CN107787258A - 纳米导电粒子沉积层的组合式光和化学烧结 - Google Patents

纳米导电粒子沉积层的组合式光和化学烧结 Download PDF

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CN107787258A
CN107787258A CN201680036281.3A CN201680036281A CN107787258A CN 107787258 A CN107787258 A CN 107787258A CN 201680036281 A CN201680036281 A CN 201680036281A CN 107787258 A CN107787258 A CN 107787258A
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nano
sintering
particle
substrate
sintered
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J·S·伦尼
M·A·迪格拉夫
M·A·巴希尔
J·克拉拉克
S·普罗特
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Dow Global Technologies LLC
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Dow Global Technologies LLC
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Abstract

由导电的纳米粒子制备的结构的材料特性通过辐射烧结接着化学烧结增强。导电的纳米粒子可通过如丝网印刷、喷墨、气溶胶和电纺丝的方法涂覆到衬底，且随后烧结衬底上的导电的纳米粒子。

Description

纳米导电粒子沉积层的组合式光和化学烧结
技术领域
本发明涉及处理纳米粒子以增强用纳米粒子制备的结构的材料特性的方法。更具体来说，本发明涉及通过辐射烧结接着化学烧结处理纳米粒子以增强用纳米粒子制备的结构的材料特性的方法。
背景技术
纳米粒子具有在各种应用(如生物学、化学、材料科学、电子、成像和药品)中有价值的特性。在电子工业中，纳米粒子通常用作催化剂，如在无电金属电镀中；它们用于形成电磁干扰(EMI)屏蔽涂层、射频干扰信号(RFI)屏蔽涂层以及用于形成用于透明传导性材料(TCM)的金属网。
在衬底上的纳米粒子的烧结在用于印刷型电子产品、增材制造或3D打印的新型材料的开发中已变得越来越重要。在衬底上的纳米粒子的沉积可使用一系列技术实现：喷墨和气溶胶印刷、丝网印刷、电纺丝、挤出沉积和标准本体涂布方法(如旋涂或棒涂)。显著挑战为达到有效的纳米粒子的烧结以获得期望的材料特性，例如致密化、强度、传导性和光学特性。烧结金属纳米粒子的已知技术是通过热、光子或化学曝露。然而，纳米粒子的低效烧结可导致由该纳米粒子制备的制品的受损和不可接受的材料特性。另外，过度的烧结(如经重复的光子曝露)可损坏在其上沉积纳米粒子的衬底。
当衬底对热敏感时，例如聚对苯二甲酸亚乙酯(PET)(Tg约67℃到81℃)能够实现在低温下的有效烧结变成一种需要。举例来说，金属纳米粒子墨沉积的结构的烧结可需要超过200℃的温度用于维持延长的时间周期，其与热敏性衬底不兼容。所以，存在对在热敏性衬底上烧结纳米粒子以增强由纳米粒子制备的制品的材料特性而不破坏衬底的方法的需要。
发明内容
方法包括将纳米粒子沉积在衬底上；以及通过辐射烧结接着化学烧结来处理在衬底上的导电的纳米粒子以形成烧结的结构。
