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CN110428973B - 3D bulk silicon micro capacitor based on MEMS technology, and manufacturing and application thereof - Google Patents

3D bulk silicon micro capacitor based on MEMS technology, and manufacturing and application thereof Download PDF

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CN110428973B
CN110428973B CN201910636397.6A CN201910636397A CN110428973B CN 110428973 B CN110428973 B CN 110428973B CN 201910636397 A CN201910636397 A CN 201910636397A CN 110428973 B CN110428973 B CN 110428973B
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electrode
carbon
bulk silicon
silicon
comb
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CN110428973A (en
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王玉容
孙雷蒙
肖东阳
胡方靖
涂良成
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Huazhong University of Science and Technology
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B81—MICROSTRUCTURAL TECHNOLOGY
    • B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
    • B81C1/00436—Shaping materials, i.e. techniques for structuring the substrate or the layers on the substrate
    • B81C1/005—Bulk micromachining
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B81—MICROSTRUCTURAL TECHNOLOGY
    • B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
    • B81C1/00436—Shaping materials, i.e. techniques for structuring the substrate or the layers on the substrate
    • B81C1/00523—Etching material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/042—Electrodes or formation of dielectric layers thereon characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/04—Electrodes or formation of dielectric layers thereon
    • H01G9/048—Electrodes or formation of dielectric layers thereon characterised by their structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/004—Details
    • H01G9/08—Housing; Encapsulation
    • H01G9/10—Sealing, e.g. of lead-in wires
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
    • H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
    • H01G9/26—Structural combinations of electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices with each other

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Abstract

本发明公开了一种3D体硅微型电容器的制作方法，包括3D体硅衬底结构的制作、适用于该3D结构活性材料的引入和电容器的三种封装与集成。首先，深硅刻蚀得到镂空的3D硅基梳齿衬底，再对梳齿的上下表面和侧壁包覆碳基导电层和活性材料，最后在表面涂敷胶状电解质，并进行封装与集成，得到所述3D体硅微型电容器。相对于传统的梳齿型平面结构，本发明提供的微型电容器电极的纵向高度得到延伸，可利用的电极表面积从二维平面扩展至三维的表面与纵向侧壁，3D电极能负载更多的活性材料，从而使比电容和比能量密度提升；且3D梳齿结构的活性材料引入方法对3D电容器的研究有重要意义，提出的封装和集成方法保证了电容器的稳定和寿命。

Figure 201910636397

The invention discloses a manufacturing method of a 3D bulk silicon microcapacitor, which includes the manufacture of a 3D bulk silicon substrate structure, the introduction of active materials suitable for the 3D structure, and three packaging and integration of the capacitor. First, a hollow 3D silicon-based comb-tooth substrate is obtained by deep silicon etching, then the upper and lower surfaces and sidewalls of the comb-tooth are coated with a carbon-based conductive layer and active material, and finally a gel electrolyte is coated on the surface, and the packaging and integrated to obtain the 3D bulk silicon microcapacitor. Compared with the traditional comb-shaped planar structure, the longitudinal height of the microcapacitor electrode provided by the present invention is extended, the available electrode surface area is expanded from a two-dimensional plane to a three-dimensional surface and longitudinal sidewall, and the 3D electrode can load more active Therefore, the specific capacitance and specific energy density can be improved; and the introduction of active materials in the 3D comb structure is of great significance to the research of 3D capacitors. The proposed packaging and integration methods ensure the stability and life of the capacitors.

Figure 201910636397

Description

3D bulk silicon micro capacitor based on MEMS technology, and manufacturing and application thereof
Technical Field
The invention belongs to a manufacturing method of a micro energy storage device, particularly relates to the technical field of micro-nano processing technology and nano material preparation and application, and more particularly relates to a 3D bulk silicon micro capacitor based on an MEMS technology, and manufacturing and application thereof.
