TWI481327B - Method for manufacturing a conductive circuit - Google Patents
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本發明係關於一種導電線路的形成方法。The present invention relates to a method of forming a conductive line.
導電線路的應用很廣，可應用在印刷電路板、觸控面板等產品。常見的導電線路製作方式有黃光微影製程與噴印製程。黃光微影製程包括將金屬薄膜壓於基板表面，再用旋轉塗佈的方法在金屬薄膜表面形成一光阻層，而後再加以光罩曝光、顯影、刻蝕，進而再加以鑽孔、壓合與電鍍等多項步驟，最後還需多項測試及修補後才能完成整個流程。近來發展的噴印製程將墨水直接噴在基板上，再經過燒結得到導電線路，加熱的溫度依照材料而不同，大約在150℃以上甚至超過在1000℃。Conductive lines are widely used in printed circuit boards, touch panels and other products. Common conductive circuit manufacturing methods include yellow light lithography process and printing process. The yellow light lithography process comprises pressing a metal film on the surface of the substrate, and then forming a photoresist layer on the surface of the metal film by spin coating, and then exposing, developing, etching, and then drilling and pressing the mask. A number of steps, such as electroplating, require a number of tests and repairs to complete the process. Recently developed printing processes spray ink directly onto the substrate and then sinter to obtain conductive lines. The heating temperature varies depending on the material, and is about 150 ° C or more and even more than 1000 ° C.
綜上所述，目前亟需製程簡化與可低溫操作的導電線路製造方法。In summary, there is a need for a method of manufacturing a conductive circuit that simplifies the process and can be operated at a low temperature.
本發明一實施例提供一種導電線路的形成方法，包括：將一金屬氧化物油墨組合物覆蓋於一基材上，形成一薄膜，其中該金屬氧化物油墨組合物包含一金屬氧化物粉體、一感光還原劑、以及一溶劑；以及，以一雷射光束對該薄膜之至少一部份進行照射，以使該薄膜照光的部份內之金屬氧化物粉 體還原成金屬，該薄膜照光的部份形成該導電線路。An embodiment of the present invention provides a method for forming a conductive line, comprising: coating a metal oxide ink composition on a substrate to form a film, wherein the metal oxide ink composition comprises a metal oxide powder, a photosensitive reducing agent, and a solvent; and irradiating at least a portion of the film with a laser beam to cause the metal oxide powder in the portion of the film to be illuminated The body is reduced to a metal, and the illuminated portion of the film forms the conductive line.
10‧‧‧基材10‧‧‧Substrate
12‧‧‧薄膜12‧‧‧ Film
12a‧‧‧預定照光區12a‧‧‧Scheduled lighting area
12b‧‧‧非照光區12b‧‧‧Non-illuminated area
14‧‧‧導電線路14‧‧‧Electrical circuit
第1至3圖係為一系列剖面結構圖，用以說明本發明一實施例所述之導電線路的形成方法。1 to 3 are a series of sectional structural views for explaining a method of forming a conductive line according to an embodiment of the present invention.
本發明一實施例提供一種導電線路的形成方法，可利用照光方式將一由金屬氧化物油墨組合物所形成的薄膜中之照光部份轉換成導電圖形，得到該導電線路。An embodiment of the invention provides a method for forming a conductive line, which can be converted into a conductive pattern by a light-emitting method to convert a light-emitting portion of a film formed of a metal oxide ink composition to obtain a conductive line.