出乎意料地，与单独使用许多常规辐射烧结和化学烧结方法相比，辐射烧结接着化学烧结导电的纳米粒子的组合改进烧结的结构的材料特性。纳米粒子的过度烧结产生具有不可接受的材料特性的烧结的结构。因此，通过烧结由辐射烧结接着化学烧结纳米粒子制备的烧结的结构的材料特性预期未被改进但是一般来说为不可接受的。然而，辐射烧结接着化学烧结的组合至少增强烧结的结构的导电性，这通常伴随着提高的透射率和降低的雾度。组合的烧结方法还实现使用热敏性衬底，而无需担心组合的烧结方法可能造成衬底损坏或烧结的结构与衬底的分层。
辐射烧结接着化学烧结的方法可用于形成电磁干扰(EMI)屏蔽涂层、射频干扰信号(RFI)屏蔽涂层、导电线迹、形成用于透明传导性材料(TCM)的金属网、增材制造(3D印刷)以及用于其中导电纳米粒子有用的任何其它领域。
附图说明
图1为在光烧结接着氯化氢曝露后的薄层电阻[欧姆/平方]与在光烧结后的薄层电阻[欧姆/平方]的曲线。
图2为在光烧结接着氯化氢曝露后的雾度[％]与在光烧结后的雾度[％]的曲线。
图3为在光烧结接着氯化氢曝露后的透射率[％]与在光烧结后的透射率的曲线。
具体实施方式
除非上下文另外明确指示，否则如在整个说明书中所使用，以下缩写具有以下含义：℃＝摄氏度；g＝克；L＝升；mL＝毫升；μL＝微升；rpm＝转/分钟；msec＝毫秒；D.I.＝去离子水；Hz＝赫兹；mPa s＝兆帕秒；s＝秒；Mw＝重均分子量；Mn＝数均分子量；m＝米；mm＝毫米；μm＝微米(micron)＝微米(micrometer)；cm＝厘米；nm＝纳米；(＝欧姆；(m＝欧姆米；sq＝平方(square)；V＝伏特；kV＝千伏特；mJ＝毫焦耳；μs＝微秒；UV＝紫外；IR＝红外；3D＝三维；SEM＝扫描电子显微照片；M＝摩尔；TGA＝热解重量分析；Tg＝玻璃态转变温度；wt％＝重量％；vol％＝体积％；VFR核＝核材料的体积流率；以及VFR壳＝壳材料的体积流率。
术语“辐射”意指以射线、波或粒子的形式辐射或传播的能量。术语“烧结”意指融合粒子使得粒子的晶粒边界融合并且形成块团。术语“块团”意指材料的聚集。术语“透射率百分比(％)”＝I/I0×100，其中I0＝进入样品的光的强度，并且I＝离开样品的光的强度。术语“雾度”意指由光散射引起的材料的浑浊度。化学式HCl＝氯化氢或盐酸。术语“膜”和“层”在整个本说明书中可互换使用。除非另外规定，否则所有百分比值都是重量％。所有数值范围都包括在内并且可按任何次序组合，但逻辑上这类数值范围被限制于总计共100％。
方法包括将纳米粒子沉积在衬底上；以及通过辐射烧结接着化学烧结处理在衬底上的纳米粒子。辐射烧结始终首先进行，其中化学烧结紧接着辐射烧结进行。在辐射烧结和化学烧结之间不存在中间步骤。辐射烧结包括光烧结和热烧结。优选地使用光烧结，因为本发明的光烧结方法比热烧结与低温衬底更相容。
用于光烧结的光源包括但不限于可具有UV到IR光谱输出范围的闪光灯如氙闪光电弧灯。光烧结可使用常规光子发生器设备(如来自Novacentrix或Xenon's SINTERON脉冲光系统的工具的Pulseforge族)进行。此类发生器能够发出在UV到短IR的宽谱上的光。光烧结可使用稳定状态或脉冲光递送进行。可将稳定状态光递送光栅化或扫描，使得在特定位置中的停留时间变短。短停留时间是优选的，因为本发明的方法优选地用于低温衬底，其中余热可导致损坏衬底并且引起涂覆到衬底的沉积的纳米粒子结构的分层。停留时间可根据制成衬底的材料和使用的光传递设备而变化。可进行小型实验以确定特定光传送设备的停留时间。
