CN112103636A - Method for realizing micro-nano graphical processing on polyimide film - Google Patents

Method for realizing micro-nano graphical processing on polyimide film Download PDF

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Publication number
CN112103636A
CN112103636A CN202010811184.5A CN202010811184A CN112103636A CN 112103636 A CN112103636 A CN 112103636A CN 202010811184 A CN202010811184 A CN 202010811184A CN 112103636 A CN112103636 A CN 112103636A
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photoresist
polyimide film
etching
aluminum layer
ppc
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刘盼
伊菲珍妮亚·扎哈瑞欧
汉克·凡·扎尔
张国旗
张靖
樊嘉杰
李梁涛
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Fudan University
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01QANTENNAS, i.e. RADIO AERIALS
    • H01Q1/00Details of, or arrangements associated with, antennas
    • H01Q1/36Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith
    • H01Q1/38Structural form of radiating elements, e.g. cone, spiral, umbrella; Particular materials used therewith formed by a conductive layer on an insulating support
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B81MICROSTRUCTURAL TECHNOLOGY
    • B81CPROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C1/00Manufacture or treatment of devices or systems in or on a substrate
    • B81C1/00349Creating layers of material on a substrate
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B81MICROSTRUCTURAL TECHNOLOGY
    • B81CPROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C1/00Manufacture or treatment of devices or systems in or on a substrate
    • B81C1/00388Etch mask forming
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B81MICROSTRUCTURAL TECHNOLOGY
    • B81CPROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C1/00Manufacture or treatment of devices or systems in or on a substrate
    • B81C1/00436Shaping materials, i.e. techniques for structuring the substrate or the layers on the substrate
    • B81C1/00523Etching material
    • B81C1/00531Dry etching
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B81MICROSTRUCTURAL TECHNOLOGY
    • B81CPROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
    • B81C1/00Manufacture or treatment of devices or systems in or on a substrate
    • B81C1/00436Shaping materials, i.e. techniques for structuring the substrate or the layers on the substrate
    • B81C1/00523Etching material
    • B81C1/00539Wet etching
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14Metallic material, boron or silicon
    • C23C14/20Metallic material, boron or silicon on organic substrates
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23CCOATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24Vacuum evaporation
    • CCHEMISTRY; METALLURGY
    • C23COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23FNON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
    • C23F1/00Etching metallic material by chemical means
    • C23F1/02Local etching

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Details Of Aerials (AREA)
  • Manufacturing Of Printed Circuit Boards (AREA)

Abstract

The invention belongs to the technical field of flexible substrates, and particularly relates to a method for realizing micro-nano graphical processing on a polyimide film. The method comprises the following specific steps: (1) firstly, spinning a PPC material on a silicon wafer, and then attaching a polyimide film on the silicon wafer; (2) depositing an aluminum layer using an evaporation process; (3) spin coating a positive photoresist layer; (4) under the action of ultraviolet irradiation, selectively exposing the photoresist coating by using a mask plate, and then carrying out soft drying; (5) chemically etching the photoresist with an etchant; (6) etching away the aluminum layer exposed outside by using dry etching and wet etching, and reserving the aluminum layer covered by the photoresist; (7) stripping the photoresist; (8) heating and separating to obtain the polyimide film. The PPC-bonded polyimide film is used for imaging, the method is simple, the effect is excellent, and the flexible antenna capable of working at 60GHz frequency can be manufactured.

