CN105058786B - Coaxial focusing electro stream printing method - Google Patents
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Abstract
本发明一种同轴聚焦电射流打印方法属于先进制造技术领域，涉及一种同轴聚焦电射流打印方法。该方法在同轴聚焦电射流打印过程中，同轴聚焦电射流打印喷头中装有两种液体，一种为所需成型材料称为内层功能液体，另一种为辅助材料称为外层液体，外层液体与内层功能液体不相溶，并且外层液体的粘度大于内层功能液体的粘度；同轴聚焦电射流打印喷头在打印中形成双层液体的同轴聚焦射流，在衬底上打印双层结构，最后，去除外层打印材料，获得内层功能结构。该方法具有打印分辨率高，材料适应性强，抗微环境干扰力强的特点，可以在常温常压下使用微米尺度的喷针实现高分辨率的图案化打印。
The invention relates to a coaxial focusing electric jet printing method, which belongs to the technical field of advanced manufacturing, and relates to a coaxial focusing electric jet printing method. In this method, during the coaxial focusing electro-jet printing process, two liquids are installed in the coaxial focusing electro-jet printing nozzle, one is the required molding material called the inner layer functional liquid, and the other is the auxiliary material called the outer layer Liquid, the outer layer liquid is incompatible with the inner layer functional liquid, and the viscosity of the outer layer liquid is greater than the viscosity of the inner layer functional liquid; the coaxial focused electrojet printing nozzle forms a coaxial focused jet of double-layer liquid during printing, and the coaxial focused jet of the double layer liquid is formed on the lining The two-layer structure is printed on the bottom, and finally, the outer printing material is removed to obtain the inner functional structure. The method has the characteristics of high printing resolution, strong material adaptability, and strong resistance to micro-environmental interference, and can use micron-scale nozzles to achieve high-resolution patterned printing at normal temperature and pressure.
Description
技术领域technical field
本发明属于先进制造技术领域，涉及一种同轴聚焦电射流打印方法。The invention belongs to the field of advanced manufacturing technology and relates to a coaxial focusing electric jet printing method.
背景技术Background technique
传统基于压电、热泡等喷墨打印方法，分辨率严重依赖喷孔尺寸，分辨率约为喷针内径的两倍，目前喷针内径为10～50微米，其打印特征尺寸将大于20微米，因此难以实现微米以下分辨率的打印制造。近年来，基于电流体动力效应的电射流打印技术成为高分辨率打印制造的热点。电射流打印是流体在电场力、机械力、流体表面张力等综合作用下，在喷针出口处形成远小于喷针内径的稳定精细射流，利用此射流进行高分辨率打印制造。与传统基于压电或热气泡式原理的喷墨打印过程相比，电射流打印具有打印分辨率高、墨水及衬底适应性广等优点。Traditional inkjet printing methods based on piezoelectric, thermal bubble, etc., the resolution is heavily dependent on the size of the nozzle hole, the resolution is about twice the inner diameter of the nozzle, currently the inner diameter of the nozzle is 10 to 50 microns, and the printed feature size will be greater than 20 microns , so it is difficult to achieve printing with sub-micron resolution. In recent years, electrojet printing technology based on electrohydrodynamic effect has become a hotspot in high-resolution printing manufacturing. Electrojet printing is a stable and fine jet that is much smaller than the inner diameter of the needle at the outlet of the needle under the combined action of electric field force, mechanical force, and fluid surface tension. This jet is used for high-resolution printing. Compared with the traditional inkjet printing process based on piezoelectric or thermal bubble principle, electrojet printing has the advantages of high printing resolution, wide adaptability of ink and substrate, etc.