光烧结方法包含用光子发生器照射导电的纳米粒子使得纳米粒子吸收能量。在光烧结中，在环境温度下能量转移到纳米粒子并且局部产生热。光烧结引起纳米粒子变得光化学激发并且因此，它们经由引起其烧结的热损耗耗散能量。优选地，光子发生器为可在短时间段内传递大量能量的闪光灯。优选地，施加到纳米粒子的光能的范围为1,000mJ/cm2到10,000mJ/cm2，更优选4,000mJ/cm2到8,000mJ/cm2。时间段范围优选为0.5μs到1毫秒，更优选1μs到5μs。灯的输出强度可通过灯电压控制。脉冲传递的持续时间可通过灯闪光宽度控制。这些参数中的每个可在连接到灯组件的电源的总动力输送规格内独立地调节。
任选地，遮罩可在光烧结之前施加到具有纳米粒子的衬底。遮罩选择性覆盖衬底的部分并且留下其它部分未被覆盖，使得在光烧结期间，在施加光时，仅具有未被覆盖的纳米粒子的衬底的那些部分烧结。
热烧结与光烧结的不同之处在于，纳米粒子连同衬底放入恒定高温的环境中。热烧结可在烘箱、红外源、热灯或将热能转移到纳米粒子和衬底的其它热传递系统中进行。热烧结温度的范围优选为30°到低于200℃，更优选50℃到150℃。本发明的热烧结温度低于常规热烧结温度以防止损坏低温衬底。导电的纳米粒子和衬底热烧结的暴露时间范围优选30秒到30分钟，更优选60秒到10分钟。
在纳米粒子和衬底通过两种辐射烧结方法中的一种处理后，纳米粒子部分聚集。然后它们通过化学烧结处理，而无需可影响纳米粒子或衬底的材料特性的任何中间过程。
化学烧结通过在室温下将辐射烧结的纳米粒子和衬底暴露到卤化物化合物的蒸气或溶液进行。此类化合物为氯化物、溴化物、氟化物和碘化物离子的来源。用于卤化物化合物溶液的溶剂包括(但不限于)水、醇、酮及其混合物。醇包括(但不限于)甲醇、乙醇、异丙醇和叔丁醇。酮包括(但不限于)丙酮。优选地溶剂为水。卤化物溶液的浓度范围为10wt％到60wt％，优选15wt％到50wt％，更优选20wt％到40wt％。卤离子的来源包括(但不限于)氯化氢、氢溴酸、氟化氢、碘化氢以及卤盐，如碱金属盐，如氯化锂。当卤化物来源为碱金属卤化物时，用于溶液的溶剂为水和有机溶剂的混合物。有机溶剂包括(但不限于)二醇、二醇醚、二醇醚乙酸酯、酮、酯、醛、醇和烷氧基化醇。通常，二醇如乙二醇、二乙二醇、三乙二醇、聚乙二醇、丙二醇和二丙二醇；二醇醚如二乙二醇单甲醚、二乙二醇单丙醚、二乙二醇单丁醚和乙二醇单甲醚；并且醇如乙醇、甲醇、异丙醇和叔丁醇。
具有部分聚集的导电的纳米粒子的衬底可浸入卤化物溶液中或暴露于该溶液的蒸气。可将溶液加热以产生发烟卤化物蒸气。优选地，将部分聚集的导电的纳米粒子暴露于卤化物蒸气，更优选地，将它们暴露于发烟卤化物蒸气以完成烧结法。化学烧结通常进行1分钟到24小时。当部分聚集的纳米粒子通过卤化物蒸气，优选地通过发烟卤化物蒸气化学烧结时，导电和光学特性的改进(如提高透射率和降低雾度)在1分钟到5分钟的时间段内快速出现。然而，在用发烟卤化物蒸气烧结后，在贮存纳米粒子时，通常烧结的纳米粒子的导电性在24小时时间段继续提高。
在化学烧结方法后，烧结的结构或膜已经完全聚集具有平滑外形的纳米粒子。不进行另外的烧结步骤。烧结的结构或膜可具有20Ω/平方和更低、通常7Ω/平方到10Ω/平方的低薄片电阻率，80％和更高、通常80％到90％的高透射率％，以及12％和更低、通常2％到5％的低雾度％。薄片电阻率可通过常规方法及设备如Delcom 737电导监视器测量。透射率百分比和雾度百分比还可通过常规方法及设备如Hunterlab Ultrascan VIS仪器测量。
导电的纳米粒子可通过本领域中已知的各种常规方法制备。不存在对在纳米粒子的制备中设想的方法的限制。
纳米粒子包括导电材料，如金属、金属氧化物和非金属如石墨、石墨烯和碳黑。优选地，用于纳米粒子的导电材料为金属。金属包括(但不限于)银、金、铂、钯、铟、铷、钌、铑、锇、铱、铝、铜、钴、镍和铁。优选地，金属为银、金、钯和铜。更优选地，银、金和铜为金属的选择。最优选地，银为金属的选择，因为它是热力学上更稳定(即抗腐蚀的)的金属中的一种。
