CN108493338B - Malleable buckling structure organic thin film functional device and preparation method thereof - Google Patents
Malleable buckling structure organic thin film functional device and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an organic thin film functional device with a ductile buckling structure and a preparation method thereof. The preparation method comprises the following steps: (1) preparing PVA and organic functional layer solution; (2) preparing a sacrificial layer; (3) preparing a bottom layer electrode; (4) preparing an organic functional layer; (5) preparing a top electrode; (6) micro-processing a device; (7) stripping the device; (8) and (4) transferring and unloading. The PVA is used as a sacrificial layer, and the flexibility (period and amplitude) of the film can be regulated and controlled by controlling the pre-stretching of the flexible substrate in the transfer printing process, so that the device realizes the functionality of the organic film and has extensibility. PVA can be dissolved by water as a sacrificial layer to realize transfer printing of the device, is non-toxic, harmless and lossless, is simple to operate, does not need expensive special equipment, greatly reduces the cost and is environment-friendly.
Description
Technical Field
The invention relates to the field of flexible electronics, in particular to an extensible buckling structure organic thin film functional device and a preparation method thereof.
Background
The flexible electronic device has very wide application prospects in various fields of biomedicine, war industry and space, information energy and the like due to unique bending, stretching and folding characteristics, such as wearable electronic equipment, electronic skin health monitoring, flexible solar cells and the like. Research and investigation show that at present, functional units of flexible electronic products are based on inorganic materials, such as a flexible PZT energy collector prepared by a Von snow group and capable of collecting energy integrated on biological tissues, a flexible inorganic semiconductor light emitting diode array prepared by a Juejun Hu group, a complete detector (artificial compound eye, artificial retina) prepared on a flexible substrate and the like. However, the following disadvantages of the inorganic flexible electronic device are difficult to overcome: the inherent rigidity of the inorganic material structure makes the inorganic material inevitably easy to break and damage in the bending and stretching process, the device is easy to damage and the preparation difficulty is increased; inorganic materials generally require an annealing temperature of 600 to 1000 ℃ or even higher, cannot be directly integrated on a flexible substrate, and need to be processed through a series of fine processing methods: such as sputtering, high-precision photoetching, wet etching, dry etching and the like, the processing process is complex, the cost is high, the used reagent has certain danger, and the environment is also greatly burdened. Therefore, there are still many problems to be solved in inorganic flexible devices, and the use of organic materials instead of inorganic functional layers is a straightforward and feasible solution.
The organic polymer has good flexibility, is better combined with a flexible substrate, has lower annealing temperature and safer and more convenient processing method. However, most of the flexible organic devices in the present stage are directly prepared on flexible substrates such as PET, PC, parylene, polyimide, etc., and the devices are limited to the substrate to a great extent, i.e. only can be bent, which greatly limits the application range. If true ductile and twistable properties are to be achieved, extremely complicated peeling and transfer steps must be performed, which is as difficult and dangerous as the preparation of inorganic flexible devices. The method needs higher process technology, has narrower application range and high cost. Meanwhile, the multi-layer composite film functional device has a huge development prospect due to the remarkable multifunctional characteristic, however, different microstructure processing technologies are often required for layers in the composite film, so that the etching processing and transfer printing of the composite film still face huge challenges.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides an extensible buckling structure organic thin film functional device and a preparation method thereof.
The invention is realized by the following technical scheme:
the organic thin film functional device with the extensible buckling structure is of a three-layer structure, wherein the top layer is an Au electrode, the middle layer is an organic functional layer, and the bottom layer is an Au electrode. The organic functional layer can be various organic layers according to application requirements, and is preferably P3HT/PVDF-TrFE, P3HT or PVDF-TrFE-CFE.
The preparation method of the organic thin film functional device with the ductile buckling structure comprises the following steps:
(1) solution preparation: preparing PVA and organic functional layer solution;
(2) preparing a sacrificial layer: preparing a PVA layer on a clean glass substrate by using a spin coating method, wherein the spin coating speed is 1000-3000 r/min, and the time is 90-180 s, so that the thickness of the PVA layer is controlled to be 200-400 nm. When the thickness is thin, the PVA film is discontinuous or the transverse dissolution rate of the PVA film is limited, and the subsequent process cannot be carried out; when the thickness is thicker, the surface flatness is too poor, which is not beneficial to the preparation of subsequent metal and functional layers, and when the sacrificial layer is removed in subsequent water bath, PVA has a certain residue, which affects the performance of the device;
(3) preparing a bottom layer electrode, namely evaporating Au electrodes with different patterns on a PVA film according to the requirements of devices by using a thermal evaporation method at the evaporation rate of 0.4-0.5 Å/s, wherein the thickness of the Au electrode is 40-60 nm, the Au electrode is not conducted and is easy to break when being too thin, and folds can be generated and precious metal materials are wasted in the buckling or subsequent extension process when being too thick;
(4) preparing an organic functional layer: according to application requirements, a functional layer of the machine is coated on the Au electrode on the bottom layer in a spinning mode, and the functional layer of the machine is subjected to heat treatment;
(5) preparing a top electrode: preparing a 40-60 nm Au top layer electrode on the organic functional layer by using a thermal evaporation method to obtain a complete organic thin film functional device;
(6) micro-processing of a device: fixing the organic thin film functional device on a working platform of a high-precision displacement platform, controlling the platform to move along an X axis through a high-precision stepping motor, cutting in a Y axis direction by using a glass cutter, and processing the organic thin film functional device into a required structure;
(7) and (3) stripping the device: attaching PDMS on the effective position of the organic thin film functional device, and soaking the PDMS in ultra-pure water at the temperature of 90-95 ℃; calculated according to the effective area, the soaking time is 12h/cm2Preferably (i.e. having a 1 cm)2The device with effective pattern area needs to be soaked for 12 h). The PVA sacrificial layer is fully dissolved, and finally the organic film functional device adhered with the PDMS is separated from the glass substrate;
(8) transfer printing: irradiating the prestretched flexible substrate Ecoflex for 6-15 minutes by using ultraviolet light, transferring the organic thin film functional device onto the Ecoflex, leading out an electrode, and unloading to obtain the extensible organic thin film functional device with the buckling structure.
