CN117177453A - 5G wave-transparent substrate and preparation method thereof - Google Patents
5G wave-transparent substrate and preparation method thereof Download PDFInfo
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- CN117177453A CN117177453A CN202311234518.7A CN202311234518A CN117177453A CN 117177453 A CN117177453 A CN 117177453A CN 202311234518 A CN202311234518 A CN 202311234518A CN 117177453 A CN117177453 A CN 117177453A
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- 239000000758 substrate Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000004005 microsphere Substances 0.000 claims abstract description 72
- 239000004964 aerogel Substances 0.000 claims abstract description 30
- 229920005989 resin Polymers 0.000 claims abstract description 30
- 239000011347 resin Substances 0.000 claims abstract description 30
- 239000002243 precursor Substances 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 22
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- 239000011248 coating agent Substances 0.000 claims abstract description 12
- 238000000576 coating method Methods 0.000 claims abstract description 12
- 239000011159 matrix material Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 239000002245 particle Substances 0.000 claims abstract description 10
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- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 10
- 230000008595 infiltration Effects 0.000 claims abstract description 8
- 238000001764 infiltration Methods 0.000 claims abstract description 8
- 238000001179 sorption measurement Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 229920001721 polyimide Polymers 0.000 claims abstract description 5
- 238000005245 sintering Methods 0.000 claims abstract description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000004642 Polyimide Substances 0.000 claims abstract description 3
- 239000011889 copper foil Substances 0.000 claims abstract description 3
- 238000005553 drilling Methods 0.000 claims abstract description 3
- 230000033001 locomotion Effects 0.000 claims abstract description 3
- 238000011282 treatment Methods 0.000 claims abstract description 3
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 claims description 16
- 229910052863 mullite Inorganic materials 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 12
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- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
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- 239000003054 catalyst Substances 0.000 claims description 9
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- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 229910052710 silicon Inorganic materials 0.000 claims description 6
- 239000010703 silicon Substances 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 239000011812 mixed powder Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 239000007921 spray Substances 0.000 claims description 4
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 3
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- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 3
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- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
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- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 3
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- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 2
- 239000005007 epoxy-phenolic resin Substances 0.000 claims description 2
- KCWYOFZQRFCIIE-UHFFFAOYSA-N ethylsilane Chemical compound CC[SiH3] KCWYOFZQRFCIIE-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
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- 239000000395 magnesium oxide Substances 0.000 claims description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 2
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 2
- 239000009719 polyimide resin Substances 0.000 claims description 2
- 238000005086 pumping Methods 0.000 claims description 2
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- 239000011787 zinc oxide Substances 0.000 claims description 2
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- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 description 1
- MWSKJDNQKGCKPA-UHFFFAOYSA-N 6-methyl-3a,4,5,7a-tetrahydro-2-benzofuran-1,3-dione Chemical compound C1CC(C)=CC2C(=O)OC(=O)C12 MWSKJDNQKGCKPA-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- MQJKPEGWNLWLTK-UHFFFAOYSA-N Dapsone Chemical compound C1=CC(N)=CC=C1S(=O)(=O)C1=CC=C(N)C=C1 MQJKPEGWNLWLTK-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
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- Compositions Of Macromolecular Compounds (AREA)
Abstract
The application relates to the technical field of 5G equipment, and discloses a 5G wave-transparent substrate and a preparation method thereof, wherein the preparation method comprises the following steps of: firstly, preparing hollow microspheres with the particle size of 70nm, then preparing an aerogel precursor, uniformly mixing the hollow microspheres into the aerogel precursor, and drying to obtain aerogel; after the aerogel is dried, the gap is smaller than 70nm, and the movement of the hollow microspheres is restrained, so that a uniformly distributed nano hollow microsphere structure is formed; then coating a resin matrix or polyimide precursor and PTFE precursor, completing resin infiltration of the surface or the whole body through vacuum adsorption, and then heating and curing to form a wave-transparent substrate base material, wherein the wave-transparent substrate base material can be subjected to treatments such as copper foil sintering, drilling and the like. According to the application, the hollow nano-microspheres are restrained by the aerogel, so that the uniform distribution of the nano-microspheres is completed, and the nano-microspheres are easier to stir uniformly under the condition of low viscosity, so that the material consistency of a matrix is realized.