导电的纳米粒子可以用一种或多种封端剂稳定或封端，以防止纳米粒子的不希望的聚集。许多常规聚合物封端剂是本领域中已知的，并且是可用的或可根据在文献中描述的方法制备。优选地，封端剂为聚甲基丙烯酸甲酯或甲基丙烯酸和甲基丙烯酸正丁酯的无规共聚物。最优选地，封端剂为甲基丙烯酸和甲基丙烯酸正丁酯的无规共聚物，所述无规共聚物沿其主链具有亲水性和疏水性部分，并且Mw低于20,000g/mol，优选1,000g/mol到10,000g/mol，更优选2,000g/mol到6,000g/mol。通常，在施用到衬底之前，导电的纳米粒子分散于水、有机溶剂或水和有机溶剂的混合物中。
可包括在纳米粒子分散液中调整用于特定应用的分散液的任选的添加剂包括(但不限于)缓冲剂、润滑剂、保湿剂、蜡、树脂、表面活性剂、着色剂、流变改性剂、增稠剂和粘着促进剂。添加剂可以以由本领域普通技术人员已知常规量包括于分散液中。优选地，纳米粒子分散液不包括此类添加剂。
用于本发明的衬底可选自各种已知的衬底。优选地，衬底为热敏性衬底。此类热敏性衬底的Tg范围为60℃到170℃，优选60℃到100℃。优选地，衬底为选自各种已知透明衬底的透明衬底，其包括：透明导电衬底和透明不导电衬底两种。优选地，透明衬底选自由以下各者组成的群组：聚对苯二甲酸亚乙酯(PET)、聚碳酸酯(PC)、聚甲基丙烯酸甲酯(PMMA)；聚萘二甲酸乙二酯(PEN)、聚醚砜(PES)、环烯烃聚合物(COP)、三乙酰纤维素(TAC)、聚乙烯醇(PVA)、聚酰亚胺(PI)、聚苯乙烯(PS)(例如，双轴拉伸的聚苯乙烯)以及玻璃(例如，可购自道康宁(Dow Corning)的玻璃和玻璃)优选地，透明衬底选自由以下各者组成的群组：玻璃、聚对苯二甲酸亚乙酯、聚碳酸酯和聚甲基丙烯酸甲酯。最优选地，透明衬底为聚对苯二甲酸亚乙酯。
喷墨印刷可为连续喷墨方法或按需滴墨方法。连续方法为其中墨的方向通过改变电磁场调节同时使用泵不断喷射墨的印刷方法。按需滴墨为根据电子信号仅在需要时分配墨的方法。按需滴墨可分成其中通过使用通过电引起机械改变的压电板生成压力的压电喷墨方法和使用通过由热产生的空心球的膨胀生成压力的热喷墨法。用于墨喷射墨纳米粒子分散液的常规参数是本领域中众所周知的，并且可用于本发明的墨纳米粒子分散液的喷墨；然而，对于具体分散液墨喷射参数的特定设置可变化，并且可涉及小型实验以达到对于特定纳米粒子分散液的期望墨喷射性能。
与喷墨印刷方法相比，气溶胶方法首先形成墨的气溶胶。将气溶胶经由加压喷嘴引导到衬底，其中将加压喷嘴安裝到印刷头。将气溶胶与聚焦气体混合，并且以聚焦的形成输送到加压的喷嘴。使用聚焦气体分配墨减少堵塞喷嘴的机率，并且还能够比用喷墨设备形成更细的沉积和更大高宽比。常规气溶胶参数可用于应用纳米粒子分散液；然而，可涉及小型实验以达到期望的性能。
电纺丝(如同轴电纺丝)可用于将纳米粒子分散液沉积在衬底上。一般来说，同轴电纺丝包括将墨核组分(其包括分散于水、有机溶剂或其混合物中的纳米粒子)以及由在水、有机溶剂或两者的混合物中的聚合物溶液的混合物组成的壳通过具有中心开口和周围环状开口的共环喷嘴进料，其中墨核组分通过中心开口进料，并且壳通过周围环状开口进料。优选地，通过周围环状开口进料的壳材料的体积流率(VFR壳)与通过中心开口进料的核材料的体积流率(VFR核)的比率大于或等于垂直于流方向的周围环状开口的横截面积(CSA环状)与垂直于流方向的中心开口的横截面积(CSA中心)的比率。更优选地，以下表达式符合处理条件：VFR壳/VFR核≥1.2*(CSA环状/CSA中心)。如同喷墨和气溶胶应用，同轴电纺丝参数可为常规的，并且可涉及小型实验以达到期望的性能。此类方法的实例公开于U.S.2014/0131078中。
包括以下实例以进一步说明本发明但并不旨在限制其范围。
实例1
纳米粒子的合成
