CN102804936A - 生产结构化金属涂层的方法 - Google Patents
生产结构化金属涂层的方法 Download PDFInfo
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- CN102804936A CN102804936A CN2010800279151A CN201080027915A CN102804936A CN 102804936 A CN102804936 A CN 102804936A CN 2010800279151 A CN2010800279151 A CN 2010800279151A CN 201080027915 A CN201080027915 A CN 201080027915A CN 102804936 A CN102804936 A CN 102804936A
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Classifications
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02104—Forming layers
- H01L21/02697—Forming conducting materials on a substrate
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1208—Pretreatment of the circuit board, e.g. modifying wetting properties; Patterning by using affinity patterns
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/0002—Lithographic processes using patterning methods other than those involving the exposure to radiation, e.g. by stamping
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/02—Details
- H01L31/0224—Electrodes
- H01L31/022408—Electrodes for devices characterised by at least one potential jump barrier or surface barrier
- H01L31/022425—Electrodes for devices characterised by at least one potential jump barrier or surface barrier for solar cells
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
- H05K2203/11—Treatments characterised by their effect, e.g. heating, cooling, roughening
- H05K2203/1173—Differences in wettability, e.g. hydrophilic or hydrophobic areas
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/10—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern
- H05K3/12—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns
- H05K3/1241—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by ink-jet printing or drawing by dispensing
- H05K3/125—Apparatus or processes for manufacturing printed circuits in which conductive material is applied to the insulating support in such a manner as to form the desired conductive pattern using thick film techniques, e.g. printing techniques to apply the conductive material or similar techniques for applying conductive paste or ink patterns by ink-jet printing or drawing by dispensing by ink-jet printing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
Abstract
本发明涉及一种在基底上生产结构化导电涂层的方法，其中首先将表面疏水化物质的单层或多层施加于基底表面上，随后根据预定图案将包含导电颗粒的物质施加于基底。本发明还涉及该方法在生产太阳能电池或印刷电路板中的用途，以及一种包括在其上施加有结构化导电表面的基底的电子元件，其中将表面疏水化材料制成的单层或多层施加于基底上，将结构化导电表面施加于单层或多层上。
Description
本发明涉及一种在基底上生产结构化金属涂层的方法。本发明还涉及该方法在太阳能电池或电路板的生产中的用途以及一种包括施加有结构化金属表面的基底的电子元件。
例如通过印刷方法在基底上生产结构化金属涂层。为此，例如通过喷墨印刷方法或激光印刷方法将含金属颗粒的墨施加于基底。例如在US-B6,241,344中公开了一种相应方法，其中将墨滴从涂覆有墨的载体喷射到要印刷的基底上。为了转印墨，在要印刷基底的位置将能量引入载体上的墨中。由此一部分墨蒸发使得其与载体分离。将以该方式分离的墨滴通过墨蒸发的压力喷射于基底上。通过能量的特定引入，可根据要印刷的图案以该方式将墨转印至基底上。例如，通过激光引入转印墨所需的能量。在其上施加墨的载体例如为旋转带，墨借助在印刷区域前的施加设备施加至该旋转带。激光器存在于该旋转带内部，使得激光背向墨的一侧作用于载体。
然而，该类方法的缺点通常为印刷品质在极大程度上取决于该方法中所涉及的条件的均匀性。因此，甚至非常小的局部差异可直接在引入能量的位置导致印刷结果的定性恶化。该类差异例如为墨涂层的厚度以及例如要印刷的基底的静电状态的差异。因此，例如由于各种压延方法，常规聚合物或纸张表面具有完全无序的表面静电荷，该表面的电势也非常不均匀。由此所得的印刷图案往往具有不精确的边缘和边界，这主要是由墨的不确定的喷射和雾化引起。不精确的边缘和边界的另一原因为墨在要印刷的基底上的不均匀流平。
为了保证水滴或油滴不润湿表面而基本保持球形形式，已知将含硅烷层施加至表面上。该层例如描述于EP-A 0 497 189中。然而，这里所述方法的涂层的缺点为要涂覆的表面需要活性氢，例如在表面上呈羟基、亚氨基或氨基形式。此外，使用该层排斥水或油。没有设想将结构化层施加于含硅烷的表面。
本发明目的是提供一种在基底上生产结构化金属涂层的方法，其中生产具有明确界定的精确边缘和边界的结构化金属层。
该目的通过一种在基底上生产结构化金属涂层的方法实现，该方法包括下列步骤：
(a)将表面疏水化物质的单层或多层(oligolayer)施加于基底表面，
(b)根据预定图案在该基底上印刷包含导电颗粒的物质。
