07-17 | 2011-04-19 | Samsung Mobile Display Co., Ltd. | Method of patterning a substrate |
| DE102008021655B4 (de) * | 2008-04-30 | 2012-06-06 | Saint-Gobain Sekurit Deutschland Gmbh & Co. Kg | Strahlungsquelle und Solarzelle |
| GB2467357B (en) | 2009-01-30 | 2011-09-21 | Cambridge Display Tech Ltd | Organic thin film transistors |
| CN102817018A (zh) * | 2012-09-13 | 2012-12-12 | 格林精密部件（惠州）有限公司 | 外壳激光成型装饰加工方法及制作设备 |
| US8795788B2 (en) * | 2012-11-14 | 2014-08-05 | Eastman Kodak Company | Method for functional printing system |
| US20140366805A1 (en) * | 2012-11-14 | 2014-12-18 | Israel Schuster | System for forming a conductive pattern |
| USD753734S1 (en) | 2013-08-07 | 2016-04-12 | Atotech Deutschland Gmbh | Device for metal deposition |
| KR20150018368A (ko) | 2013-08-09 | 2015-02-23 | 주식회사 엘지화학 | 전자기파의 직접 조사에 의한 도전성 패턴 형성 방법과, 도전성 패턴을 갖는 수지 구조체 |
| CN105789057B (zh) * | 2014-12-24 | 2019-05-10 | 欣兴电子股份有限公司 | 线路板的制造方法 |
| JP2017028079A (ja) * | 2015-07-22 | 2017-02-02 | イビデン株式会社 | プリント配線板の製造方法およびプリント配線板 |
| JP2018019018A (ja) * | 2016-07-29 | 2018-02-01 | ローム・アンド・ハース電子材料株式会社 | 非導電性基材表面へのめっき方法 |
| US10781520B2 (en) | 2017-12-04 | 2020-09-22 | Laurie Johansen | Metallic sheet with deposited structured images and method of manufacture |
| CN117547970B (zh) * | 2024-01-12 | 2024-04-02 | 广东海洋大学 | 一种光热催化船舶废气处理的方法 |
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| US5084299A (en) * | 1989-08-10 | 1992-01-28 | Microelectronics And Computer Technology Corporation | Method for patterning electroless plated metal on a polymer substrate |
| US5192581A (en) * | 1989-08-10 | 1993-03-09 | Microelectronics And Computer Technology Corporation | Protective layer for preventing electroless deposition on a dielectric |
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| US20080283275A1 (en) | 2008-11-20 |
| WO2005079126A2 (en) | 2005-08-25 |
| CN1961620A (zh) | 2007-05-09 |
| US7867686B2 (en) | 2011-01-11 |
| GB0402960D0 (en) | 2004-03-17 |
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