CN113371703A - Graphene-improved silicon integrated energy storage thin film and preparation method thereof - Google Patents
Graphene-improved silicon integrated energy storage thin film and preparation method thereof Download PDFInfo
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- 239000010703 silicon Substances 0.000 title claims abstract description 106
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- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/194—After-treatment
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/08—Oxides
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- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
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- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
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Abstract
The invention discloses a graphene-improved silicon integrated energy storage film and a preparation method thereof, wherein the graphene-improved silicon integrated energy storage film comprises a silicon substrate, a graphene layer and an energy storage film layer, wherein the graphene layer is arranged between the silicon substrate and the energy storage film layer; the preparation method comprises the following steps: and transferring copper-based graphene to the surface of the silicon substrate by adopting a conventional wet transfer method, and then preparing one or more energy storage thin film layers on the surface of the graphene to obtain the graphene-improved silicon integrated energy storage thin film. The graphene layer is additionally arranged in the silicon integrated energy storage film, Van der Waals epitaxy of the energy storage film is carried out on the surface of the graphene, and the graphene layer is used for preventing silicon elements from diffusing so as to improve the crystallization quality of the energy storage film; meanwhile, the excellent thermal conductivity of the graphene layer is utilized, the heat dissipation of the energy storage film is enhanced, and thermal runaway is effectively avoided, so that the energy storage density of the energy storage film is remarkably improved, and the application of the energy storage film in a high-temperature environment is facilitated.
Description
Technical Field
The invention relates to the field of energy storage thin film materials, in particular to a graphene-improved silicon integrated energy storage thin film and a preparation method thereof.
Background
The dielectric energy storage film has the characteristics of high energy storage density, high charging and discharging speed, integration and the like, and shows obvious advantages in the energy storage application of integrated circuits. However, most dielectric films and silicon substrates cannot be grown with high crystal quality due to lattice mismatch. It is necessary to optimize the crystallization quality of the silicon integrated energy storage thin film to improve the energy storage performance of the thin film.
In recent years, with the trend of portability and multi-functionalization of electronic devices, the integration level, power density and junction temperature of integrated circuits are increasing. Under high temperature and high electric field, the leakage current of the dielectric energy storage film is increased sharply, and energy loss caused by the leakage current further causes local temperature rise inside the film material, so that the energy storage performance is greatly reduced, and even the dielectric material is broken down, namely the dielectric material is out of control thermally at high temperature. Therefore, the energy storage characteristics and reliability of the silicon integrated dielectric energy storage film at high temperature are in need of improvement. The conventional method for optimizing the dielectric energy storage film is usually realized by doping modification of a dielectric material or design of a multilayer dielectric film, and in view of the disclosed technical means, no optimization strategy for dealing with the thermal runaway problem exists, and for the problem, the high-temperature energy storage performance of the dielectric energy storage film still has a room for improvement.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a silicon integrated energy storage film improved by graphene and a preparation method thereof; the invention is applied to a semiconductor integrated circuit, and can effectively improve the energy storage density of the silicon integrated energy storage film at high temperature.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the utility model provides a silicon integrated energy storage film of graphite alkene improvement, includes silicon substrate, graphite alkene layer and energy storage film layer, and graphite alkene layer sets up in the silicon substrate surface, and the energy storage film layer sets up on graphite alkene layer surface.
Preferably, the graphene layer is single-layer graphene or multi-layer graphene.
Preferably, in the graphene layer, the number of graphene layers is 1-10.
Preferably, the energy storage thin film is one or more of a ferroelectric thin film, a relaxor ferroelectric thin film and an antiferroelectric thin film, and the energy storage thin film layer is a single-layer energy storage thin film or a multi-layer energy storage thin film.
Preferably, the thickness of the energy storage thin film is 10-1000 nm.
Preferably, the energy storage film is 0.85BaTiO3-0.15Bi(Mg0.5Zr0.5)O3A film.
Preferably, the silicon substrate is semiconductor silicon.
Preferably, the silicon substrate is a P-type (100) silicon wafer doped with boron element.