Background
The rapid development of portable electronic devices makes the miniaturized and conveniently integrated power supply become a research hotspot, and the energy storage device can be integrated with a chip while increasing the density of the device and realizing the power supply function, thereby simplifying the overall structure of the system. Supercapacitors are attractive energy storage devices due to their high energy density, cycle efficiency and charge-discharge ratio relative to batteries. Conventional supercapacitors are too bulky for micro devices and conventional fabrication methods are not compatible with microelectronic fabrication processes. In consideration of miniaturization, system complexity reduction and the like, designing an energy storage device capable of being integrated with a micro device is a major research direction.
The micro capacitor has rapid development in recent years, and the power density and the energy density are remarkably improved while the size is continuously reduced. The micro capacitor can be made into a film electrode with a traditional sandwich structure, a fibrous electrode with a core-shell structure or a planar interdigital electrode structure. The novel energy storage device is used as an independent power supply to be integrated with a micro-mechanical system, and has wide application prospect.
The planar electrode array has superior performance compared with the traditional sandwich structure and the fiber structure. First, due to the small gap between the interdigital array of the electrodes and the removal of the membrane, the ion transport resistance in the electrolyte inside the electrodes will be significantly reduced and a high frequency response will be obtained, thereby increasing its power density, which is crucial for future miniaturized portable electronic devices. Secondly, the plane electrode can be used for manufacturing a micron-sized electrode structure through a photoetching process, an electrode array is miniaturized, the control precision is high, and the electrode surface area and the capacitance performance can be further improved through the introduction of an active material; finally, the planar electrode structure makes the micro capacitor more easily integrated with the IC chip.
In order to improve the overall energy storage characteristic of the micro capacitor, the 3D structure is an effective means at present, and based on the advantages of the planar electrode, the 3D structure can load more active materials on the side wall of the structure within the same area by utilizing the extension of the longitudinal height, so that the energy storage capacity of the micro capacitor is improved. In the 3D comb tooth structure reported in the current literature, after the material stack is grown, the thickness is from hundreds of nanometers to several micrometers, and the surface area and the load mass of the active material are limited, so that the capacitance storage and the specific energy density are insufficient to meet the requirements.
Disclosure of Invention
Aiming at the defects or the improvement requirements of the prior art, the invention provides a 3D bulk silicon micro capacitor based on the MEMS technology, and a manufacturing method and an application thereof, wherein an electrode substrate with a horizontal surface and a longitudinal side wall is obtained on the surface of a silicon substrate through deep etching, a carbon-based conductive material and an active material are sequentially coated on the horizontal surface and the surface of the longitudinal side wall of the electrode structure substrate, and an electrolyte is coated and then packaged to obtain the 3D bulk silicon micro capacitor, so that the technical problem that the whole energy storage capacity of the existing 3D bulk micro capacitor device is limited is solved.
In order to achieve the above objects, according to one aspect of the present invention, there is provided a method for fabricating a 3D bulk silicon micro capacitor, comprising the steps of:
(1) manufacturing an array pattern on the surface of a silicon-based substrate through a photoetching process, etching according to the array pattern, and etching to penetrate through the substrate to obtain a hollow 3D bulk silicon electrode;
(2) carrying out hydrophilic treatment on the 3D bulk silicon electrode obtained in the step (1) to enable the surface of the electrode to have hydrophilicity, so as to obtain the hydrophilic 3D bulk silicon electrode;
(3) masking the frame part for electrical connection in the 3D bulk silicon electrode obtained in the step (2), and coating the electrode surface of the non-masked part with a carbon-based conductive layer to obtain a 3D carbon-silicon composite electrode coated with the carbon-based conductive layer;
(4) coating an active material on the surface of the electrode of the 3D carbon-silicon composite electrode coated with the carbon-based conductive layer obtained in the step (3) to obtain a 3D carbon-silicon composite electrode coated with the active material;
(5) removing the mask of the frame part for electrical connection, and packaging and integrating the 3D carbon-silicon composite electrode to obtain the 3D bulk silicon micro capacitor;
wherein the electrode surface comprises both the horizontal surface and the vertical surface of the electrode structure obtained by etching.
Preferably, the 3D bulk silicon electrode structure is comb-shaped.
