CN106205876A - A kind of preparation method of flexible fiber element base transparent conductive material - Google Patents
A kind of preparation method of flexible fiber element base transparent conductive material Download PDFInfo
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- 239000004020 conductor Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000013305 flexible fiber Substances 0.000 title 1
- 229920002678 cellulose Polymers 0.000 claims abstract description 70
- 239000001913 cellulose Substances 0.000 claims abstract description 70
- 239000000758 substrate Substances 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000001755 magnetron sputter deposition Methods 0.000 claims abstract description 17
- 238000002834 transmittance Methods 0.000 claims abstract description 15
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 10
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910052709 silver Inorganic materials 0.000 claims abstract description 8
- 239000004332 silver Substances 0.000 claims abstract description 8
- 238000004544 sputter deposition Methods 0.000 claims description 24
- 238000000137 annealing Methods 0.000 claims description 15
- 239000012298 atmosphere Substances 0.000 claims description 14
- 238000005516 engineering process Methods 0.000 claims description 10
- 229920001046 Nanocellulose Polymers 0.000 claims description 6
- 239000002131 composite material Substances 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 4
- 229920002749 Bacterial cellulose Polymers 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 3
- 239000005016 bacterial cellulose Substances 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000004627 regenerated cellulose Substances 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 59
- 230000007547 defect Effects 0.000 description 11
- 238000013508 migration Methods 0.000 description 5
- 230000005012 migration Effects 0.000 description 5
- 239000002356 single layer Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 239000000428 dust Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 239000002042 Silver nanowire Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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Abstract
本发明公开一种柔性纤维素基透明导电材料的制备方法，涉及导电纤维素薄膜的制备，尤其是涉及一种采用四步骤制备纤维素薄膜导电材料的方法。提供一种高导电性、高透光率的基于纤维素衬底的透明导电材料的制备方法。通过磁控溅射在纤维素薄膜衬底上生长第一层氧化铟锡（ITO）导电层，进而在第一层ITO上生长第二层银（Ag）导电层，在第二层Ag导电层上生长第三层ITO导电层，退火得到高导电性、高透光率的“ITO/Ag/ITO/纤维素”柔性纤维素基透明导电材料。
The invention discloses a method for preparing a flexible cellulose-based transparent conductive material, relates to the preparation of a conductive cellulose film, and in particular relates to a method for preparing a cellulose film conductive material in four steps. Provided is a preparation method of a transparent conductive material based on a cellulose substrate with high conductivity and high light transmittance. The first layer of indium tin oxide (ITO) conductive layer was grown on the cellulose film substrate by magnetron sputtering, and then the second layer of silver (Ag) conductive layer was grown on the first layer of ITO, and the second layer of Ag conductive layer The third layer of ITO conductive layer is grown on it, and annealed to obtain "ITO/Ag/ITO/cellulose" flexible cellulose-based transparent conductive material with high conductivity and high light transmittance.
Description
技术领域technical field
本发明涉及一种柔性纤维素基透明导电材料的制备方法，尤其是涉及一种采用四步骤制备柔性纤维素基透明导电材料。The invention relates to a preparation method of a flexible cellulose-based transparent conductive material, in particular to a method for preparing a flexible cellulose-based transparent conductive material through four steps.
背景技术Background technique
纤维素因其具有来源丰富、价格低廉、可生物降解、可再生性、轻量级、可绕曲性等优点在电子领域具有广阔的发展前景。同时，纤维素薄膜具有良好的热稳定性、化学稳定性、光学性能、力学性能等物理化学性能，有望取代塑料、玻璃等基底制备新一代“绿色”电子器件，而引起全世界科学家的关注。各国科学家通过不同的制备方法将各种电子器件构建在透明导电的纤维素衬底上，如显示器、晶体管、有机发光二极管(OLED)、锂电池、太阳能电池等。Cellulose has broad development prospects in the field of electronics due to its advantages such as abundant sources, low price, biodegradability, renewability, light weight, and flexibility. At the same time, cellulose film has good physical and chemical properties such as thermal stability, chemical stability, optical properties, and mechanical properties. It is expected to replace plastic, glass and other substrates to prepare a new generation of "green" electronic devices, which has attracted the attention of scientists all over the world. Scientists from various countries have built various electronic devices on transparent and conductive cellulose substrates through different preparation methods, such as displays, transistors, organic light-emitting diodes (OLEDs), lithium batteries, solar cells, etc.
