TWI548723B - A composition of patterning etchant and patterning processes - Google Patents
A composition of patterning etchant and patterning processes Download PDFInfo
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本發明涉及一種使用二氧化氯為蝕刻劑的導電線路圖案化製程與蝕刻劑之化學組成,尤指一種應用於透明導電基材構造並藉此形成特定氧化區域圖案化(Patterning)之技術,其所形成的透明導電線路圖案化導電基材的應用包括印刷電子(Printed Electronics)、感應器(Sensor)、顯示器(Display)、有機發光二極體(OLED)、觸控面板(Touch Panel)、電子線路板(Electronic Circuit Board)、電極(Electrode)、冷光片(EL)、電熱板(Heater)、天線(Antenna)、太陽能電池(Solar Cell)。 The present invention relates to a chemical composition of a conductive line patterning process and an etchant using chlorine dioxide as an etchant, and more particularly to a technique for applying a transparent conductive substrate structure and thereby forming a specific oxidized region patterning. Applications of the patterned transparent conductive trace patterned conductive substrate include Printed Electronics, Sensors, Displays, Organic Light Emitting Diodes (OLEDs), Touch Panels, and Electronics Electronic Circuit Board, Electrode, Cold Light (EL), Heater, Antenna, Solar Cell.
習用導電基材的導電線路圖案化技術例如:美國專利US 8,252,386 B2(Samsung Electronics Co.,Ltd.)揭露一種形成導電高分子膜的方法,係混合一感光樹脂(Photosensitive Polymer Resin)與一種氧化劑(oxidant)的混合物,其係塗佈於一透明底材上,再利用氣相聚合Vapor-Phase Polymerization(VPP)的方式,在其透明底材上的氧化劑混合物表面形成導電膜,然後使用UV光照射含有感光性壓克力聚脂(Polyester Acrylate)或壓克力環氧樹脂(Epoxy Acylate)的感光聚合物以形成導電線路。另一美國發明專利6,649,327揭露在一基材上形成一導電高分子化合物層,並利用光罩區分將被 照射與不被照射的區塊,接著使用輻射光照射,然後移除光罩,在底材上形成所需的圖案。另一美國發明專利5,200,032揭露一種利用二氧化氯氣體來與晶圓(Wafer)的金屬銅層進行反應,來形成可氣化(Volatile)之銅化合物CuClxOy,並藉此來移除銅層之電線路圖案化技術。另一美國發明專利6,340,496(Agfa-Gevaert)則揭露一種含有ClO、BrO-、MnO4 -、Cr2O7-、S2O8-、H2O2氧化物的印刷溶液來提高底材上導電高分子的電氣阻抗。本發明係利用二氧化氯之特有的高度氧化能力之特性,其氧化的能力非由鹵素-氯原子所提供,而是由其結構中的氧原子所提供,也較一氧化氯(ClO)安全且不破壞大氣之臭氧層。另外因此本發明之圖案化製程與蝕刻劑,與其他物質反應時,二氧化氯不會氯化(Chlorination)其他物質而形成對環境具汙染性、破壞臭氧層或致癌性的有機鹵化物(THMs),例如三氯甲烷,因此,二氧化氯常應用於飲用水之消毒,本發明人應用二氧化氯之高氧力特性來轉而應用於透明導電線路圖案化之應用,發現具有非常優異之圖案化(Patterning)效果,且蝕刻後的蝕刻痕色差少且不明顯,對於光電、電子、觸控等產業等具有相當之利用價值。所形成的透明導電基材可應用於包括印刷電子(Printed Electronics)、感應器(Sensor)、顯示器(Display)、有機發光二極體(OLED)、觸控面板(Touch Panel)、電子線路板(Electronic Circuit Board)、電極(Electrode)、冷光片(EL)、電熱片(Heater)、天線(Antenna)、太陽能電池(Solar Cell)等應用,具有非常有效之蝕刻效果、容易控制氧化程度、製程簡化、蝕刻後的導電膜表面無高低差之問題、蝕刻痕色差少且不明顯、對使用人員的安全性高、生產成本低等優點。藉此將可有效控制品質,祈使減少損耗,降低製造成本,進而大幅提高生產效率。 A conductive line patterning technique for a conventional conductive substrate, for example, US Pat. No. 8,252,386 B2 (Samsung Electronics Co., Ltd.) discloses a method of forming a conductive polymer film by mixing a photosensitive resin (Photosensitive Polymer Resin) with an oxidizing agent ( a mixture of oxidant, which is coated on a transparent substrate, and then formed into a conductive film on the surface of the oxidant mixture on the transparent substrate by means of Vapor-Phase Polymerization (VPP), and then irradiated with UV light. A photopolymer containing photosensitive acrylic (Epoxy Acrylate) or acrylic epoxy (Epoxy Acylate) to form a conductive line. Another U.S. Patent No. 6,649,327 discloses the formation of a layer of a conductive polymer compound on a substrate, and the use of a mask to distinguish between the blocks to be illuminated and not to be illuminated, followed by irradiation with radiant light, and then the reticle is removed, at the bottom. The desired pattern is formed on the material. Another U.S. Patent No. 5,200,032 discloses the use of chlorine dioxide gas to react with a metal copper layer of a wafer to form a vaporizable copper compound CuCl x O y and thereby remove copper. Layer electrical circuit patterning technology. Another U.S. Patent No. 6,340,496 (Agfa-Gevaert) discloses a printing solution containing ClO, BrO - , MnO 4 - , Cr 2 O7-, S 2 O 8 -, H 2 O 2 oxides to improve conductivity on the substrate. The electrical impedance