Preferably, step (3) performs coating of the carbon-based conductive layer by:
(3-1) dissolving a carbon-based compound precursor in a volatile solvent to obtain a precursor solution;
(3-2) placing the 3D bulk silicon electrode in the precursor solution, and coating a carbon-based conducting layer on the surface of the electrode by a hydrothermal method; the carbon-based compound precursor is a hydrocarbon.
Preferably, step (3) performs coating of the carbon-based conductive layer by:
(3-1) dissolving a carbon-based compound precursor in a volatile solvent to obtain a precursor solution;
(3-2) placing the 3D bulk silicon electrode in the precursor solution, soaking, taking out, drying, and then reducing and decomposing the precursor on the surface of the electrode by a chemical vapor deposition method to form a carbon-based conductive layer, wherein the precursor is a hydrocarbon.
Preferably, the carbon-based conductive layer is a carbon nanotube or graphene nanostructure, and the coating of the carbon-based conductive layer in step (3) is performed by the following method:
(3-1) sequentially coating a buffer layer and a catalyst layer on the surface of the electrode by an electron beam evaporation coating method, a magnetron sputtering coating method, a thermal evaporation coating method, a chemical vapor deposition method, an atomic layer deposition method, a sol-gel method, a hydrothermal method or an electroplating method;
(3-2) depositing a carbon nano tube or graphene nano structure carbon-based conducting layer on the surface of the electrode sequentially coated with the buffer layer and the catalytic layer by adopting plasma enhanced chemical vapor deposition or chemical vapor deposition;
the buffer layer is used for isolating the catalytic layer from the electrode substrate and preventing the catalytic layer from permeating into the substrate; the catalyst layer is used for catalyzing the growth of carbon nanotubes or graphene.
Preferably, the step (4) of coating the electrode surface with an active material specifically comprises:
(4-1) carrying out hydrophilic treatment on the 3D carbon-silicon composite electrode in the step (3), specifically: carrying out surface hydrophilic treatment on the electrode by using a plasma oxygen cleaning technology or Pirahan;
and (4-2) growing an active material on the surface of the electrode after the hydrophilic treatment.
Preferably, the active material is a single nanomaterial or a composite nanomaterial, the active material being operable to increase one or more of the specific surface area, electrochemical activity, capacitive properties and conductive capacity of the electrode.
According to another aspect of the invention, the 3D bulk silicon micro-capacitor manufactured by the manufacturing method is provided.
According to another aspect of the present invention, there is provided an application of the 3D bulk silicon micro-capacitor for energy storage and power supply, acceleration sensing, vibration sensing, shock sensing or a filter.
In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
(1) according to the manufacturing method of the 3D bulk silicon micro capacitor, the silicon substrate is deeply etched to obtain the electrode structure with a certain longitudinal space, compared with a planar electrode, the longitudinal height of the electrode is extended and utilized, and the specific surface area of the electrode is increased; after the active material is introduced into the structure, compared with a planar electrode, the specific surface area of the electrode which can be utilized is expanded from a two-dimensional surface to a three-dimensional surface and a side wall, and the utilization of the longitudinal space of the side wall enables the electrode to load more active material, so that the specific energy density is further improved; and the silicon-based structure has stable physical and chemical properties and has the properties of high temperature resistance, corrosion resistance and the like required when part of active materials are introduced.
(2) The MEMS technology can carry out graphical manufacturing on a silicon wafer through a semiconductor process, the geometric dimension of a device can be defined according to requirements, and a miniaturized 3D bulk silicon electrode is obtained; along with the reduction of the width and the clearance of the comb teeth, the transmission path of electrolyte ions can be further shortened, so that the reduction of the resistance of ion transmission is limited, in the same area, the width of the comb teeth is reduced, the specific surface area of the electrode can be obviously increased, and the control of the contrast capacitance and the specific power density can be realized by the comb teeth and the electrode. The introduction of the method for coating the carbon-based conducting layer by the 3D silicon-based structure overcomes the problem of poor conductivity of silicon as a 3D electrode substrate, and is suitable for introducing an active material with high capacity density later to further improve the electrochemical performance of the capacitor;
(3) the manufactured silicon-based capacitor chip can adopt a mature packaging process, so that the structure is protected, the stable work and the long-term reliability of the silicon-based capacitor chip are ensured, the micro structure can be directly integrated on a substrate (comprising multiple types) to realize electrical connection, the silicon-based capacitor chip has good integration, the required work target parameters can be obtained through the series-parallel connection structure of the silicon-based capacitor chip, the energy supply requirements of different chips are met, and the silicon-based capacitor chip has universality and wide application value.