优选地，将表面疏水化物质的单层施加于基底的表面。然而，在不同情况下还可形成含有2或3个亚层的层。
通过将表面疏水化物质的单层或多层施加至基底表面，保证施加至基底并包含导电颗粒的物质较小程度地移动或最佳地不移动而是保持它的结构。通过仅施加一个单层或多层，此外保证尤其是在包括半导体材料的基底的情况下，可使表面疏水化物质对结构化金属涂层和半导体基底的性能的影响最小化，使得没有不利地影响要生产的产品的性能。此外以该方式可获得的更精确的边缘轮廓具有的优点为可印刷具有基本上小于100μm的结构的清晰高分辨率印刷图像。该具有小于100μm的结构的高分辨率印刷图像有利于例如太阳能电池的生产。对于太阳能电池的生产，通常将银糊料通过丝网印刷技术施加至晶片的氮化硅涂覆或钝化表面上。然而，基本上小于100μm的结构不能通过丝网印刷方法可靠地印刷。或由例如US5,021,808已知，借助吸收激光的墨印刷，其中将墨施加于透明连续薄膜，并使激光从后侧聚焦于该薄膜前侧，使得其中存在的吸收激光的薄膜加热至墨的部分溶剂突然蒸发的程度。以该方法将墨滴转印至基底，例如太阳能晶片。然而，仅粘度显著低于相应丝网印刷糊料的粘度的墨适用于印刷。然而，在将墨转印至结构化且用氮化硅涂覆的晶片后，观察到墨在表面上的移动。通过在已涂覆氮化硅或钝化的晶片上根据本发明涂覆表面疏水化物质，降低或在理想情况下甚至抑制移动。产生的印刷图像因此具有甚至更清晰的边缘且更精细的印刷图像是可能的。
除了氮化硅涂覆的晶片以外，还可使用涂覆有氧化铝(Al2O3)或碳化硅(SiC)的晶片。
在太阳能电池的情况下，印刷图像通常具有2-3个较宽的条带，随后将用于连接多个电池的带子与该条带焊接在一起。此外，电池具有良好导电性的非常薄的网格。对该网格的要求非常高。它必须高度导电但必须仅尽可能少地阻挡入射光。为此，必须尽可能窄并最大厚度地施加网格的各条轨道。
为了获得导电网格，使用在溶剂中包含导电颗粒的墨。
为了生产结构化金属涂层施加至基底的导电颗粒优选包含银、铜、铁、锡、镍或这些金属的混合物或合金。非常特别优选地，特别是在太阳能电池的生产中，使用包含银和/或任选的镍的导电颗粒。所用颗粒可具有本领域熟练技术人员已知的任何所需形状。还可使用两种或更多种不同的颗粒，其中颗粒的尺寸、形状或材料可不同。通常使用不同形状的颗粒，例如球形颗粒和层状颗粒。颗粒还可尤其在尺寸上不同。
颗粒尺寸的选择通常使得要印刷的结构的尺寸显著大于颗粒的最大尺寸。优选地，使用尺寸不大于10μm的颗粒。特别地，还可使用纳米颗粒作为要施加至基底的物质中的颗粒。
颗粒分散于其中的合适溶剂为本领域熟练技术人员已知的任何所需溶剂。合适的溶剂例如为水或有机溶剂。
通常存在于包含导电颗粒的物质中的基体材料例如为ABS(丙烯腈-丁二烯-苯乙烯)；ASA(丙烯腈-苯乙烯-丙烯酸酯)；丙烯酸化的丙烯酸酯；醇酸树脂；乙酸烷基乙烯基酯；烯烃-乙酸乙烯酯共聚物，特别是亚甲基-乙酸乙烯酯(methylene-vinyl acetate)、乙烯-乙酸乙烯酯、丁烯-乙酸乙烯酯；烯烃-氯乙烯共聚物；氨基树脂；醛树脂和酮树脂；纤维素和纤维素衍生物，特别是羟烷基纤维素，纤维素酯，例如乙酸纤维素、丙酸纤维素、丁酸纤维素、羧基烷基纤维素、硝酸纤维素；环氧丙烯酸酯；环氧树脂；改性环氧树脂，例如双官能或多官能双酚A或双酚F树脂，多官能环氧酚醛清漆树脂，溴化环氧树脂，环脂族环氧树脂；脂族环氧树脂，缩水甘油基醚，乙烯基醚，乙烯-丙烯酸共聚物；烃树脂；MABS(含有丙烯酸酯单元的透明ABS)；三聚氰胺树脂，马来酐共聚物；甲基丙烯酸酯；天然橡胶；合成橡胶；氯橡胶；天然树脂；松香；紫胶；酚树脂；苯氧基树脂，聚酯；聚酯树脂如苯基酯树脂；聚砜；聚醚砜；聚酰胺；聚酰亚胺；聚苯胺类；聚吡咯类；聚对苯二甲酸丁二醇酯(PBT)；聚碳酸酯(例如来自Bayer AG的