根據本發明一些實施例，該導電線路的形成方法，包括：將金屬氧化物油墨組合物覆蓋於基材上，形成薄膜；以及，以雷射光束對該薄膜之至少一部份進行照射，以使薄膜照光的部份內的金屬氧化物粉體(例如為氧化銅粉體)還原成金屬(例如為銅)，將該薄膜照光的部份轉換成該導電線路。其中，金屬氧化物油墨組合物包含金屬氧化物粉體、感光還原劑以及溶劑。薄膜的厚度可視加工方式或應用需求調整，例如可約介於50nm~10000nm之間，但不以此為限。此外，金屬氧化物油墨組合物可更包含醇胺類化合物，使油墨中金屬粉體分散均勻。根據本發明實施例，該金屬氧化物粉體係為氧化銀粉體、氧化銅粉體、或其混合。According to some embodiments of the present invention, a method of forming the conductive line includes: covering a metal oxide ink composition on a substrate to form a film; and irradiating at least a portion of the film with a laser beam to The metal oxide powder (for example, copper oxide powder) in the portion where the film is illuminated is reduced to a metal (for example, copper), and the illuminated portion of the film is converted into the conductive line. Among them, the metal oxide ink composition contains a metal oxide powder, a photosensitive reducing agent, and a solvent. The thickness of the film can be adjusted according to the processing mode or application requirements, for example, it can be between 50 nm and 10000 nm, but not limited thereto. Further, the metal oxide ink composition may further contain an alcohol amine compound to uniformly disperse the metal powder in the ink. According to an embodiment of the invention, the metal oxide powder system is a silver oxide powder, a copper oxide powder, or a mixture thereof.
金屬氧化物油墨組合物所使用的金屬氧化物粉體的粒徑可約介於1-100nm之間，若金屬氧化物粉體的粒徑過大，則成形之薄膜易有孔隙，造成特性不佳，若粒徑過小，則易聚集，不易分散與成膜。金屬氧化物粉體在金屬氧化物油墨組合物中的含量可約介於10g/L-200g/L之間，若濃度過高，則 不易均勻分散於溶劑中，造成成膜品質不佳，若濃度過低，則易導致成膜結構鬆散，特性降低。感光還原劑可為乙二醇、丙二醇、聚乙二醇、或聚丙二醇。感光還原劑在金屬氧化物油墨組合物中的濃度可約介於10-1 mol/L至20mol/L之間，若濃度過高，則不易成膜；若濃度過低，則金屬氧化物還原不完全。金屬氧化物油墨組合物所添加的溶劑可為水、甲醇、乙醇或異丙醇等。醇胺類化合物例如為乙醇胺(ethanolamine、MEA)、二乙醇胺(diethanolamine、DEA)、或三乙醇胺(triethanolamine、TEA)，醇胺類化合物在金屬氧化物油墨組合物中的濃度可約介於10-1 mol/L至5mol/L。根據一些實施例，本發明所述之金屬氧化物油墨組合物不需額外添加助劑，例如不需另添加酸或鹼幫助金屬氧化物粉體還原。The metal oxide powder used in the metal oxide ink composition may have a particle diameter of about 1 to 100 nm. If the particle size of the metal oxide powder is too large, the formed film is likely to have pores, resulting in poor properties. If the particle size is too small, aggregation tends to occur, and it is difficult to disperse and form a film. The content of the metal oxide powder in the metal oxide ink composition may be between about 10 g/L and 200 g/L. If the concentration is too high, it is difficult to uniformly disperse in the solvent, resulting in poor film formation quality. If the concentration is too low, the film formation structure is loose and the characteristics are lowered. The photosensitive reducing agent may be ethylene glycol, propylene glycol, polyethylene glycol, or polypropylene glycol. The concentration of the photosensitive reducing agent in the metal oxide ink composition may be between about 10 -1 mol/L and 20 mol/L. If the concentration is too high, the film formation is not easy; if the concentration is too low, the metal oxide is reduced. incomplete. The solvent to be added to the metal oxide ink composition may be water, methanol, ethanol or isopropanol or the like. The alcohol amine compound is, for example, ethanolamine (MEA), diethanolamine (DEA), or triethanolamine (TEA), and the concentration of the alcohol amine compound in the metal oxide ink composition may be about 10 - 1 mol/L to 5 mol/L. According to some embodiments, the metal oxide ink composition of the present invention does not require additional additives, for example, without the addition of an acid or a base to assist in the reduction of the metal oxide powder.