美国专利I.A.Aksay et al.,Electrohydrodynamic printing andmanufacturing,2009/0233057 A1，US中，采用单喷针和单锥-射流模式，打印微米级分辨率图。美国伊利诺伊大学厄巴纳-香槟分校Roger的文章：J.A.Roger et al.,NanoscalePatterns of Oligonucleotides Formed by Electrohydrodynamic Jet Printing withApplications in Biosensing and Nanomaterials Assembly,Nano Lett.,8(2008),4210-4216，通过降低喷针-衬底间距来增强轴向电场力对射流的聚焦作用，打印出微米尺度的蛋白质图案、皮克级聚乙烯液滴、氧化铟锌场效应管微器件、亚微米级嵌段共聚物薄膜图案和DNA点阵图案。韩国顺天乡大学K.Choi et al.,Fine resolution drop-on-demandelectrohydrodynamic patterning of conductive silver tracks on glasssubstrate,Appl.Phys.A-Mater.Sci.Process.,111(2013),593-600.文章中采用金属Ag墨水，打印微米金属Ag导电电路。但是，以上电射流打印都是基于单锥-射流模式进行打印制造。在单锥-射流模式下，施加于射流的电场切向力有限，导致射流尺寸受限，其打印分辨局限于微米尺度，打印分辨率难以进一步提高。此外，现有基于单锥-射流打印技术通过不断降低喷针内径，来提高打印分辨率，这将导致对墨水适应性差，例如高粘度、高浓度的墨水将引起喷针堵塞。而且，在这种模式下打印，射流容易受到周围温度、湿度、振动等微环境干扰，导致射流不稳定，进而影响打印的精度和控制性。In the US patent I.A.Aksay et al., Electrohydrodynamic printing and manufacturing, 2009/0233057 A1, US, a single nozzle and a single cone-jet mode are used to print micron-level resolution images. Article by Roger of the University of Illinois at Urbana-Champaign: J.A.Roger et al., Nanoscale Patterns of Oligonucleotides Formed by Electrohydrodynamic Jet Printing with Applications in Biosensing and Nanomaterials Assembly, Nano Lett., 8(2008), 4210-4216, by reducing the jet The needle-substrate spacing is used to enhance the focusing effect of the axial electric field force on the jet, and to print micron-scale protein patterns, picogram-level polyethylene droplets, indium zinc oxide field-effect transistor microdevices, and submicron-scale block copolymer films patterns and DNA lattice patterns. K.Choi et al., Suncheon Hsiang University, South Korea, Fine resolution drop-on-demandelectrohydrodynamic patterning of conductive silver tracks on glass substrate, Appl.Phys.A-Mater.Sci.Process., 111(2013), 593-600. Article Metal Ag ink is used to print micron metal Ag conductive circuit. However, the above electro-jet printing is based on the single-cone-jet mode for printing and manufacturing. In the single cone-jet mode, the tangential force of the electric field applied to the jet is limited, resulting in a limited size of the jet, and its printing resolution is limited to the micron scale, making it difficult to further improve the printing resolution. In addition, the existing single-cone-jet printing technology improves the printing resolution by continuously reducing the inner diameter of the nozzle, which will lead to poor adaptability to ink, such as high viscosity and high concentration ink will cause nozzle clogging. Moreover, when printing in this mode, the jet is easily disturbed by micro-environment such as ambient temperature, humidity, vibration, etc., resulting in unstable jet, which in turn affects the accuracy and controllability of printing.
发明内容Contents of the invention
本发明为克服上述现有技术的不足，发明了一种同轴聚焦电射流打印方法，利用电射流打印是流体在电场力、机械力、流体表面张力等综合作用下，在喷针出口处形成远小于喷针内径的稳定精细射流。电场力同时作用于同轴内外层液体，外层液体锥-射流形变产生的粘滞力与内层液体的电场切向力叠加，共同作用于内层液体，可以提高内层液体射流形变的切向力，降低射流尺寸，免受外部微环境的干扰影响，进而提高打印分辨率和控制性。In order to overcome the shortcomings of the above-mentioned prior art, the present invention has invented a coaxial focusing electro-jet printing method, which uses electro-jet printing to form a fluid at the outlet of the nozzle under the comprehensive action of electric field force, mechanical force, and fluid surface tension. A steady fine jet that is much smaller than the inner diameter of the needle. The electric field force acts on the inner and outer layers of the coaxial liquid at the same time, the viscous force generated by the cone-jet deformation of the outer layer liquid and the electric field tangential force of the inner layer liquid are superimposed, acting together on the inner layer liquid, which can increase the shear of the jet deformation of the inner layer liquid Steering force, reducing the size of the jet, free from the interference of the external micro-environment, thereby improving the printing resolution and controllability.