目前，制备透明导电的纤维素薄膜的方法主要是以涂布的方式。其主要以纳米纤维素薄膜为衬底，纳米银线、石墨烯、碳纳米管等作为导电物质，在衬底上进行涂布。但由于银纳米线易与氧气反应形成氧化银而丧失导电性，无法保证透明导电纤维素薄膜导电性能的稳定性；石墨烯和碳纳米管作为导电物质，存在着与纤维素薄膜的结合性较差、透光率低等缺陷，导致制备透明纤维素薄膜导电性、透光性差，影响其进一步应用发展的空间。所以，以涂布的方式制备柔性纤维素基透明导电材料目前仍处于实验室研究阶段。At present, the method of preparing transparent and conductive cellulose films is mainly in the form of coating. It mainly uses nano-cellulose film as the substrate, and nano-silver wires, graphene, carbon nanotubes, etc. as conductive substances are coated on the substrate. However, because silver nanowires are easy to react with oxygen to form silver oxide and lose conductivity, the stability of the conductive properties of transparent conductive cellulose films cannot be guaranteed; graphene and carbon nanotubes, as conductive substances, have poor bonding with cellulose films Defects such as poor and low light transmittance lead to poor conductivity and light transmittance of the prepared transparent cellulose film, which affects the space for its further application and development. Therefore, the preparation of flexible cellulose-based transparent conductive materials by coating is still in the stage of laboratory research.
利用磁控溅射的方法在纤维素薄膜衬底上生长单层ITO导电材料（参见图1），实现制备柔性纤维素基透明导电材料。该方法的制备成本低、效率较高，可以实现导电薄膜大面积和卷对卷制备，适合工业化生产。然而，纤维素衬底上生长单层ITO导电材料的透光率还较低、导电性较差，主要受到以下两个方面的影响：一方面，ITO 薄膜的生长温度越高，ITO的组成原子在基底上的迁移程度越高，薄膜的组分越均匀，薄膜质量越高，但由于纤维素薄膜所能承受的温度比较低，在较低的温度下制备柔性纤维素基透明导电材料，ITO 薄膜的质量差，导致纤维素薄膜导电性下降。A single layer of ITO conductive material (see Figure 1) is grown on a cellulose film substrate by magnetron sputtering to realize the preparation of a flexible cellulose-based transparent conductive material. The method has low preparation cost and high efficiency, can realize large-area and roll-to-roll preparation of the conductive film, and is suitable for industrial production. However, the light transmittance and poor conductivity of a single-layer ITO conductive material grown on a cellulose substrate are mainly affected by the following two aspects: On the one hand, the higher the growth temperature of the ITO film, the higher the ITO constituent atoms The higher the degree of migration on the substrate, the more uniform the composition of the film and the higher the quality of the film, but because the temperature that the cellulose film can withstand is relatively low, the flexible cellulose-based transparent conductive material, ITO, is prepared at a lower temperature The quality of the film is poor, resulting in a decrease in the conductivity of the cellulose film.
另一方面，由于纤维素衬底材料为有机材料，而ITO 材料为无机半导体材料，两者的晶格结构差异巨大。ITO 半导体直接在纤维素基底上生长，由于二者晶格失配度很大，由于晶格应力的存在，生长的ITO薄膜晶格发生畸变，因此生长的ITO容易产生晶格缺陷，甚至产生裂纹，导致纤维素薄膜导电性差。同时，生长的ITO薄膜的晶格缺陷密度高，在半导体禁带中形成缺陷能级，对可见光产生吸收，导致薄膜的可见光透光率下降。On the other hand, since the cellulose substrate material is an organic material, and the ITO material is an inorganic semiconductor material, the lattice structures of the two differ greatly. The ITO semiconductor is grown directly on the cellulose substrate. Due to the large lattice mismatch between the two, the lattice stress of the grown ITO film is distorted, so the grown ITO is prone to lattice defects and even cracks. , resulting in poor conductivity of the cellulose film. At the same time, the lattice defect density of the grown ITO film is high, and defect energy levels are formed in the semiconductor forbidden band, which absorbs visible light, resulting in a decrease in the visible light transmittance of the film.