Compared with the prior art, the invention has the following beneficial effects:
1. the PVA is used as a sacrificial layer, and the flexibility (period and amplitude) of the film can be regulated and controlled by controlling the pre-stretching of the flexible substrate in the transfer printing process, so that the device realizes the functionality of the organic film and has extensibility.
2. The PVA is used as a sacrificial layer, can be dissolved by water to realize transfer printing of the device, is non-toxic, harmless and harmless, is simple to operate, does not need expensive special equipment, greatly reduces the cost and is environment-friendly. The microstructure processing technology avoids complex operations such as photoetching and etching in the traditional preparation technology, avoids using dangerous chemical reagents and operations, and has the characteristics of environmental protection and safety.
3. The preparation method of the invention does not depend on the middle functional layer, and can be implemented only by the characteristic of the functional layer which can reach the preparation condition (insoluble in water and stable within 100 ℃) no matter the functional layer is a single-layer film or a multi-layer composite film.
4. The processing device for the organic film microstructure, which is constructed by using the high-precision electric displacement table and the T-shaped glass cutting table, can process the PVA sacrificial layer, the organic functional layer and the corresponding electrode layer into required structures, and the processing precision can reach the micron order.
Drawings
FIG. 1 is a flow chart of a method for manufacturing a flexible structure extensible organic thin film functional device according to the present invention;
FIG. 2 is an SEM topography of a flexible device obtained in example 2 of the present invention;
FIG. 3 shows the tensile condition I of the flexible memory obtained in example 1 of the present inventiondsA response curve;
FIG. 4 shows the data I of the flexible memory obtained in example 1 of the present invention under illuminationdsA response curve;
FIG. 5 shows the different gate voltages I of the flexible memory obtained in example 1 of the present inventiondsA response curve.
Detailed Description
Example 1:
preparing PVA sacrificial layer with thickness of 300 nm on a clean glass substrate by a spin coating method, wherein spin coating parameters comprise rotating speed of 2000r/min and time of 90 s.A mask plate is placed on a PVA film, 50 nmAu source/drain electrodes are evaporated by a thermal evaporation method, the evaporation rate is 0.4 Å/s.A functional layer is spin coated, a layer of P3HT is spin coated, the spin coating parameters comprise rotating speed of 1000 r/min, time of 30 s and drying at 60 ℃ for 1 h, then a layer of PVDF-TrFE is spin coated, the spin coating parameters comprise rotating speed of 1000 r/min, time of 90 s and drying for 10 min, and a 50 nm Au gate electrode is further vapor coated on a composite film, so that the device is prepared.
Example 2:
preparing PVA and PVDF-TrFE solution, preparing a PVA sacrificial layer with the thickness of 400 nm on a clean glass substrate by a spin-coating method, wherein the spin-coating parameters comprise the rotation speed of 1500 r/min and the time of 180 s, the thermal evaporation method is adopted, the evaporation speed is 0.5 Å/s, an Au electrode with the thickness of 40 nm is evaporated on a PVA film, then a PVDF-TrFE functional layer is spin-coated, the spin-coating parameters comprise the rotation speed of 3000r/min, the time of 90 s and the drying time of 60 ℃ for 10 min, the device is fixed on a panel of a precision electric displacement table, the device is moved to a proper position by a controller, the device is moved by a high-precision stepper motor, a glass cutter is used for cutting line segments with equal distance on the film, the attached PDMS is soaked in pure water at the temperature of 92 ℃ for 60 h, the PVA sacrificial layer is fully dissolved, the film adhered on the PDMS is separated from the glass substrate, the pre-stretched Ecoflex is irradiated by ultraviolet, the separated film is transferred to the Ecoflex, and finally the bottom electrode is led out from an oven at the temperature of 120 ℃ for 2.