本发明采用的技术方案是一种同轴聚焦电射流打印的方法，其特征是：该方法在同轴聚焦电射流打印过程中，同轴聚焦电射流打印喷头1中装有两种液体，一种为所需成型材料称为内层功能液体7，另一种为辅助材料称为外层液体8，外层液体与内层功能液体不相溶；并且，外层液体的粘度大于内层功能液体的粘度；同轴聚焦电射流打印喷头1在打印中形成双层液体的同轴聚焦射流，在衬底上打印双层结构，最后，去除外层打印材料，获得内层功能结构；方法的具体步骤如下：The technical solution adopted in the present invention is a method for coaxial focusing electrojet printing, which is characterized in that: during the process of coaxial focusing electrojet printing, the coaxial focusing electrojet printing nozzle 1 is equipped with two kinds of liquids, one One is the required molding material called the inner layer of functional liquid 7, and the other is the auxiliary material called the outer layer of liquid 8, the outer layer of liquid and the inner layer of functional liquid are incompatible; and the viscosity of the outer layer of liquid is greater than the inner layer of functional liquid The viscosity of the liquid; the coaxial focused electro-fluidic printing nozzle 1 forms a coaxial focused jet of a double-layer liquid during printing, and prints a double-layer structure on the substrate. Finally, the outer printing material is removed to obtain the inner functional structure; the method Specific steps are as follows:
1)同轴聚焦电射流打印系统安装1) Coaxial focused electro-jet printing system installation
首先，将计算机16分别与显微镜17和XY运动平台基板12相连，XY运动平台基板12通过接地极板19接地；第一微量注射泵13通过硅橡胶管18连接到同轴聚焦电射流打印喷头1的上端进口，第二微量注射泵14通过硅橡胶管连接到同轴聚焦电射流打印喷头1的左侧进口，高压电源15与同轴聚焦电射流打印喷头1左下端相连；First, the computer 16 is connected to the microscope 17 and the XY motion platform substrate 12 respectively, and the XY motion platform substrate 12 is grounded through the grounding plate 19; the first micro injection pump 13 is connected to the coaxial focusing electro-jet printing nozzle 1 through the silicon rubber tube 18 The upper inlet of the upper end, the second micro-injection pump 14 is connected to the left inlet of the coaxial focusing electro-jet printing nozzle 1 through a silicone rubber tube, and the high-voltage power supply 15 is connected to the left lower end of the coaxial focusing electro-jet printing nozzle 1;
2)同轴聚焦电射流的实现2) Realization of coaxial focused electrojet
在同轴聚焦电射流打印前，首先选择内层功能液体7和外层液体8，选择好后，通过第一微量注射泵13和第二微量注射泵14分别将内层功能液体7和外层液体8注入到同轴聚焦电射流打印喷头1中；对内层功能液体和外层液体施加不同的高压电场,调节内层功能液体和外层液体的流量、电压；在X-Y运动平台基板12上放置衬底11，调节喷针与衬底的间距，即工作高度；Before coaxial focusing electro-jet printing, the inner layer functional liquid 7 and the outer layer liquid 8 are first selected. The liquid 8 is injected into the coaxial focusing electro-jet printing nozzle 1; different high-voltage electric fields are applied to the inner layer functional liquid and the outer layer liquid to adjust the flow rate and voltage of the inner layer functional liquid and the outer layer liquid; on the X-Y motion platform substrate 12 Place the substrate 11, adjust the distance between the nozzle and the substrate, that is, the working height;
3)同轴聚焦电射流打印双层结构3) Coaxial focused electro-jet printing double-layer structure
