CN115623851A - Flexible bendable piezoelectric oxide film and preparation method and application thereof - Google Patents

Flexible bendable piezoelectric oxide film and preparation method and application thereof Download PDF

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CN115623851A
CN115623851A CN202211336278.7A CN202211336278A CN115623851A CN 115623851 A CN115623851 A CN 115623851A CN 202211336278 A CN202211336278 A CN 202211336278A CN 115623851 A CN115623851 A CN 115623851A
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陈祖煌
邵俊达
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Shenzhen Graduate School Harbin Institute of Technology
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Abstract

The invention provides a flexible bendable piezoelectric oxide film and a preparation method and application thereof, wherein the preparation method comprises the following steps: step S1, preparing water-soluble strontium aluminate Sr 3 Al 2 O 6 Lead magnesium niobate-lead titanate solid solution target and SrTiO 3 A substrate; s2, adopting a laser pulse deposition mode to Sr strontium aluminate 3 Al 2 O 6 The target material is deposited on the substrate for the first time, and thenPerforming secondary deposition treatment on the lead magnesium niobate-lead titanate solid solution target to obtain a lead magnesium niobate-lead titanate film growing on the sacrificial layer; and S3, immersing the product obtained in the step S2 in water, and transferring the lead magnesium niobate-lead titanate film to a flexible substrate after the sacrificial layer is dissolved. The film obtained by the technical scheme of the invention has good flexibility, can eliminate the clamping effect of the substrate, and has ultrahigh dielectric, ferroelectric, piezoelectric and other electrical responses; and the preparation method is simple.

Description

Flexible bendable piezoelectric oxide film and preparation method and application thereof
Technical Field
The invention belongs to the technical field of piezoelectric materials, and particularly relates to a flexible bendable piezoelectric oxide film, and a preparation method and application thereof.
Background
The urgent need for the development of mems based on devices such as actuator structure and sensing toward smaller size, higher integration density, faster and stronger driving capability has promoted barium titanate (BaTiO) 3 BTO), lead zirconate titanate (PbZr) 1-x Ti x O 3 PZT), etc., which are sensitive to external field stimuli (electric field, pressure, temperature). The integration in flexible electronics in the form of flexible films has very important applications, such as flexible circuits, flexible sensing and wearable medical devices. The development of flexible devices with excellent performance requires that the piezoelectric film has an ultrahigh piezoelectric coefficient while ensuring good flexibility. However, the conventional method for manufacturing a flexible piezoelectric film is usually limited by the clamping effect of the substrate, or by factors such as forming an interface passivation layer, a schottky depletion layer, and a significant level of charge injection layer between the film and the electrode, which causes an order of magnitude degradation compared with bulk and single crystal electrical response. In contrast, based on the continuous search for ultrahigh voltage performance materials, focused ion beam/wet etching, organic precursors, laser etching, sacrificial layer construction, and the like are used to improve performance. The focused ion beam/wet etching reduces the interaction between the substrate and the film by transversely etching the film structure into an island-shaped structure or constructing a vacuum cavity structure by wet etching in the longitudinal direction so as to improve the performance; the organic precursor is added into the coating solution to form a macroscopic porous structure in the subsequent heat treatment process, so that the separation between the organic precursor and the substrate is realized; the laser etching refers to selecting laser with a certain specific wavelength positioned in band gap energy of the substrate and the piezoelectric film, so that an irradiation laser beam can penetrate through the substrate, and then locally evaporating an interface between the substrate and the film, thereby peeling the flexible piezoelectric film; constructing the sacrificial layer means growing a soluble sacrificial layer between the substrate and the film,for example, the LSMO sacrificial layer which is relatively matched with the perovskite structure piezoelectric film in lattice can be dissolved in potassium iodide (KI) solution under ultraviolet light, and finally the self-supporting flexible piezoelectric film is obtained.
