CN1326435C - Conductor track structures and method for production thereof - Google Patents
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- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
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- C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
- C23C18/1612—Process or apparatus coating on selected surface areas by direct patterning through irradiation means
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Abstract
本发明涉及用于制造不导电承载材料上的导体轨道结构的方法,该导体轨道结构由金属晶核及后续在金属核上涂覆的金属化层构成,其中金属晶核通过电磁照射实现的精细分布地包含在承载材料中的不导电金属化合物的断裂而形成。本发明的特征在于,不导电的金属化合物由高度热稳定的、在含水的酸性或碱性金属化电解液中稳定且不溶解的无机氧化物构成,这些氧化物是具有尖晶石结构的较高阶氧化物,或者是简单的d-金属氧化物或其混合物或与尖晶石结构同族的混合金属化合物,并且所述的氧化物在未被照射的区域内保持不变。所采用的无机氧化物是耐热的,在焊接温度作用之后仍保持稳定。导体轨道结构可靠而简单地被制造,并且获得非常高的附着性。The invention relates to a method for producing a conductor track structure on a non-conductive carrier material, the conductor track structure consisting of a metal nucleus and a subsequent metallization layer applied to the metal nucleus, wherein the metal nucleus is fine-tuned by electromagnetic irradiation Formed by the fracture of non-conductive metal compounds distributedly contained in the carrier material. The invention is characterized in that the non-conductive metal compound consists of highly thermally stable, stable and insoluble inorganic oxides in aqueous acidic or basic metallization electrolytes, which are relatively Higher order oxides, either simple d-metal oxides or mixtures thereof or mixed metal compounds of the same family as the spinel structure, and said oxides remain unchanged in the non-irradiated regions. The inorganic oxides used are heat-resistant and remain stable after soldering temperature exposure. The conductor track structure is produced reliably and simply and achieves very high adhesion.
Description
本发明涉及在不导电的载体材料上的导体轨道结构的制造方法。The invention relates to a method for producing a conductor track structure on a non-conductive carrier material.
在专利申请DE 197.23734.7-34和DE 1973346.9以及专业期刊“金属表面”(″metalloberflche″)第54卷第11期(2000年)“聚合物的精细结构的金属化”(″Feinstrukturierte Metallisierung von Polymeren″所公开的方法中,为了制造精细的、附着的导电导轨结构,在不导电的承载材料中掺入不导电的金属螯合络合物,并且由它利用激光射线裂解出所构造的金属化晶核,这些金属化晶核引起被照射表面区中接着发生的化学还原反应金属化。)In patent applications DE 197.23734.7-34 and DE 1973346.9 and in the professional journal "Metal Surfaces" ("metalloberflche") Vol. 54 No. 11 (2000) "Metallization of fine structures of polymers" ("Feinstrukturierte Metallisierung In the method disclosed by von Polymeren, in order to produce fine, adherent conductive rail structures, a non-conductive metal chelate complex is doped into a non-conductive carrier material, and the constructed metal is cleaved from it by means of laser radiation. metallization nuclei which cause metallization in the ensuing chemical reduction reaction in the irradiated surface region.)
这种方法可用于由热塑性的塑料采用喷铸方法制造电路载体。此外可用其它方法来制造三维喷铸电路载体,即所谓“模块化的互连器件”的方法具有以下优点:制造用的工具开销可保持相对较低。此外所需的生产过程的步骤可以减少,因为未蜕变的金属螯合络合物可保留在电路载体表面未被照射的区域中。对于中等大小件数也可以非常经济地生产,并且可以实现特别精细的结构图分辨率。This method can be used to produce circuit carriers from thermoplastics by injection molding. In addition, the three-dimensional injection-molded circuit carrier can be produced by other methods, the so-called "modular interconnection device" method, which has the advantage that the tool outlay for production can be kept relatively low. In addition, the number of steps in the production process required can be reduced, since untransformed metal chelate complexes can remain in the unirradiated regions of the circuit carrier surface. It can also be produced very economically in medium-sized piece quantities and achieves particularly fine structural drawing resolutions.