通过在ITO薄膜中引入透明的Ag纳米插入层（参见图2），制备ITO/Ag/ITO三明治结构的透明导电层，Ag良好的导电性可以极大提高ITO/Ag/ITO复合膜的整体导电性。同时，由于Ag具有良好的延展性，可以释放晶格之间的应力，降低ITO薄膜中的晶格缺陷浓度，提高ITO薄膜的导电性和透光率，从而制备出高导电性、高透光率的柔性纤维素基透明导电材料导电材料。By introducing a transparent Ag nano-intercalation layer into the ITO film (see Figure 2), a transparent conductive layer of ITO/Ag/ITO sandwich structure is prepared, and the good conductivity of Ag can greatly improve the overall conductivity of the ITO/Ag/ITO composite film sex. At the same time, due to the good ductility of Ag, it can release the stress between the lattices, reduce the concentration of lattice defects in the ITO film, and improve the conductivity and light transmittance of the ITO film, thereby preparing a high-conductivity, high-transmittance High rate flexible cellulose based transparent conductive material conductive material.
发明内容Contents of the invention
本发明的目的在于针对现有的纤维素薄膜衬底上生长单层ITO透明导电材料存在ITO晶格缺陷浓度高、薄膜裂纹较多、导电性不稳定、透光率低等问题，提供一种提高柔性纤维素基透明导电的制备方法。The purpose of the present invention is to solve the problems of high ITO lattice defect concentration, many film cracks, unstable conductivity and low light transmittance in the existing single-layer ITO transparent conductive material grown on the cellulose film substrate, and to provide a Preparation method for improving transparent conductivity of flexible cellulose bases.
本发明的技术方案是利用Ag具有良好的导电性、延展性能等优点，先在纤维素薄膜衬底上生长第一层ITO导电层，再在第一层ITO上生长第二层Ag导电层，维持纤维素基良好的导电性，进而在第二层Ag上生长第三层ITO导电层，最后退火提高复合膜电学和光学性能，从而得到高导电性和高透光率的“ITO/Ag/ITO/纤维素”柔性纤维素基透明导电材料。The technical solution of the present invention is to utilize the advantages of Ag having good conductivity and ductility, first grow the first layer of ITO conductive layer on the cellulose film substrate, and then grow the second layer of Ag conductive layer on the first layer of ITO, Maintain the good conductivity of the cellulose base, and then grow the third layer of ITO conductive layer on the second layer of Ag, and finally anneal to improve the electrical and optical properties of the composite film, so as to obtain "ITO/Ag/ ITO/cellulose" flexible cellulose-based transparent conductive material.
本发明的目的是这样实现的，所述的一种柔性纤维素基透明导电材料的制备方法，其特征在于包括以下步骤：The purpose of the present invention is achieved in that the preparation method of a flexible cellulose-based transparent conductive material is characterized in that it comprises the following steps:
1）在纤维素薄膜衬底上通过磁控溅射技术生长出第一层氧化铟锡（ITO）导电层，所述磁控溅射的溅射温度在30~150℃，溅射功率30~200W；1) The first layer of indium tin oxide (ITO) conductive layer is grown on the cellulose film substrate by magnetron sputtering technology. The sputtering temperature of the magnetron sputtering is 30~150℃, and the sputtering power is 30~ 200W;
2）在第一层氧化铟锡（ITO）导电层上通过磁控溅射技术生长出第二层银（Ag）导电层，所述磁控溅射的溅射温度在30~150℃，溅射功率10~100W；2) On the first layer of indium tin oxide (ITO) conductive layer, the second layer of silver (Ag) conductive layer is grown by magnetron sputtering technology. The sputtering temperature of the magnetron sputtering is 30~150°C. Radiation power 10~100W;
3）在第二层银（Ag）导电层上通过磁控溅射技术生长出第三层ITO导电层，所述磁控溅射的溅射温度在30~150℃，溅射功率为30~200W；3) On the second layer of silver (Ag) conductive layer, the third layer of ITO conductive layer is grown by magnetron sputtering technology. The sputtering temperature of the magnetron sputtering is 30~150℃, and the sputtering power is 30~ 200W;
4） 对步骤（3）生长成的复合薄膜进行退火，得到高导电性、高透光率的“ITO/Ag/ITO/纤维素”柔性纤维素基透明导电材料。4) Anneal the composite film grown in step (3) to obtain "ITO/Ag/ITO/cellulose" flexible cellulose-based transparent conductive material with high conductivity and high light transmittance.