In the existing method for preparing the flexible piezoelectric film by eliminating the substrate clamping effect, a film structure needs to be accurately analyzed and controlled based on a focused ion beam/wet etching method, along with the change of the thickness, the energy of the focused ion beam and the technological parameters of a vacuum cavity constructed by the wet etching method need to be continuously adjusted, so that the development potential of large-scale application of the flexible piezoelectric film is limited, and the piezoelectric film is not completely stripped, so that the performance is limited by the etching method. The organic precursor-based method has strict requirements on the heat treatment process due to the need of constructing a macroscopic porous structure, and meanwhile, the improvement of various electrical responses of the piezoelectric film has certain limitations due to certain interaction between the film and the substrate. The laser etching mode is relatively simple to operate, and the stripped flexible piezoelectric film cannot generate adverse effects such as performance decline and the like, but the method is not universal and can only be applied to stripping of specific substrates and films, such as the sapphire substrate with large band gap energy difference, the PZT film and laser with specific wavelength are selected for stripping; the method for constructing the soluble sacrificial layer based on laser pulse deposition is very friendly to the perovskite single crystal piezoelectric thin film, but the processing mode of the soluble sacrificial layer becomes a difficult problem which is always puzzled by people, such as the problem of pollution and corrosion caused by processing KI solution of the LSMO sacrificial layer.
Disclosure of Invention
Aiming at the technical problems, the invention discloses a flexible bendable piezoelectric oxide film, a preparation method and application thereof, and the obtained film can eliminate the clamping effect of a substrate while having good flexibility, has ultrahigh dielectric, ferroelectric, piezoelectric and other electrical responses, and can meet the requirements of development in the fields of self-voltage-supply electric sensors, micro implantable medical equipment and the like.
In contrast, the technical scheme adopted by the invention is as follows:
a preparation method of a flexible bendable piezoelectric oxide film comprises the following steps:
step S1, preparing water-soluble strontium aluminate Sr 3 Al 2 O 6 Lead magnesium niobate-lead titanate solid solution target and substrate; wherein the lead magnesium niobate-lead titanate solid solution is 0.68Pb (Mg) 1/3 Nb 2/3 )O 3 -0.32PbTiO 3 Abbreviated as 0.68PMN-0.32PT; further, the substrate is SrTiO 3 A substrate.
S2, adopting a laser pulse deposition mode to Sr strontium aluminate 3 Al 2 O 6 Performing a first deposition treatment on the (SAO) target material on the substrate, strontium aluminate Sr 3 Al 2 O 6 The deposition thickness of the target is not less than 20nm; then carrying out secondary deposition treatment on the lead magnesium niobate-lead titanate solid solution target to obtain a lead magnesium niobate-lead titanate film growing on the sacrificial layer;
and S3, immersing the product obtained in the step S2 in water, and transferring the lead magnesium niobate-lead titanate film to a flexible substrate after the sacrificial layer is dissolved.
By adopting the technical scheme, strontium aluminate Sr is utilized 3 Al 2 O 6 Is used as a sacrificial layer, and strontium aluminate Sr is deposited by laser pulse 3 Al 2 O 6 Depositing and growing on the substrate, and then depositing lead magnesium niobate-lead titanate on the sacrificial layer; the piezoelectric oxide film can be transferred to the flexible substrate PDMS by dissolving the sacrificial layer through bubble water treatment, the preparation method is simple, and most importantly, the prepared single-crystal piezoelectric oxide film realizes high-quality epitaxial growth, maintains the stability of phase and orientation after transfer, and eliminates the clamping effect of the substrate while having good flexibility. Meanwhile, the film has an atomic-level smooth surface, and the roughness rms of the film can be as low as 400pm.
As a further improvement of the invention, in step S2, strontium aluminate Sr is added 3 Al 2 O 6 The conditions for the first deposition treatment of the target material on the substrate are as follows: the temperature of the substrate is 700 to 800 ℃, the oxygen pressure of the reaction cavity is 2 to 3Pa, and the laser energy density is 1.3 to 1.5J/cm 2 The pulse frequency is 2-4Hz. Further, in step S2, aluminum is addedStrontium acid Sr 3 Al 2 O 6 The conditions for the first deposition treatment of the target material on the substrate are as follows: the temperature of the substrate is 750 ℃, the oxygen pressure of the reaction cavity is 2.5Pa, and the laser energy density is 1.4J/cm 2 The pulse frequency is 3Hz, and the sputtering time is 30min;
as a further improvement of the present invention, in step S2, the conditions for performing the second deposition treatment on the lead magnesium niobate-lead titanate solid solution target material are as follows: the temperature of the substrate is 520 to 550 ℃, the oxygen pressure of the reaction cavity is 25 to 29Pa, and the laser energy density is 0.9 to 1.1J/cm 2 The pulse frequency is 4-6Hz. Further, in step S2, the conditions for performing the second deposition process on the 0.68PMN-0.32PT target are as follows: the temperature of the substrate is 525 ℃, the oxygen pressure of the reaction cavity is 27Pa, and the laser energy density is 1J/cm 2 The pulse frequency is 5Hz; the sputtering time was 120min.