相对于所谓的优点,上述方法的缺点在于上述金属螯合络合物的热稳定性对于现代高温塑料-如LCP-的加工处理温度处于临界范围内。因此该方法仅能有限制地应用在对于将来的无铅焊接工艺变得越来越重要的材料领域中。此外金属螯合合成体必须采用相对较高的掺杂,以在激光作用下得到足够密度的晶核用于快速金属化。然而高的合成体成份通常会损害承载材料所需的重要性能,如断裂强度和韧性。The disadvantage of the above-mentioned methods, relative to the alleged advantages, is that the thermal stability of the above-mentioned metal chelate complexes is in the critical range for the processing temperatures of modern high-temperature plastics, such as LCP. This method can therefore only be used to a limited extent in the field of materials which will become more and more important for future lead-free soldering processes. In addition, metal chelate composites must be doped relatively high in order to obtain sufficient density of crystal nuclei for rapid metallization under laser action. However, a high composite composition often compromises important properties required for load-bearing materials, such as fracture strength and toughness.
此外,Erlangen-Nürnberg大学LFT的工作报告1999公开了一种类似的方法,其中由激光射线分离出的金属化晶核不像上面所述那样化学结合,而是通过金属微粒的隔离而物理钝化。因为被隔离的微粒明显大于典型的金属螯合合成体的分子,这里比可通过激光分离出的金属螯合合成体导致“塑料中的小量掺入与激光照射后的高晶核密度”之间更大的矛盾。Furthermore, the working report 1999 of the LFT of the University of Erlangen-Nürnberg discloses a similar method in which the metallized nuclei separated by the laser beam are not chemically bonded as described above, but are physically passivated by the isolation of metal particles . Since the isolated particles are significantly larger than the molecules of typical metal chelate complexes, the ratio between metal chelate complexes that can be isolated by laser results here in "small incorporation in plastics and high crystal nucleus density after laser irradiation". greater contradictions.
WO 0035259A2描述了一种用于在不导电承载材料上制造精细的金属导体轨道结构的方法,其中一个由有机络合剂构成的不导电重金属合成物被涂覆在承载材料上或嵌入到承载材料中,承载材料在产生导体轨道结构的区域内有选择性地由紫外线照射,同时重金属晶核被分离出来,并且此区域被以化学方式还原金属化。这里可通过简单且可靠的方法制造导体轨道的精细结构。WO 0035259A2 describes a method for producing fine metal conductor track structures on non-conductive carrier materials, in which a non-conductive heavy metal composition consisting of organic complexing agents is coated on or embedded in the carrier material In this method, the carrier material is selectively irradiated with ultraviolet light in the region where the conductor track structure is produced, while the heavy metal nuclei are separated and the region is chemically reductively metallized. Here, the fine structure of the conductor tracks can be produced in a simple and reliable manner.
本发明的目的在于在电路载体上提供可简单并可靠地生产的导体轨道结构,此结构含有相对少量的形成晶核的添加物成份,并且在焊接温度下仍然稳定,此外本发明的目的还在于给出一种简单而可靠的制造导体轨道结构的方法,其中可以采用合成或喷铸,以及现代高温塑料。The object of the invention is to provide a simple and reliable producible conductor track structure on a circuit carrier, which contains a relatively small amount of nucleating additive components and is stable at soldering temperatures, and it is also an object of the invention to A simple and reliable method of fabricating conductor track structures is given, in which synthetic or spray-cast, as well as modern high-temperature plastics can be employed.