)；聚酯丙烯酸酯；聚醚丙烯酸酯；聚乙烯；聚亚乙基噻吩类(polyethylene thiophenes)；聚萘甲酸乙二醇酯；聚对苯二甲酸乙二醇酯(PET)；聚对苯二甲酸乙二醇酯-乙二醇(PETG)；聚丙烯；聚甲基丙烯酸甲酯(PMMA)；聚苯醚(PPO)；聚苯乙烯(PS)；聚四氟乙烯(PTFE)；聚四氢呋喃；聚醚(例如聚乙二醇、聚丙二醇)，聚乙烯基化合物，特别是聚氯乙烯(PVC)，PVC共聚物，PVdC，聚乙酸乙烯酯及其共聚物，呈溶液和作为分散体的任选部分水解的聚乙烯醇，聚乙烯醇缩醛，聚乙酸乙烯酯，聚乙烯基吡咯烷酮，聚乙烯基醚，聚丙烯酸乙烯基酯和聚甲基丙烯酸乙烯基酯及其共聚物，聚丙烯酸酯和聚苯乙烯共聚物，例如聚苯乙烯-马来酐共聚物；聚苯乙烯(硬质或非硬质)；未交联或与异氰酸酯交联的聚氨酯；聚氨酯丙烯酸酯；苯乙烯-丙烯酸酯共聚物；苯乙烯-丁二烯嵌段共聚物(例如来自BASF AG的
或
来自CPC的K-ResinTM)；蛋白质如酪蛋白；苯乙烯-异戊二烯嵌段共聚物；三嗪树脂，双马来酰亚胺-三嗪树脂(BT)，氰酸酯酯树脂(CE)，烯丙基化的聚苯醚(APPE)。此外，两种或更多种聚合物的混合物可形成基体材料。
此外，基体材料还可包含填料。合适的填料例如为玻璃料或有机金属化合物。
合适的溶剂例如为脂族和芳族烃(例如正辛烷、环己烷、甲苯、二甲苯)，醇(例如甲醇、乙醇、1-丙醇、2-丙醇、1-丁醇、2-丁醇、戊醇)，多元醇，例如甘油、乙二醇、丙二醇、新戊二醇，烷基酯(例如乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸丁酯、乙酸异丁酯、乙酸异丙酯、3-甲基丁醇)，烷氧基醇(例如甲氧基丙醇、甲氧基丁醇、乙氧基丙醇)，烷基苯(例如乙苯、异丙苯)，丁基乙二醇，丁基二甘醇，乙酸烷基乙二醇酯(如乙酸丁基乙二醇酯、乙酸丁基二甘醇酯)，二甲基甲酰胺(DMF)，双丙酮醇，二甘醇二烷基醚，二甘醇单烷基醚，二丙二醇二烷基醚，二丙二醇单烷基醚，二甘醇烷基醚乙酸酯，二丙二醇烷基醚乙酸酯，二
烷，二丙二醇和二亚丙基醚(dipropyleneether)，二甘醇和二亚乙基醚，DBE(二元酯)，醚(例如乙醚、四氢呋喃)，氯化乙烯，乙二醇，乙酸乙二醇酯，乙二醇二甲基酯，甲酚，内酯(例如丁内酯)，酮(例如丙酮、2-丁酮、环己酮、甲基乙基酮(MEK)、甲基异丁基酮(MIBK))，甲基二甘醇，二氯甲烷，亚甲基二醇，乙酸甲基乙二醇酯，甲基苯酚(邻-、间-、对甲酚)，吡咯烷酮(例如N-甲基-2-吡咯烷酮)，丙二醇，碳酸异丙烯酯，四氯化碳，甲苯，三羟甲基丙烷(TMP)，芳族烃和混合物，脂族烃和混合物，单萜醇(如萜品醇)，单异丁酸2，2，4-三甲基-1，3-戊二醇酯
水和两种或更多种这些溶剂的混合物。
通过施加表面疏水化物质的单层，避免或限制了包含导电颗粒的物质的移动。施加表面疏水化物质的单层通过本领域熟练技术人员已知的任何所需方法进行。表面疏水化物质通常通过气相沉积、喷雾或浸渍施加至基底的表面上。如果表面疏水化物质通过气相沉积施加至基底，则气相沉积优选在减压下进行。气相沉积所用压力范围为大气压力至10-6毫巴(绝对)，优选100毫巴(绝对)至10-6毫巴(绝对)。气相沉积通常在10-500℃，优选10-100℃的温度下，特别是在室温下进行。
如果通过喷雾进行表面疏水化物质的施加，则包含表面疏水化物质的溶液通常通过喷雾浸渍施加至基底并随后干燥。在干燥时，表面疏水化物质的自组织单层沉积于基底上。在其中将要涂覆的基底浸渍于包含表面疏水化物质的溶液中或将基底置于高度稀释的表面疏水化物质的溶液中的新兴方法中，表面疏水化物质的自组织单层沉积于基底的表面上。为了避免洗掉已与表面反应的硅烷，通常在喷雾或浸渍后用溶剂洗涤或清洗基底。
合适的表面疏水化物质优选为化合物(S)，该化合物具有至少一个，优选正好一个至少单烷氧基化，例如单-至三烷氧基化，优选正好三烷氧基化甲硅烷基和至少一个，优选正好一个具有疏水性能的基团R。
化合物(S)优选为下式的那些：
Xn-Si-R(4-n)
其中：
X为烷氧基、羧酸如乙酸根、卤素如氯、胺或羟基，n为1-3的整数，优选3。