Drawings
Fig. 1 is a top view of a MEMS-3D bulk silicon micro-capacitor of the present invention packaged and integrated in three different ways.
FIG. 2 is a top view and a perspective view of a silicon comb electrode obtained by deep etching.
FIG. 3 is a schematic top view and cross-sectional view of a silicon-based conductive layer grown on the surface and sidewalls of a silicon comb electrode.
Fig. 4 is a top view and a cross-sectional view of the surface and the side wall of the 3D carbon-silicon composite electrode on which the silicon-based conductive layer is grown are coated with the active material.
Fig. 5 shows a first embodiment of packaging and integration: and (3) a top view for fixing the lower surfaces of the comb teeth and the insulating base through the viscous glue by the electrode.
Fig. 6 shows the packaging and integration of the first embodiment: and (4) a top view of the electrode after the electrolyte is coated on the surface.
Fig. 7 shows the packaging and integration of the first embodiment: and after the manufactured capacitor is attached and fixed to the substrate, the top view of the electrode and the substrate after electrical connection is realized through an aluminum wire by adopting a routing technology.
Fig. 8 shows another wire bonding method in the first embodiment of packaging and integration: and depositing a conductive Pad point on the exposed silicon surface at one end of the electrode frame, and electrically connecting the electrode and the substrate by a gold wire by adopting a routing technology.
Fig. 9 shows the packaging and integration of the second embodiment: after the active material is grown, alloy layers for packaging are deposited on the lower surfaces of two ends of the electrode frame, and patterned packaging alloy is deposited on the insulating base, wherein the left figure is a top view of the lower surface after the electrode is turned over, and the right figure is a top view after the packaging alloy is deposited on the insulating base.
Packaging and integration of embodiment two of fig. 10: and aligning the lower surface of the electrode on which the packaging alloy is deposited with the insulating base, and adopting hot-press bonding under the action of the solder to realize the electrical connection and the fixed top view of the electrode and the insulating base.
Fig. 11 shows the packaging and integration of the second embodiment: and (4) a top view of the electrode after the electrolyte is coated on the surface.
Fig. 12 shows the packaging and integration of the second embodiment: and after the manufactured capacitor is attached and fixed to the substrate, the top view of the substrate is formed after the exposed packaging alloy on the insulating base is electrically connected with the substrate through a gold thread by adopting a routing technology.
The same reference numbers will be used throughout the drawings to refer to the same or like elements or structures, wherein:
101-a silicon comb electrode; 102-a carbon-based conductive layer; 103-an active material; 201-an insulating base; 202-an electrolyte; 203-packaging alloy; 204-substrate, 205-conductive Pad, 206 a-aluminum line; 206 b-gold wire.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention provides a method for manufacturing a 3D bulk silicon micro capacitor, which comprises the following steps:
(1) and manufacturing an array pattern on the surface of the silicon-based substrate through a photoetching process, etching according to the array pattern, and etching to penetrate through the substrate to obtain the hollow 3D bulk silicon electrode.
(2) Carrying out hydrophilic treatment on the 3D bulk silicon electrode obtained in the step (1) to ensure that the surface of the electrode has hydrophilicity, so as to obtain the hydrophilic 3D bulk silicon electrode;
(3) and (3) masking the frame part for electrical connection in the 3D bulk silicon electrode obtained in the step (2), and coating the surface of the non-masked part with a carbon-based conductive layer to obtain the 3D carbon-silicon composite electrode coated with the carbon-based conductive layer, as shown in fig. 3.
(4) And (4) coating the surface of the 3D carbon-silicon composite electrode coated with the carbon-based conductive layer in the step (3) with an active material to obtain the 3D carbon-silicon composite electrode coated with the active material, as shown in FIG. 4.
