WO2024021035A1 - 一种微流控芯片 - Google Patents

一种微流控芯片 Download PDF

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Publication number
WO2024021035A1
WO2024021035A1 PCT/CN2022/109019 CN2022109019W WO2024021035A1 WO 2024021035 A1 WO2024021035 A1 WO 2024021035A1 CN 2022109019 W CN2022109019 W CN 2022109019W WO 2024021035 A1 WO2024021035 A1 WO 2024021035A1
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electrode
layer
substrate
area
oxide
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English (en)
French (fr)
Inventor
孟鸿
蔡雨露
张虎
杨标
张超红
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Peking University Shenzhen Graduate School
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Peking University Shenzhen Graduate School
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01L—CHEMICAL OR PHYSICAL LABORATORY APPARATUS FOR GENERAL USE
    • B01L3/00—Containers or dishes for laboratory use, e.g. laboratory glassware; Droppers
    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
    • G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
    • G01N21/66—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light electrically excited, e.g. electroluminescence
    • G01N21/69—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light electrically excited, e.g. electroluminescence specially adapted for fluids, e.g. molten metal

Definitions

  • the invention relates to the field of microfluidic technology, and in particular to a microfluidic chip based on an asymmetric planar structure light-emitting device.
  • Microfluidics refers to the science and technology involved in systems that use microchannels (tens to hundreds of microns in size) to process or manipulate tiny fluids. It is a field involving chemistry, fluid physics, microelectronics, new materials, The emerging intersection of biology and biomedical engineering.
  • the characteristic of microfluidic chips is that they can integrate most biological and chemical processes on one chip, which facilitates the detection and control of biological and chemical processes. Therefore, microfluidic chips have performed well in many fields such as biology, chemistry, and medicine. It has great application prospects and has gradually developed into a new multi-disciplinary research field.
  • This patent mainly uses dielectric wetting type droplet manipulation technology, utilizing the dielectric wetting phenomenon of droplets on the hydrophobic surface, and by controlling the change of droplet contact angle on the microelectrode array to achieve precise control of discrete droplets without Relying on components such as micropumps, microvalves or micromixers, it does not even require complex three-dimensional fluid channels. It has the advantages of simple construction and dynamic configuration, so it is especially suitable for biological and chemical microsystems with high integration, high performance and complex operation. analysis system.
  • Biomedical applications mostly use fluorescent labeling methods. Chemiluminescence requires a large and clumsy external light-emitting device, which adds difficulties to portability and cost. At the same time, traditional sandwich structure devices have limitations in transparency and operability due to the layout of the top electrode. Although planar electrodes can solve the fundamental problem of open experiments, they increase the operating voltage and bring additional energy waste.
  • the present invention provides a microfluidic chip, which overcomes the problem of high operating voltage of planar electrodes.
  • the solution of the present invention to solve the above technical problems is to provide a microfluidic chip, which includes a chip substrate and a cover plate.
  • the chip substrate includes an electrode base, an electrode substrate, a dielectric layer, a luminescent layer, and a hydrophobic layer; wherein, the The electrode substrate includes a layer of large-area electrodes and several small-area electrodes embedded on the large-area electrode for driving the movement of droplets.
  • the large-area electrode and the several small-area electrodes are electrically insulated.
  • the large-area electrode and the several small-area electrodes are formed on the same plane; each of the small-area electrodes includes a substrate, a port, an electrode assembly, and an electrode lead; The large-area electrode is connected to the ground, and the small-area electrode is connected to the power generator.
  • a droplet moving area and an electrode expansion area are provided on the electrode substrate, and electrode leads are provided through the electrode expansion area to individually control the energization of each of the small-area electrodes;
  • the plurality of small-area electrodes are distributed in the droplet moving area.
  • the size of the droplet is larger than the size of the small-area electrode.
  • the contact angle of the droplet becomes smaller due to the electric field force. , thus partially extending into the first electrode, which appears macroscopically as the droplet moving towards the energized electrode, and the light-emitting layer under the first electrode is also successfully excited by the electric field and the conductive effect of the droplet. From this, The chip achieves luminescence that changes as the position of the droplet changes.
  • the device has six layers in total, the first layer is an electrode base, the second layer is an electrode substrate, the third layer is a dielectric layer, the fourth layer is a light-emitting layer, and the fifth layer is a hydrophobic layer, and the sixth layer is a cover plate.