根据本发明的一个方面,提供一种用于制造不导电的承载材料上的导体轨道结构的方法,其中所述导体轨道结构由金属晶核以及后续在金属晶核上涂覆的金属化层构成,所述金属晶核通过电磁辐射实现的精细分布地包含在所述承载材料中的不导电金属化合物的断裂而形成,高度热稳定的、在含水的酸性或碱性金属化电解液中稳定且不溶解的、不导电的基于尖晶石的较高阶氧化物或者结构类似尖晶石的简单的d-金属氧化物或其混合物或者混合金属化合物被掺入所述承载材料中,所述承载材料被加工成构件或作为涂层涂覆在构件上,并且在要产生导体轨道结构的区域内借助电磁射线分离出重金属晶核,然后该区域被化学还原金属化。不导电的金属化合物由高度热稳定的、在含水的酸性或碱性金属化电解液中稳定且不溶解的无机氧化物构成,这些氧化物是具有尖晶石结构的较高阶氧化物,或者是结构类似尖晶石的简单的d-金属氧化物或其混合物或者混合金属化合物,这样可以使在承载材料表面上未被照射的区域内金属化合物保持不变。所使用的无机氧化物是耐热的,这样它们在焊接温度作用后仍保持稳定,即仍然不导电,并且在用于金属化的电解液中保持稳定。在有选择性的塑料粉末激光烧结情况下(实际上“快速成型”比有选择性的激光烧结更为人所知),所使用的无机氧化物是特别耐热的,这样在粉末状的输出材料局部熔化时可以形成一个构件,它也是不导电的并且在用于金属化的电解液中是稳定的。同样这些方法可考虑由液相材料制造构件。“导体轨道结构”这一概念也包括电子技术中经常为屏蔽目的而进行的全表面金属化这一极端情况。According to one aspect of the invention, there is provided a method for producing a conductor track structure on a non-conductive carrier material, wherein the conductor track structure consists of a metal nucleus and a metallization layer subsequently applied on the metal nucleus , the metal nuclei are formed by the fragmentation of a finely distributed non-conductive metal compound contained in the carrier material by electromagnetic radiation, are highly thermally stable, stable in aqueous acidic or alkaline metallization electrolytes and Insoluble, non-conductive spinel-based higher-order oxides or simple d-metal oxides or mixtures or mixed metal compounds similar in structure to spinels are incorporated into the carrier material, the carrier material The material is processed into a component or applied as a coating, and heavy metal nuclei are separated by means of electromagnetic radiation in the region where the conductor track structure is to be produced, and the region is then metallized by chemical reduction. Non-conductive metal compounds composed of highly thermally stable, stable and insoluble inorganic oxides in aqueous acidic or basic metallization electrolytes, which are higher order oxides with a spinel structure, or These are simple d-metal oxides or their mixtures or mixed metal compounds with a structure similar to spinel, so that the metal compounds remain unchanged in the non-irradiated regions of the surface of the carrier material. The inorganic oxides used are heat-resistant so that they remain stable after the soldering temperature, ie remain non-conductive, and are stable in the electrolyte used for the metallization. In the case of selective laser sintering of plastic powders (actually "rapid prototyping" is better known than selective laser sintering), the inorganic oxides used are particularly heat-resistant, so that the output material in powder form Partial melting can form a component that is also non-conductive and stable in the electrolyte used for metallization. These methods also allow for the production of components from liquid-phase materials. The term "conductor track structure" also includes the extreme case of full-surface metallization, which is often used for shielding purposes in electronics.
根据本发明的一个具有优点的实施方式,借助于一束电磁射线同时分离出重金属晶核,并通过蚀损来形成一个增附表面。这样通过简单的手段实现了被隔离的金属导电轨道良好的附着性。According to an advantageous embodiment of the invention, the heavy metal nuclei are simultaneously detached by means of an electromagnetic beam and an adhesion-promoting surface is formed by erosion. This achieves good adhesion of the isolated metal conductor tracks by simple means.
此外无机氧化物含有铜是有好处的。Furthermore, it is advantageous for the inorganic oxide to contain copper.
按照本发明的一个具有优点的实施方式,不导电的载体材料除至少含有尖晶石外还至少含有热稳定的有机金属螯合合成体。According to an advantageous embodiment of the invention, the non-conductive carrier material contains, in addition to at least spinel, at least a thermally stable organometallic chelate complex.
不导电的承载材料最好是热塑性或硬塑性塑料。不导电的承载材料可以包含一种或多种有机填充物质,它们例如由硅酸和/或硅酸衍生物构成。The non-conductive carrier material is preferably thermoplastic or duroplastic. The non-conductive carrier material can contain one or more organic filler substances, which consist, for example, of silicic acid and/or silicic acid derivatives.