(5) And removing the mask of the frame part for electrical connection, and packaging and integrating the electrode to obtain the 3D bulk silicon micro capacitor, as shown in figure 1.
Wherein the electrode surface comprises both horizontal surfaces and vertical surfaces obtained by etching of the electrode structure. The vertical surfaces, i.e. the sides, are also denoted as sidewalls in the present invention, the horizontal and vertical surfaces, i.e. the sides or sidewalls, together constituting the electrode.
The 3D bulk silicon micro capacitor based on the MEMS technology is manufactured by adopting a semiconductor micro-nano processing technology. The method comprises the steps of obtaining a 3D bulk silicon comb electrode by deep etching through a photoetching process, sequentially coating carbon materials and active materials with nano structures on the surface and the side wall of a comb tooth, finally coating an electrolyte, packaging and integrating with a target chip to realize power supply.
In some embodiments, the 3D bulk silicon electrode structure of the present invention is in the shape of a hollow comb.
The substrate is etched and penetrated through by deep etching in the 3D bulk silicon micro capacitor provided by the invention, and the comb tooth electrode structure with certain longitudinal depth is obtained. The thickness of the silicon-based substrate, the width of the comb teeth and the comb tooth gaps obtained by etching can be selected according to actual application requirements.
In some embodiments, the 3D bulk silicon electrode is a 3D bulk silicon comb-tooth-shaped electrode, the width of the comb teeth is more than 10 micrometers, the distance between the comb teeth is more than 10 micrometers, and the thickness of the monolithic silicon substrate is generally 100-1000 micrometers.
The etching may be wet etching or dry etching.
In some embodiments, as shown in fig. 2, the hollowed-out 3D bulk silicon electrode obtained in step (1) is obtained by performing pretreatment such as cleaning on a silicon-based substrate, performing a photolithography process on the front surface of the substrate to form an array pattern, and performing deep etching to obtain a 3D bulk silicon comb electrode 101.
In some embodiments, step (2) is performed by hydrophilic treatment of the electrode by plasma oxygen cleaning techniques or by Pirahan.
The mask in step (3) of the present invention is a conventional mask processing method, and may be covered or wrapped by an adhesive tape or silicone grease, for example.
The carbon-based conductive layer in step (3) of the present invention includes, but is not limited to, amorphous carbon, graphite, carbon nanotubes, or graphene.
In some embodiments, step (3) coats the carbon-based conductive layer by: dissolving a carbon-based compound precursor in a volatile solvent to obtain a precursor solution; and coating the carbon-based conducting layer on the surface of the 3D bulk silicon electrode in the precursor solution by a hydrothermal method.
In other embodiments, step (3) coats the carbon-based conductive layer by: dissolving a carbon-based compound precursor in a volatile solvent to obtain a precursor solution; and uniformly soaking the 3D bulk silicon electrode in the precursor solution, taking out, quickly drying, and reducing and decomposing the precursor on the surface of the electrode by a chemical vapor deposition method to form a carbon-based conductive layer. The volatile solvent is water, acetone or isopropanol, etc.
In some embodiments, the carbon-based compound precursor is a hydrocarbon. It should be understood by those skilled in the art that any hydrocarbon capable of coating the carbon-based conductive layer on the surface of the electrode by a hydrothermal method may be suitable. The hydrocarbon compound of the present invention includes, but is not limited to, saccharides, photoresist, etc., wherein the saccharides include glucose, sucrose, fructose, etc.
In experiments, it is found that when a hydrocarbon is used as a carbon-based compound precursor, a precursor solution formed after the hydrocarbon is dissolved may have a certain viscosity, and when the width of the comb teeth of the comb electrode and the distance between the comb teeth are relatively small, deformation or adhesion occurs between the comb teeth, which causes a short circuit of a final capacitor; under this condition, can adjust broach width or broach interval, or volatile solvent can adopt acetone or isopropyl alcohol, because its volatilization rate is faster, can avoid broach electrode structure to take place to warp or broach bonding.