As a further improvement of the invention, the second deposition process is completed at 10 4 Annealing is carried out under the Pa oxygen pressure, the temperature of the annealing is 520 to 550 ℃, and the time of the annealing is 5 to 15min.
As a further improvement of the present invention, in step S3, the flexible substrate is PDMS.
As a further improvement of the invention, in step S1, the substrate is (001) -oriented SrTiO 3
As a further improvement of the present invention, in step S1, the substrate is cleaned and dried before use. Further, srTiO 3 The single crystal is sequentially placed in acetone, ethanol and deionized water for ultrasonic washing, and then is placed in a nitrogen atmosphere for drying.
The invention also discloses a flexible bendable piezoelectric oxide film which is prepared by the preparation method of the flexible bendable piezoelectric oxide film.
As a further improvement of the invention, the roughness rms of the flexible bendable piezoelectric oxide thin film is not more than 700pm and can be as low as 400pm.
The invention also discloses application of the flexible bendable piezoelectric oxide film, which is used for self-powered voltage electric sensing devices and micro implantable medical equipment.
Compared with the prior art, the invention has the beneficial effects that:
firstly, the technical scheme of the invention selects a relaxation ferroelectric oxide single crystal film PMN-0.32PT with ultrahigh electrical response near a morphotropic phase boundary as a core material for energy supply of a flexible hybrid electronic system, and solves the problem of energy supply of continuous operation of a wearable portable flexible electronic device; the defect that the multi-principal-element characteristic of the material is difficult to prepare can be effectively overcome by a laser pulse deposition mode; the preparation method of the self-supporting flexible piezoelectric thin film is that the single crystal thin film is epitaxially grown on the water-soluble sacrificial layer and then the self-supporting flexible piezoelectric thin film is obtained by peeling, so that the obtained flexible thin film has high performance and good quality, has good flexibility, eliminates the clamping effect of a substrate, and has ultrahigh dielectric, ferroelectric, piezoelectric and other electrical responses.
Secondly, the preparation process of the technical scheme of the invention is simple, and the defects of complex preparation process, high cost, easiness in damage, difficulty in large-scale production, environmental pollution caused by etching waste liquid and the like of the traditional flexible piezoelectric film are avoided. The preparation method can simplify the preparation process of the flexible piezoelectric film, save the cost, is favorable for improving the quality of the flexible film and lays a foundation for the large-scale production of the flexible piezoelectric oxide film.
Drawings
FIG. 1 is a comparative XRD plot of a piezoelectric oxide film of example 1 of the present invention before and after transfer to PDMS.
Fig. 2 is a result of measuring the roughness of the piezoelectric oxide thin film of example 1 of the present invention.
FIG. 3 is a graph comparing ferroelectric polarization curves of the piezoelectric oxide thin film of example 1 of the present invention before and after transfer to PDMS.
FIG. 4 shows the results of measurements of dielectric constant of the piezoelectric oxide thin film of example 1 of the present invention under different DC biases before and after transfer to PDMS.
FIG. 5 shows SrTiO thin films oriented at (001) orientation for piezoelectric oxide thin films according to example 1 of the present invention 3 And (3) testing the dielectric constant frequency dependence under different direct current background bias voltages on the substrate.
Fig. 6 is a test result of the frequency dependence of the dielectric constant of the piezoelectric oxide thin film of example 1 of the present invention under different dc background bias transferred to PDMS.
FIG. 7 shows SrTiO films oriented at (001) orientation for piezoelectric oxide thin films according to example 1 of the present invention 3 The results of the Rayleigh analysis at a series of different dc bias voltages on the substrate.