  • the luminescent material of the luminescent layer is an inorganic powder electroluminescent material, selected from one of zinc-copper sulfide, zinc-manganese sulfide, and zinc-aluminum sulfide;
  • the luminescent material is at least two of OLED red, green, blue and yellow;
  • the OLED red, green, blue and yellow adopts a doping structure of host material and guest material
  • the host material is selected from 4 ,4,4'-Tris(carbazol-9-yl)triphenylamine, 4,4'-N,N-dicarbazole-biphenyl, 9,9'-(2,6-pyridyldiyldi-3 ,1-phenylene)bis-9H-carbazole, 2,2'-(1,3-phenyl)bis[5-(4-tert-butylphenyl)-1,3,4-oxadiazole] , LGH001, LGH002, at least one of 2,6-DCzPPy;
  • the guest materials include blue light guest materials, green light guest materials, yellow light guest materials, and red light guest materials:
  • the blue light guest material is selected from the group consisting of bis(4,6-difluorophenylpyridine-N, C2)pyridinylcarboxylate, bis(3,5-difluoro-2-(2-pyridyl-KN) Phenyl-KC) (tetrakis(1H-pyrazolyl-KN)boric acid (1-)-KN2,KN2')-iridium, bis(2-hydroxyphenylpyridine)beryllium, Flrpic, LGD001, LRD001, LBD001 at least one of;
  • the green light guest material is selected from the group consisting of tris(2-phenylpyridine)iridium and bis(2-phenylpyridine-C2) acetylacetonate. ,N) At least one of iridium(III);
  • the yellow light guest material is selected from bis(4-phenyl-thiophene[3,2-c]pyridine-C2,N)iridium(III) acetylacetonate, bis(4-(4-tert-butyl) acetylacetonate At least one of base-phenyl)-thiophene[3,2-c]pyridine-C2,N)iridium(III);
  • the red light guest material is selected from at least one of tris(1-phenylisoquinoline)iridium and (acetylacetonate)bis(2-methyldibenzo[f,h]quinoxaline)iridium;
  • the mass ratio of the host material and the guest material is (1-50):1;
  • the luminescent material is an organic small molecule material, an organic polymer material, a quantum dot luminescent material, a perovskite luminescent material, a superconducting oxide, a perovskite oxygen ion conductor, an organic-inorganic composite perovskite, an inorganic perovskite, or a rare earth material.
  • the thickness of the luminescent layer is between 20 nm and 1000 ⁇ m, the use temperature is between 20-300 degrees Celsius;
  • the preparation method of the luminescent material is vacuum evaporation, magnetron sputtering, epitaxial technology, chemical vapor deposition, spin coating, blade coating sputtering, plasma transfer, inkjet printing and other known film forming methods.
  • the hydrophobic material of the hydrophobic layer is polyolefin, polycarbonate, polyamide, polyacrylonitrile, polyester, acrylate, molten paraffin, polytetrafluoroethylene (PTFE) , at least one of fluorinated polyethylene, fluorocarbon wax or other synthetic fluorine-containing polymers and polymers modified with inorganic micro-nano structures; the upper surface of the hydrophobic layer is the flow channel for the sample solution.
  • PTFE polytetrafluoroethylene
  • the dielectric layer material is made of organic high dielectric constant materials including polyvinylidene fluoride, polytetrafluoroethylene, polyvinylidene fluoride-trifluoroethylene copolymer (P( VDF-TrFE), P(VDF-TrFE-CTFE), P(VDF-TrFE-CFE)), polystyrene, polyvinyl alcohol, polyvinylpyrrolidone, polymethyl methacrylate, tetrafluoroethylene hexafluoropropyl Copolymer, poly4-methyl-1-pentene, polypropylene, polyethylene, polychlorotrifluoroethylene, polyphenylene ether, polycarbonate, ethylcellulose, CYTOP, polyethylene terephthalate , parylene (p-xylene polymer) and inorganic high dielectric constant materials including barium titanate, hafnium dioxide, zinc oxide, nickel oxide, aluminum trioxid
  • the small-area electrode is composed of a substrate, a port, an electrode and an electrode lead.
  • the port sends a voltage signal to the electrode assembly through the electrode lead; the small-area electrode is independently controlled.
  • the gap between the electrodes is between 500 nm and 5 mm, and the voltage is alternating current or direct current, between 2 v and 2 kv.
  • the cover plate is composed of a layer of hydrophobic material to facilitate chip packaging; the material of the cover plate is at least one of glass, plastic, ceramic, and high molecular polymer.
  • the electrode substrate is prepared using at least one method of photolithography, electron beam evaporation, physics, chemical vapor deposition and magnetron sputtering;
  • the electrode substrate is a pre-made base material diaphragm of a certain size, selected from the following: silicon base, PDMS (polydimethylsiloxane, polydimethylsiloxane) base, glass base or polymer film base;
  • the electrodes of the electrode substrate can be any conductive material, including metal oxides such as indium tin oxide (ITO); silver, iron, magnesium-silver alloy, aluminum, nickel, palladium, gold, copper, platinum, magnesium-aluminum alloy , copper-silver alloy, aluminum-copper alloy, iron-copper-silver alloy and other metals or metal alloys or modified or unmodified graphene, graphite, carbon black (including superconducting carbon black), carbon fiber, single-walled carbon nanotubes, and more Carbon-based conductive materials such as wall carbon nanotubes or doped or undoped PEDOT, PANi, Ppy and other conductive polymer materials or conductive elastomers or conductive oxides such as indium tin oxide (ITO), fluorine-doped indium oxide (FTO) ), zinc indium oxide (ZTO), antimony tin oxide (ATO) or a combination of several.
  • ITO indium tin oxide
  • FTO fluorine-
  • the microfluidic chip provided by the present invention solves the problems of complex testing process, high cost, high driving voltage of the open structure, etc., and gives the microfluidic technology the characteristics of real-time light emission, which facilitates biochemical reactions. Monitoring has broad application prospects.
  • FIG. 1 Device preparation flow chart
  • FIG. 1 Schematic diagram of device structure
  • FIG. 1 Schematic diagram of electrode substrate
  • FIG. 4 Schematic diagram of the droplet movement process
  • the microfluidic chip of the present invention adopts a technical solution based on a new asymmetric planar electrode of a coplanar electrode, which reduces the operating voltage and maintains the original droplet movement performance.
  • a layer of luminescent material is added.
  • the droplets serve as a bridge layer connecting the two electrodes and can cause the corresponding luminescent material on the electrodes to emit light, thereby achieving a luminescent display.
  • the beneficial effect of the present invention is to overcome the problem of high operating voltage of planar electrodes, reduce costs and save resources.