上述纤维素薄膜衬底为纳米纤维素膜、再生纤维素膜或细菌纤维素膜。The above-mentioned cellulose film substrate is a nanocellulose film, a regenerated cellulose film or a bacterial cellulose film.
第一层ITO导电层厚度为50~500nm。The thickness of the first ITO conductive layer is 50-500 nm.
第二层Ag导电层的厚度为2~20nm。The thickness of the second Ag conductive layer is 2-20 nm.
第三层ITO导电层的厚度为50~500nm。The thickness of the third ITO conductive layer is 50-500 nm.
所述的退火的氛围至少有一种选自真空、氧气氛、氩气氛、氮气氛、氢气气氛或空气气氛，退火温度为30~150℃，退火时间为1~24h。The annealing atmosphere is at least one selected from vacuum, oxygen atmosphere, argon atmosphere, nitrogen atmosphere, hydrogen atmosphere or air atmosphere, the annealing temperature is 30-150°C, and the annealing time is 1-24h.
具体地说，本发明包括以下步骤：Specifically, the present invention comprises the following steps:
1）通过磁控溅射技术，在纤维素薄膜衬底上生长第一层ITO导电层，溅射温度为30~150℃，溅射功率为30~200W；1) By magnetron sputtering technology, grow the first layer of ITO conductive layer on the cellulose film substrate, the sputtering temperature is 30~150℃, and the sputtering power is 30~200W;
2）第一层ITO上生长第二层Ag导电层，溅射温度在30~150℃，溅射功率10~100W；2) The second layer of Ag conductive layer is grown on the first layer of ITO, the sputtering temperature is 30~150℃, and the sputtering power is 10~100W;
3）升高温度，在第二层Ag上生长第三层ITO导电层，溅射温度在30~150℃，溅射功率为30~200W；3) Increase the temperature to grow the third layer of ITO conductive layer on the second layer of Ag, the sputtering temperature is 30~150℃, and the sputtering power is 30~200W;
4）对生长的复合薄膜进行退火，得到高导电性、高透光率的“ITO/Ag/ITO/纤维素”柔性纤维素基透明导电材料。4) Anneal the grown composite film to obtain "ITO/Ag/ITO/cellulose" flexible cellulose-based transparent conductive material with high conductivity and high light transmittance.
纤维素薄膜最好为纳米纤维素膜、再生纤维素膜、细菌纤维素膜。The cellulose film is preferably a nanocellulose film, a regenerated cellulose film, or a bacterial cellulose film.
第一层ITO）导电层生长厚度最好为50~500nm。The growth thickness of the first layer of ITO) conductive layer is preferably 50~500nm.
第二层Ag导电层生长厚度最好为2~20nm。The growth thickness of the second Ag conductive layer is preferably 2-20 nm.
第三层ITO导电层生长厚度最好为50~500nm。The growth thickness of the third ITO conductive layer is preferably 50-500 nm.
所述退火的氛围包括真空、氧气氛、氩气氛、氮气氛、氢气气氛、空气气氛等，退火温度为30~150℃，退火时间为1~24h。The annealing atmosphere includes vacuum, oxygen atmosphere, argon atmosphere, nitrogen atmosphere, hydrogen atmosphere, air atmosphere, etc., the annealing temperature is 30-150°C, and the annealing time is 1-24h.
与现有的纤维素薄膜衬底上生长单层ITO透明导电材料的制备方法相比，本发明具有以下突出的优点：Compared with the preparation method of growing a single-layer ITO transparent conductive material on the existing cellulose film substrate, the present invention has the following outstanding advantages:
1）在ITO生长纳米Ag层，利用Ag材料的良好延展性，释放ITO之间的晶格应力，减少由晶格应力产生的晶格缺陷和薄膜裂纹，由此提高导电性和透光率。1) The nano-Ag layer is grown on the ITO, and the good ductility of the Ag material is used to release the lattice stress between the ITO and reduce the lattice defects and film cracks caused by the lattice stress, thereby improving the conductivity and light transmittance.