The invention also provides a preparation method of the graphene-improved silicon integrated energy storage film, which comprises the following steps:
transferring the graphene layer to the surface of a silicon substrate, and then cleaning and drying;
and preparing an energy storage thin film layer on the surface of the graphene layer, then annealing, and obtaining the graphene-improved silicon integrated energy storage thin film after the annealing is finished.
Preferably, the preparation method of the graphene-modified silicon integrated energy storage thin film further comprises pretreatment of a silicon substrate, and the pretreatment process of the silicon substrate comprises: ultrasonically cleaning the cut silicon substrate by using acetone, absolute ethyl alcohol and deionized water in sequence, and blow-drying by using high-pressure nitrogen after cleaning to remove impurities on the surface of the substrate; placing the cleaned silicon substrate in absolute ethyl alcohol for storage for later use;
transferring the graphene layer to the surface of the silicon substrate, and then cleaning and drying the graphene layer, wherein the process comprises the following steps:
spin-coating polymethyl methacrylate on the graphene surface of the single-layer copper-based graphene, and then heating and drying at 60-120 ℃ for 30-120 minutes until the polymethyl methacrylate is completely cured; floating copper-based graphene spin-coated with polymethyl methacrylate on the surface of 0.5-2mol/L ferric trichloride solution for 2-3 hours until a copper substrate of a single-layer copper-based graphene is completely etched to obtain a polymethyl methacrylate-supported graphene film; transferring the obtained polymethyl methacrylate supported graphene film into deionized water to be cleaned, transferring the graphene film to the surface of a pretreated silicon substrate, draining water, heating and drying, wherein the heating temperature is 60-80 ℃, and the heating time is 30-120 minutes; sequentially cleaning with acetone and absolute ethyl alcohol to dissolve polymethyl methacrylate on the surface of the graphene film to obtain silicon-based single-layer graphene;
preparing an energy storage thin film layer on the surface of the graphene layer, and then annealing the energy storage thin film layer, wherein the process comprises the following steps:
depositing 0.85BaTiO on the surface of the graphene film of the silicon-based single-layer graphene by a radio frequency magnetron sputtering method3-0.15Bi(Mg0.5Zr0.5)O3An energy storage thin film; the pressure of the radio frequency magnetron sputtering is 0.1-1mbar, the radio frequency sputtering power is 60-150W, and the temperature of the silicon substrate is 600-; and after the deposition is finished, carrying out in-situ annealing at the deposition temperature, wherein the annealing pressure is 200-800mbar, the annealing heat preservation time is 15-30 minutes, and then naturally cooling to the room temperature along with the equipment to obtain the graphene-improved silicon integrated energy storage film.
The invention has the following beneficial effects:
according to the silicon integrated energy storage film improved by graphene, the graphene layer is additionally arranged between the silicon substrate and the energy storage film layer, silicon elements in the silicon substrate can be prevented from diffusing to the energy storage film by using graphene layer resistance, and the graphene layer is used as a two-dimensional material, so that no dangling bond exists under an ideal condition, and van der Waals epitaxy can be realized on the surface of the graphene, so that the graphene layer is beneficial to improving the crystallization quality of the energy storage film, and further the breakdown electric field and the energy storage density are improved; the graphene has the in-plane thermal conductivity as high as 5300W/m.K, and the graphene can enhance the heat dissipation of the energy storage film and effectively avoid thermal runaway by utilizing the excellent thermal conductivity of the graphene layer, so that the energy storage density and the reliability of the energy storage film at high temperature are improved.
Drawings
Fig. 1 is a schematic cross-sectional view of a graphene-modified silicon-integrated energy storage thin film provided by the present invention.
Fig. 2 is an X-ray diffraction 2Theta scan of the graphene-modified silicon integrated energy storage thin film of the embodiment of the invention and a conventional silicon integrated energy storage thin film.
Fig. 3 is a weibull distribution of the breakdown fields of the graphene modified silicon integrated energy storage thin film of the embodiment of the invention and a conventional silicon integrated energy storage thin film.