  • ITO substrate 1Cleaning of ITO substrate. First, hand-wash the ITO sheet using a cleaning agent commonly used in the electronics industry, and then rinse it with distilled water. Then use acetone, distilled water and isopropyl alcohol to clean ultrasonically for 15 minutes each, blow dry with nitrogen, and then treat with Plasma for 5 minutes.
  • a cleaning agent commonly used in the electronics industry
  • acetone, distilled water and isopropyl alcohol to clean ultrasonically for 15 minutes each, blow dry with nitrogen, and then treat with Plasma for 5 minutes.
  • the sheet is etched to remove unnecessary ITO parts and retain the desired pattern. Specifically, 18.7% volume fraction of concentrated hydrochloric acid is first prepared, the etching liquid is placed on a hot stage, heated to 55°C, and etched for 12 minutes.
  • 8Remove glue Place the etched sheet in an acetone solution and conduct the first 5-min ultrasound to remove most of the photoresist protective layer. Considering that there will be a certain amount of hydrochloric acid remaining in the etched sheet, this will be brought into the acetone solution and further etch the ITO. Therefore, it is necessary to change the acetone solution once, and then perform a second 5-minute ultrasonic gel removal. Rinse the degummed sheet with isopropyl alcohol, and then blow dry the sheet with nitrogen.
  • the luminescent layer uses four different colors of inorganic electroluminescent materials and the binder polyvinylidene fluoride (PVDF) mixed in a mass ratio of 1:5, and the solvent N,N-dimethylformamide (DMF).
  • the spin coating method was used with a rotation speed of 2000 rpm for 60 s, and then placed on a heating stage and heated at 100 °C for 3 h.
  • the conductive glass ITO was ultrasonically cleaned with acetone, treated with plasma for 2 min, and the hydrophobic layer was infiltrated on one side of the electrode for 60 s. The excess hydrophobic material was immediately removed and dried at 60°C for 1 hour to serve as a cover plate.
  • Figure 1 is a step flow chart of Embodiment 1.
  • Figure 2 is a schematic structural diagram of Embodiment 1.
  • FIG 3 is a schematic diagram of an electrode substrate in Embodiment 1.
  • the electrode substrate is composed of a large-area electrode and several small-area electrode units of equal area.
  • the small-area electrode includes a droplet moving area and an electrode expansion area.
  • Figure 4 is a schematic diagram of the specific process of the droplet moving area in Example 1.
  • the initial state of the droplet (1) is affected by the electric field force of the first driving electrode, which reduces the contact angle, resulting in a change in the shape of the droplet (2).
  • the first driving electrode voltage When it is 0V, the droplet macroscopically causes the droplet to move toward the first driving electrode in order to maintain its original shape (3).
  • Figure 5 shows the comparison of the luminous brightness of two planar electrodes with different area ratios.
  • the small-area electrode has a higher relative brightness.
  • Figure 6 Voltage-brightness relationship between planar structure and sandwich structure devices. Under the same voltage drive, microfluidic chips based on asymmetric planar structure light-emitting devices can achieve brightness comparable to that of sandwich structure devices.
  • ITO substrate 1Cleaning of ITO substrate. First, hand-wash the ITO sheet using a cleaning agent commonly used in the electronics industry, and then rinse it with distilled water. Then use acetone, distilled water and isopropyl alcohol to clean ultrasonically for 15 minutes each, blow dry with nitrogen, and then treat with Plasma for 5 minutes.
  • a cleaning agent commonly used in the electronics industry
  • acetone, distilled water and isopropyl alcohol to clean ultrasonically for 15 minutes each, blow dry with nitrogen, and then treat with Plasma for 5 minutes.
  • the sheet is etched to remove unnecessary ITO parts and retain the desired pattern. Specifically, 18.7% volume fraction of concentrated hydrochloric acid is first prepared, the etching liquid is placed on a hot stage, heated to 55°C, and etched for 12 minutes.
  • 8Remove glue Place the etched sheet in an acetone solution and conduct the first 5-min ultrasound to remove most of the photoresist protective layer. Considering that there will be a certain amount of hydrochloric acid remaining in the etched sheet, this will be brought into the acetone solution and further etch the ITO. Therefore, it is necessary to change the acetone solution once, and then perform a second 5-minute ultrasonic gel removal. Rinse the degummed sheet with isopropyl alcohol, and then blow dry the sheet with nitrogen.
  • the ZnMgO solution was spin-coated on the electrode cleaned with ethanol, acetone, and isopropyl alcohol at a speed of 5000 rpm for 60 s, and heated at 100°C for 5 min;
  • magnetron sputtering technology is used to sputter 300 nm SiO 2 as a dielectric layer.
  • the conductive glass ITO was ultrasonically cleaned with acetone, treated with plasma for 2 min, and the hydrophobic layer was infiltrated on one side of the electrode for 60 s. The excess hydrophobic material was immediately removed and dried at 60°C for 1 hour to serve as a cover plate.