首先，請參照第1圖，將金屬氧化物油墨組合物覆 蓋於基材10上以形成薄膜12，其中將金屬氧化物油墨組合物覆蓋於基材10上的方式包含浸入塗佈法、旋轉塗佈法、凹版印刷法、網版印刷法、噴灑塗佈法、刮刀塗佈法、或噴墨印刷法。 其中基材10可為任何基材，例如玻璃、矽晶圓、PET塑膠、PI塑膠或PEN塑膠。此外，該基材10可為一可撓曲基材，例如薄型玻璃、PET(Polyethylene terephthalate)塑膠、PI(Polyimide)塑膠或PEN(Polyethylene naphthalate)塑膠。其中，該薄膜12具有一預定照光區12a以及一非照光區12b。First, please refer to Figure 1 to cover the metal oxide ink composition. Covering the substrate 10 to form a film 12, wherein the metal oxide ink composition is coated on the substrate 10, including a dip coating method, a spin coating method, a gravure printing method, a screen printing method, and a spray coating method. Method, knife coating method, or inkjet printing method. The substrate 10 can be any substrate such as glass, germanium wafer, PET plastic, PI plastic or PEN plastic. In addition, the substrate 10 can be a flexible substrate such as thin glass, PET (Polyethylene terephthalate) plastic, PI (Polyimide) plastic or PEN (Polyethylene naphthalate) plastic. The film 12 has a predetermined illumination area 12a and a non-illumination area 12b.
接著，請參照第2圖，以一雷射光束對薄膜12之至 少一部份(預定照光區12a)進行照射，以使薄膜12照光的部份內之金屬氧化物粉體還原成金屬，將薄膜12照光的部份(預定照 光區12a)轉換成導電線路14。雷射光束的波長可約介於0.125μm至11μm之間，若波長過短，則容易將直接氣化，無產生還原反應，若波長過長，則熱影響過大，易損毀基材。雷射光束的能量密度可約介於0.03J/cm2 至10J/cm2 之間，若能量密度過高，則將直接損毀基材，若能量密度過低，則不足以激發還原反應。在一實施例中，薄膜中之感光還原劑經雷射光束照射後可能轉變為醛類，進而使金屬氧化物粉體還原成金屬(例如將氧化銅粉體還原成銅、或將氧化銀粉體還原成銀)，提升導電性。在另一實施例中，可選擇性利用光罩或聚焦光源等方式以雷射光束對薄膜之部份區域進行照射，製作圖案化導電線路，並可製作欲形成之線寬，在實施例中線寬甚至可達小於30μm，在此圖案化步驟中亦可視需求調整照光與未照光之面積比例。Next, referring to FIG. 2, at least a portion of the film 12 (predetermined illumination region 12a) is irradiated with a laser beam to reduce the metal oxide powder in the portion illuminated by the film 12 to metal. The portion of the film 12 that is illuminated (the predetermined illumination region 12a) is converted into a conductive line 14. The wavelength of the laser beam can be between about 0.125 μm and 11 μm. If the wavelength is too short, it is easy to vaporize directly, and no reduction reaction occurs. If the wavelength is too long, the heat influence is too large, and the substrate is easily damaged. The energy density of the laser beam may be between about 0.03 J/cm 2 and 10 J/cm 2 . If the energy density is too high, the substrate will be directly damaged. If the energy density is too low, the reduction reaction is insufficient. In one embodiment, the photosensitive reducing agent in the film may be converted into an aldehyde after being irradiated by the laser beam, thereby reducing the metal oxide powder to a metal (for example, reducing the copper oxide powder to copper or silver oxide powder). The body is reduced to silver) to improve conductivity. In another embodiment, a portion of the film may be selectively irradiated with a laser beam by means of a reticle or a focusing light source to form a patterned conductive line, and a line width to be formed may be formed, in an embodiment. The line width can even be less than 30 μm, and the ratio of the area of the illuminated light to the unilluminated can also be adjusted in the patterning step.