of the polymer. The present invention utilizes the characteristic characteristics of the high oxidizing power of chlorine dioxide, whose oxidizing ability is not provided by a halogen-chlorine atom, but is provided by an oxygen atom in its structure, and is also safer than chlorine monoxide (ClO). And does not destroy the ozone layer of the atmosphere. In addition, when the patterning process and the etchant of the present invention react with other substances, chlorine dioxide does not chlorinate other substances to form organic halides (THMs) which are polluting to the environment, depleting the ozone layer or causing carcinogenicity. For example, chloroform, therefore, chlorine dioxide is often used for disinfection of drinking water. The inventors applied the high oxygen property of chlorine dioxide to apply to the patterning of transparent conductive lines, and found that it has a very excellent pattern. The patterning effect is small, and the difference in etching marks after etching is small and inconspicuous, and has considerable value for use in industries such as photovoltaics, electronics, and touch. The formed transparent conductive substrate can be applied to include printed electronic (Printed Electronics), sensors, displays, organic light emitting diodes (OLEDs), touch panels (Touch Panels), electronic circuit boards ( Electronic Circuit Board, Electrode, EL, Heater, Antenna, Solar Cell, etc., with very effective etching effect, easy control of oxidation, and simplified process There is no problem of the difference in the surface of the conductive film after etching, the difference in etching marks is small and not obvious, the safety to the user is high, and the production cost is low. This will effectively control the quality, avoiding the loss and reducing the manufacturing cost, and thus greatly improving the production efficiency.
本發明提供一種含有二氧化氯的蝕刻劑與導電線路圖案化的製程,其中含有二氧化氯的上述水性蝕刻劑的酸鹼度(ph值)為8.0以下,以2.0至6.0為佳,所述的蝕刻劑為氣體、液體、膏狀物其中之一種型態。其製程包括將一含有本質性導電之共軛導電高分子及奈米銀絲(silver nanowires)中之一者之透明的一導電層覆蓋於一底材表面,將上述之含有二氧化氯的蝕刻劑覆蓋於上述導電層上之預定不須導電之區域來提高所接觸的導電層,亦可使用一遮蔽材覆蓋上述導電層之預定需要導電的一第一區域,使未覆蓋上述遮蔽材之上述導電層的一第二區域接觸含有二氧化氯的一氣體及含有二氧化氯的一水性蝕刻劑中之一者,使上述第二區域的電氣阻抗提高100倍以上至完全不導電而形成一非導電區,以及在上述非導電區以外的上述第一區域形成所需的一導電線路。 The present invention provides a process for patterning a etchant containing chlorine dioxide and a conductive line, wherein the aqueous etchant containing chlorine dioxide has a pH (pH) of 8.0 or less, preferably 2.0 to 6.0, and the etching is performed. The agent is one of a gas, a liquid, and a paste. The process comprises covering a surface of a substrate with a transparent conductive layer containing one of a substantially conductive conjugated conductive polymer and silver nanowires, and etching the chlorine dioxide containing the above. The agent covers the predetermined conductive layer on the conductive layer to improve the contacted conductive layer, and a masking material may be used to cover a first region of the conductive layer that is required to be electrically conductive, so that the above-mentioned shielding material is not covered. Contacting a second region of the conductive layer with one of a gas containing chlorine dioxide and an aqueous etchant containing chlorine dioxide to increase the electrical impedance of the second region by more than 100 times to completely non-conductive to form a non-conducting layer The conductive region, and the first region outside the non-conductive region, form a desired conductive line.
當使用含有二氧化氯的上述氣體時,在未覆蓋上述遮蔽材的上述第二區域接觸含有二氧化氯的上述氣體後,剝除上述遮蔽材。 When the gas containing chlorine dioxide is used, the gas containing chlorine dioxide is brought into contact with the second region not covering the masking material, and then the masking material is removed.