Fig. 4 is a variation rule of the energy storage density of the graphene-modified silicon integrated energy storage thin film and the conventional silicon integrated energy storage thin film according to the electric field strength at room temperature.
Fig. 5 is a change rule of the energy storage density of the graphene-modified silicon integrated energy storage thin film and the conventional silicon integrated energy storage thin film with temperature at high temperature according to the embodiment of the present invention.
In the figure: 1 is a silicon substrate, 2 is a graphene layer, and 3 is an energy storage thin film layer.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention easier to understand, the present invention will be further described with reference to the accompanying drawings and the following embodiments. It should be understood that the example described herein is only intended to describe one embodiment of the present invention and should not be taken as limiting the scope of the invention.
Referring to fig. 1, the graphene-modified silicon integrated energy storage thin film of the present invention mainly includes a silicon substrate 1, a graphene layer 2 vertically stacked on the silicon substrate, and an energy storage thin film layer 3 vertically stacked on the graphene layer. Wherein: the silicon substrate 1 may be semiconductor silicon; the graphene layer 2 can adopt single-layer graphene or multi-layer graphene, and the number of graphene layers is 1-10; the energy storage thin film layer 3 can be a single-layer energy storage thin film or a multi-layer energy storage thin film, and the energy storage thin film is one or more of a ferroelectric thin film, a relaxor ferroelectric thin film and an antiferroelectric thin film.
The preparation method of the graphene-improved silicon integrated energy storage film comprises the following steps: and transferring copper-based graphene to the surface of the silicon substrate by adopting a conventional wet transfer method, and then preparing one or more energy storage thin film layers on the surface of the graphene to obtain the graphene-improved silicon integrated energy storage thin film. The preparation of the energy storage thin film layer adopts magnetron sputtering, pulsed laser deposition, atomic layer deposition or chemical solution deposition method, and the energy storage thin film layer with the thickness of 10-1000nm is deposited.
The graphene layer is additionally arranged in the silicon integrated energy storage film, Van der Waals epitaxy of the energy storage film is carried out on the surface of the graphene, and the graphene layer is used for preventing silicon elements from diffusing so as to improve the crystallization quality of the energy storage film; meanwhile, the excellent thermal conductivity of the graphene layer is utilized, the heat dissipation of the energy storage film is enhanced, and thermal runaway is effectively avoided, so that the energy storage density of the energy storage film is remarkably improved, and the application of the energy storage film in a high-temperature environment is facilitated.
Examples
The preparation method of the graphene-improved silicon integrated energy storage film comprises the following steps:
(1) silicon substrate pretreatment
A P-type (100) silicon wafer doped with boron is selected, the thickness is 375 mu m, and the resistivity is less than 0.0015 omega cm. The silicon wafer was cut to the desired size, i.e. 10mm by 10mm size, with a diamond pen. Sequentially carrying out ultrasonic cleaning on the cut silicon substrate by using acetone, absolute ethyl alcohol and deionized water, and blow-drying by using high-pressure nitrogen to remove impurities on the surface of the substrate to obtain a cleaned silicon substrate; and (4) placing the cleaned silicon substrate in clean absolute ethyl alcohol for storage for later use.
(2) Preparation of silicon-based single-layer graphene
Selecting single-layer copper-based graphene grown by a commercial chemical vapor deposition method, cutting the single-layer copper-based graphene into the size which is the same as that of a silicon substrate, namely 10mm by 10mm, spin-coating polymethyl methacrylate (PMMA) on the surface of the graphene to be used as a supporting layer, and heating and drying the graphene at the temperature of 80 ℃ for 30 minutes. And floating the copper-based graphene spin-coated with PMMA on the surface of a 1mol/L ferric trichloride solution for 2-3 hours until the copper substrate is completely etched, so as to obtain the PMMA-supported graphene film. Transferring the obtained PMMA-supported graphene film into deionized water to be cleaned, transferring the PMMA-supported graphene film to the surface of the silicon substrate cleaned in the step (1), draining water, heating and drying, wherein the heating temperature is 80 ℃, and the heating time is 30 minutes; and sequentially cleaning with acetone and absolute ethyl alcohol to dissolve the PMMA supporting layer on the surface of the graphene, so as to obtain the silicon-based single-layer graphene.