FIG. 8 shows the results of Rayleigh analysis of the piezoelectric oxide thin film of example 1 of the present invention under a series of different DC biases transferred to PDMS.
Fig. 9 is the open circuit voltage test results of the flexible device of example 2 of the present invention under manual bending.
Fig. 10 is a test result of short circuit current of the flexible device of example 2 of the present invention under manual bending.
FIG. 11 is an optical micrograph of piezoelectric oxide thin films transferred onto a PDMS substrate using sacrificial layers of different thicknesses according to example 1 and comparative example 1 of the present invention; wherein (a) is the film of comparative example 1 and (b) is the film of example 1.
Fig. 12 is an XRD pattern of the piezoelectric oxide thin film of comparative example 2 of the present invention before transfer to PDMS.
Detailed Description
Preferred embodiments of the present invention are described in further detail below.
Example 1
A preparation method of a flexible bendable piezoelectric oxide film comprises the following steps:
step S1, pre-burning to prepare water-soluble strontium aluminate Sr 3 Al 2 O 6 0.68PMN-0.32PT solid solution of lead magnesium niobate-lead titanate; using SrTiO 3 The substrate was cleaned and dried, and then used. Wherein strontium aluminate Sr 3 Al 2 O 6 The firing of lead magnesium niobate-lead titanate solid solution 0.68PMN-0.32PT adopts the prior art.
S2, adopting a laser pulse deposition mode to Sr strontium aluminate 3 Al 2 O 6 The target material is deposited on the substrate for the first time, and then the 0.68PMN-0.32PT target material is subjected to the second deposition treatmentPerforming secondary deposition treatment to obtain a lead magnesium niobate-lead titanate film growing on the sacrificial layer;
the conditions of the first deposition treatment were: the temperature of the substrate is 750 ℃, the oxygen pressure of the reaction cavity is 2.5Pa, and the laser energy density is 1.4J/cm 2 The pulse frequency is 3Hz, and the sputtering time is 30min; the deposition thickness is 20nm;
the conditions of the second deposition treatment are as follows: the temperature of the substrate is 525 ℃, the oxygen pressure of the reaction cavity is 27Pa, and the laser energy density is 1J/cm 2 The pulse frequency is 5Hz; the sputtering time was 120min.
After the second deposition treatment is finished, it is unified at 10 4 Annealing under Pa oxygen pressure, wherein the temperature of the annealing is 500 to 550 ℃, and the time of the annealing is 5 to 15min.
And S3, immersing the product obtained in the step S2 in water, and transferring the lead magnesium niobate-lead titanate film to a flexible substrate PDMS after the sacrificial layer is dissolved, so as to obtain the flexible bendable piezoelectric oxide film.
The prepared single crystal piezoelectric oxide film realizes high-quality epitaxial growth, and maintains the stability of phase and orientation after transfer. Meanwhile, the film has an atomic-level smooth surface, and the roughness rms of the film can be as low as 400pm.
XRD before and after the transfer of the flexible piezoelectric oxide thin film prepared in this example is shown in fig. 1, and it can be seen that the prepared single crystal piezoelectric oxide thin film realizes high-quality epitaxial growth and maintains stability of phase and orientation after the transfer. As shown in FIG. 2, the picture of the surface roughness detection of the flexible piezoelectric oxide film shows that the film has an atomically smooth surface, and the rms of the roughness of the film can be as low as 400pm.
The comparison graph of the polarization curves of the ferroelectrics of the piezoelectric oxide film prepared in the embodiment before and after being transferred to PDMS is shown in FIG. 3, and it can be seen that the prepared flexible piezoelectric oxide film can still maintain the typical ferroelectric polarization curve shape of the relaxor, and the saturation polarization intensity of the flexible piezoelectric oxide film is only 37 μ C/cm before and after being peeled off under the electric field of 600 kV/cm 2 To 34. Mu.C/cm 2 Meanwhile, the horizontal offset of the polarization curve is only 40 kV/cm. The press prepared in this exampleThe results of the dielectric constant measurements of the electrical oxide film at different dc biases before and after transfer to PDMS are shown in fig. 4, which produced a significant increase in dielectric constant at 1 kHz, from 1027 to 1391, indicating that the effects from substrate clamping have been largely eliminated.