优选地，X为乙氧基、甲氧基或氯，其中当n大于1时，各基团X还可相互独立地为所述基团之一，各基团X可彼此不同。
R为含有1-20个碳原子的有机疏水基团，其中在n＜3的情况下，基团R可不同。
优选地，R为C1-C20烷基、C6-C18芳基或C5-C12环烷基。
C1-C20烷基的实例为甲基、乙基、异丙基、正丙基、正丁基、异丁基、仲丁基、叔丁基、正己基、正庚基、正辛基、2-乙基己基、正癸基、正十一烷基、正十二烷基、正十四烷基、正十六烷基、正十八烷基和正二十烷基。
C1-C4烷基的实例为甲基、乙基、异丙基、正丙基、正丁基、异丁基、仲丁基和叔丁基。
C5-C12环烷基的实例为环戊基、环己基、环庚基、环辛基、环壬基、环癸基、环十一烷基和环十二烷基；优选环戊基、环己基和环庚基；特别优选环己基。
C6-C18芳基例如为苯基、1-萘基、2-萘基、1-蒽基、2-蒽基、9-蒽基、1-菲基、2-菲基、3-菲基、4-菲基、9-菲基、三联苯基，优选苯基、1-萘基和2-萘基，特别优选苯基。
基团R优选为C1-C20烷基或C6-C18芳基，特别优选C1-C20烷基，非常特别优选C6-C12烷基。
优选的基团R为甲基、乙基、异丙基、正丙基、正丁基、异丁基、仲丁基、叔丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基和苯基；特别优选甲基、乙基、正丁基、异丁基、叔丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基和苯基；非常特别优选异丁基、戊基、己基、庚基、辛基、壬基、癸基、十一烷基、十二烷基和苯基。
合适的化合物(S)例如为异辛基三甲氧基硅烷、异辛基三乙氧基硅烷、正丁基三甲氧基硅烷、正丁基三乙氧基硅烷、异丁基三甲氧基硅烷、异丁基三乙氧基硅烷、苯基三甲氧基硅烷和苯基三乙氧基硅烷。
在特别优选的实施方案中，R为部分氟化或全氟化的C4-C20烷基，优选C4-C18烷基，特别是C8-C12烷基。
如果R为部分氟化的烷基，则优选使用通式(I)的硅烷：
其中，R1、R2、R3相互独立地为C1-C20烷基、C6-C18芳基或C5-C12环烷基、甲氧基、乙氧基或氯，其中基团R1、R2、R3中的至少一个为甲氧基、乙氧基或氯，n1为0-20，优选1-4的整数，特别是2，n2为0-20，优选4-10，特别是6-8的整数。
如果将硅烷用作表面疏水化物质，则它们通常以基团R1、R2、R3中的至少一个结合至基底的表面。基团R4自基底伸出并形成疏水表面。
可用作表面疏水化物质的合适硅烷例如为正辛基三氯硅烷、正壬基三氯硅烷、正癸基三氯硅烷、正十一烷基三氯硅烷、正十二烷基三氯硅烷、苯基三氯硅烷、正辛基三乙氧基硅烷、正壬基三乙氧基硅烷、正癸基三乙氧基硅烷、正十一烷基三乙氧基硅烷、正十二烷基三乙氧基硅烷、苯基三乙氧基硅烷、正辛基三甲氧基硅烷、正壬基三甲氧基硅烷、正癸基三甲氧基硅烷、正十一烷基三甲氧基硅烷、正十二烷基三甲氧基硅烷、苯基三甲氧基硅烷、正辛基二甲基氯硅烷、正壬基二甲基氯硅烷、正癸基二甲基氯硅烷、正十一烷基二甲基氯硅烷、正十二烷基二甲基氯硅烷、苯基二甲基氯硅烷、1H，1H-全氟辛基三氯硅烷、1H，1H-全氟癸基三氯硅烷、1H，1H-全氟十二烷基三氯硅烷、1H，1H-全氟辛基三乙氧基硅烷、1H，1H-全氟癸基三乙氧基硅烷、1H，1H-全氟十二烷基三乙氧基硅烷、1H，1H-全氟辛基三甲氧基硅烷、1H，1H-全氟癸基三甲氧基硅烷、1H，1H-全氟十二烷基三甲氧基硅烷、1H，1H-全氟辛基二甲基氯硅烷、1H，1H-全氟癸基二甲基氯硅烷、1H，1H-全氟十二烷基二甲基氯硅烷、1H，1H，2H，2H-全氟辛基三氯硅烷、1H，1H，2H，2H-全氟癸基三氯硅烷、1H，1H，2H，2H-全氟十二烷基三氯硅烷、1H，1H，2H，2H-全氟辛基三乙氧基硅烷、1H，1H，2H，2H-全氟癸基三乙氧基硅烷、1H，1H，2H，2H-全氟十二烷基三乙氧基硅烷、1H，1H，2H，2H-全氟辛基三甲氧基硅烷，1H，1H，2H，2H-全氟癸基三甲氧基硅烷、1H，1H，2H，2H-全氟十二烷基三甲氧基硅烷、1H，1H，2H，2H-全氟辛基二甲基氯硅烷、1H，1H，2H，2H-全氟癸基二甲基氯硅烷、1H，1H，2H，2H-全氟十二烷基二甲基氯硅烷。