(3) Preparation of energy storage thin film layer
Delivering the silicon-based single-layer graphene prepared in the step (2) into a vacuum deposition chamber of radio frequency magnetron sputtering equipment, and placing the silicon-based single-layer graphene in a sampleOn the table, a layer of 0.85BaTiO is deposited3-0.15Bi(Mg0.5Zr0.5)O3(BT-BMZ) film. The radio frequency magnetron sputtering pressure is 0.2mbar, the radio frequency sputtering power is 100W, the substrate temperature is 700 ℃, and the target material is a BT-BMZ ceramic target material. The thickness of the deposited BT-BMZ film is 380 nm. After deposition, in-situ annealing is carried out at 700 ℃, the annealing pressure is 200mbar, the annealing heat preservation time is 15 minutes, and then the temperature is naturally reduced to room temperature along with the equipment.
Thus, the silicon integrated energy storage thin film with improved graphene is manufactured in the embodiment.
The graphene-modified silicon integrated energy storage thin film prepared in the embodiment is subjected to crystal structure characterization and electrical property characterization, and compared with a conventional silicon integrated energy storage thin film, the results are as follows.
Fig. 2 is an X-ray diffraction 2Theta scan of the graphene-modified silicon integrated energy storage thin film and a conventional silicon integrated energy storage thin film according to this embodiment. It can be seen that the diffraction peak intensities of (110) and (220) of the silicon integrated energy storage thin film modified by the graphene are obviously enhanced compared with those of the conventional silicon integrated energy storage thin film, and the graphene layer is helpful for crystallization of the energy storage thin film.
Fig. 3 shows weibull distributions of breakdown fields of the graphene-modified silicon integrated energy storage thin film and the conventional silicon integrated energy storage thin film according to an embodiment of the present invention. It can be seen that the breakdown electric field of the silicon integrated energy storage thin film improved by the graphene is improved compared with that of the conventional silicon integrated energy storage thin film, and the graphene layer is beneficial to improving the breakdown electric field of the silicon integrated energy storage thin film.
Fig. 4 is a change rule of the energy storage density of the graphene-improved silicon integrated energy storage thin film and the conventional silicon integrated energy storage thin film at room temperature along with the electric field strength according to the embodiment of the present invention. It can be seen that due to the improvement of the breakdown electric field, the energy storage density of the silicon integrated energy storage thin film improved by the graphene is also improved, which indicates that the graphene layer is beneficial to improving the energy storage density of the silicon integrated energy storage thin film.
Fig. 5 is a change rule of the energy storage density of the graphene-modified silicon integrated energy storage thin film and the conventional silicon integrated energy storage thin film with temperature at high temperature according to the embodiment of the present invention. It can be seen that, with the rise of temperature, the effect of the graphene layer on improving the energy storage density is enhanced, which shows that the energy storage density of the silicon integrated energy storage film improved by the graphene of the embodiment is effectively improved at high temperature.
The silicon integrated energy storage film improved by the graphene has the following advantages:
(1) the energy storage film is integrated on a silicon substrate and can be widely applied to semiconductor integrated circuits.
(2) The graphene layer can effectively prevent silicon elements in the substrate from diffusing to the energy storage film, and the energy storage film can realize Van der Waals epitaxy on the surface of the graphene, so that the crystallization quality of the energy storage film is improved, and the breakdown electric field and the energy storage density are further improved;
(3) according to the invention, the excellent thermal conductivity of the graphene layer is utilized, so that the heat dissipation of the energy storage film is enhanced, and thermal runaway is effectively avoided, thereby improving the energy storage density and reliability of the energy storage film at high temperature;
(4) the graphene improvement method is suitable for various silicon integrated energy storage films, and the preparation method is simple.