调节好内层功能液体和外层液体的流量、电压和工作高度后，开始打印，由同轴聚焦电射流打印喷头1出口处形成稳定的同轴射流4，同轴射流4由内层功能液体形成内射流5和外层液体形成外射流6构成；保持稳定同轴射流，根据打印图案，由电脑控制X-Y运动平台的运动轨迹，在衬底11上进行打印，每个打印图案单元为双层结构9，内层结构由内层功能液体组成，外层包裹结构由外层液体组成；After adjusting the flow rate, voltage and working height of the inner layer functional liquid and the outer layer liquid, start printing, and a stable coaxial jet 4 is formed at the outlet of the coaxial focusing electro-jet printing nozzle 1, and the coaxial jet 4 is formed by the inner layer functional liquid The inner jet 5 is formed and the outer jet 6 is formed by the outer layer of liquid; the coaxial jet is kept stable, and the computer controls the movement track of the X-Y motion platform according to the printing pattern, and prints on the substrate 11, and each printing pattern unit is a double layer Structure 9, the inner structure is composed of the inner functional liquid, and the outer wrapping structure is composed of the outer liquid;
4)外层打印材料的去除4) Removal of outer printing material
当双层结构图案打印完成后，在室温下搁置一定时间，以获得稳定结构；根据外层液体的物理特性，采用溶剂溶解方法去除外层包裹打印材料；去除外层打印材料后，将得到仅有内层材料组成的打印图案10。When the double-layer structure pattern is printed, it is left at room temperature for a certain period of time to obtain a stable structure; according to the physical properties of the outer liquid, the outer wrapping printing material is removed by solvent dissolution; after removing the outer printing material, only There is a printed pattern 10 composed of inner layer material.
本发明的显著效果是采用此方法进行打印，具有打印分辨率高、材料适应性强、抗微环境干扰力强的特点。利用同轴聚焦电射流打印方法，先利用同轴聚焦电射流打印双层结构，再去除外层包裹材料，可以在常温常压下使用微米尺度的喷针实现高分辨率的图案化打印，本发明实现了电射流打印分辨率和控制性的进一步提升。The remarkable effect of the invention is that the method is used for printing, which has the characteristics of high printing resolution, strong material adaptability, and strong resistance to micro-environmental interference. Using the coaxial focused electrojet printing method, the coaxial focused electrojet is used to print the double-layer structure first, and then the outer wrapping material is removed, and high-resolution patterned printing can be achieved using micron-scale nozzles at room temperature and pressure. The invention further improves the resolution and controllability of electrojet printing.
附图说明Description of drawings
图1为同轴聚焦电射流打印系统简图，图2为同轴聚焦电射流打印简图，其中：1-同轴聚焦电射流打印喷头，2-内喷针，3-外喷针，4-同轴射流，5-内射流，6-外射流，7-内层功能液体，8-外层液体，9-双层结构图案，10-内层结构图案，11-衬底，12-XY运动平台基板，13-第一微量注射泵，14--第二微量注射泵，15-高压电源，16-计算机，17-显微镜，18-硅橡胶管，19-接地极板。Figure 1 is a schematic diagram of the coaxial focusing electro-jet printing system, and Figure 2 is a schematic diagram of the coaxial focusing electro-jet printing, in which: 1-coaxial focusing electro-jet printing nozzle, 2-inner nozzle, 3-outer nozzle, 4 -coaxial jet, 5-inner jet, 6-outer jet, 7-inner functional liquid, 8-outer liquid, 9-double-layer structure pattern, 10-inner layer structure pattern, 11-substrate, 12-XY Motion platform substrate, 13-the first micro-injection pump, 14-the second micro-injection pump, 15-high voltage power supply, 16-computer, 17-microscope, 18-silicone rubber tube, 19-grounding plate.