In some embodiments, the carbon-based conductive layer is a carbon nanotube or graphene nanostructure, and the step (3) coats the carbon-based conductive layer by:
(3-1) sequentially coating buffer layers and catalyst layers on the upper and lower surfaces and the side surfaces of the 3D bulk silicon electrode by a common method of material deposition, such as electron beam evaporation coating, magnetron sputtering coating, thermal evaporation coating, chemical vapor deposition, atomic layer deposition, sol-gel method, hydrothermal method, or electroplating method; the buffer layer is made of SiO2、Al、TiN、Al2O3Or zeolite, etc.; the catalyst layer is made of Ni, Ti, Fe and Fe2O3Co, Cu, Mo, Pd, Au or Ag, etc.;
(3-2) coating the carbon nanotube or graphene nanostructure carbon-based conducting layer on the surface of the electrode sequentially coated with the buffer layer and the catalytic layer by adopting PECVD or CVD;
the buffer layer is used for isolating the catalytic layer from the electrode substrate and preventing the catalytic layer from diffusing into the substrate; the catalyst layer is used for catalyzing the growth of carbon nanotubes or graphene.
In some embodiments, the frame portion for electrical connection is masked and covered or wrapped with tape to coat the surface and sidewalls of the comb teeth electrode with a carbon-based conductive layer 102, including but not limited to amorphous carbon, graphite, carbon nanotubes, or graphene, as shown in fig. 3.
In some embodiments, the step (4) of coating the surface of the carbon-silicon composite electrode with the active material specifically includes:
(4-1) carrying out hydrophilic treatment on the 3D carbon-silicon composite electrode coated with the carbon-based conductive layer in the step (3), specifically: carrying out hydrophilic treatment on the electrode by using a plasma oxygen cleaning technology or Pirahan; in some embodiments, a plasma oxygen cleaning technique at low power may be used.
And (4-2) growing an active material on the surface of the electrode after the hydrophilic treatment by adopting a hydrothermal method or a plating method.
In some embodiments, the active material is comprised of a single material or a composite material. The active material can be used to increase the specific surface area, electrochemical activity, capacitance characteristics, conductivity, etc. of the structure according to the kind of nanomaterial. Including, but not limited to, one or more of zinc oxide, manganese oxide, vanadium oxide, tungsten oxide, titanium nitride, titanium carbide nanowires/rods, and the like.
In some embodiments, the active material 103 is coated on the surface and the side wall of the comb teeth electrode coated with the carbon-based conductive layer, and the process first needs to perform hydrophilic treatment on the comb teeth structure by plasma oxygen cleaning technology under low power or Pirahan, mask the frame portion for electrical connection, and grow the active material on the comb teeth in a precursor solution for growing the active material by a hydrothermal method or an electroplating method, as shown in FIG. 4.
And (5) carrying out hydrophilic treatment on the comb tooth part, removing the mask of the frame part for electrical connection, coating electrolyte on the surface of the electrode, and packaging and integrating the electrode to obtain the 3D bulk silicon micro capacitor. Alternatively, the electrolyte may be applied first and then the mask of the frame portion removed.
The packaging and integration method for preparing the 3D bulk silicon micro capacitor can adopt a chip packaging and integration mode.
In some embodiments, step (5) of packaging and integrating the electrodes comprises the steps of:
(5-1) coating adhesive glue on the lower surface of the frame part of the electrode structure, attaching the adhesive glue to the insulating base 201, and heating and curing at 100-200 ℃ to realize electrode fixation, as shown in fig. 5. The insulating base may be a glass or polymer material.
(5-2) separating the positive and negative electrodes by using a laser scribing technique, as shown in FIG. 6.
(5-3) subjecting the comb-tooth part to a hydrophilic treatment, and coating a gel-like electrolyte 202 on the surface thereof, as shown in FIG. 6; in some embodiments, when the comb gap is small, the structure may be placed in a vacuum if the electrolyte is allowed to sufficiently enter the comb gap;
(5-4) after the coating is finished, putting the electrolyte into an oven, and removing excessive water and air bubbles in the electrolyte at a proper temperature.