在本发明的方法中,高度热稳定的、在含水的酸性或碱性金属化电解液中稳定且不溶解的、不导电的基于尖晶石的较高阶氧化物被掺入承载材料中,承载材料被加工成构件或作为涂层涂覆在构件上,并且在要产生导体轨道结构的区域内借助电磁射线分离出重金属晶核,此区域然后被化学还原金属化,尤其是还可以使得在承载材料表面未被照射的区域中无机金属化合物仍可保持基于尖晶石的较高阶氧化物的形式。所使用的无机氧化物通常是耐热的,因此可以使用合成或喷铸,以及现代高温塑料。此外,它们在焊接温度作用后仍保持稳定,即它们仍不导电并在用于金属化的电解液中保持稳定。In the process of the invention, highly thermally stable, stable and insoluble in aqueous acidic or alkaline metallization electrolytes, non-conductive spinel-based higher order oxides are incorporated into the carrier material, The carrier material is processed into the component or applied as a coating on the component, and heavy metal nuclei are separated by means of electromagnetic radiation in the region where the conductor track structure is to be produced, and this region is then chemically reduced to metallize, in particular also making it possible to The inorganic metal compound can remain in the form of a spinel-based higher order oxide in the non-irradiated regions of the carrier material surface. The inorganic oxides used are generally heat-resistant, so synthetic or spray-cast, as well as modern high-temperature plastics can be used. Furthermore, they remain stable after the soldering temperature, ie they remain non-conductive and stable in the electrolyte used for metallization.
按照本发明的一个具有优点的实施方式,借助一束电磁射线同时分离出重金属晶核,且通过蚀损来形成一个增附表面。这样通过简单的手段实现了被隔离的金属导电轨道良好的附着性。According to an advantageous embodiment of the invention, the heavy metal nuclei are simultaneously detached by means of an electromagnetic beam and an adhering surface is formed by erosion. This achieves good adhesion of the isolated metal conductor tracks by simple means.
此外无机氧化物含有铜是有好处的。Furthermore, it is advantageous for the inorganic oxide to contain copper.
按照本发明的一个具有优点的实施方式,不导电的承载材料除至少含有一种无机氧化物外还至少含有热稳定的有机金属螯合合成体。According to an advantageous embodiment of the invention, the non-conductive carrier material contains, in addition to at least one inorganic oxide, at least a thermally stable organometallic chelate complex.
不导电的承载材料最好是热塑性或硬塑性塑料。但是承载材料也可由其它合适的非导电材料,例如陶瓷材料构成。不导电的承载材料还可包含一种或多种有机填充物质,它们例如由硅酸和/或硅酸衍生物构成。The non-conductive carrier material is preferably thermoplastic or duroplastic. However, the carrier material can also consist of other suitable non-conductive materials, for example ceramic materials. The non-conductive carrier material can also contain one or more organic filler substances, which consist, for example, of silicic acid and/or silicic acid derivatives.
具有优点的是利用激光器的电磁射线分离出重金属晶核。激光的波长最好可以为248nm,308nm,335nm,532nm,1064nm或10600nm。It is advantageous to use the electromagnetic radiation of the laser to separate out the heavy metal nuclei. Preferably, the wavelength of the laser can be 248nm, 308nm, 335nm, 532nm, 1064nm or 10600nm.
下面借助一个实施例说明本发明:The present invention is illustrated below by means of an embodiment:
在一台挤压机中用70%质量的聚对苯二甲酸丁二醇酯(polybuthylentherephthalat)和25%质量的热解硅酸,以90m2/g的BET表面积(用布鲁璃厄-埃梅特-泰勒法测定的催化剂表面积)和5%的含铜尖晶石PK3095(Ferro公司出品)合成。颗粒以喷铸方法被加工成一个构件,例如一个外壳。此外壳然后在要形成导体轨道的区域内以一定的强度照射激光射线,激光射线由一台二极管激励的Nd:YAG激光器(掺钕钇铝石榴石激光器)产生,所采用的激光强度形成与被构造的晶核相连接的很小的联结蚀损。在含有软化水的超声净化槽中进行短时间处理之后,此外壳被悬挂在通用的化学还原镀铜槽中。在被照射的区域中形成导体轨道。In an extruder with 70% by mass of polybutylene terephthalate (polybutylentherephthalat) and 25% by mass of pyrogenic silicic acid, with a BET surface area of 90m 2 /g (using Brueger-Angstrom) Catalyst surface area determined by Metter-Taylor method) and 5% copper-containing spinel PK3095 (manufactured by Ferro Company) was synthesized. The particles are processed by injection molding to form a component, for example a housing. The housing is then irradiated with laser beams at a certain intensity in the area where the conductor track is to be formed. The laser beam is generated by a diode-excited Nd:YAG laser (neodymium-doped yttrium aluminum garnet laser). Small junction erosion where the crystal nuclei of the structure are connected. After a short treatment in an ultrasonic cleaning bath with demineralized water, the housing is suspended in a conventional chemical reduction copper plating bath. Conductor tracks are formed in the irradiated area.