如下制备银纳米粒子和墨。首先，将23.6g具有亲水性片段和疏水性片段的其中在水/丙二醇混合物(10:90wt/wt)中47摩尔％部分来自甲基丙烯酸且53摩尔％部分来自甲基丙烯酸正丁酯的封端溶液20wt％甲基丙烯酸/甲基丙烯酸正丁酯无规共聚物放入反应烧瓶中，并且将315g二乙醇胺、114g丙二醇和附加20g D.I.水添加到该烧瓶。如通过相对于聚苯乙烯校准的凝胶渗透色谱法(GPC)测定，无规共聚物的重均分子量为4000g/mol。将混合物以500rpm的速率搅拌1小时以获得澄清溶液。溶液的pH大约为8。然后在室温下在剧烈搅拌(1000rpm的搅拌速率)下将刚制备的硝酸银溶液(67mL的在D.I.水中的50wt％溶液)快速添加到反应混合物。在添加硝酸银溶液时，形成淡褐色的沉淀，其立刻重新溶解。然后在15分钟内将反应混合物的温度升高到75℃，并且允许反应3小时。在反应结束时，混合物的颜色已变成茶褐色，这指示高浓度的银纳米粒子。
允许反应混合物冷却，并且添加500mL丙酮以促进固体材料从溶液沉淀。倾析上清液，并且将在烧瓶底部中的糊状物重新分散于800mL水/1-丙氧基-2-丙醇(75/25wt/wt)中，并且在10000rpm下离心1小时。在环境条件中干燥由离心产生的固体团块以获得约50g纳米粒子材料。如通过TGA(在空气下加热高达600℃)测定，这种材料的纯度高于98wt％银。粒子的粒度通过使用多个图像的SEM图像分析测量。发现平均尺寸为56nm。
实例2
纳米粒子分散液的制备
将45g干燥纳米粒子(纯度>98wt％银)放入球磨罐(35mL)中，并且添加18g分散溶剂(水/1-丙氧基-2-丙醇/叔丁醇，35/15/50，以混合物重量计)。在15Hz下将混合物球磨3小时。如通过来自赛默飞世尔(ThermoFisher)的RS600变流仪测量，这种处理产生约25mL粘度为约30mPa s的70wt％银纳米粒子墨。变流仪具有直径为25mm并且间隙高度为1mm的平行夹具。测量是在20℃下进行的。
实例3
在透明衬底上纳米粒子分散液的同轴电纺丝
配备有单个同轴喷嘴的电纺丝机器(来自IME科技(IME Technologies)的型号EC-DIG)用于电纺丝实例2的银纳米粒子分散液作为在65:35wt/wt的异丙醇与水的混合物中的5.25wt％聚氧化乙烯核组分和壳组分(Mn＝400kg/mol)。使用的喷嘴是同轴喷嘴(来自IME科技(IME Technologies)的EM-CAX)，其有具有垂直于直径为0.4mm的材料流方向的圆形截面的内开口；以及具有垂直于材料流方向并且与内开口同心的环状截面的外开口；并且具有0.6mm内径和1.2mm外径。当纺丝材料时，将核组分通过同轴喷嘴的内开口进料，并且将壳组分通过同轴喷嘴的外开口进料。使用控制核组分的体积流率(VFR核)和壳组分的体积流率(VFR壳)的独立的注射器泵(来自IME科技的EP-NE1)，将核和壳组分通过同轴喷嘴进料，使得VFR壳/VFR核的流动速率比率为10:1。电纺丝方法在气候受控制的实验室中在20℃和25％到35％的相对湿度下在环境大气压条件下进行。
衬底是可购自惠普(Hewlett-Packard)的188μm厚×12.7cm宽×30.5cm长透明的、柔性HP 52聚对苯二甲酸亚乙酯(PET)膜。衬底围绕来自IME科技的模组EM-RDC旋转鼓轮收集器的转鼓缠绕。
用于纺丝操作的剩余参数如下：在旋转衬底和针之间的距离设置为11cm；喷嘴设置为5kV；在衬底下方的板设置为-0.2kV；在旋转鼓轮收集器上的转鼓旋转速率(y轴)设置为500rpm到1000rpm；针扫描速度(x轴)设置为5mm/秒；针扫描距离设置为12cm；并且总纺丝时间设置为4分钟。银纳米粒子金属网在PET衬底上形成。在衬底上的纳米粒子线网的直径为约5μm±1μm。
实例4
光烧结银纳米粒子涂覆的PET膜的管线