具体实施方式detailed description
以下结合技术方案和附图详细说明本发明的具体实施方式。同轴聚焦电射流打印是将内层液体和外层液体分别通入同轴聚焦电射流打印喷头的内外喷针中，内外层液体要不相溶，而且，外层液体粘度大于内层液体，外层液体的作用是对内层液体射流提供更大的剪切力并保护内层液体。在适当的流量下施加一定的电压，则在同轴聚焦电射流打印喷针出口处将形成一股同轴聚焦电射流。提高了内层液体射流形变的切向力，降低射流尺寸，免受外部微环境的干扰影响，利用此同轴聚焦电射流先打印双层结构，再去除外层包裹材料，在常温常压下即可使用微米尺度的喷针实现高分辨率的图案化打印。The specific implementation manners of the present invention will be described in detail below in conjunction with the technical solutions and accompanying drawings. Coaxial focusing electro-jet printing is to pass the inner layer liquid and outer layer liquid into the inner and outer nozzles of the coaxial focusing electro-jet printing head respectively. The function of the outer liquid is to provide greater shear force to the inner liquid jet and protect the inner liquid. When a certain voltage is applied at an appropriate flow rate, a coaxial focused electric jet will be formed at the outlet of the coaxial focused electric jet printing needle. The tangential force of the deformation of the inner liquid jet is improved, the size of the jet is reduced, and it is free from the interference of the external micro-environment. The coaxial focused electric jet is used to print the double-layer structure first, and then remove the outer wrapping material. High-resolution patterned printing can be achieved using micron-scale nozzles.
实施例的具体实施步骤如下：The concrete implementation steps of embodiment are as follows:
1)同轴聚焦电射流打印系统安装1) Coaxial focused electro-jet printing system installation
附图1为同轴聚焦电射流打印系统简图，其中，计算机16分别与显微镜17和XY运动平台基板12相连，XY运动平台基板12通过接地极板19接地。第一微量注射泵13通过硅橡胶管18连接到同轴聚焦电射流打印喷头1的上端进口，第二微量注射泵14通过硅橡胶管连接到同轴聚焦电射流打印喷头1的左侧进口，高压电源15与同轴聚焦电射流打印喷头1左侧下端相连。Accompanying drawing 1 is the schematic diagram of the coaxial focusing electro-jet printing system, wherein, the computer 16 is connected with the microscope 17 and the XY motion platform substrate 12 respectively, and the XY motion platform substrate 12 is grounded through the grounding plate 19 . The first micro-injection pump 13 is connected to the upper inlet of the coaxial focusing electro-jet printing nozzle 1 through a silicone rubber tube 18, and the second micro-injection pump 14 is connected to the left inlet of the coaxial focusing electro-jet printing nozzle 1 through a silicon rubber tube. The high-voltage power supply 15 is connected to the left lower end of the coaxial focusing electro-jet print head 1 .
2)同轴聚焦电射流的实现2) Realization of coaxial focused electrojet
选用SiO2纳米悬浮液和硅油分别为内层功能液体7和外层液体8，SiO2为所需成型材料，硅油为外层包裹材料，SiO2和硅油互不相溶，SiO2粘度为71cSt，硅油粘度为20000cSt。如图1所示，先通过第一微量注射泵13和第二微量注射泵14将SiO2纳米悬浮液和硅油分别注入同轴聚焦电射流打印喷头1的内喷针2和外喷针3中。其中，内喷针和外喷针的内径分别为130μm和0.8mm。对SiO2和硅油施加高压电场，当场强达到5～8KV时，在同轴聚焦电射流打印喷针出口处形成同轴聚焦射流，内层射流5为SiO2纳米悬浮液，外层射流6为硅油。Select SiO 2 nano-suspension and silicone oil as the inner layer functional liquid 7 and outer layer liquid 8 respectively, SiO 2 is the required molding material, silicone oil is the outer layer wrapping material, SiO 2 and silicone oil are incompatible with each other, and the viscosity of SiO 2 is 71cSt , The viscosity of silicone oil is 20000cSt. As shown in Figure 1 , SiO nano-suspension and silicone oil are respectively injected into the inner spray needle 2 and the outer spray needle 3 of the coaxial focusing electro-jet printing nozzle 1 by the first micro-injection pump 13 and the second micro-injection pump 14 . Wherein, the inner diameters of the inner spray needle and the outer spray needle are 130 μm and 0.8 mm, respectively. Apply a high-voltage electric field to SiO 2 and silicone oil. When the field strength reaches 5-8KV, a coaxial focused jet is formed at the exit of the coaxial focused electric jet printing needle. The inner jet 5 is SiO 2 nano-suspension, and the outer jet 6 is silicone oil.