如果将该方法用于太阳能电池的生产中，则基底通常为包含半导体材料的晶片。通常而言，将基于硅的材料用作半导体材料。在其上施加结构化金属涂层的晶片表面通常首先用氮化硅涂覆或钝化。用氮化硅涂覆或钝化还在目前生产的太阳能电池的情况下进行且对本领域熟练技术人员是已知的。然后将表面疏水化物质以单层或多层施加于钝化的表面或涂覆有氮化硅的表面。将常用于太阳能电池且由包含导电颗粒的物质构成的网格印刷于表面疏水化物质的单层或多层上。由于用表面疏水化物质涂覆，可印刷网格窄轨道使得印刷的轨道仅轻微地阻挡光的入射(instance)。如果要获得较大的网格轨道厚度，则可以多个层印刷包含导电颗粒的物质。通过印刷包含导电颗粒的物质，随后使存在于该物质中的基体材料固化和使溶剂蒸发，在表面上获得了结构化金属涂层。用于太阳能电池的生产中且包含导电颗粒的物质通常包含50-90重量％的导电颗粒，优选65-85重量％的导电颗粒，特别是70-80重量％的导电颗粒；0-20重量％的基体材料，优选1-15重量％的基体材料，特别是3-10重量％的基体材料；和0-30重量％的溶剂，优选5-25重量％的溶剂，特别是5-20重量％的溶剂。由于加入溶剂，包含导电颗粒的物质的粘度可根据所用印刷方法调节。
适于施加包含导电颗粒的物质的印刷方法为本领域熟练技术人员已知的任何所需印刷方法。常规印刷方法例如为丝网印刷方法、喷墨印刷方法、移印方法或激光印刷方法。包含导电颗粒的物质优选通过激光印刷方法施加。
在合适的激光印刷方法中，首先将包含导电颗粒且预期用于印刷的物质施加至载体。将该物质施加至载体可通过本领域熟练技术人员已知的任何所需方法进行。包含导电颗粒的物质通常借助转印辊施加至载体。
优选将柔性载体用作墨载体。特别是涂覆有要印刷且包含导电颗粒的物质的墨载体呈带状。非常特别优选地，该柔性载体为薄膜。该载体的厚度优选为1μm至约500μm。有利地将载体设计为具有尽可能小的厚度使得通过该载体引入的能量不会分散于载体中并由此产生清晰的印刷图像。例如，对所用能量透明的聚合物适合作为载体材料。
用于使墨蒸发并将其转印至要印刷的基底的能量优选为激光。激光的优点为可将所用激光束聚焦于非常小的横截面上。因此，定向的能量引入是可能的。为使包含导电颗粒的物质至少部分从载体上蒸发并将其施加于基底，需将激光器的光转化为热。为此，例如包含导电颗粒的物质此外可包含吸收激光并将其转化为热的合适吸收剂。然而，或者还可以用合适的吸收剂涂覆在其上施加包含导电颗粒的物质的载体，或由此类吸收剂生产所述载体。然而，优选由对激光辐射透明的材料生产载体，并优选将激光转化为热的吸收剂存在于包含导电颗粒的物质中。例如，碳黑、金属氮化物或金属氧化物适合作为吸收剂。
可用于将能量引入墨中的合适激光器例如为纤维激光器，该激光器以基模(base mode)操作。
如果要印刷的基底与在其上施加包含导电颗粒且预期用于印刷的物质的载体之间的间隙具有0-2mm，特别是0.01-1mm的印刷间隙，则还进一步改善印刷图像。载体与要印刷的基底之间的印刷间隙越小，墨滴在撞击要印刷的基底时发散的程度越小，印刷图像保持越均匀。然而，还应保证要印刷的基底不与涂覆有包含导电颗粒的物质的载体接触，使得包含导电颗粒的物质不会在不希望的位置上转印至要印刷的基底上。
除太阳能电池的生产外，本发明方法还适合例如用于生产任何所需的其它电子元件，例如用于生产电路板。如果通过本发明方法生产电路板，则所用基底通常为作为合适电路板基底的电介质。常规电路板基底例如由增强或未增强聚合物生产。合适的聚合物例如为基于双-和多官能双酚A和F的环氧树脂、环氧酚醛清漆树脂、溴化环氧树脂、环脂族环氧树脂、双马来酰亚胺三嗪树脂、聚酰亚胺、酚树脂、氰酸酯酯、三聚氰胺树脂或氨基树脂、苯氧基树脂、烯丙基化聚苯醚、聚砜、聚酰胺、聚硅氧烷和含氟树脂及其组合。