在上述第一區域的表面形成所需的一導電線路後,亦可使用水、PH值低於7的酸性溶液、除光阻劑及有機溶劑中之一者,除去留在上述非導電區之表面的上述氣體的遮蔽材。 After forming a desired conductive line on the surface of the first region, one of water, a pH solution having a pH lower than 7, a photoresist, and an organic solvent may be used to remove the remaining non-conductive region. A masking material for the above gas on the surface.
較佳者,含有二氧化氯的上述氣體係由穩定態二氧化氯水溶液(Stabilized Chlorine Dioxide Solution)、sodium chlorite(NaClO2)、sodium chlorate(NaClO3)、sodium chlorite(亞氯酸鈉)加入酸或加入其還原劑(如檸檬酸、鹽酸、草酸、過氧化氫、二氧化硫、甲醇)等所產生,亦可藉由加熱安定化二氧化氯前驅物(Stabilized Chlorine Dioxide Precursor)之水溶液所產生, 其加熱的溫度高於50度C,以超過65度C為佳。 Preferably, the gas system containing chlorine dioxide is added to the acid by a Stabilized Chlorine Dioxide Solution, sodium chlorite (NaClO2), sodium chlorate (NaClO3), sodium chlorite (sodium chlorite) or added. The reducing agent (such as citric acid, hydrochloric acid, oxalic acid, hydrogen peroxide, sulfur dioxide, methanol) or the like may be produced by heating an aqueous solution of a stabilized chlorine dioxide dioxide precursor (Stabilized Chlorine Dioxide Precursor). The heating temperature is higher than 50 degrees C, preferably more than 65 degrees C.
較佳者,含有二氧化氯之上述水性蝕刻劑進一步含有一水溶 性樹脂及一增粘劑中之一者,上述水溶性樹脂或上述增粘劑至少包括聚乙烯醇(PVA)、水溶性纖維素(CMC)、聚乙烯吡咯烷酮(PVP)及煙狀矽酸鹽(Fumed Silica)中之一者。 Preferably, the above aqueous etchant containing chlorine dioxide further contains a water soluble solution And one of the resin and the tackifier, the water-soluble resin or the tackifier comprises at least polyvinyl alcohol (PVA), water-soluble cellulose (CMC), polyvinylpyrrolidone (PVP) and fumed citrate One of (Fumed Silica).
較佳者,含有二氧化氯的上述水性蝕刻劑含有至少一種醇類 及/或水溶性酮類,例如:甲醇、乙醇、丙醇、丁醇、甲基乙基酮(MEK)與介面活性劑(Surfactant)中之一者。 Preferably, the above aqueous etchant containing chlorine dioxide contains at least one alcohol And/or a water-soluble ketone such as one of methanol, ethanol, propanol, butanol, methyl ethyl ketone (MEK) and a surfactant (Surfactant).
較佳者,含有二氧化氯的上述水性蝕刻劑的酸鹼度(ph值)為 8.0以下。 Preferably, the pH of the above aqueous etchant containing chlorine dioxide is 8.0 or less.
此外,將含有二氧化氯的水性蝕刻劑覆蓋與接觸上述導電層 的方法包括:網版印刷(Screen Printing)、轉印(Transfer Printing)、凹版印刷(Gravure)、凸版印刷(Letterpress)、噴墨(Inkjet)、浸泡(Dipping)、旋轉塗佈法(Spin Coating)、噴塗(Spray)法、逗號塗佈法(Comma Coating)、線棒塗佈法(RDS Coating)、平版印刷(Lithography)、狹縫式塗佈法(Die Coating)、簾幕式塗佈法(Curtain Coating)、超音波塗佈法(Supersonic Spray Coating)與滾筒塗佈法(Roller Coating)其中之一。 In addition, an aqueous etchant containing chlorine dioxide is coated and contacted with the above conductive layer The methods include: Screen Printing, Transfer Printing, Gravure, Letterpress, Inkjet, Dipping, and Spin Coating. , Spray method, Comma coating, RDS coating, Lithography, Die coating, curtain coating Curtain Coating), one of Supersonic Spray Coating and Roller Coating.
較佳者,含有二氧化氯的上述水性蝕刻劑含有碳酸鹽,為碳 酸鈉及碳酸氫鈉中之一者。二氧化氯係利用加熱安定化二氧化氯前驅物之水溶液所產生,加熱的溫度高於50度C,以超過65度C為佳。 Preferably, the above aqueous etchant containing chlorine dioxide contains carbonate as carbon One of sodium and sodium bicarbonate. The chlorine dioxide is produced by heating an aqueous solution of a stabilized chlorine dioxide precursor, and the heating temperature is higher than 50 ° C, preferably more than 65 ° C.