Description

Method for realizing micro-nano graphical processing on polyimide film
Technical Field
The invention relates to a method for realizing micro-nano graphical processing on a polyimide film, belonging to the technical field of flexible substrates.
Background
The main advantage of flexible substrates is the ability to fold or scroll the circuit board in several geometries depending on the needs and specifications of the design, thereby providing a higher performance solution at a lower cost. Polyimide, as a flexible substrate material, has excellent chemical, mechanical and thermal properties as well as excellent high temperature stability (up to 400 ℃). Its high porosity indicates its very low dielectric constant, which makes it suitable for use in a variety of microelectronic applications. The micro-nano graphical processing is realized on the polyimide, the flexible radio frequency antenna can be prepared, and the antenna can roll, stretch and bend according to application requirements. The cost of the wearable wireless device can be reduced and the application range can be expanded.
There are many studies on patterning on a flexible substrate. Such as polyimide-based Flexible Inverted F Antennas (FIFA), polyethylene terephthalate (PET) -based flexible antennas for UHF operation, and paper as an alternative substrate option for RFID antennas. In the above studies, the antenna was designed to operate at low frequencies (2.4 GHz), with a larger size structure. To operate at higher frequencies, radio frequency systems (including antennas) are required to be reduced in size. When the antenna is designed to work at 60GHz, the traditional screen printing patterning processing mode cannot realize the small size, so that the micro-nano patterning processing technology is required to obtain the small-size antenna.
Disclosure of Invention
The invention provides a complete process method capable of manufacturing micro-nano patterns on a polyimide film of a flexible substrate. By using the process, the flexible antenna capable of working at the frequency of 60GHz can be manufactured.
The technical scheme of the invention is specifically introduced as follows.
A method for realizing micro-nano graphical processing on a polyimide film comprises the following specific steps:
(1) firstly, spinning a PPC material of the polypropylene carbonate on a silicon wafer, then attaching a polyimide film on the silicon wafer, curing the PPC at the temperature of 150-180 ℃ for 1.5-2.5 h to remove a solvent and stabilize a polymer, and finally flattening the film by a short-time wafer bonding technology;
(2) depositing an aluminum layer on the sample of step (1) using an evaporation process;
(3) spin-coating a positive photoresist layer on the sample of step (2);
(4) under the action of ultraviolet irradiation, selectively exposing the photoresist coating by using a mask plate, and then carrying out soft drying;
(5) chemically etching the photoresist by using an etching agent to etch the exposed positive photoresist, wherein the unexposed part is reserved to form a specific pattern;
(6) etching the aluminum layer by using an AL0.6glass formula through dry etching, and removing the aluminum layer exposed outside through wet etching to keep the aluminum layer covered by the photoresist;
(7) exposing the sample subjected to wet etching to ultraviolet rays, and removing the residual photoresist by using acetone;
(8) heating the sample of the stripped photoresist at the temperature of 200-250 ℃, and decomposing the PPC material into water and carbon dioxide to obtain the polyimide film for realizing micro-nano graphical processing.
In the invention, in the step (1), the thickness of the polyimide film is 10-150 μm, and the technological conditions of the wafer bonding technology are as follows: at a temperature of 35 deg.C, a 500N force is applied for 3 min.
In the invention, in the step (2), the thickness of the aluminum layer is 0.1-2 μm, and the thickness of the positive photoresist layer is 1-3 μm.
In the invention, in the step (4), the width of the conductive gap of the mask is 2 μm-130mm, the soft drying temperature is 95 ℃, and the soft drying time is 1 min. Preferably, the width of the conductive gap of the mask is 12 μm-125 mm.
In the present invention, in step (5), the etchant is alkaline TMAH developer.
In the invention, in the step (6), the specific process parameters of the dry etching are as follows: sputtering for 0.5-1 s, cooling at 25 ℃ for 3-5 min, sputtering for 0.5-1 s, cooling again for 3-5 min, and repeating the above steps until the thickness meets the requirement of 0.6 μm.
In the invention, hydrofluoric acid is used for wet etching in the step (6).
Compared with the prior art, the invention has the beneficial effects that:
1) the invention provides a process for carrying out micro-nano graphical processing on a flexible substrate, wherein the working frequency of an antenna is related to the graphic size of the antenna, and the smaller the size, the higher the working frequency;
2) the process adopts the steps of dry etching firstly and wet etching secondly, and the width of the conductive gap of the obtained coplanar microstrip transmission line (CPW) can be only 12 microns, even can be only 2 microns at minimum;
3) the manufactured antenna is measured, and the reflection coefficient of the antenna is determined by using a Suss semi-automatic probe station and an Anritsu network analyzer to test in a frequency band of 50-65 GHz, so that the resonance frequency of the antenna is obtained. It has been measured that the antenna can operate at frequencies slightly below 60GHz (53 GHz) at a coplanar microstrip transmission line (CPW) conductive gap width of 125 microns. Therefore, the working frequency of the flexible antenna is improved from 2.4GHz to about 60GHz, and the possibility is provided for manufacturing the flexible millimeter wave sensor;
4) the thickness of the flexible substrate also affects the operating frequency of the antenna, with thicker thicknesses giving higher frequencies. Fig. 2 and 3 show the relationship between the frequency and the dielectric constant of the flexible substrate with 25 micrometers and the flexible substrate with 125 micrometers, and it can be seen that the increase of the thickness by 100 micrometers can increase the operating frequency corresponding to the antenna on the substrate by 3-8 orders of magnitude. The dielectric constant and frequency relationship can also prove that the capacitance of the parasitic antenna is related to the thickness of the flexible substrate, and further the bandwidth of the antenna can be influenced. As the thickness of the substrate increases, its parasitic capacitance decreases and the bandwidth increases. Therefore, the invention can adjust the thickness of the polyimide film to adapt the antenna to different working frequencies.
Drawings
FIG. 1 is a flowchart of the image formation process of the PPC-bonded Kapton thin films.
Fig. 2 is a graph of frequency versus dielectric constant for a 25 micron flexible substrate.
Fig. 3 shows the frequency versus dielectric constant for a 125 micron flexible substrate.
Fig. 4 is a diagram of the antenna and coplanar microstrip transmission line obtained after dry etching and wet etching in example 1; (a) is a schematic diagram of the conductor gap and conductor width of the antenna, and (b) is a specific parameter.
FIG. 5 is a small-sized antenna pattern obtained after dry etching and wet etching in example 1; (a) is a schematic diagram of the conductor gap and conductor width of the antenna, and (b) is a specific parameter.
Detailed Description
The technical scheme of the invention is explained in detail in the following by combining the drawings and the embodiment.
Example 1
As shown in fig. 1, the micro-nano patterning process of the antenna and the coplanar microstrip transmission line (CPW) on the polyimide film is implemented as follows:
(a) firstly, a layer of PPC (polypropylene carbonate) material is coated on a silicon chip in a spinning way, then a polyimide film (Kapton @) with the thickness of 125 +/-5 mu m is laminated on the silicon chip, and then the PPC is solidified for 2 hours at 160 ℃ so as to remove the solvent and stabilize the polymer, thereby simplifying the etching process. Finally, the film is subjected to a wafer bonding technique (500N, 35 ℃) for a short time (3 minutes) to be as flat as possible;
(b) depositing a 2 μm thick aluminum layer using an evaporation process;
(c) spin coating a positive photoresist layer with the thickness of 3 mu m;
(d) under the action of ultraviolet irradiation, selectively exposing the photoresist coating by using a CPW mask with a conductive gap width of 12 mu m to obtain a small-size CPW pattern, and soft-baking at 95 ℃ for 1 minute;
(e) carrying out chemical etching on the photoresist by using an etching agent, etching the exposed positive photoresist, and reserving the unexposed part to form a specific pattern;
(f) the aluminum layer is etched by an etching process, so that the aluminum layer exposed outside can be etched, and the aluminum layer covered by the photoresist is remained. First dry etch was performed using an al0.6glass formulation. The specific technological parameters are 1s of sputtering, 5 minutes of cooling at 25 ℃, 1s of sputtering again and 5 minutes of cooling again, and the process is circulated until the thickness meets the requirement of 0.6 mu m. The metal pattern was then patterned by wet etching (0.55% HF) for 1 minute. The process can achieve the best effect, and the lines are smooth and clear under the observation of a microscope;
(g) and stripping the photoresist. To avoid any damage to the aluminum layer, the sample was exposed to uv light after wet etching, and then the remaining photoresist was removed with acetone;