为在没有移动边缘的情况下将清晰结构施加于电路板基底，根据本发明首先用表面疏水化物质的单层涂覆电路板基底。在电路板的生产中，还优选将上述硅烷用作表面疏水化物质。
在电路板的生产中，除上述金属外，导电颗粒还可为碳颗粒，例如呈纳米管形式。
借助本发明方法可生产任何所需的电子元件，特别是太阳能电池或电路板。由本发明方法生产的电子元件通常包括在其上施加结构化导电表面的基底，其中将表面疏水化材料的单层施加至该基底，将结构化导电表面施加至该单层。
如果电子元件为太阳能电池，则基底通常为包含半导体材料，特别是含硅半导体材料的晶片。如果电子元件为电路板，则基底为电路板基底。
实施例
首先将200μl 1H，1H，2H，2H-全氟辛基三乙氧基硅烷置于真空干燥器中。然后将涂覆有氮化硅的预加工多晶硅晶片引入真空干燥器中。密闭真空干燥器并施加动态油泵真空3分钟。此后，使晶片表面经由气相与1H，1H，2H，2H-全氟辛基三乙氧基硅烷于静态真空中接触12小时。1H，1H，2H，2H-全氟辛基三乙氧基硅烷形成有效的表面钝化，润湿特性改变，且根据Owens and Wendt测量的表面能降低约40.1mN/m至约12.6mN/m。
Claims (11)
1.一种在基底上生产结构化导电涂层的方法，包括下列步骤：
(a)将表面疏水化物质的单层或多层施加于基底表面，
(b)根据预定图案在基底上印刷包含导电颗粒的物质。
2.根据权利要求1的方法，其中通过气相沉积、喷雾或浸渍将表面疏水化物质的单层或多层施加至基底表面。
3.根据权利要求1或2的方法，其中表面疏水化物质为通式SiR1R2R3R4的硅烷，其中R1、R2和R3在每种情况下相互独立地为C1-C20烷基、C6-C18芳基或C5-C12环烷基、甲氧基、乙氧基或氯，基团R1、R2或R3中的至少一个为甲氧基、乙氧基或氯，R4任选为部分氟化或全氟化的C1-C20烷基。
4.根据权利要求1-3中任一项的方法，其中基底为包含半导体材料的晶片。
5.根据权利要求1-4中任一项的方法，其中晶片涂覆有氮化硅涂层、氧化铝涂层或碳化硅涂层。
6.根据权利要求1-5中任一项的方法，其中包含导电颗粒的物质包含50-90重量％的导电颗粒、0-20重量％的基体材料和0-30重量％的溶剂。
7.根据权利要求1-6中任一项的方法，其中导电颗粒包含银、铜、铁和/或锡。
8.根据权利要求1-7任一项的方法在生产太阳能电池或电路板中的用途。
9.一种电子元件，包括施加有结构化导电表面的基底，其中将表面疏水化材料的单层或多层施加于基底，将结构化导电表面施加于该单层或多层。
10.根据权利要求9的电子元件，其中基底为包含半导体材料的晶片或电路板基底。
11.根据权利要求9或10的电子元件，其中所述元件为太阳能电池或电路板。
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| KR20120110084A (ko) | 2012-10-09 |
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| SG176819A1 (en) | 2012-01-30 |
| RU2012101934A (ru) | 2013-07-27 |
| US20120132274A1 (en) | 2012-05-31 |
| IL216898A (en) | 2015-03-31 |
| EP2446720A2 (de) | 2012-05-02 |
| IL216898A0 (en) | 2012-03-01 |
| AU2010264870A1 (en) | 2012-01-19 |
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