Claims (10)
1. The utility model provides a silicon integrated energy storage film of graphite alkene improvement which characterized in that, includes silicon substrate (1), graphite alkene layer (2) and energy storage film layer (3), and graphite alkene layer (2) set up in silicon substrate (1) surface, and energy storage film layer (3) set up in graphite alkene layer (2) surface.
2. The graphene-modified silicon-integrated energy storage thin film according to claim 1, wherein the graphene layer (2) is single-layer graphene or multi-layer graphene.
3. The graphene-modified silicon-integrated energy storage thin film according to claim 1, wherein the number of graphene layers in the graphene layer (2) is 1-10.
4. The graphene-modified silicon-integrated energy storage thin film according to claim 1, wherein the energy storage thin film (3) is one or more of a ferroelectric thin film, a relaxor ferroelectric thin film and an antiferroelectric thin film, and the energy storage thin film layer (3) is a single-layer energy storage thin film or a multi-layer energy storage thin film.
5. The graphene-modified silicon-integrated energy storage thin film according to claim 1, wherein the thickness of the energy storage thin film (3) is 10-1000 nm.
6. The graphene-modified silicon-integrated energy storage thin film according to claim 1, wherein the energy storage thin film (3) is 0.85BaTiO3-0.15Bi(Mg0.5Zr0.5)O3A film.
7. The graphene-modified silicon-integrated energy storage thin film according to claim 1, wherein the silicon substrate (1) is semiconductor silicon.
8. The graphene-modified silicon integrated energy storage thin film according to claim 1, wherein the silicon substrate (1) is a P-type (100) silicon wafer doped with boron element.
9. A preparation method of a silicon integrated energy storage film improved by graphene is characterized by comprising the following steps:
transferring the graphene layer (2) to the surface of the silicon substrate (1), and then cleaning and drying;
and preparing an energy storage thin film layer (3) on the surface of the graphene layer (2), annealing, and obtaining the graphene-improved silicon integrated energy storage thin film after the annealing is finished.
10. The method for preparing the graphene-modified silicon integrated energy storage thin film according to claim 9, further comprising a pretreatment of the silicon substrate (1), wherein the pretreatment of the silicon substrate (1) comprises: ultrasonically cleaning the cut silicon substrate by using acetone, absolute ethyl alcohol and deionized water in sequence, and blow-drying by using high-pressure nitrogen after cleaning to remove impurities on the surface of the substrate; placing the cleaned silicon substrate in absolute ethyl alcohol for storage for later use;
transferring the graphene layer (2) to the surface of the silicon substrate (1), and then cleaning and drying the graphene layer, wherein the process comprises the following steps:
spin-coating polymethyl methacrylate on the graphene surface of the single-layer copper-based graphene, and then drying to completely cure the polymethyl methacrylate; floating copper-based graphene spin-coated with polymethyl methacrylate on the surface of a ferric trichloride solution, and etching away a copper substrate of a single-layer copper-based graphene to obtain a polymethyl methacrylate-supported graphene film; transferring the obtained polymethyl methacrylate supported graphene film into deionized water to be cleaned, transferring the graphene film to the surface of the pretreated silicon substrate (1), draining water, and heating and drying; sequentially cleaning with acetone and absolute ethyl alcohol to dissolve polymethyl methacrylate on the surface of the graphene film to obtain silicon-based single-layer graphene;
preparing an energy storage thin film layer (3) on the surface of the graphene layer (2), and then annealing the energy storage thin film layer, wherein the process comprises the following steps:
depositing 0.85BaTiO on the surface of the graphene film of the silicon-based single-layer graphene by a radio frequency magnetron sputtering method3-0.15Bi(Mg0.5Zr0.5)O3An energy storage thin film; the pressure of the radio frequency magnetron sputtering is 0.1-1mbar, the radio frequency sputtering power is 60-150W, and the temperature of the silicon substrate is 600-; and after the deposition is finished, carrying out in-situ annealing at the deposition temperature, wherein the annealing pressure is 200-800mbar, the annealing heat preservation time is 15-30 minutes, and then naturally cooling to the room temperature along with the equipment to obtain the graphene-improved silicon integrated energy storage film.
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