3)同轴聚焦电射流打印双层结构3) Coaxial focused electro-jet printing double-layer structure
在X-Y运动平台基板12上放置衬底11，衬底11采用硅片，调节喷针与衬底的间距，即工作高度为2cm。通过第一微量注射泵13设置内层液体的流量为0.001μl/min，通过第二微量注射泵14设置外层液体的流量为10μl/min，调节高压电源14的电压为6.0kv，调节出同轴聚焦电射流后，保持稳定同轴聚焦电射流；设定X-Y运动平台的运动速度为40mm/s，利用计算机15控制平台运动，在衬底11上打印图案，如附图2所示。每个打印图案单元为双层结构9，内层结构由SiO2组成，外层包裹结构由硅油组成，打印双层结构特征尺寸为160μm。The substrate 11 is placed on the base plate 12 of the XY motion platform. The substrate 11 is a silicon wafer, and the distance between the nozzle and the substrate is adjusted, that is, the working height is 2 cm. The flow rate of the inner layer liquid is set to 0.001 μl/min by the first micro-injection pump 13, the flow rate of the outer layer liquid is set to 10 μl/min by the second micro-injection pump 14, and the voltage of the high-voltage power supply 14 is adjusted to 6.0kv, and the same After the axial focusing electric jet, keep the coaxial focused electric jet stable; set the moving speed of the XY motion platform to 40mm/s, use the computer 15 to control the movement of the platform, and print patterns on the substrate 11, as shown in Figure 2. Each printed pattern unit is a double-layer structure 9, the inner layer structure is composed of SiO 2 , the outer layer wrapping structure is composed of silicone oil, and the characteristic size of the printed double-layer structure is 160 μm.
4)外层打印材料的去除4) Removal of outer printing material
根据硅油的物理特性，本案例采用溶剂溶解的方法去除外层打印材料。双层结构打印完成后，在室温下放置5～10min，以获得稳定的双层打印结构；取适量异丙醇，盛入洁净玻璃培养皿中；将打印双层结构的硅片放入培养皿中，保证打印结构完全浸入到异丙醇中，10min后取出衬底11并用异丙醇冲洗1～2min，得到SiO2材料打印结构10，形成的SiO2特征尺寸为80～300nm。According to the physical characteristics of silicone oil, in this case, the method of solvent dissolution is used to remove the outer printing material. After the double-layer structure is printed, place it at room temperature for 5-10 minutes to obtain a stable double-layer printed structure; take an appropriate amount of isopropanol and put it into a clean glass petri dish; put the silicon wafer with the printed double-layer structure into the petri dish , ensure that the printed structure is completely immersed in isopropanol, take out the substrate 11 after 10 minutes and rinse with isopropanol for 1-2 minutes, and obtain the printed structure 10 of SiO 2 material, and the formed SiO 2 characteristic size is 80-300nm.
本发明一种同轴聚焦电射流打印的方法，先利用同轴聚焦电射流打印双层结构，再去除外层材料，在微米尺度喷针和常温常压的条件下，实现高分辨率的打印，其打印分辨率为亚微米或纳米级。与单喷针电射流打印相比，同轴聚焦电射流打印可以显著提高打印分辨率，并可以提高对材料的适应性、降低对喷针的制作精度要求及降低微环境的干扰。A coaxial focusing electrojet printing method of the present invention first uses coaxial focusing electrojet to print a double-layer structure, and then removes the outer layer material, and realizes high-resolution printing under the conditions of micron-scale spray needles and normal temperature and pressure , and its printing resolution is submicron or nanometer level. Compared with single-needle electro-jet printing, coaxial focusing electro-jet printing can significantly improve the printing resolution, improve the adaptability to materials, reduce the requirements for the manufacturing accuracy of the nozzles, and reduce the interference of the micro-environment.
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| CN107601425B (en) * | 2017-08-10 | 2020-06-16 | 大连理工大学 | A method of printing and manufacturing nanobeam structures |
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