2）由于纳米级Ag具有高导电性，在ITO中插入Ag纳米层制备ITO/Ag/ITO三明治结构薄膜，可以极大提高复合薄膜的导电性。2) Due to the high conductivity of nanoscale Ag, inserting Ag nanolayers into ITO to prepare ITO/Ag/ITO sandwich structure films can greatly improve the conductivity of composite films.
3）柔性纤维素基透明导电材料生长一层Ag，在相同导电性要求的情况下，可以减少ITO生长厚度，提高柔性纤维素基透明导电材料的透光率。3) A layer of Ag is grown on the flexible cellulose-based transparent conductive material. Under the same conductivity requirements, the growth thickness of ITO can be reduced and the light transmittance of the flexible cellulose-based transparent conductive material can be improved.
4）由于金属Ag具有高迁移的特性，在生长第一层ITO后可填充ITO表面的高低起伏缺陷，提高薄膜的表面平整度，提高柔性纤维素基透明导电材料的透光率。4) Due to the high migration characteristics of metal Ag, after the growth of the first layer of ITO, it can fill the high and low fluctuation defects on the ITO surface, improve the surface flatness of the film, and improve the light transmittance of the flexible cellulose-based transparent conductive material.
附图说明Description of drawings
图1 为纤维素薄膜衬底上生长单层ITO导电材料示意图。Figure 1 is a schematic diagram of growing a single layer of ITO conductive material on a cellulose film substrate.
图2 为本发明“ITO/Ag/ITO/纤维素”柔性纤维素基透明导电材料结构示意图。Fig. 2 is a schematic diagram of the structure of the "ITO/Ag/ITO/cellulose" flexible cellulose-based transparent conductive material of the present invention.
图3 为本发明实施例在纤维素薄膜衬底上生长“ITO/Ag/ITO”具体过程图。Fig. 3 is a specific process diagram of growing "ITO/Ag/ITO" on a cellulose film substrate according to an embodiment of the present invention.
图中的标号为：1. 衬底； 2. ITO导电层；3. Ag导电层；4. ITO导电层。The symbols in the figure are: 1. substrate; 2. ITO conductive layer; 3. Ag conductive layer; 4. ITO conductive layer.
具体实施方式detailed description
下面通过具体实施例阐述，以进一步阐明本发明的实质性特点和显著进步。Set forth below by specific embodiment, to further illustrate the substantive characteristics and remarkable progress of the present invention.
实施例1Example 1
参见附图3，柔性纤维素基透明导电材料制备采用纳米纤维素作为衬底1，首先用纯N2处理3min以彻底去除衬底表面粉尘（过程a）；再通过磁控溅射技术，在溅射温度110℃生长第一层氧化铟锡（ITO）导电层（过程b），溅射功率为110W，厚度约为300nm；继而关闭ITO源，打开Ag源，降低温度到60℃在ITO和纤维素薄膜衬底上生长第二层银（Ag）导电层（过程c），生长厚度约为10nm，这时生长出的纳米Ag层具有高迁移的特性，可填充ITO表面的高低起伏缺陷，使表面平整；关闭Ag源，打开ITO源，升高温度到110℃生长第三层ITO导电层（过程d），溅射功率为110W，厚度约为300nm；最后在纯Ar气氛中，退火温度60℃，退火时间约为12h退火，制得柔性纤维素基透明导电材料（过程f）。Referring to Figure 3, the flexible cellulose-based transparent conductive material is prepared using nanocellulose as the substrate 1, firstly treated with pure N 2 for 3 minutes to completely remove the dust on the surface of the substrate (process a); and then through magnetron sputtering technology, in The sputtering temperature is 110°C to grow the first layer of indium tin oxide (ITO) conductive layer (process b), the sputtering power is 110W, and the thickness is about 300nm; then the ITO source is turned off, the Ag source is turned on, and the temperature is lowered to 60°C. The second layer of silver (Ag) conductive layer is grown on the cellulose film substrate (process c), and the growth thickness is about 10nm. At this time, the nano-Ag layer grown has the characteristics of high migration and can fill the high and low fluctuation defects on the ITO surface. Make the surface smooth; turn off the Ag source, turn on the ITO source, raise the temperature to 110°C to grow the third ITO conductive layer (process d), the sputtering power is 110W, and the thickness is about 300nm; finally, in the pure Ar atmosphere, the annealing temperature 60 ℃, the annealing time is about 12h, and the flexible cellulose-based transparent conductive material is prepared (process f).