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Abstract

本发明提供了一种微流控芯片，包括芯片基板和盖板，芯片基板包括电极基底、电极基板、介电层、发光层、疏水层；其中电极基板由一层大面积电极和嵌于大面积电极上的若干小面积电极单元组成，电极单元包括基片、端口、电极组件、电极引线。本发明的微流控芯片在医学、化学、生物学等多方面具有一定的应用前景，例如碱基序列识别、化学反应监测等。

Description

一种微流控芯片 技术领域
本发明涉及微流控技术领域，具体涉及一种基于非对称平面结构发光器件的微流控芯片。
 背景技术
微流控（Microfluidics）是指使用微管道（尺寸为数十到数百微米）处理或操纵微小流体的系统所涉及的科学和技术，是一门涉及化学、流体物理、微电子、新材料、生物学和生物医学工程的新兴交叉学科。微流控芯片的特点在于，能将大部分生物、化学过程集总到一块芯片上，便于生物、化学过程的检测与控制，因此微流控芯片在生物、化学、医学等多个领域都表现出巨大的应用前景，逐渐发展为多学科交叉的新型研究领域。本专利主要利用介电润湿型的液滴操纵技术，利用液滴在疏水化表面的介电润湿现象，通过控制微电极阵列上液滴接触角变化，实现离散液滴的精确控制，不依赖微泵、微阀或微混合器等元件，甚至无需复杂的三维流体通道，具有构建简单、可动态配置的优点，因此特别适用于高集成度、高性能、操作复杂的生物、化学微全分析体系。
 技术问题
生物医学方面的使用多使用荧光标记法，化学发光需要外置的庞大笨拙的发光装置，这给便携性和成本都增加了困难。同时传统的三明治结构器件存在因为顶部电极的布局导致透明性和可操作性的局限性，而平面电极虽然可以解决开放性实验的根本问题但是增大了操作电压，带来额外的能源浪费。
 技术解决方案
为了解决上述技术问题，本发明提供一种微流控芯片，克服了平面电极操作电压较高的问题。
本发明解决上述技术问题的方案在于，提供一种微流控芯片，包括芯片基板和盖板，所述芯片基板包括电极基底、电极基板、介电层、发光层、疏水层；其中，所述电极基板包括一层大电极和嵌于所述大面积电极上用于驱动液滴移动的若干小面积电极，所述大面积电极和所述若干小面积电极之间电绝缘。
优选的，在本发明的一个实施例中，所述大面积电极和所述若干小面积电极共同形成于同一平面；每个所述小面积电极包括基片、端口、电极组件、电极引线；所述大面积电极接地，所述小面积电极连接电源发生器。
优选的，在本发明的一个实施例中，所述电极基板上设置液滴移动区和与电极拓展区，并通过电极拓展区设置电极引线连单独控制每个所述小面积电极的通电情况；所述液滴移动区内分布有所述若干小面积电极。
优选的，在本发明的一个实施例中，液滴的尺寸大于所述小面积电极的尺寸，在液滴前进方向上的第一电极在通电后，因为电场作用力使得液滴接触角变小，从而部分延展进入第一电极，宏观上表现为液滴向通电的电极移动，且该第一电极下的发光层受电场作用和液滴的导电作用也被成功激发出的光，由此所述芯片实现了随液滴位置变化而变化的发光。
所述装置一共有六层，所述第一层为电极基底，所述第二层为电极基板，所述第三层为介电层，所述第四层为发光层，所述第五层为疏水层，所述第六层为盖板。
优选的，在本发明的一个实施例中，所述发光层的发光材料为无机粉末电致发光材料，选自如硫化锌铜、硫化锌锰、硫化锌铝中的一种；
或者，所述发光材料为OLED红绿蓝黄中的至少两种；
所述OLED红绿蓝黄采用主体材料和客体材料的掺杂结构，所述主体材料选自4 ,4 ,4 '-三（咔唑-9-基）三苯胺、4 ,4 '-N ,N-二咔唑-联苯、9 ,9 '-（2 ,6-吡啶二基二-3 ,1-亚苯）双-9H-咔唑、2 ,2 '-（1 ,3-苯基）二[5-（4-叔丁基苯基）-1 ,3 ,4-恶二唑]、LGH001、LGH002、2 ,6-DCzPPy中的至少一种；
所述客体材料包括蓝光客体材料、绿光客体材料、黄光客体材料、红光客体材料：
其中，所述蓝光客体材料选自双（4 ,6-二氟苯基吡啶-N, C2）吡啶甲酰合铱、双（3 ,5-二氟-2-（2-吡啶基-KN）苯基-KC）（四（1H-吡唑基-KN）硼酸（1-）-KN2 ,KN2 '）-铱、二（2-羟基苯基吡啶）合铍、Flrpic、LGD001、LRD001、LBD001中的至少一种；
所述绿光客体材料选自三（2-苯基吡啶）合铱、乙酰丙酮酸二（2-苯基吡啶-C2 ,N）合铱(III)中的至少一种；
所述黄光客体材料选自乙酰丙酮酸二(4-苯基-噻吩[3 ,2-c]吡啶-C2 ,N)合铱(III) 、乙酰丙酮酸二(4-(4-叔丁基-苯基)-噻吩[3 ,2-c]吡啶-C2 ,N)合铱(III) 中的至少一种；
所述红光客体材料选自三(1-苯基异喹啉)铱、(乙酰丙酮)双(2-甲基二苯并[f ,h]喹喔啉)合铱中的至少一种；