根據一些實施例，請參照第3圖，在對該薄膜12照 光之後可更進一步地將薄膜12未照光的部份(非照光區12b)移除。移除的方式可使用有機溶劑(例如乙醇、丙酮或異丙醇)或水清洗，可在移除後可視需求形成其他介電層或絕緣層。在本發明其他實施例，亦可不移除薄膜未照光的部份，將其作為絕緣層。According to some embodiments, please refer to FIG. 3, in the film 12 The unlit portion (non-illuminated region 12b) of the film 12 can be further removed after the light. The means of removal can be washed with an organic solvent such as ethanol, acetone or isopropanol or water, and other dielectric or insulating layers can be formed as needed after removal. In other embodiments of the present invention, the unilluminated portion of the film may not be removed as an insulating layer.
根據本發明一些實施例，導電線路形成方法可適 合在具有低裂解溫度的可撓曲基材上(例如裂解溫度小於400℃的塑膠基板)形成導電線路，由於導電線路形成方法可不使用加熱製程、真空製程或鍛燒製程，除製程簡化之外，可避免可撓曲基材因過高的製程溫度而受損或裂解，亦可適用於3D 或曲面之結構上直接形成導線。According to some embodiments of the present invention, a conductive line forming method is suitable The conductive substrate is formed on a flexible substrate having a low cracking temperature (for example, a plastic substrate having a cracking temperature of less than 400 ° C), and the conductive circuit forming method can be used without a heating process, a vacuum process, or a calcination process, except for process simplification. Can avoid the damage or cracking of the flexible substrate due to excessive process temperature, and can also be applied to 3D Or directly form a wire on the surface of the surface.
為了讓本發明之上述和其他目的、特徵、和優點能更明顯易懂，下文特舉數實施例配合所附圖示，作詳細說明如下：【實施例】The above and other objects, features and advantages of the present invention will become more apparent and understood.
雖然本發明已以數個較佳實施例揭露如上，然其並非用以限定本發明，任何熟習此技藝者，在不脫離本發明之精神和範圍內，當可作任意之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。While the invention has been described above in terms of several preferred embodiments, it is not intended to limit the invention, and the invention may be modified and modified without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims.
實施例1Example 1
將粒徑約50nm之氧化銅粉末1.5g於100ml之乙醇中混合(濃度約0.2M)，待分散均勻後，加入12.5ml之乙二醇、與5ml之乙醇胺混合，得到一混合溶液，將上述混合溶液以旋轉塗佈方式於玻璃基板上形成一薄膜，接著以波長約1.064μm能量密度約0.15J/cm2 之電射照射薄膜約0.1分鐘，可得到厚度約100nm線寬約50μm之銅導線，片電阻約0.5ohm/square，電阻係數約5x10-6 Ω．cm，請參照表1。1.5 g of copper oxide powder having a particle diameter of about 50 nm is mixed in 100 ml of ethanol (concentration: about 0.2 M), and after being uniformly dispersed, 12.5 ml of ethylene glycol is added, and 5 ml of ethanolamine is mixed to obtain a mixed solution. The mixed solution is formed into a film on a glass substrate by spin coating, and then irradiated with an electron beam having an energy density of about 0.15 μm/cm 2 of about 1.064 μm for about 0.1 minute to obtain a copper wire having a thickness of about 100 nm and a line width of about 50 μm. The sheet resistance is about 0.5 ohm/square and the resistivity is about 5x10 -6 Ω. Cm, please refer to Table 1.
實施例2Example 2
如實施例1所述之方式進行，除了所製備的混合溶液中不包含5ml之乙醇胺。將所得之混合溶液以旋轉塗佈方式於玻璃基板上形成一薄膜，接著以波長約1.064μm能量密度約0.15J/cm2 之電射照射薄膜約0.1分鐘，可得到厚度約100nm線寬約50μm之銅導線，電阻係數約8.6x10-6 Ω．cm，請參照表1。This was carried out as described in Example 1, except that 5 ml of ethanolamine was not contained in the mixed solution prepared. The obtained mixed solution was formed into a film on a glass substrate by spin coating, and then irradiated with an electric wave having an energy density of about 0.15 μm/cm 2 of about 1.064 μm for about 0.1 minute to obtain a thickness of about 100 nm and a line width of about 50 μm. The copper wire has a resistivity of about 8.6x10 -6 Ω. Cm, please refer to Table 1.