从在其上银纳米粒子的管线经由根据实例3的同轴电纺丝沉积的的衬底上切割5cm×2.5cm的样品膜。然后在传送带上以7m/分钟的速率将样品通过来自Novacentrix的Pulseforge 3100光子发生器进料。光子发生器设置为200V以产生在3Hz频率下的2000μs脉冲以连续模式产生6076mJ/cm2的光能。离开光子发生器的样品是金属网透明导体。
用Delcom 737电导监测器测量银网样品的薄层电阻，并且在HunterlabUltrascan VIS仪器上测量透射率％和雾度％。结果显示于下表中。
表1
实例5
光烧结和化学烧结银纳米粒子涂覆的PET膜的管线
然后在通风橱下通过将其暴露到来自含37％氯化氢水溶液的烧杯的氯化氢蒸气一分钟来化学烧结该来自实例4的银网样品。在24小时后测量薄层电阻、透射率％和雾度％。结果在表2中。
表2
将用于光烧结和光烧结接着用氯化氢蒸气化学烧结的每个参数的值标绘在图1到图3中。
如上表中和在图1中所示，通过光烧结接着用氯化氢化学烧结处理的样品与仅光烧结相比具有降低的薄层电阻。除其中对于光烧结和光烧结接着化学烧结的雾度％相同的样品2之外，当样品通过两种烧结方法处理时，雾度％是降低的。通过使用两种烧结方法，透射率％示出一些增加。最显著的结果是观察到在样品经光烧结且随后化学烧结两者后薄层电阻的下降，由此增加样品的导电性。
实例6
化学烧结银纳米粒子涂覆的PET膜的管线
银纳米粒子和银纳米粒子分散液如上文所描述制备。通过如以上实例3中的所描述的同轴电纺丝将银纳米粒子分散液施加到PET膜。如下表中所示处理银管线样品。
表3
HCl蒸气和HCl浸渍实验产生具有与在表1和表2中所描述的那些可比的薄层电阻的样品；然而，必须指出仅化学处理的样品包含较大量的沉积的纳米粒子，如由其降低的透射率表示。此结果为期望材料的最终薄层电阻在烧结时具有较低理论最小值。
实例5(表2)的烧结方法，其中在表3中除雾度％＝11.3的表2的实例1之外所有化学处理样品，首先通过光烧结接着化学烧结来烧结的样品示出改进雾度％。在化学烧结1小时后测量的，在实例5中表2的样品1和样品5中对于通过光烧结接着用HCl蒸气化学烧结处理的样品的薄层电阻比仅化学处理样品的薄层电阻低的多，由此这两种样品具有比仅化学烧结的那些样品更高的导电性。在实例5中的表2的样品2到样品4具有比通过在LiCl溶液(无论溶液是2wt％异丙醇还是2wt％水)中浸渍来化学烧结的纳米粒子更低的薄层电阻，由此具有比仅用LiCl溶液化学烧结的纳米粒子更高的导电性。

Claims (9)

1.一种方法，其包含：
a)在衬底上沉积导电的纳米粒子；以及
b)通过辐射烧结接着化学烧结来处理在所述衬底上的所述导电的纳米粒子以形成烧结的结构。
2.根据权利要求1所述的方法，其中所述辐射烧结选自光烧结和热烧结。
3.根据权利要求2所述的方法，其中所述辐射烧结为光烧结。
4.根据权利要求1所述的方法，其中所述化学烧结通过卤化物蒸气或通过卤化物溶液进行。
5.根据权利要求1所述的方法，其中所述纳米粒子通过电纺丝、喷墨、气溶胶、凹版印刷或丝网印刷沉积在所述衬底上。
6.根据权利要求1所述的方法，其中所述衬底选自聚对苯二甲酸亚乙酯、聚碳酸酯、聚甲基丙烯酸甲酯、聚萘二甲酸乙二酯、聚醚砜、环烯烃聚合物、三乙酰纤维素、聚乙烯醇、聚酰亚胺、聚苯乙烯和玻璃。
7.根据权利要求6所述的方法，其中所述衬底的Tg的范围为60℃到170℃。
8.根据权利要求1所述的方法，其中所述纳米粒子包含金属、金属氧化物、导电的非金属或其混合物。
9.根据权利要求8所述的方法，其中所述金属选自银、金、铂、钯、铟、铷、钌、铑、锇、铱、铝、铜、钴、镍和铁。
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