Meanwhile, the intercept of the dielectric constant frequency dependence under a series of DC biases is plotted with the DC bias according to Rayleigh's law, and the result is shown in FIGS. 5-8, and it can be seen that the intercept α i of the high field region is promoted from 727.95 ± 12.14 to 1100.61 ± 11.83. This further illustrates that the significantly improved electrical response of the fabricated flexible piezoelectric oxide film results from the elimination of the contribution of substrate clamping.
Example 2
By combining magnetron sputtering, 10 pairs of interdigital electrodes with finger length of 4.7 mm, finger width of 200 μm and finger pitch of 200 μm are deposited on the surface of the flexible bendable piezoelectric oxide thin film transferred to PDMS obtained in this example 1, and then PET is used for coating and packaging to prepare a flexible device, and the open-circuit voltage and the short-circuit current of the flexible device measured under manual bending are shown in fig. 9-10. During the bending cycle, the voltage and current output were sufficiently stable, indicating good flexibility of the prepared film. The open-circuit voltage and the short-circuit current of the flexible thin film device of 10mm-10mm can reach 6V and 20 nA respectively, and the calculated current density can reach 71.31 muA/cm 2 The energy density exceeds 100 mW/cm 2 The value is far larger than that of the ultrathin piezoelectric layer prepared based on BTO, znO, PVDF and other systems reported in the prior literature.
It can be seen that the piezoelectric oxide thin film prepared in example 1 can also have good flexibility and ultra-high piezoelectric properties in practical applications.
The technical scheme of the embodiment selects a perovskite type relaxor ferroelectric solid solution lead magnesium niobate-lead titanate (0.68 Pb (Mg) 1/3 Nb 2/3 )O 3 -0.32 PbTiO 3 0.68PMN-0.32 PT) was used to make bendable piezoelectric oxide films due to different valence states of Mg 2+ And Nb 5+ Occupy the same position, therefore, the chemical structure and the composition are not uniformly distributed, and huge electrical response can be shownShould be used. The cubic symmetry relaxor PMN and the tetragonal symmetry piezoelectric PbTiO 3 (PTO) composition of PMN-xPT solid solution, which can increase the characteristic temperature Tm to room temperature and stabilize the phase type after cooling when the PTO content reaches more than 10%. An almost vertical Morphotropic Phase Boundary (MPBs) is generated near the x = 0.32-0.35 component, and the ultra-high ferroelectric, dielectric and piezoelectric properties are expressed, wherein the piezoelectric coefficient is 3~5 times, 10-20 times of BTO and 60-90 times of ZnO near the MPB component of PZT. However, current research on single crystal flexible piezoelectric oxide thin films with stronger electrical response compared to polycrystalline and high polymer films has focused mainly on PZT and BTO systems due to their multi-principal element characteristics, which lead to difficulty in fabrication. Therefore, the prepared monocrystal flexible piezoelectric PMN-xPT film can provide huge application potential in the field of flexible mixed electronics.
Comparative example 1
On the basis of example 1, in this comparative example, a sacrificial layer of strontium aluminate Sr was deposited 3 Al 2 O 6 The thickness of (2) was 10nm, and the rest was the same as in example 1. Comparing the flexible piezoelectric oxide thin films transferred onto the PDMS substrate of example 1 and comparative example 1 under an optical microscope, it can be seen that the sample of comparative example 1 with 10nm strontium aluminate generates more cracks, while the sacrificial layer of example 1 with thickness of 20nm flattens the surface of the flexible thin film and the cracks disappear completely, as shown in fig. 11.
Comparative example 2
In this comparative example, the deposition temperature of the 0.68PMN-0.32PT target material for the second deposition treatment was 500 ℃ based on example 1, and the rest was the same as example 1. The XRD test results of this comparative example before transfer to the flexible substrate are shown in fig. 12, and it can be seen that a distinct pyrochlore phase appears in the vicinity of 35 ° in comparative example 2.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, numerous simple deductions or substitutions may be made without departing from the spirit of the invention, which shall be deemed to belong to the scope of the invention.

