CN106098244B - 一种大面积柔性功能石墨烯薄膜的卷对卷印刷制备方法 - Google Patents

一种大面积柔性功能石墨烯薄膜的卷对卷印刷制备方法 Download PDF

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CN106098244B
CN106098244B CN201610380610.8A CN201610380610A CN106098244B CN 106098244 B CN106098244 B CN 106098244B CN 201610380610 A CN201610380610 A CN 201610380610A CN 106098244 B CN106098244 B CN 106098244B
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阳军亮
张楚俊
胡巧
吴涵
丁孔贤
孙永明
姜宗清
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Shenzhen Jiawei Photovoltaic Lighting Co Ltd
Central South University
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Abstract

本发明公开了一种基于卷对卷印刷技术制备大面积、导电性可控的功能石墨烯薄膜的制备方法；通过调控石墨烯墨水性能和印刷技术参数，在柔性基底上卷对卷印刷制备出具有可控厚度和可控导电性能的均匀、大面积石墨烯薄膜；厚度可调控在10纳米到10微米之间，方块电阻可调控在10欧姆/口到3000欧姆/口之间；该石墨烯薄膜的卷对卷印刷制备方法快速高效、工艺简单、重复性好、成本低，具有广泛的应用前景。

Description

一种大面积柔性功能石墨烯薄膜的卷对卷印刷制备方法
技术领域
本发明涉及一种基于卷对卷印刷技术制备大面积、柔性、导电性可控的石墨烯薄膜的制备方法；属于高性能导电功能薄膜制备技术领域。
背景技术
自2004年单层石墨烯报道以来(Science,2004,306,666-669)，吸引了全球众多研究人员对石墨烯的关注，使得石墨烯成为材料领域和凝聚态物理领域中一颗闪耀的明星，进而发展出少数层石墨烯和三维石墨烯，展现出广泛的应用前景。石墨烯电子传导速率可高达8×105ms-1，电子在石墨烯中传输阻力很小，石墨烯薄层半导体的电子迁移率可高达200000cm2v-1s-1，比硅半导体高100倍，比砷化镓高20倍，因此石墨烯是一种优异的电子材料。
作为功能材料的石墨烯，由于优异的化学稳定性、柔韧性、导电性、透明性、导热性等综合性能，在电子器件、太阳能电池器件、储能器件等功能器件和功能薄膜领域等都具有重大的应用前景。常规的化学气相沉积技术制备石墨烯的速度慢，效率低，成本高，而且难以制备出大面积的石墨烯薄膜。如何高效率、低沉本制备大面积石墨烯薄膜成为推进其产业化的关键技术难题之一。基于此，本发明专利采用简单的卷对卷印刷制备技术，在环境条件下快速高效、低成本地卷对卷印刷制备大面积、可控厚度和可控导电性能的功能石墨烯薄膜。
发明内容
本发明所述的大面积、柔性、可控导电性的石墨烯薄膜的制备方法，基于不同粘度、不同浓度的水性和油性石墨烯墨水材料，在环境条件下应用卷对卷印刷技术在柔性基底上制备出具有可控厚度和可控导电性的均匀、大面积石墨烯薄膜。
本发明所述的大面积、柔性、可控导电性的石墨烯薄膜的制备方法，所述基底为柔性基底，具体包括聚对苯二甲酸乙二酯(PET)、聚萘二甲酸乙二醇酯(PEN)、聚酰亚胺(PI)。
本发明所述的大面积、柔性、可控导电性的石墨烯薄膜的制备方法，所述石墨烯墨水材料的粘度在10厘泊到1000厘泊，石墨烯固含量浓度在2％到10％。
本发明所述的大面积、柔性、可控导电性的石墨烯薄膜的制备方法，所述水性石墨烯墨水是指将少数层石墨烯分散到溶剂水中，所述油性石墨烯墨水是指将少数层石墨烯分散到溶剂丙二醇甲醚醋酸酯或甲基吡咯烷酮中。
本发明所述的大面积、柔性、可控导电性的石墨烯薄膜的制备方法，所述卷对卷印刷是 指卷对卷凹版印刷或卷对卷微凹版印刷或卷对卷狭缝涂布技术以0.20米/分钟到100米/分钟速度印刷制备成膜，烘箱干燥温度50度到150度，干燥时间1分钟到30分钟。
本发明所述的大面积、柔性、可控导电性的石墨烯薄膜的制备方法，所述印刷制备的石墨烯薄膜的厚度在10纳米到5微米。
本发明所述的大面积、柔性、可控导电性的石墨烯薄膜的制备方法，所述印刷制备的石墨烯薄膜的方块电阻在10欧姆/口到3000欧姆/口。
本发明所述的大面积、柔性、可控导电性的石墨烯薄膜的制备方法可潜在应用于柔性光电器件及光伏器件。
附图说明
【图1】在PET基底上卷对卷凹版印刷油性石墨烯墨水而获得的石墨烯薄膜进行中的照片图(a)和印刷后的大约800纳米厚的石墨烯薄膜照片图(b)。
【图2】在PET基底上卷对卷凹版印刷油性石墨烯墨水获得的石墨烯薄膜的光学显微镜形貌图(a-c)和扫描电子显微镜形貌图(d-f)。(a,d)大约150纳米石墨烯薄膜，(b,e)大约500纳米石墨烯薄膜，(c,f)大约800纳米石墨烯薄膜。
具体实施方式与实施例
以下实施方式和实施例是对本发明内容的进一步的说明，而不是限制本发明的保护范围。
实施例1
取20ml固含量为5％、黏度为300厘泊的油性石墨烯溶液作为卷对卷凹版印刷的墨水材料。
参考卷对卷印刷设备发明专利(CN201420230074.X)所述，对该石墨烯墨水材料进行卷对卷凹版印刷制备，柔性PET基底宽度为15cm，以0.5m/min基底走带速度进行印刷制备，可以形成均匀的石墨烯功能薄膜，并通过120度烘箱原位进行干燥退火处理10分钟。图1(a)是在PET基底上卷对卷凹版印刷石墨烯薄膜进行中的照片图以及图1(b)为印刷后的大约800纳米厚的石墨烯薄膜照片图。通过调控印刷辊的速度，可以调控印刷石墨烯薄膜的厚度和导电性能。石墨烯的厚度可以在50纳米到5微米范围内进行调控，表征薄膜导电特性的方块电阻可以在在10欧姆/口到3000欧姆/口之间进行调控。
不同厚度的印刷石墨烯薄膜的形貌如图2所示，在大面积范围内形貌分布基本均匀。基于不同厚度的石墨烯薄膜，放置在四探针方阻测试仪样品台上，用四探针均匀压在薄膜上， 分别测试不同厚度薄膜上6个点的方阻以验证薄膜的导电性及均匀性，结果如表1所示。测试结果表明通过印刷参数可以调控印刷石墨烯薄膜的厚度，进而调整印刷石墨烯薄膜的导电特性，大约800纳米的印刷石墨烯薄膜方块电阻可以降到19欧姆/口。
表1基于卷对卷凹版印刷制备的不同厚度石墨烯薄膜的方块电阻值
实施例2
取20ml固含量为5％、黏度为80厘泊的水性石墨烯溶液作为卷对卷微凹版印刷的墨水材料。
参考卷对卷印刷设备发明专利(CN201420230074.X)所述，对该石墨烯墨水材料进行卷对卷微凹版印刷制备，柔性PET基底宽度为15cm，以0.3m/min基底走带速度进行印刷制备，可以形成均匀的石墨烯功能薄膜，并通过140度烘箱原位进行干燥退火处理15分钟。通过调控印刷辊的速度，可以调控印刷石墨烯薄膜的厚度和导电性能。石墨烯的厚度可以在20纳米到1微米范围内进行调控，表征薄膜导电特性的方块电阻可以在在30欧姆/口到5000欧姆/口之间进行调控。
基于不同厚度的石墨烯薄膜，放置在四探针方阻测试仪样品台上，用四探针均匀压在薄膜上，分别测试不同厚度薄膜上6个点的方阻以验证薄膜的导电性及均匀性，结果如表2所示。测试结果表明通过印刷参数可以调控印刷石墨烯薄膜的厚度，进而调整印刷石墨烯薄膜的导电特性。
实施例3
取20ml固含量为5％、黏度为100厘泊的油性石墨烯溶液作为卷对卷狭缝涂布的墨水材料。
参考卷对卷印刷设备发明专利(CN201420230074.X)所述，对该石墨烯墨水材料进行卷对卷狭缝涂布制备，柔性PET基底宽度为15cm，以0.5m/min基底走带速度进行，设定狭缝涂布参数中的垫片厚度可调控从2微米到10微米，将制备好的石墨烯墨水倒入注墨系统的注射管，连接注射管与狭缝涂布头，设置注墨速率为2～5μL/cm2，形成均匀的石墨烯功能薄膜，并通过120度烘箱原位进行干燥退火处理10分钟。通过调控垫片厚度和注墨速率，可以调控印刷石墨烯薄膜的厚度和导电性能。石墨烯的厚度可以在50纳米到5微米范围内进行调控，表征薄膜导电特性的方块电阻可以在10欧姆/口到3000欧姆/口之间进行调控。
表2基于卷对卷微凹版印刷制备的不同厚度石墨烯薄膜的方块电阻值