再者,上述遮蔽材為光阻(photoresist)、可剝膠(strippable ink/coating)、保護膜、可溶性膠、可溶性油墨及塗料中之一者。上述導電線 路含有本質性導電之共軛導電高分子,至少包括PEDOT/PSS、Polyaniline (PANI)及Polypyrrole(PPy)中之一者或奈米銀絲(Silver Nanowire)。 Furthermore, the masking material is photoresist and strippable. Ink/coating), one of protective film, soluble glue, soluble ink and coating. The above conductive wire The circuit contains an intrinsically conductive conjugated conductive polymer, including at least one of PEDOT/PSS, Polyaniline (PANI), and Polypyrrole (PPy) or Silver Nanowire.
較佳者,蝕刻氣體中的二氧化氯含量在100ppm以上,在含有二氧化氯的上述水性蝕刻劑與上述氣體中,二氧化氯的含量為15%以下。 Preferably, the chlorine dioxide content in the etching gas is 100 ppm or more, and the content of chlorine dioxide in the aqueous etchant containing chlorine dioxide and the gas is 15% or less.
較佳者,上述導電線路應用於印刷電子、感應器、顯示器、有機發光二極體、觸控面板、電子線路板、電極、冷光片、電熱板、天線及太陽能電池中之一者。 Preferably, the conductive circuit is applied to one of a printed electronic device, a sensor, a display, an organic light emitting diode, a touch panel, an electronic circuit board, an electrode, a luminescent film, a hot plate, an antenna, and a solar cell.
本發明更提供一種設有導電基材的電子裝置,包括一底材,以及一圖案化具感應器功能之一導電線路,設於上述底材的表面且與電子裝置內所設的電路電氣連接,其中上述導電線路藉由一含有二氧化氯之一氣體及一水性蝕刻劑中之一者於一含有本質性導電的共軛導電高分子及奈米銀絲中之一者之透明的一導電層上所形成,上述導電層區分為預訂需要導電的一第一區域以及未覆蓋一遮蔽材的一第二區域,上述導電線路形成於上述第一區域。 The invention further provides an electronic device provided with a conductive substrate, comprising a substrate, and a conductive circuit having a patterned inductor function, which is disposed on the surface of the substrate and electrically connected to a circuit provided in the electronic device. The conductive line is transparent to one of a conjugated conductive polymer and a nano-silver wire containing one of chlorine dioxide and one of an aqueous etchant. Formed on the layer, the conductive layer is divided into a first region that needs to be electrically conductive and a second region that is not covered with a masking material, and the conductive line is formed in the first region.
又,本發明更提供一種應用於透明導電基材的導電線路圖案化之去除導電性用的蝕刻劑,係包括二氧化氯。 Further, the present invention further provides an etchant for removing conductivity of a conductive line patterned on a transparent conductive substrate, which comprises chlorine dioxide.
較佳者,上述蝕刻劑為氣體、液體、膏狀物其中之一種型態。 Preferably, the etchant is one of a gas, a liquid, and a paste.
較佳者,上述透明導電基材含有本質性導電之共軛導電高分子,至少包括PEDOT/PSS、Polyaniline(PANI)及Polypyrrole(PPy)中之一者。 Preferably, the transparent conductive substrate comprises an intrinsically conductive conjugated conductive polymer comprising at least one of PEDOT/PSS, Polyaniline (PANI) and Polypyrrole (PPy).
較佳者,上述透明導電基材含有奈米銀絲(Silver Nanowire)。 Preferably, the transparent conductive substrate comprises a silver nanowire.
較佳者,當蝕刻劑為含有二氧化氯的上述水性蝕刻劑時,進一步含有至少一種醇類、水溶性酮類、介面活性劑其中之一。 Preferably, when the etchant is the above aqueous etchant containing chlorine dioxide, it further contains at least one of an alcohol, a water-soluble ketone, and an interfacial surfactant.
以下進一步說明本發明之具體實施方式。 Specific embodiments of the invention are further described below.
1‧‧‧導電基材 1‧‧‧Electrical substrate
2‧‧‧電子裝置 2‧‧‧Electronic devices
10‧‧‧底材 10‧‧‧Substrate
20‧‧‧導電層 20‧‧‧ Conductive layer
21‧‧‧感應器 21‧‧‧ sensor
60‧‧‧遮蔽材 60‧‧‧Mask
201‧‧‧非導電區 201‧‧‧Non-conducting area
202‧‧‧導電線路 202‧‧‧Electrical circuit
S210~S260‧‧‧步驟 S210~S260‧‧‧Steps
第一圖係本發明應用於電子裝置之構造示意圖;第二圖係根據本發明一實施例之方法流程圖;以及第三圖係根據本發明一實施例之製程示意圖。 The first diagram is a schematic diagram of the structure of the present invention applied to an electronic device; the second diagram is a flowchart of a method according to an embodiment of the present invention; and the third diagram is a schematic diagram of a process according to an embodiment of the present invention.