Claims (10)

1. A preparation method of a flexible bendable piezoelectric oxide film is characterized by comprising the following steps: the method comprises the following steps:
step S1, preparing water-soluble strontium aluminate Sr 3 Al 2 O 6 Lead magnesium niobate-lead titanate solid solution target and substrate; the lead magnesium niobate-lead titanate solid solution is 0.68Pb (Mg) 1/3 Nb 2/3 )O 3 -0.32PbTiO 3
S2, adopting a laser pulse deposition mode to Sr strontium aluminate 3 Al 2 O 6 The target material is deposited on the substrate for the first time, and strontium aluminate Sr is formed 3 Al 2 O 6 Is not less than 20nm; then carrying out secondary deposition treatment on the lead magnesium niobate-lead titanate solid solution target to obtain a lead magnesium niobate-lead titanate film growing on the sacrificial layer;
and S3, immersing the product obtained in the step S2 in water, and transferring the lead magnesium niobate-lead titanate film to a flexible substrate after the sacrificial layer is dissolved.
2. The method for preparing a flexible bendable piezoelectric oxide thin film according to claim 1, characterized in that: in step S2, strontium aluminate Sr is added 3 Al 2 O 6 The conditions for the first deposition treatment of the target material on the substrate are as follows: the temperature of the substrate is 700 to 800 ℃, the oxygen pressure of the reaction cavity is 2 to 3Pa, and the laser energy density is 1.3 to 1.5J/cm 2 The pulse frequency is 2-4Hz.
3. The method for preparing a flexible bendable piezoelectric oxide thin film according to claim 2, characterized in that: in step S2, the conditions for performing the second deposition treatment on the lead magnesium niobate-lead titanate solid solution target are as follows: the temperature of the substrate is 520 to 550 ℃, the oxygen pressure of the reaction cavity is 25 to 29Pa, and the laser energy density is 0.9 to 1.1J/cm 2 The pulse frequency is 4-6Hz.
4. Method for preparing a flexible bendable piezoelectric oxide thin film according to claim 3The method is characterized in that: in step S2, strontium aluminate Sr is added 3 Al 2 O 6 The conditions for the first deposition treatment of the target material on the substrate are as follows: the temperature of the substrate is 750 ℃, the oxygen pressure of the reaction cavity is 2.5Pa, and the laser energy density is 1.4J/cm 2 The pulse frequency is 3Hz, and the sputtering time is 30min;
in step S2, the conditions for the second deposition treatment of the 0.68PMN-0.32PT target material are as follows: the temperature of the substrate is 525 ℃, the oxygen pressure of the reaction cavity is 27Pa, and the laser energy density is 1J/cm 2 The pulse frequency is 5Hz; the sputtering time was 120min.
5. The method for preparing a flexible bendable piezoelectric oxide thin film according to claim 4, characterized in that: after the second deposition process is completed, at 10 4 Annealing is carried out under the Pa oxygen pressure, the temperature of the annealing is 520 to 550 ℃, and the time of the annealing is 5 to 15min.
6. The method of making a flexible, bendable piezoelectric oxide film of any of claims 1~5, wherein: in step S3, the flexible substrate is PDMS.
7. The method of preparing a flexible bendable piezoelectric oxide film according to claim 6, characterized in that: in step S1, the substrate is (001) -oriented SrTiO 3
8. A flexible bendable piezoelectric oxide film characterized by: the flexible bendable piezoelectric oxide film is prepared by the method as claimed in any one of claims 1~7.
9. A flexible bendable piezoelectric oxide film according to claim 8, characterized in that: the roughness rms is not greater than 700pm.
10. Use of a flexible bendable piezoelectric oxide film according to claim 8, characterized in that: it is used in self-powered voltage sensing devices, micro implantable medical devices.
CN202211336278.7A 2022-10-28 2022-10-28 Flexible bendable piezoelectric oxide film and preparation method and application thereof Pending CN115623851A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117604461A (en) * 2023-11-29 2024-02-27 成光新材料科技(无锡)有限公司 Preparation method of epitaxial pleated film

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117604461A (en) * 2023-11-29 2024-02-27 成光新材料科技(无锡)有限公司 Preparation method of epitaxial pleated film

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