所述主体材料和所述客体材料的质量比为（1-50）：1；
或所述发光材料为有机小分子材料、有机聚合物材料、量子点发光材料、钙钛矿发光材料超导体氧化物、钙钛矿氧离子导体、有机无机复合钙钛矿、无机钙钛矿、稀土配合物的电致发光材料、多种核/壳结构的半导体材料中的至少一种；
所述发光层的厚度在20 nm和1000 μm之间，使用温度在20-300摄氏度之间；
所述发光材料的制备方法是真空蒸发，磁控溅射，外延技术，化学气相沉积，旋涂法，刮涂法溅射、等离子渡、喷墨打印等已知的成膜方法。
优选的，在本发明的一个实施例中，所述疏水层的疏水材料为聚烯烃、聚碳酸酯、聚酰胺、聚丙烯腈、聚酯、丙烯酸酯、熔融石蜡、聚四氟乙烯（PTFE）、氟化聚乙烯、氟碳蜡或其他合成含氟的聚合物以及无机微纳结构修饰的聚合物中的至少一种；所述疏水层的上表面即为样本溶液的流动通道。
优选的，在本发明的一个实施例中，所述介电层材料由有机高介电常数材料包括聚偏氟乙烯、聚四氟乙烯、聚偏二氟乙烯－三氟乙烯共聚物(P(VDF-TrFE)，P(VDF-TrFE-CTFE) ，P(VDF-TrFE-CFE))、聚苯乙烯、聚乙烯醇、聚乙烯吡咯烷酮、聚甲基丙烯酸甲酯、四氟乙烯六氟丙基共聚物、聚4-甲基-1-戊烯、聚丙烯、聚乙烯、聚三氟氯乙烯、聚苯醚、聚碳酸酯、乙基纤维素、CYTOP、聚对苯二甲酸乙二醇酯、派瑞林(对二甲苯聚合物)以及无机高介电常数材料包括钛酸钡、二氧化铪、氧化锌、氧化镍、三氧化二铝、二氧化钛、二氧化锡、氧化铈、氧化锆、四氧化钒，五氧化二钒、钙钛矿型金属氧化物(ABO3)、五氧化二钽、二氧化硅、氧氮化硅、氮化硅、氧化钇氧化铝中的其中一种或者几种复合制备而成。优选的，聚偏二氟乙烯－三氟乙烯共聚物、聚苯乙烯、聚乙烯醇、聚乙烯吡咯烷酮、聚甲基丙烯酸甲酯中的一种或者几种制备而成。
优选的，在本发明的一个实施例中，所述小面积电极是由基板，端口，电极和电极引线构成，所述端口通过所述电极引线发送电压信号给电极组件；小面积电极是独立控制的，电极之间间隙在500 nm-5 mm之间，所述电压为交流电或直流电，2 v-2 kv之间。
优选的，在本发明的一个实施例中，所述盖板由一层疏水材料构成，便于芯片的封装；所述盖板的材料是玻璃、塑料、陶瓷、高分子聚合物的至少一种。
优选的，在本发明的一个实施例中，所述电极基底的制备使用光刻、电子束蒸发、物理、化学气相沉积和磁控溅射的至少一种方法制备；
所述电极基底是预先制作的一定尺寸的基底材料膜片，选自如下：硅基底、PDMS（polydimethylsiloxane，聚二甲基硅氧烷）基底、玻璃基底或高分子膜基底；
所述电极基板的电极可以是任何能够导电的材料，包括铟锡氧化物(ITO)等金属氧化物；银、铁、镁银合金、铝、镍、钯、金、铜、铂、镁铝合金、铜银合金、铝铜合金、铁铜银合金等金属或者金属合金或者改性或不改性的石墨烯、石墨、炭黑(包括超导炭黑)、碳纤维、单壁碳纳米管、多壁碳纳米管等炭系导电材料或者掺杂或不掺杂的PEDOT、PANi、Ppy等导电高分子材料或者导电弹性体或者导电氧化物如氧化铟锡(ITO)、氟掺杂氧化铟(FTO)、氧化铟锌(ZTO)、氧化锡锑(ATO)中的一种或者几种复合。
 有益效果
实施本发明，具有如下有益效果：本发明提供的微流控芯片解决了测试过程复杂，成本昂贵、开放式结构驱动电压大等问题，并赋予微流控技术实时发光的特点，便于对生化反应进行监测，具有广阔的应用前景。
 附图说明
图1 器件制备流程图；
图2 器件结构示意图；
图3 电极基板示意图；
图4 液滴移动过程示意图；
图5 不同面积比的平面电极电压-发光亮度关系；
图6 平面结构与三明治结构器件电压-亮度关系。
 本发明的实施方式
下面结合附图和具体实施例对本发明的技术方案进行详细的说明，但是所述实施例的说明，仅仅是本发明的一部分实施例，其中大部分并不仅限于此。
本发明的微流控芯片，所采用的技术方案基于共平面电极的新型非对称平面电极，降低了操作电压并且维持了原有的液滴移动性能，除此之外增加了一层发光材料，使得在给电极施加电压的同时，液滴作为连接两个电极之间的桥层可以使所述电极上面对应的发光材料发光，从而实现发光显示。与现有技术相比，本发明的有益效果是克服了平面电极操作电压较高的问题，降低了成本节约了资源。
实施例1
1、驱动电极制备：
①ITO 基片的清洗。首先使用电子工业常用的清洗剂手洗 ITO 片材，然后使用蒸馏水冲淋干净。随后依次使用丙酮、蒸馏水和异丙醇各超声清洗 15 分钟，用氮气吹干，随后用 Plasma 处理 5 分钟即可。
②涂胶。将 ITO 置于匀胶机的吸盘上，吸取少量的负性光刻胶水 NPR-1500 于 ITO的表面，打开匀胶机设置转速为 3000 rpm，时间为 40 s。经过旋涂后，ITO 的表面形成一层均匀的 NPR-1500 薄膜。