Example 3:
preparing PVA and P3HT solution, preparing a PVA sacrificial layer with the thickness of 200 nm on a clean glass substrate by a spin coating method, wherein the spin coating parameters comprise the rotation speed of 4000 r/min and the time of 90 s, then spin coating a P3HT functional layer, the spin coating parameters comprise the rotation speed of 2000r/min, the time of 30 s and the drying time of 60 ℃ for 10 min, the evaporation rate of 0.3 Å/s is adopted by a thermal evaporation method, an Au circular electrode with the thickness of 60 nm and the diameter of 0.3 mm is evaporated on the PVA film on which a mask plate is placed, then the device is fixed on a panel of a precision electric displacement table, the device is controlled to move by a controller, the film is evenly divided into 4 small parts by a glass cutter, the PDMS is respectively attached, then the PDMS is soaked in pure water at the temperature of 90 ℃ for 12h, the PVA sacrificial layer is fully dissolved, the film adhered on the PDMS is separated from the glass substrate, the Ecoflex is irradiated by ultraviolet, the pre-stretched Ecoflex, then the separated film is transferred to the Ecoflex, and finally, the.
Example 4:
preparing PVA and PVDF-TrFE-CFE solution, preparing a PVA sacrificial layer with the thickness of 300 nm on a clean glass substrate by a spin coating method, wherein the spin coating parameters comprise the rotation speed of 2000r/min and the time of 180 s, an Au electrode with the thickness of 40 nm is evaporated on a PVA film by a thermal evaporation method, the evaporation rate is 0.5 Å/s, then a PVDF-TrFE-CFE functional layer is spin coated, the spin coating parameters comprise the rotation speed of 3000r/min, the time of 90 s and the drying time of 60 ℃ for 10 min, then the device is fixed on a panel of a precise electric displacement table, the device is controlled to move by a controller, a glass cutter is used for cutting line segments with equal distances on the film, the PDMS is attached, then the PDMS is soaked in pure water with the temperature of 90 ℃ for 48 h, the PVA sacrificial layer is fully dissolved, the film adhered on the PDMS is separated from the glass substrate, the Ecoflex pre-stretched by ultraviolet irradiation is transferred onto the Ecoflex, a bottom electrode is extracted, and finally, the Ecoflex is annealed in an oven with the temperature of 120 ℃.
Claims (1)
1. A malleable buckling structure organic thin film functional device is characterized in that the device is of a three-layer structure, the top layer is an Au electrode, the middle layer is an organic functional layer, and the bottom layer is an Au electrode;
the organic functional layer is P3HT/PVDF-TrFE, P3HT or PVDF-TrFE-CFE;
the preparation method comprises the following steps:
(1) solution preparation: preparing PVA and organic functional layer solution;
(2) preparing a sacrificial layer: preparing a PVA layer on a clean glass substrate by using a spin coating method, wherein the spin coating speed is 1000-3000 r/min, and the time is 90-180 s, so that the thickness of the PVA layer is controlled to be 200-400 nm;
(3) preparing a bottom layer electrode, namely evaporating an Au electrode with different patterns on the PVA film layer according to the requirement of a device by using a thermal evaporation method at the evaporation rate of 0.4-0.5 Å/s, wherein the thickness of the Au electrode is 40-60 nm;
(4) preparing an organic functional layer: according to application requirements, a corresponding organic functional layer is spin-coated on the bottom Au electrode, and the organic functional layer is subjected to heat treatment;
(5) preparing a top electrode: preparing a 40-60 nm Au top layer electrode on the organic functional layer by using a thermal evaporation method to obtain a complete organic thin film functional device;
(6) micro-processing of a device: fixing the organic thin film functional device on a working platform of a high-precision displacement platform, controlling the platform to move along an X axis through a high-precision stepping motor, cutting in a Y axis direction by using a glass cutter, and processing the organic thin film functional device into a required structure;
(7) and (3) stripping the device: attaching PDMS on the effective position of the organic thin film functional device, and soaking the PDMS in ultra-pure water at the temperature of 90-95 ℃; the PVA sacrificial layer is fully dissolved, and finally the organic film functional device adhered with the PDMS is separated from the glass substrate;
(8) transfer printing: irradiating the prestretched flexible substrate Ecoflex for 6-15 minutes by using ultraviolet light, transferring the organic thin film functional device onto the Ecoflex, leading out an electrode, and unloading to obtain the extensible organic thin film functional device with the buckling structure.
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| CN109285946A (en) * | 2018-11-19 | 2019-01-29 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of the transferable electronic device of flexibility |
| CN110251281B (en) * | 2019-06-24 | 2020-08-18 | 华中科技大学 | Preparation method of flexible electronic skin and product thereof |
| CN110620166A (en) * | 2019-08-26 | 2019-12-27 | 合肥工业大学 | Method for preparing ultra-flexible optical detector on neutral plane with zero stress |
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| CN101120433A (en) * | 2004-06-04 | 2008-02-06 | 伊利诺伊大学评议会 | Methods and devices for fabricating and assembling printable semiconductor elements |
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