(h) and (5) separating the film. PPC is a polymeric material used as a temporary bonding medium between silicon wafers and Kapton @ thin films prior to wafer bonding, exhibiting high stability within 180 ℃. When heated above 200 c, it will separate into water and carbon dioxide without any polymer remaining. So that it can be easily removed by heating at 200 ℃.
Fig. 4 is a diagram of the antenna and coplanar microstrip transmission line pattern obtained after dry etching and wet etching in example 1. (a) Is a schematic diagram of the conductor gap and conductor width of the antenna, and (b) is a specific parameter.
Fig. 5 is a small-sized antenna pattern obtained after the dry etching and the wet etching in example 1. (a) Is a schematic diagram of the conductor gap and conductor width of the antenna, and (b) is a specific parameter.
Example 2
As shown in fig. 1, the micro-nano patterning process for implementing a small-sized antenna and a signal transmission microstrip line on a polyimide film has the following steps:
(a) firstly, a layer of PPC (polypropylene carbonate) material is coated on a silicon chip in a spinning way, then a polyimide film (Kapton thin film) with the thickness of 127 mu m is attached on the silicon chip, and then the PPC is solidified for 2h at 180 ℃ so as to remove the solvent and stabilize the polymer, thereby simplifying the etching process. Finally, the film is subjected to a wafer bonding technique (500N, 35 ℃) for a short time (3 minutes) to be as flat as possible;
(b) depositing a 2 μm thick aluminum layer using an evaporation process;
(c) spin coating a positive photoresist layer with the thickness of 3 mu m;
(d) under the action of ultraviolet irradiation, selectively exposing the photoresist coating by using a microstrip line mask plate with a designed conductive gap width of 125 mu m to obtain a small-size microstrip line pattern, and soft-baking for 1 minute at 95 ℃;
(e) carrying out chemical etching on the photoresist by using an etching agent, etching the exposed positive photoresist, and reserving the unexposed part to form a specific pattern;
(f) the aluminum layer is etched by an etching process, so that the aluminum layer exposed outside can be etched, and the aluminum layer covered by the photoresist is remained. First dry etch was performed using an al0.6glass formulation. The specific technological parameters are 1s of sputtering, 5 minutes of cooling at 25 ℃, 1s of sputtering again and 5 minutes of cooling again, and the process is circulated until the thickness meets the requirement of 0.6 mu m. The metal pattern was then patterned by wet etching (0.55% HF) for 1 minute. The process can achieve the best effect, and the lines are smooth and clear under the observation of a microscope;
(g) and stripping the photoresist. To avoid any damage to the aluminum layer, the sample was exposed to uv light after wet etching, and then the remaining photoresist was removed with acetone;
(h) and (5) separating the film. PPC is a polymeric material used as a temporary bonding medium between silicon wafers and Kapton @ thin films prior to wafer bonding, exhibiting high stability within 180 ℃. When heated above 200 c, it will separate into water and carbon dioxide without any polymer remaining. So that it can be easily removed by heating at 200 ℃.
The process realizes the micro-nano graphical processing of the antenna and the transmission line on the flexible substrate. During etching, due to the steps of first dry etching and second wet etching adopted by the process, the width of the conductive gap of the coplanar microstrip transmission line (CPW) obtained in the embodiment 1 is only 12 micrometers, and the electromagnetic coupling transition of high-frequency signals can be better performed. And the width of the conductive gap of the microstrip line obtained in embodiment 2 is only 125 micrometers, so that the operating frequency of the flexible antenna is improved from 2.4GHz to 60GHz, and the manufacturing of the flexible millimeter wave sensor is possible. During testing, the final structure is completed through wafer measurement in a 50-65 GHz frequency band by using a Suss semi-automatic probe station and an Anritsu network analyzer so as to determine the reflection coefficient of the antenna and further obtain the resonant frequency of the antenna. Experimental results show that the design can operate accurately at frequencies slightly below 60GHz (53 GHz).
The invention can be used for preparing flexible antennas and millimeter wave sensors (such as vehicle-mounted radio frequency radars and millimeter wave human body induction sensors) in wearable equipment.
The process can also realize the metal aluminum micro-nano graphical processing of 2 mu m-10mm seam width on the polyimide film.