第一圖係根據本發明一實施例之應用於電子裝置之構造示意圖。 The first figure is a schematic view of a configuration applied to an electronic device according to an embodiment of the present invention.
在第一圖中,導電基材1應用於各種不同功能之電子裝置,例如第一圖所示具備感應器21(Sensor)功能之電子裝置。在一實施例中,導電基材1也可應用於包括印刷電子(Printed Electronics)、感應器(Sensor)、顯示器(Display)、有機發光二極體(OLED)、觸控面板(Touch Panel)、電子線路板(Electronic Circuit Board)、電極(Electrode)、冷光片(EL)、電熱片(Heater)、天線(Antenna)、太陽能電池(Solar Cell)等不同功能之電子裝置。 In the first figure, the conductive substrate 1 is applied to various electronic devices of different functions, such as the electronic device having the sensor 21 (Sensor) function shown in the first figure. In an embodiment, the conductive substrate 1 can also be applied to include Printed Electronics, a sensor, a display, an organic light emitting diode (OLED), a touch panel, and a touch panel. Electronic devices with different functions such as Electronic Circuit Board, Electrode, Cold Light (EL), Heater, Antenna, and Solar Cell.
在一實施例中,底材10可為塑膠膜,如透明的PET膜、PI膜等塑膠材質,或是玻璃、陶瓷等無機材料。在一實施例中,透明導電層可包含有透明導電高分子或含奈米銀線中之一者,並覆蓋於該底材10的表面。 In one embodiment, the substrate 10 can be a plastic film, such as a transparent PET film, a PI film, or the like, or an inorganic material such as glass or ceramic. In an embodiment, the transparent conductive layer may include one of a transparent conductive polymer or a nano-silver-containing wire and cover the surface of the substrate 10.
第二圖係根據本發明一實施例之方法流程圖。在步驟S210中,將含有本質性導電的共軛導電高分子及/或奈米銀絲的透明導電層覆蓋於底材的表面。在步驟S220中,使用遮蔽材覆蓋導電層之預定需要導電的一區域。在步驟S230中,使未覆蓋遮蔽材的其他區域接觸含有二氧化氯的氣體及/或含有二氧化氯的水性蝕刻劑,藉此氧化以進行蝕刻,使得未覆蓋 遮蔽材的其他區域之電氣阻抗提高100倍以上至完全不導電以形成非導電區。在步驟S240中,覆蓋有遮蔽材的區域為導電層區,在導電層區形成所需之圖案化的導電線路。在步驟S250中,直接剝除遮蔽材或使用水、有機溶劑移除遮蔽材。在步驟S260中,使用水、PH值低於7.0的酸性溶液及有機溶劑中之一者,除去留在非導電區之表面的氣體及/或水性蝕刻劑的殘留物。 The second figure is a flow chart of a method in accordance with an embodiment of the present invention. In step S210, a transparent conductive layer containing a substantially conductive conjugated conductive polymer and/or nanosilver is coated on the surface of the substrate. In step S220, a masking material is used to cover a region of the conductive layer that is intended to be electrically conductive. In step S230, other regions not covered with the masking material are brought into contact with a gas containing chlorine dioxide and/or an aqueous etchant containing chlorine dioxide, thereby oxidizing to perform etching so as not to cover The electrical impedance of other areas of the masking material is increased by more than 100 times to completely non-conductive to form a non-conductive area. In step S240, the area covered with the masking material is a conductive layer area, and the desired patterned conductive line is formed in the conductive layer area. In step S250, the masking material is directly stripped or the masking material is removed using water or an organic solvent. In step S260, the gas and/or the residue of the aqueous etchant remaining on the surface of the non-conductive region are removed using one of water, an acidic solution having a pH of less than 7.0, and an organic solvent.
第三圖係根據本發明一實施例之製程示意圖。 The third figure is a schematic diagram of a process in accordance with an embodiment of the present invention.
在第三圖中,含有本質性導電的共軛導電高分子及/或奈米 銀絲的透明導電層20覆蓋於底材10的表面。遮蔽材60覆蓋導電層20之預定需要導電的一區域。 In the third figure, a conjugated conductive polymer and/or nanoparticle containing an intrinsically conductive A transparent conductive layer 20 of silver wire covers the surface of the substrate 10. The masking material 60 covers an area of the conductive layer 20 that is intended to be electrically conductive.