③前烘。将旋涂好负性光刻胶的 ITO 基片放置于高温热台上并设置温度为 150 ℃，用秒表精确计时 120 s 后取下来，静等冷却。该步骤的目的是除去光刻胶中的一些溶剂，同时加强光刻胶在 ITO 表面上的附着力。
④曝光。将前烘过后的 ITO 几片放在光刻机吸盘上，在其上部放置设计好的掩模版。开启光刻机的基片上升按钮，让含有光刻胶的基片紧紧的贴合 ITO 玻璃片材，进行 28.3 s 曝光。
⑤后烘。将曝光后的基片置于 120 ℃的热台上，烘烤 65 s。
⑥显影。依次将经过后烘的片材放入显影液体中，用秒表精确计时 8-9 s 后将片材迅速从显影液中取出置于蒸馏水中涮洗。然后用高压氮气吹干片材。
⑦刻蚀。将显影完成后片材进行刻蚀，以去除不需要的 ITO 部分，并保留需要的图案。具体的先配置 18.7%体积分数的浓盐酸，将该刻蚀液体置于热台上加热至 55 ℃，刻蚀12分钟。
⑧去胶。将刻蚀完成后的片材置于丙酮溶液中，进行第一次 5 min 超声以去除大部分的光刻胶保护层。考虑到刻蚀完成后的片材会有一定的盐酸残留，这将会带入到丙酮溶液中，会进一步的刻蚀 ITO。因此需要换一次丙酮溶液，然后进行第二次 5 min 超声去胶。用异丙醇将去胶后的片材冲淋一下，随后用氮气吹干片材即可。
⑨检测。将最终得到的具有想要图案的 ITO 电极置于显微镜下观察和测量，检测电极图案是否正确，且图案的尺寸误差是否在自己的接受范围内。同时用源表测量不同图案处的短路与断路情况，是否满足自己的设计需求。
2、介电层和发光层制备：
称取1 g PVDF-HFP粉末，将其溶解在5 ml DFM溶液中，50 ℃搅拌过夜。将混合均匀的介电层材料继续以3000 rpm，60 s进行旋涂，接着放置在加热台上，100 ℃加热3 h。
发光层使用四种不同颜色的无机电致发光材料和粘结剂聚偏氟乙烯(PVDF)以1:5的质量比混合，溶剂N,N-二甲基甲酰胺(DMF)。使用旋涂法，转速为2000 rpm，持续60 s，随后放置在加热台上，100 ℃加热3 h。
3、疏水层制备：
将疏水材料用吸管吸取几滴，浸润60 s，立即除去多余的疏水材料，并在60 ℃下烘干。
用丙酮超声清洗导电玻璃ITO，利用plasma处理2 min，将疏水层浸润电极一面60 s，立即去除多余的疏水材料，并在60 ℃下烘干1小时，作为盖板。
4、器件封装：
在电极基板边缘四周涂覆一定厚度的封装胶，并注入一定体积的液体，用盖板进行封装。
图1为实施例1的步骤流程图。
图2为实施例1的结构示意图。
图3为实施例1为电极基板示意图，电极基板由一个大面积电极和等面积的若干小面积电极单元构成，其中小面积电极包括液滴移动区和电极扩展区。
图4为实施例1液滴移动区的具体过程示意图。当给第一驱动电极施加一定电压后，初始状态的液滴（1）受到第一驱动电极的电场力作用减小了接触角，导致了液滴形状变化（2），在第一驱动电极电压为0V时，液滴为了保持自身原有的形态而宏观上导致液滴向第一驱动电极移动（3）。
图5 为不同面积比的两平面电极发光亮度的对比，小面积电极相对亮度更高。
图6平面结构与三明治结构器件电压-亮度关系，在相同电压驱动下，基于非对称平面结构发光器件的微流控芯片，可达到与三明治结构器件相比拟的亮度。
实施例2
1、驱动电极制备：
①ITO 基片的清洗。首先使用电子工业常用的清洗剂手洗 ITO 片材，然后使用蒸馏水冲淋干净。随后依次使用丙酮、蒸馏水和异丙醇各超声清洗 15 分钟，用氮气吹干，随后用 Plasma 处理 5 分钟即可。
②涂胶。将 ITO 置于匀胶机的吸盘上，吸取少量的负性光刻胶水 NPR-1500 于 ITO的表面，打开匀胶机设置转速为 3000 rpm，时间为 40 s。经过旋涂后，ITO 的表面形成一层均匀的 NPR-1500 薄膜。
③前烘。将旋涂好负性光刻胶的 ITO 基片放置于高温热台上并设置温度为 150 ℃，用秒表精确计时 120 s 后取下来，静等冷却。该步骤的目的是除去光刻胶中的一些溶剂，同时加强光刻胶在 ITO 表面上的附着力。
④曝光。将前烘过后的 ITO 几片放在光刻机吸盘上，在其上部放置设计好的掩模版。开启光刻机的基片上升按钮，让含有光刻胶的基片紧紧的贴合 ITO 玻璃片材，进行 28.3 s 曝光。
⑤后烘。将曝光后的基片置于 120 ℃的热台上，烘烤 65 s。
⑥显影。依次将经过后烘的片材放入显影液体中，用秒表精确计时 8-9 s 后将片材迅速从显影液中取出置于蒸馏水中涮洗。然后用高压氮气吹干片材。
⑦刻蚀。将显影完成后片材进行刻蚀，以去除不需要的 ITO 部分，并保留需要的图案。具体的先配置 18.7%体积分数的浓盐酸，将该刻蚀液体置于热台上加热至 55 ℃，刻蚀12分钟。
⑧去胶。将刻蚀完成后的片材置于丙酮溶液中，进行第一次 5 min 超声以去除大部分的光刻胶保护层。考虑到刻蚀完成后的片材会有一定的盐酸残留，这将会带入到丙酮溶液中，会进一步的刻蚀 ITO。因此需要换一次丙酮溶液，然后进行第二次 5 min 超声去胶。用异丙醇将去胶后的片材冲淋一下，随后用氮气吹干片材即可。