(5-5) attaching and fixing the structure and the substrate 204, and realizing the electrical connection between the 3D bulk silicon capacitor and the substrate by adopting an aluminum wire 206a through a routing technology, wherein the method is a first packaging scheme and is shown in fig. 7;
or the insulating base and the comb-tooth part are masked, conductive Pad points 205 are deposited at two ends of the upper surface of the silicon-based frame, and the capacitor and the substrate are electrically connected by a wire bonding technology and a gold wire 206b, wherein the method is a second packaging scheme, as shown in fig. 8.
And (5-6) finally, covering an insulating upper cover, fixing the upper cover and sealing the gap, so that the capacitor is prevented from being interfered by the external environment, and the electrolyte is prevented from deteriorating.
And (5-7) stacking and fixing a plurality of capacitors, and realizing parallel connection of the capacitors by a routing technology.
In other embodiments, the step (5) of packaging and integrating the electrodes includes the following steps:
(5-1) masking the comb-teeth part of the electrode, depositing packaging alloy 203 at two ends of the lower surface of the frame, depositing patterned packaging alloy 203 corresponding to two ends of the lower surface of the frame on the insulating base 201, aligning and attaching the two parts as shown in fig. 9, and performing thermal compression bonding under the action of solder to realize electrical connection.
(5-2) separating the positive and negative electrodes by using a laser scribing technique, as shown in FIG. 10.
(5-3) removing the mask material of the comb tooth portions, subjecting the comb tooth portions to hydrophilic treatment, and applying a gel-like electrolyte 202 on the surfaces thereof, as shown in FIG. 11, the structure can be placed in a vacuum when the comb tooth gaps are small, if the electrolyte is allowed to sufficiently enter the comb tooth gaps.
(5-4) after the coating is finished, putting the electrolyte into an oven, and removing excessive water and air bubbles in the electrolyte at a proper temperature.
(5-5) the structure is bonded and fixed with the substrate 204, and the electrodes, the insulating base and the substrate are electrically connected by gold wires through a wire bonding technology, as shown in fig. 12.
And (5-6) finally, covering an insulating upper cover, fixing the upper cover and sealing the gap, so that the capacitor is prevented from being interfered by the external environment, and the electrolyte is prevented from deteriorating.
And (5-7) stacking and fixing a plurality of capacitors, and realizing parallel connection of the capacitors by a routing technology.
All the steps can finely adjust the preparation sequence and the structural design according to the actual situation.
The invention provides a method for manufacturing a 3D bulk silicon micro capacitor based on an MEMS technology, which mainly adopts a semiconductor micro-nano processing technology, obtains a required electrode structure by deeply etching a silicon wafer, takes the electrode structure as a substrate, introduces carbon-based conductive materials on the surface and the side wall of the substrate, uniformly coats the carbon-based conductive materials, reduces the resistance of a silicon-based structure, coats active materials on the surface and the side wall to enable the capacitor to have excellent electrochemical performance, and finally coats an electrolyte on the capacitor to realize packaging and integrate with a device to be powered. The 3D bulk silicon micro-capacitor prepared and packaged by the invention can be used for energy storage and power supply, acceleration sensing, vibration or impact sensing, filters and the like.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (6)

1. A manufacturing method of a 3D bulk silicon micro capacitor is characterized by comprising the following steps:
(1) manufacturing an array pattern on the surface of a silicon-based substrate through a photoetching process, etching according to the array pattern, and etching to penetrate through the substrate to obtain a hollow 3D bulk silicon electrode; the 3D bulk silicon electrode structure is in a comb shape; wherein, the width of the comb teeth is more than 10 microns, and the distance between the comb teeth is more than 10 microns;
(2) carrying out hydrophilic treatment on the 3D bulk silicon electrode obtained in the step (1) to enable the surface of the electrode to have hydrophilicity, so as to obtain the hydrophilic 3D bulk silicon electrode;
(3) masking the frame part for electrical connection in the 3D bulk silicon electrode obtained in the step (2), and coating the electrode surface of the non-masked part with a carbon-based conductive layer to obtain a 3D carbon-silicon composite electrode coated with the carbon-based conductive layer; wherein, the coating of the carbon-based conductive layer is carried out by the following method:
(3-1) dissolving a carbon-based compound precursor in a volatile solvent to obtain a precursor solution;
(3-2) placing the 3D bulk silicon electrode in the precursor solution, and coating a carbon-based conducting layer on the surface of the electrode by a hydrothermal method; the carbon-based compound precursor is a hydrocarbon;
the volatile solvent is acetone or isopropanol, and the deformation of the comb electrode structure or the bonding of the comb teeth can be avoided by adjusting the width of the comb teeth or the space between the comb teeth and selecting the volatile solvent;
(4) coating an active material on the surface of the electrode of the 3D carbon-silicon composite electrode coated with the carbon-based conductive layer obtained in the step (3) to obtain a 3D carbon-silicon composite electrode coated with the active material;
(5) removing the mask of the frame part for electrical connection, and packaging and integrating the 3D carbon-silicon composite electrode to obtain the 3D bulk silicon micro capacitor;
wherein the electrode surface comprises both the horizontal surface and the vertical surface of the electrode structure obtained by etching.