接著,未覆蓋遮蔽材60的其他區域接觸含有二氧化氯的氣體 及/或含有二氧化氯的水性蝕刻劑,藉此氧化以進行蝕刻,使未覆蓋遮蔽材60的其他區域之電氣阻抗提高100倍以上至完全不導電以形成非導電區201。在覆蓋有遮蔽材60的區域則為導電層區,所需之圖案化的導電線路202形成在導電層區中以進一步構成導電基材1。其中,導電線路202與電子裝置內所設的電路電氣連接。此外,預定不需導電的非導電區201的電氣阻抗為導電層區(即導電線路202)的100倍以上至完全不導電。 Next, other areas not covered by the masking material 60 are exposed to a gas containing chlorine dioxide. And/or an aqueous etchant containing chlorine dioxide, thereby oxidizing to etch, increasing the electrical impedance of other regions of the uncovered mask 60 by more than 100 times to being completely non-conductive to form the non-conductive region 201. The region covered with the masking material 60 is a conductive layer region, and the desired patterned conductive traces 202 are formed in the conductive layer region to further constitute the conductive substrate 1. The conductive line 202 is electrically connected to a circuit provided in the electronic device. In addition, the electrical impedance of the non-conductive region 201 that is not intended to be electrically conductive is more than 100 times that of the conductive layer region (ie, the conductive trace 202) to be completely non-conductive.
在一實施例中,遮蔽材60可為光阻(photoresist)、可剝膠 (strippable ink/coating/mask)、保護膜、可溶性膠、可溶性油墨及塗料中之一者。透明導電層線路20含有本質性導電之共軛導電高分子,至少包括PEDOT/PSS、Polyaniline(PANI)及Polypyrrole(PPy)中之一者。 In an embodiment, the masking material 60 can be photoresist, peelable (strippable ink/coating/mask), one of protective film, soluble glue, soluble ink and paint. The transparent conductive layer line 20 contains an intrinsically conductive conjugated conductive polymer, including at least one of PEDOT/PSS, Polyaniline (PANI), and Polypyrrole (PPy).
使未覆蓋遮蔽材60的其他區域接觸含有二氧化氯的氣體及/ 或含有二氧化氯的水性蝕刻劑及在導電層區形成所需的導電線路202後,當 使用的遮蔽材為可剝膠或保護膜時,直接剝除遮蔽材60。當使用的遮蔽材為光阻、可溶性膠、可溶性油墨/塗料時,亦使用水、PH值低於7.0的酸性溶液及、去光阻劑、及有機溶劑中之一者,除去留在非導電區之表面的上述之遮蔽材。 The other areas that are not covered with the masking material 60 are exposed to a gas containing chlorine dioxide and/or Or an aqueous etchant containing chlorine dioxide and after forming the desired conductive line 202 in the conductive layer region, When the masking material used is a peelable rubber or a protective film, the masking material 60 is directly peeled off. When the masking material used is photoresist, soluble glue, soluble ink/coating, one of water, pH-lowering acidic solution, photoresist, and organic solvent is used to remove the non-conductive The above-mentioned masking material on the surface of the zone.
其中,含有二氧化氯的氣體係由穩定態二氧化氯水溶液 (Stabilized Chlorine Dioxide Solution)、sodium chlorite(NaClO2)、sodium chlorate(NaClO3)、sodium chlorite(亞氯酸鈉)加入酸或加入其還原劑(如檸檬酸、鹽酸、草酸、過氧化氫、二氧化硫、甲醇)等所產生,即二氧化氯係藉由一化學還原劑還原氯酸根離子而產生。此外,含有二氧化氯之水性蝕刻劑亦可含有水溶性樹脂及增粘劑中之一者,又該水溶性樹脂及/或增粘劑至少包括聚乙烯醇(PVA)、水溶性纖維素(CMC)、PVP(Polyvinylpyrrolidone)及煙狀矽酸鹽(Fumed Silica)中之一者。 Among them, the gas system containing chlorine dioxide is composed of a stable aqueous solution of chlorine dioxide. (Stabilized Chlorine Dioxide Solution), sodium chlorite (NaClO2), sodium chlorate (NaClO3), sodium chlorite (sodium chlorite) added to the acid or added to its reducing agent (such as citric acid, hydrochloric acid, oxalic acid, hydrogen peroxide, sulfur dioxide, methanol And the like, that is, chlorine dioxide is produced by reducing chlorate ions by a chemical reducing agent. In addition, the aqueous etchant containing chlorine dioxide may also contain one of a water-soluble resin and a tackifier, and the water-soluble resin and/or tackifier includes at least polyvinyl alcohol (PVA) and water-soluble cellulose ( One of CMC), PVP (Polyvinylpyrrolidone) and Fumed Silica.