实施例2Example 2
参见附图3，柔性纤维素基透明导电材料制备采用纳米纤维素作为衬底1，首先用纯N2处理3min以彻底去除衬底表面粉尘（过程a）；再通过磁控溅射技术，在溅射温度110℃生长第一层氧化铟锡（ITO）导电层（过程b），溅射功率为90W，厚度约为250nm；继而关闭ITO源，打开Ag源，降低温度到40℃在ITO和纤维素薄膜衬底上生长第二层银（Ag）导电层（过程c），生长厚度约为6nm，这时生长出的纳米Ag层具有高迁移的特性，可填充ITO表面的高低起伏缺陷，使表面平整；关闭Ag源，打开ITO源，升高温度到110℃生长第三层ITO导电层（过程d），溅射功率为90W，厚度约为250nm；最后在纯空气气氛中，退火温度30℃，退火时间约为12h退火，制得柔性纤维素基透明导电材料（过程f）。Referring to Figure 3, the flexible cellulose-based transparent conductive material is prepared using nanocellulose as the substrate 1. First, it is treated with pure N 2 for 3 minutes to completely remove the dust on the surface of the substrate (process a); and then through magnetron sputtering technology, in The sputtering temperature is 110°C to grow the first layer of indium tin oxide (ITO) conductive layer (process b), the sputtering power is 90W, and the thickness is about 250nm; then the ITO source is turned off, the Ag source is turned on, and the temperature is lowered to 40°C. The second layer of silver (Ag) conductive layer is grown on the cellulose film substrate (process c), and the growth thickness is about 6nm. At this time, the nano-Ag layer grown has the characteristics of high migration and can fill the high and low fluctuation defects on the ITO surface. Make the surface smooth; turn off the Ag source, turn on the ITO source, raise the temperature to 110°C to grow the third ITO conductive layer (process d), the sputtering power is 90W, and the thickness is about 250nm; finally in the pure air atmosphere, the annealing temperature 30 ℃, the annealing time is about 12h, and the flexible cellulose-based transparent conductive material is prepared (process f).
实施例3Example 3
参见附图3，柔性纤维素基透明导电材料制备采用纳米纤维素作为衬底1，首先用纯N2处理3min以彻底去除衬底表面粉尘（过程a）；再通过磁控溅射技术，在溅射温度80℃生长第一层氧化铟锡（ITO）导电层（过程b），溅射功率为90W，厚度约为200nm；继而关闭ITO源，打开Ag源，降低温度到30℃在ITO和纤维素薄膜衬底上生长第二层银（Ag）导电层（过程c），生长厚度约为3nm，这时生长出的纳米Ag层具有高迁移的特性，可填充氧ITO表面的高低起伏缺陷，使表面平整；关闭Ag源，打开ITO源，升高温度到80℃生长第三层ITO导电层（过程d），溅射功率为90W，厚度约为200nm；最后在氮气气氛中，退火温度90℃，退火时间约为6h退火，制得柔性纤维素基透明导电材料（过程f）。Referring to Figure 3, the flexible cellulose-based transparent conductive material is prepared using nanocellulose as the substrate 1, firstly treated with pure N 2 for 3 minutes to completely remove the dust on the surface of the substrate (process a); and then through magnetron sputtering technology, in The sputtering temperature is 80°C to grow the first layer of indium tin oxide (ITO) conductive layer (process b), the sputtering power is 90W, and the thickness is about 200nm; then the ITO source is turned off, the Ag source is turned on, and the temperature is lowered to 30°C. The second layer of silver (Ag) conductive layer is grown on the cellulose film substrate (process c), and the growth thickness is about 3nm. At this time, the nano-Ag layer grown has the characteristics of high migration and can fill the high and low fluctuation defects on the surface of oxygen ITO , to make the surface smooth; turn off the Ag source, turn on the ITO source, raise the temperature to 80°C to grow the third ITO conductive layer (process d), the sputtering power is 90W, and the thickness is about 200nm; finally, in the nitrogen atmosphere, the annealing temperature 90 ℃, the annealing time is about 6h, and the flexible cellulose-based transparent conductive material is prepared (process f).
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