⑨检测。将最终得到的具有想要图案的 ITO 电极置于显微镜下观察和测量，检测电极图案是否正确，且图案的尺寸误差是否在自己的接受范围内。同时用源表测量不同图案处的短路与断路情况，是否满足自己的设计需求。
2、介电层和发光层制备：
首先将ZnMgO溶液按照5000 rpm转速，经过60 s旋涂在经过乙醇，丙酮，异丙醇清洗后的电极上，并且在100 ℃下加热5 min；
0.4 wt%的聚乙烯亚胺/２－甲氧基乙醇，以3000 rpm的转速旋涂60 s并在真空烘箱干燥30 min；
接着配置0.5 mg/ml的PDY132/甲苯溶液，按照转速5000 rpm，60 s进行旋涂。
接着按照3000 rpm，60 s旋涂含有一定比例多壁碳纳米管的聚(3,4-亚乙二氧基噻吩)-聚(苯乙烯磺酸)（pedot: pss）溶液，在120 ℃加热台上加热30分钟；
最后使用磁控溅射技术，溅射300 nm的SiO 2作为介电层。
3、疏水层制备：
将疏水材料用吸管吸取几滴，浸润60 s，立即除去多余的疏水材料，并在60 ℃下烘干。
用丙酮超声清洗导电玻璃ITO，利用plasma处理2 min，将疏水层浸润电极一面60 s，立即去除多余的疏水材料，并在60 ℃下烘干1小时，作为盖板。
4、器件封装：
在电极基板边缘四周涂覆一定厚度的封装胶，并注入一定体积的液体，用盖板进行封装。
以上实施例进一步说明本发明的内容，但不应理解为对本发明的限制。在不背离本发明精神和实质的情况下，对本发明方法、步骤或条件所作的修改和替换，均属于本发明的范围。若未特别指明，实施例中所用的技术手段为本领域技术人员所熟知的常规手段。

Claims (10)

  1. 一种微流控芯片，其特征在于，包括芯片基板和盖板，所述芯片基板包括电极基底、电极基板、介电层、发光层、疏水层；其中，所述电极基板包括一层大电极和嵌于所述大面积电极上用于驱动液滴移动的若干小面积电极，所述大面积电极和所述若干小面积电极之间电绝缘。
  2. 根据权利要求1所述的基于非对称平面结构发光器件的微流控芯片，其特征在于，所述大面积电极和所述若干小面积电极共同形成于同一平面；每个所述小面积电极包括基片、端口、电极组件、电极引线；所述大面积电极接地，所述小面积电极连接电源发生器。
  3. 根据权利要求1所述的基于非对称平面结构发光器件的微流控芯片，其特征在于，所述电极基板上设置液滴移动区和与电极拓展区；所述液滴移动区内分布有所述若干小面积电极。
  4. 根据权利要求1所述的一种基于非对称平面结构发光器件的微流控芯片，其特征在于，液滴的尺寸大于所述小面积电极的尺寸；
    所述微流控芯片一共有六层，所述第一层为电极基底，所述第二层为电极基板，所述第三层为介电层，所述第四层为发光层，所述第五层为疏水层，所述第六层为盖板。
  5. 根据权利要求1所述的一种基于非对称平面结构发光器件的微流控芯片，其特征在于，所述发光层的发光材料为无机粉末电致发光材料，选自如硫化锌铜、硫化锌锰、硫化锌铝中的一种；
    或者，所述发光材料为OLED红绿蓝黄中的至少两种；
    所述OLED红绿蓝黄采用主体材料和客体材料的掺杂结构，所述主体材料选自4 ,4 ,4 '-三（咔唑-9-基）三苯胺、4 ,4 '-N ,N-二咔唑-联苯、9 ,9 '-（2 ,6-吡啶二基二-3 ,1-亚苯）双-9H-咔唑、2 ,2 '-（1 ,3-苯基）二[5-（4-叔丁基苯基）-1 ,3 ,4-恶二唑]、LGH001、LGH002、2 ,6-DCzPPy中的至少一种；
    所述客体材料包括蓝光客体材料、绿光客体材料、黄光客体材料、红光客体材料：
    其中，所述蓝光客体材料选自双（4 ,6-二氟苯基吡啶-N, C2）吡啶甲酰合铱、双（3 ,5-二氟-2-（2-吡啶基-KN）苯基-KC）（四（1H-吡唑基-KN）硼酸（1-）-KN2 ,KN2 '）-铱、二（2-羟基苯基吡啶）合铍、Flrpic、LGD001、LRD001、LBD001中的至少一种；
    所述绿光客体材料选自三（2-苯基吡啶）合铱、乙酰丙酮酸二（2-苯基吡啶-C2 ,N）合铱(III)中的至少一种；
    所述黄光客体材料选自乙酰丙酮酸二(4-苯基-噻吩[3 ,2-c]吡啶-C2 ,N)合铱(III) 、乙酰丙酮酸二(4-(4-叔丁基-苯基)-噻吩[3 ,2-c]吡啶-C2 ,N)合铱(III) 中的至少一种；
    所述红光客体材料选自三(1-苯基异喹啉)铱、(乙酰丙酮)双(2-甲基二苯并[f ,h]喹喔啉)合铱中的至少一种；
    所述主体材料和所述客体材料的质量比为（1-50）：1；