还要指出,在本领域中认为金属与非金属,如碳化物、氧化物或硫化物的简单的无机结合是稳定的,并且仅在高能量供给的情况下在基本金属中同时可馈送还原介质时才适用。此外,在环境空气中,尤其在非贵重金属情况下,形成的金属与空气中的氧气会立即发生反应形成金属氧化物。令人惊奇的是按照本发明,具有精细分布地嵌入塑料基体中的尖晶石结构的金属氧化物在常规环境空气中可用Nd:YAG激光器剥离出来并还原成金属。在能量很高、然而非常短的激光脉冲作用下同时形成的塑料的气态分解产物覆盖在形成的金属晶核上,形成足够的屏蔽作用。Note also that simple inorganic combinations of metals with non-metals such as carbides, oxides or sulfides are considered in the art to be stable and simultaneously feedable reducing media in the base metal only with high energy supply only applies when. Furthermore, in ambient air, especially in the case of non-noble metals, the formed metal reacts immediately with the oxygen in the air to form metal oxides. Surprisingly, according to the invention, metal oxides having a finely distributed spinel structure embedded in a plastic matrix can be exfoliated with an Nd:YAG laser in normal ambient air and reduced to metal. The gaseous decomposition products of the plastic formed at the same time under the action of very high-energy, but very short laser pulses cover the formed metal nuclei and form a sufficient shielding effect.
Claims (15)
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10132092.2 | 2001-07-05 | ||
| DE10132092A DE10132092A1 (en) | 2001-07-05 | 2001-07-05 | Track structures and processes for their manufacture |
| EP01130189.2 | 2001-12-19 | ||
| EP01130189A EP1274288B1 (en) | 2001-07-05 | 2001-12-19 | Conducting path structures and method of making |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1518850A CN1518850A (en) | 2004-08-04 |
| CN1326435C true CN1326435C (en) | 2007-07-11 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB028126092A Ceased CN1326435C (en) | 2001-07-05 | 2002-06-19 | Conductor track structures and method for production thereof |
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| Country | Link |
|---|---|
| JP (1) | JP3881338B2 (en) |
| CN (1) | CN1326435C (en) |
| WO (1) | WO2003005784A2 (en) |
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| US8883900B2 (en) | 2010-10-25 | 2014-11-11 | Sabic Global Technologies B.V. | Electroless plating performance of laser direct structuring materials |
| CN103249572A (en) * | 2010-10-26 | 2013-08-14 | 沙特基础创新塑料Ip私人有限责任公司 | Laser Directly Structured Materials with Full Color Capability |
| CN103249572B (en) * | 2010-10-26 | 2016-06-22 | 沙特基础全球技术有限公司 | Laser Directly Structured Materials with Full Color Capability |
| CN103313505A (en) * | 2012-03-13 | 2013-09-18 | 昆山联滔电子有限公司 | Conductor track structure on non-conductive bearing material and manufacturing method of conductor track structure |
| CN103313505B (en) * | 2012-03-13 | 2016-05-25 | 昆山联滔电子有限公司 | The manufacture method of the conductor track structure on non-conductive loading material |
Also Published As
| Publication number | Publication date |
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| CN1518850A (en) | 2004-08-04 |
| WO2003005784A3 (en) | 2003-04-24 |
| JP3881338B2 (en) | 2007-02-14 |
| WO2003005784A2 (en) | 2003-01-16 |
| JP2004534408A (en) | 2004-11-11 |
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