Claims (3)

1.一种大面积、柔性、可控导电性的石墨烯薄膜的制备方法，其特征如下，基于粘度在10厘泊到1000厘泊变化、固含量浓度在2％到10％变化的不同水性和油性石墨烯墨水材料，在环境条件下应用卷对卷印刷技术在柔性基底上制备具有可控厚度和可控导电性的均匀、大面积石墨烯薄膜；所述卷对卷印刷是指卷对卷凹版印刷或卷对卷微凹版印刷或卷对卷狭缝涂布技术以0.20米/分钟到100米/分钟速度印刷制备成膜；烘箱干燥温度50摄氏度到150摄氏度，干燥时间1分钟到30分钟；通过调控印刷辊的速度或者调控垫片厚度和注墨速率，最终使得石墨烯薄膜的厚度在10纳米到5微米、方块电阻在10欧姆/口到3000欧姆/口范围内变化；
所述柔性基底具体包括聚对苯二甲酸乙二酯(PET)、聚萘二甲酸乙二醇酯(PEN)、聚酰亚胺(PI)。
2.如权利要求1所述的一种大面积、柔性、可控导电性的石墨烯薄膜的制备方法，其特征在于，所述水性石墨烯墨水是指将少数层石墨烯分散到溶剂水中，所述油性石墨烯墨水是指将少数层石墨烯分散到溶剂丙二醇甲醚醋酸酯或甲基吡咯烷酮中。
3.如权利要求1所述的一种大面积、柔性、可控导电性的石墨烯薄膜的制备方法制备的大面积石墨烯薄膜在柔性光电器件及光伏器件中的应用。
CN201610380610.8A 2016-06-01 2016-06-01 一种大面积柔性功能石墨烯薄膜的卷对卷印刷制备方法 Expired - Fee Related CN106098244B (zh)

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