在本發明之一實施例中,含有二氧化氯的水性蝕刻劑含有至 少一種醇類及/或水溶性酮類。舉例而言,醇類包括甲醇、乙醇、丙醇、丁醇,而水溶系酮類包括甲基乙基酮(MEK)。此外,含有二氧化氯的水性蝕刻劑的酸鹼度(PH值)為8.0以下。在一實施例中,含有二氧化氯的水性蝕刻劑的酸鹼度以介於2.0至6.0之間為最佳。在一實施例中,含有二氧化氯的水性蝕刻劑含有碳酸鹽,為碳酸鈉與碳酸氫鈉中之一者。在一實施例中,二氧化氯係利用加熱安定化二氧化氯前驅物之水溶液所產生,加熱的溫度高於50度C。在另一實施例中,加熱的溫度以高於65度C為佳。 In an embodiment of the invention, the aqueous etchant containing chlorine dioxide contains Less alcohol and/or water soluble ketones. For example, alcohols include methanol, ethanol, propanol, butanol, while water soluble ketones include methyl ethyl ketone (MEK). Further, the aqueous etchant containing chlorine dioxide has a pH (pH) of 8.0 or less. In one embodiment, the aqueous etchant containing chlorine dioxide has a pH of between 2.0 and 6.0. In one embodiment, the aqueous etchant containing chlorine dioxide contains a carbonate which is one of sodium carbonate and sodium bicarbonate. In one embodiment, the chlorine dioxide is produced by heating an aqueous solution of a stabilized chlorine dioxide precursor at a temperature above 50 degrees C. In another embodiment, the temperature of the heating is preferably above 65 degrees C.
在本發明之一實施例中,在含有二氧化氯的蝕刻氣體中的二 氧化氯的含量為100ppm以上,以5%以上為佳。而水性蝕刻劑中,二氧化氯 的含量為15%以下。此外,在進行利用水性蝕刻劑或氣體對導電層進行導電線路圖案化之過程中,可利用提高蝕刻溫度至室溫以上,以提升蝕刻的強度與效率。 In one embodiment of the invention, two of the etching gases containing chlorine dioxide The content of the chlorine oxide is 100 ppm or more, preferably 5% or more. In aqueous etchants, chlorine dioxide The content is 15% or less. In addition, in the process of patterning the conductive layer by using an aqueous etchant or gas, the etching temperature can be increased to room temperature or higher to increase the strength and efficiency of the etching.
含有二氧化氯的水性蝕刻劑覆蓋與接觸上述導電層的方法 包括:網版印刷(Screen Printing)、轉印(Transfer Printing)、凹版印刷(Gravure)、凸版印刷(Letterpress)、噴墨(Inkjet)、浸泡(Dipping)、旋轉塗佈法(Spin Coating)、噴塗(Spray)法、逗號塗佈法(Comma Coating)、線棒塗佈法(RDS Coating)、平版印刷(Lithography)、狹縫式塗佈法(Die Coating)、簾幕式塗佈法(Curtain Coating)、超音波塗佈法(Supersonic Spray Coating)、滾筒塗佈法(Roller Coating)與浸泡法(Dipping)中之一者。 Method for covering and contacting the above conductive layer with an aqueous etchant containing chlorine dioxide Including: Screen Printing, Transfer Printing, Gravure, Letterpress, Inkjet, Dipping, Spin Coating, Spray (Spray) method, Comma Coating, RDS Coating, Lithography, Die Coating, Curtain Coating ), one of Supersonic Spray Coating, Roller Coating, and Dipping.