2. A manufacturing method of a 3D bulk silicon micro capacitor is characterized by comprising the following steps:
(1) manufacturing an array pattern on the surface of a silicon-based substrate through a photoetching process, etching according to the array pattern, and etching to penetrate through the substrate to obtain a hollow 3D bulk silicon electrode; the 3D bulk silicon electrode structure is in a comb shape; wherein, the width of the comb teeth is more than 10 microns, and the distance between the comb teeth is more than 10 microns;
(2) carrying out hydrophilic treatment on the 3D bulk silicon electrode obtained in the step (1) to enable the surface of the electrode to have hydrophilicity, so as to obtain the hydrophilic 3D bulk silicon electrode;
(3) masking the frame part for electrical connection in the 3D bulk silicon electrode obtained in the step (2), and coating the electrode surface of the non-masked part with a carbon-based conductive layer to obtain a 3D carbon-silicon composite electrode coated with the carbon-based conductive layer; wherein, the coating of the carbon-based conductive layer is carried out by the following method:
(3-1) dissolving a carbon-based compound precursor in a volatile solvent to obtain a precursor solution;
(3-2) placing the 3D bulk silicon electrode in the precursor solution, soaking, taking out, drying, and reducing and decomposing the precursor on the surface of the electrode by a chemical vapor deposition method to form a carbon-based conductive layer, wherein the precursor is a hydrocarbon;
the volatile solvent is acetone or isopropanol, and the deformation of the comb electrode structure or the bonding of the comb teeth can be avoided by adjusting the width of the comb teeth or the space between the comb teeth and selecting the volatile solvent;
(4) coating an active material on the surface of the electrode of the 3D carbon-silicon composite electrode coated with the carbon-based conductive layer obtained in the step (3) to obtain a 3D carbon-silicon composite electrode coated with the active material;
(5) removing the mask of the frame part for electrical connection, and packaging and integrating the 3D carbon-silicon composite electrode to obtain the 3D bulk silicon micro capacitor;
wherein the electrode surface comprises both the horizontal surface and the vertical surface of the electrode structure obtained by etching.
3. The manufacturing method according to claim 1 or 2, wherein the step (4) of coating the electrode surface with an active material is specifically:
(4-1) carrying out hydrophilic treatment on the 3D carbon-silicon composite electrode in the step (3), specifically: carrying out surface hydrophilic treatment on the electrode by using a plasma oxygen cleaning technology or Pirahan;
and (4-2) growing an active material on the surface of the electrode after the hydrophilic treatment.
4. The method of claim 1 or 2, wherein the active material is a single nanomaterial or a composite nanomaterial, and the active material is operable to increase one or more of the specific surface area, electrochemical activity, capacitive characteristics, and conductive capacity of the electrode.
5. The 3D bulk silicon micro-capacitor manufactured by the manufacturing method according to any one of claims 1 to 4.
6. The use of the 3D bulk silicon micro-capacitor as claimed in claim 5 for energy storage and supply, acceleration sensing, vibration sensing, shock sensing or filters.
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