Claims (7)

1. A method for realizing micro-nano graphical processing on a polyimide film is characterized by comprising the following specific steps:
(1) firstly, spinning a PPC material of the polypropylene carbonate on a silicon wafer, then attaching a polyimide film on the silicon wafer, curing the PPC at the temperature of 150-180 ℃ for 1.5-2.5 h to remove a solvent and stabilize a polymer, and finally flattening the film by a short-time wafer bonding technology;
(2) depositing an aluminum layer on the sample of step (1) using an evaporation process;
(3) spin-coating a positive photoresist layer on the sample of step (2);
(4) under the action of ultraviolet irradiation, selectively exposing the photoresist coating by using a mask plate, and then carrying out soft drying;
(5) chemically etching the photoresist by using an etching agent to etch the exposed positive photoresist, wherein the unexposed part is reserved to form a specific pattern;
(6) etching the aluminum layer by using an AL0.6glass formula through dry etching, and removing the aluminum layer exposed outside through wet etching to keep the aluminum layer covered by the photoresist;
(7) exposing the sample subjected to wet etching to ultraviolet rays, and removing the residual photoresist by using acetone;
(8) heating the sample of the stripped photoresist at the temperature of 200-250 ℃, and decomposing the PPC material into water and carbon dioxide to obtain the polyimide film for realizing micro-nano graphical processing.
2. The method according to claim 1, wherein in the step (1), the thickness of the polyimide film is 10-150 μm, and the process conditions of the wafer bonding technology are as follows: at a temperature of 35 deg.C, a 500N force is applied for 3 min.
3. The method as claimed in claim 1, wherein in the step (2), the aluminum layer has a thickness of 0.1 to 2 μm and the positive photoresist layer has a thickness of 1 to 3 μm.
4. The method of claim 1, wherein in the step (4), the width of the conductive gap of the mask is 2 μm-130mm, the soft drying temperature is 95 ℃, and the soft drying time is 1 min.
5. The method of claim 1, wherein in step (5), the etchant is alkaline TMAH developer.
6. The method according to claim 1, wherein in step (6), the specific process parameters of the dry etching are as follows: sputtering for 0.5-1 s, cooling at 25 ℃ for 3-5 min, sputtering for 0.5-1 s, cooling again for 3-5 min, and repeating the above steps until the thickness meets the requirement of 0.6 μm.
7. The method of claim 1, wherein in step (6), hydrofluoric acid is used for wet etching.
CN202010811184.5A 2020-08-13 2020-08-13 Method for realizing micro-nano graphical processing on polyimide film Pending CN112103636A (en)

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CN113215574A (en) * 2021-02-01 2021-08-06 南京大学 Wet etching method for quantum chip of sapphire substrate aluminum-plated film
CN114954876A (en) * 2022-05-20 2022-08-30 嘉兴学院 Bionic soft fish and preparation and driving method thereof

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113215574A (en) * 2021-02-01 2021-08-06 南京大学 Wet etching method for quantum chip of sapphire substrate aluminum-plated film
CN114954876A (en) * 2022-05-20 2022-08-30 嘉兴学院 Bionic soft fish and preparation and driving method thereof
CN114954876B (en) * 2022-05-20 2023-08-18 嘉兴学院 Preparation and driving method of bionic soft fish

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Application publication date: 20201218