在本發明一實施例中,使用含有二氧化氯之水性蝕刻劑的製 程。其中,該水性蝕刻劑的PH值為3,含有碳酸鹽,包括碳酸鈉。接著,使用一PET保護膠膜為遮蔽材覆蓋於一PEDOT/PSS透明導電高分子膜(原始電氣阻抗為90ohm/sq.)的表面上之預定需要導電的特定區域上。然後,將上述含有二氧化氯的水性蝕刻劑藉由印刷方式,例如網版印刷方式(Screen Printing Method),將水性蝕刻劑接觸上述遮蔽材之PEDOT/PSS透明導電高分子膜的預定不需要導電性的區域,來氧化蝕刻劑所接觸之需要進行氧化的區域以形成非導電區201,使此區域的透明導電高分子膜降低其導電性,電阻大幅度提高一千萬倍至一億倍以上,至約10 x E+9~+10ohm/sq.以上或至完全不導電。此外,覆蓋遮蔽材之特定區域的導電膜形成導電線路202。其中,可利用加熱方式進一步提高蝕刻強度與效率,最後,以黏除之方式除去上述之水性蝕刻劑。若蝕刻劑為可溶性,利用水或低於PH值7.0的酸性溶 液或有機溶劑等清除液,將非導電區201表面上的蝕刻劑殘留物除去。另可進一步使用直接剝除或使用黏除之方式除去PET保護膠膜。 In an embodiment of the invention, an aqueous etchant containing chlorine dioxide is used. Cheng. Wherein, the aqueous etchant has a pH of 3 and contains carbonate, including sodium carbonate. Next, a PET protective film was used as a masking material over a specific area on the surface of a PEDOT/PSS transparent conductive polymer film (original electrical impedance of 90 ohm/sq.) which was intended to be electrically conductive. Then, the above-mentioned aqueous etchant containing chlorine dioxide is subjected to a printing method, such as a screen printing method, and the predetermined etching resistance of the PEDOT/PSS transparent conductive polymer film contacting the aqueous etchant to the masking material is not required to be conductive. a region that is oxidized by the etchant to be oxidized to form a non-conductive region 201, so that the transparent conductive polymer film in the region reduces its conductivity, and the resistance is greatly increased by 10 million times to more than 100 million times. , to about 10 x E+9~+10 ohm/sq. or above or not at all. Further, the conductive film covering a specific region of the masking material forms the conductive line 202. Among them, the etching strength and efficiency can be further improved by heating, and finally, the above aqueous etchant is removed by adhesion. If the etchant is soluble, use water or an acidic solution below pH 7.0. A cleaning solution such as a liquid or an organic solvent removes the etchant residue on the surface of the non-conductive region 201. Alternatively, the PET protective film can be removed by direct stripping or by adhesion.
在本發明之另一實施例中,使用含有二氧化氯之氣體的導電 線路圖案化製程。其中,使用一遮蔽材覆蓋於一PEDOT/PSS透明導電高分子膜(原始電氣阻抗為90ohm/sq.)或含有奈米銀絲透明導電膜(原始電氣阻抗為20ohm/sq.)的表面上之預定需要導電的特定區域上。將上述含有二氧化氯的蝕刻氣體接觸未覆蓋上述遮蔽材之導電膜區域,來氧化蝕刻劑所接觸之需要進行氧化的區域以形成非導電區201,使此區域的透明導電高分子膜降低其導電性,電阻大幅度提高一千萬倍至一億倍以上,至約10 x E+9~+10ohm/sq.以上或至完全不導電。此外,未接觸蝕刻氣體的特定區域之導電膜形成導電線路202。最後,若使用的遮蔽層為可剝膠/油墨塗料或保護膜時,以黏除之方式除去上述之水性蝕刻劑。若遮蔽層具可溶性,可利用水或低於PH值7.0的酸性溶液、去光阻劑或有機溶劑等清除液,除去非導電區201表面上的遮蔽層。 In another embodiment of the invention, the use of a gas containing chlorine dioxide is conductive Line patterning process. Wherein, a masking material is used to cover a PEDOT/PSS transparent conductive polymer film (the original electrical impedance is 90 ohm/sq.) or a surface containing a nanowire transparent conductive film (the original electrical impedance is 20 ohm/sq.). It is scheduled to be on a specific area that needs to be electrically conductive. The etching gas containing chlorine dioxide is contacted with a region of the conductive film not covering the masking material to oxidize a region to be oxidized contacted by the etchant to form a non-conductive region 201, so that the transparent conductive polymer film in the region is lowered. Conductivity, resistance is greatly increased by 10 million times to more than 100 million times, to about 10 x E+9~+10 ohm/sq. or above. Further, the conductive film that is not in contact with a specific region of the etching gas forms the conductive line 202. Finally, if the masking layer used is a peelable/ink coating or a protective film, the above-mentioned aqueous etchant is removed by adhesion. If the masking layer is soluble, the masking layer on the surface of the non-conductive region 201 may be removed by using water or a cleaning solution such as an acidic solution, a photoresist or an organic solvent lower than pH 7.0.
以上之實施說明及圖式所示,係本創作較佳實施例之一者,並非以此侷限本創作,是以,舉凡與本創作之構造、裝置、特徵等近似或相雷同者,均應屬本創作之創設目的及申請專利範圍之內,僅此聲明。 The above description of the implementation and the drawings are one of the preferred embodiments of the present invention, and are not limited to the creation of the present invention. Therefore, any similar or similar structure to the structure, device, and features of the present creation should be It is the creation purpose of this creation and the scope of patent application, only this statement.
1‧‧‧導電基材 1‧‧‧Electrical substrate
2‧‧‧電子裝置 2‧‧‧Electronic devices
10‧‧‧底材 10‧‧‧Substrate
21‧‧‧感應器 21‧‧‧ sensor
202‧‧‧導電線路 202‧‧‧Electrical circuit
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