    或所述发光材料为有机小分子材料、有机聚合物材料、量子点发光材料、钙钛矿发光材料超导体氧化物、钙钛矿氧离子导体、有机无机复合钙钛矿、无机钙钛矿、稀土配合物的电致发光材料、多种核/壳结构的半导体材料中的至少一种；
    所述发光层的厚度在20 nm和1000 μm之间，使用温度在20-300摄氏度之间；
    所述发光材料的制备方法选自如下中的一种：真空蒸发、磁控溅射、外延技术、化学气相沉积、旋涂法、刮涂法溅射、等离子渡、喷墨打印。
  6. 根据权利要求1所述的微流控芯片，其特征在于，所述疏水层的疏水材料为聚烯烃、聚碳酸酯、聚酰胺、聚丙烯腈、聚酯、丙烯酸酯、熔融石蜡、聚四氟乙烯、氟化聚乙烯、氟碳蜡或其他合成含氟的聚合物以及无机微纳结构修饰的聚合物中的至少一种；所述疏水层的上表面即为样本溶液的流动通道。
  7. 根据权利要求1所述的微流控芯片，其特征在于，所述介电层材料由有机高介电常数材料包括聚偏氟乙烯、聚四氟乙烯、聚偏二氟乙烯－三氟乙烯共聚物、聚苯乙烯、聚乙烯醇、聚乙烯吡咯烷酮、聚甲基丙烯酸甲酯、四氟乙烯六氟丙基共聚物、聚4-甲基-1-戊烯、聚丙烯、聚乙烯、聚三氟氯乙烯、聚苯醚、聚碳酸酯、乙基纤维素、CYTOP、聚对苯二甲酸乙二醇酯、派瑞林以及无机高介电常数材料包括钛酸钡、二氧化铪、氧化锌、氧化镍、三氧化二铝、二氧化钛、二氧化锡、氧化铈、氧化锆、四氧化钒，五氧化二钒、钙钛矿型金属氧化物ABO3、五氧化二钽、二氧化硅、氧氮化硅、氮化硅、氧化钇氧化铝中的其中一种或者几种复合制备而成。
  8. 根据权利要求1所述的微流控芯片，其特征在于，所述小面积电极是由基板，端口，电极和电极引线构成，所述端口通过所述电极引线发送电压信号给电极组件；每个所述小面积电极是独立控制的，电极之间间隙在500 nm-5 mm之间，所述电压为交流电或直流电，2 v-2 kv之间。
  9. 根据权利要求1所述的微流控芯片，其特征在于，所述盖板由一层疏水材料构成，便于芯片的封装；所述盖板的材料是玻璃、塑料、陶瓷、高分子聚合物的至少一种。
  10. 根据权利要求1所述的微流控芯片，其特征在于，所述电极基底的制备使用光刻、电子束蒸发、物理、化学气相沉积和磁控溅射的至少一种方法制备；
    所述电极基底是预先制作的一定尺寸的基底材料膜片，选自如下：硅基底、PDMS基底、玻璃基底或高分子膜基底；
    所述电极基板的电极可以是任何能够导电的材料，包括金属或者金属合金、炭系导电材料、导电高分子材料、导电弹性体、导电氧化物；
    金属或者金属合金选自如下中的至少一种：银、铁、镁银合金、铝、镍、钯、金、铜、铂、镁铝合金、铜银合金、铝铜合金、铁铜银合金；
    炭系导电材料选自如下中的至少一种：改性或不改性的石墨烯、石墨、炭黑、碳纤维、单壁碳纳米管、多壁碳纳米管；
    导电高分子材料选自如下中的至少一种：掺杂或不掺杂的PEDOT、PANi、Ppy；
    导电氧化物选自如下中的至少一种：氧化铟锡、氟掺杂氧化铟、氧化铟锌、氧化锡锑。
PCT/CN2022/109019 2022-07-29 2022-07-29 一种微流控芯片 Ceased WO2024021035A1 (zh)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102500436A (zh) * 2011-09-28 2012-06-20 复旦大学 基于电润湿的单面二维驱动数字微流控芯片
CN107335490A (zh) * 2017-08-15 2017-11-10 肇庆市华师大光电产业研究院 一种基于液‑液电润湿效应的可编程控制的微流控芯片
CN109078661A (zh) * 2018-08-09 2018-12-25 京东方科技集团股份有限公司 微流控芯片及其检测和驱动方法、片上实验室系统
CN114130437A (zh) * 2021-11-03 2022-03-04 北京大学深圳研究生院 一种电致发光微流控液滴移动装置

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102500436A (zh) * 2011-09-28 2012-06-20 复旦大学 基于电润湿的单面二维驱动数字微流控芯片
CN107335490A (zh) * 2017-08-15 2017-11-10 肇庆市华师大光电产业研究院 一种基于液‑液电润湿效应的可编程控制的微流控芯片
CN109078661A (zh) * 2018-08-09 2018-12-25 京东方科技集团股份有限公司 微流控芯片及其检测和驱动方法、片上实验室系统
CN114130437A (zh) * 2021-11-03 2022-03-04 北京大学深圳研究生院 一种电致发光微流控液滴移动装置

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