實施例3Example 3
將粒徑約50nm之氧化銅粉末1.5g於100ml之乙醇中混合(濃度約0.2M)，待分散均勻後，加入12.5ml之乙二醇、與5ml之乙醇胺混合，得到一混合溶液。接著，將上述混合溶液以旋轉塗佈方式於PET基板上形成一薄膜，接著以波長約1.064μm能量密度約0.15J/cm2 之電射照射薄膜約0.1分鐘，可得到厚度約100nm線寬約50μm之銅導線，電阻係數約9x10-6 Ω．cm。請參照表2，係顯示為實施例1及實施例3的比較。1.5 g of copper oxide powder having a particle diameter of about 50 nm was mixed in 100 ml of ethanol (concentration: about 0.2 M), and after uniform dispersion, 12.5 ml of ethylene glycol was added, and 5 ml of ethanolamine was mixed to obtain a mixed solution. Next, the mixed solution is formed into a film on the PET substrate by spin coating, and then the film is irradiated with an electric energy having a wavelength of about 1.064 μm and an energy density of about 0.15 J/cm 2 for about 0.1 minute to obtain a line width of about 100 nm. 50μm copper wire, the resistance coefficient is about 9x10 -6 Ω. Cm. Please refer to Table 2 for comparison of Example 1 and Example 3.
實施例4Example 4
如實施例1所述之方式進行，除了將乙二醇的量由12.5ml降低至8ml。將所得之混合溶液以旋轉塗佈方式於玻璃基板上形成一薄膜，接著以波長約1.064μm能量密度約0.15J/cm2 之電射照射薄膜約0.1分鐘，可得到厚度約100nm線寬約50μm之銅導線，電阻係數約1x10-5 Ω．cm。請參照表2，係顯示實施例1及實施例4的比較。This was carried out as described in Example 1, except that the amount of ethylene glycol was reduced from 12.5 ml to 8 ml. The obtained mixed solution was formed into a film on a glass substrate by spin coating, and then irradiated with an electric wave having an energy density of about 0.15 μm/cm 2 of about 1.064 μm for about 0.1 minute to obtain a thickness of about 100 nm and a line width of about 50 μm. The copper wire has a resistivity of about 1x10 -5 Ω. Cm. Referring to Table 2, a comparison between Example 1 and Example 4 is shown.
實施例5Example 5
如實施例1所述之方式進行，除了將乙二醇的量由12.5ml增加至25ml。將所得之混合溶液以旋轉塗佈方式於玻璃基板上形成一薄膜，接著以波長約1.064μm能量密度約0.15J/cm2 之電射照射薄膜約0.1分鐘，可得到厚度約100nm線寬約50μm之銅導線，電阻係數約9x10-6 Ω．cm。請參照表2，係顯示實施例1及實施例5的比較。This was carried out as described in Example 1, except that the amount of ethylene glycol was increased from 12.5 ml to 25 ml. The obtained mixed solution was formed into a film on a glass substrate by spin coating, and then irradiated with an electric wave having an energy density of about 0.15 μm/cm 2 of about 1.064 μm for about 0.1 minute to obtain a thickness of about 100 nm and a line width of about 50 μm. The copper wire has a resistivity of about 9x10 -6 Ω. Cm. Referring to Table 2, a comparison between Example 1 and Example 5 is shown.
比較實施例1Comparative Example 1
將粒徑約50nm之氧化銅粉末1.5g於100ml之乙醇中混合(濃度約0.2M)，待分散均勻後，加入12.5ml之乙二醇、與5ml之乙醇胺混合，得到一混合溶液。將上述混合溶液以旋轉塗佈方式於玻璃基板上形成一薄膜，量測其電阻(約大於1000Ω‧cm)。接著對該薄膜進行一加熱製程，加熱溫度為400℃而加熱時間約60分鐘。觀察加熱後之薄膜，薄膜之外型顏色仍維持黑色，並量測其電阻值(約大於1000Ω‧cm，與加熱前相同)，表示無還原反應發生。1.5 g of copper oxide powder having a particle diameter of about 50 nm was mixed in 100 ml of ethanol (concentration: about 0.2 M), and after uniform dispersion, 12.5 ml of ethylene glycol was added, and 5 ml of ethanolamine was mixed to obtain a mixed solution. The above mixed solution was formed into a film on a glass substrate by spin coating, and its electric resistance (about more than 1000 Ω ‧ cm) was measured. The film was then subjected to a heating process at a heating temperature of 400 ° C and a heating time of about 60 minutes. The film after heating was observed, and the color of the film was maintained black, and the resistance value (about 1000 Ω ‧ cm, which is the same as before heating) was measured, indicating that no reduction reaction occurred.
比較實施例2Comparative Example 2
將粒徑約50nm之氧化銅粉末25g於100ml之乙醇中 混合，待分散均勻後，加入12.5ml之乙二醇、與5ml之乙醇胺混合，得到一混合溶液(金屬氧化物油墨組合物)。將上述混合溶液以旋轉塗佈方式於玻璃基板上形成一薄膜。接著以波長約1.064μm能量密度約0.15J/cm2 之電射照射薄膜約0.1分鐘。觀察照光後所得之薄膜，發現其顏色偏黑，表示金屬氧化物油墨組合物的還原反應並不完全。25 g of copper oxide powder having a particle diameter of about 50 nm was mixed in 100 ml of ethanol, and after uniform dispersion, 12.5 ml of ethylene glycol was added and mixed with 5 ml of ethanolamine to obtain a mixed solution (metal oxide ink composition). The above mixed solution was formed into a film on a glass substrate by spin coating. The film was then irradiated with an electron beam having a wavelength of about 1.064 μm and an energy density of about 0.15 J/cm 2 for about 0.1 minute. The film obtained after the illuminating was observed to find that the color was black, indicating that the reduction reaction of the metal oxide ink composition was not complete.
實施例6Example 6
將粒徑約50nm之氧化銀粉末1.5g於100ml之乙醇中混合(濃度約0.2M)，待分散均勻後，加入12.5ml之乙二醇、與5ml之乙醇胺混合，得到一混合溶液，將上述混合溶液以旋轉塗佈方式於玻璃基板上形成一薄膜，接著以波長約1.064μm能量密度約0.15J/cm2 之電射照射薄膜約0.1分鐘，可得到厚度約100nm線寬約50μm之銀導線，電阻係數約3.7x10-6 Ω．cm。1.5 g of silver oxide powder having a particle diameter of about 50 nm is mixed in 100 ml of ethanol (concentration: about 0.2 M), and after being uniformly dispersed, 12.5 ml of ethylene glycol is added, and 5 ml of ethanolamine is mixed to obtain a mixed solution. The mixed solution is formed into a film on a glass substrate by spin coating, and then irradiated with an electric wave having an energy density of about 0.15 μm/cm 2 of about 1.064 μm for about 0.1 minute to obtain a silver wire having a thickness of about 100 nm and a line width of about 50 μm. The resistivity is about 3.7x10 -6 Ω. Cm.
雖然本發明已以數個較佳實施例揭露如上，然其並非用以限定本發明，任何熟習此技藝者，在不脫離本發明之精神和範圍內，當可作任意之更動與潤飾，因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。While the invention has been described above in terms of several preferred embodiments, it is not intended to limit the invention, and the invention may be modified and modified without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims.
10‧‧‧基材10‧‧‧Substrate
14‧‧‧導電線路14‧‧‧Electrical circuit
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| TW201330738A (en) * | 2011-09-06 | 2013-07-16 | Henkel Corp | Conductive material and process |
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