Description
Technical Field
The application relates to the technical field of 5G equipment, and particularly discloses a 5G wave-transparent substrate and a preparation method thereof.
Background
With the perfection of 5G technology, more and more occasions begin to advance the installation and use of 5G equipment. However, with the increase of power and frequency, the requirements of 5G devices in application occasions are correspondingly increased, and in the advanced electronic manufacturing technology field of high-frequency PCB substrates, some low dielectric constant (Dk) and low dielectric loss (Df) materials, especially some low Dk and low Df resin materials, are urgently needed. When the feature size of the electronic component is gradually reduced, that is, the integration level is continuously improved, a resistor-capacitor (RC) delay is increased, so that a series of problems such as signal transmission delay, noise interference enhancement, power loss increase and the like occur, which greatly limit the development of high-speed performance of the electronic component. The dielectric constant of air is 1, proper air is introduced into the microwave dielectric material, so that the dielectric constant of the microwave dielectric material can be effectively reduced, the hollow ceramic powder is introduced as the filler, however, the traditional mixing mode is likely to generate the phenomenon of uneven mixing due to different densities of the filler and the organic resin, the powder with high density is easy to accumulate at dead angles, the filler with low density is easy to agglomerate in the material, and the traditional method for preparing the microwave dielectric substrate by mechanical mixing is not suitable for preparing the hollow ceramic powder filler substrate. Therefore, developing a uniformly filled substrate, especially a substrate filled with nano-microspheres, to improve the dielectric constant uniformity of the substrate is currently an important direction.
Disclosure of Invention
The application mainly solves the technical problems that a 5G wave-transmitting substrate and a preparation method thereof are provided, the problem that the traditional mixing mode is likely to generate uneven mixing due to different densities of filler and organic resin, powder with high density is easy to accumulate at dead angles, filler with low density is easy to agglomerate in materials, and the traditional method for preparing the microwave dielectric substrate by mechanical mixing is not suitable for preparing the hollow ceramic powder filler substrate is solved.
In order to solve the above technical problems, according to one aspect of the present application, more specifically, a 5G wave-transparent substrate and a method for preparing the same, which comprises the following steps:
s1, preparing nano hollow microspheres: preparing hollow microspheres with the particle size of 70nm and an aerogel precursor in advance, uniformly mixing the hollow microspheres into the aerogel precursor, and drying to obtain aerogel; the air gap of the aerogel is smaller than 70nm, so that the movement of the hollow microspheres is restrained, and a uniformly distributed nano hollow microsphere structure is formed;
s2, coating a resin matrix or polyimide precursor and PTFE precursor on the nano hollow microsphere structure, finishing surface or whole resin infiltration in a vacuum adsorption mode, and then heating and curing to form a wave-transmitting substrate base material, wherein copper foil can be sintered on the base material, and drilling treatment can be carried out to form the wave-transmitting substrate.
Further, the hollow microsphere is one of mullite microsphere, silicon dioxide microsphere and aluminum oxide microsphere; the hollow microsphere is preferably modified by a surface silane coupling agent, and is more suitable for adsorption and uniformity of aerogel precursors.
Furthermore, the particle size in the hollow microsphere shell is smaller than 50nm, so that the free path of air is restricted, and the heat energy generation caused by Brownian motion is reduced.
Furthermore, the aerogel is mullite fiber reinforced structure aerogel, and the compression resistance of the aerogel is improved.
Further, the resin matrix is polyimide resin, epoxy resin or phenolic resin.
Preferably, the ultraviolet photosensitive resin is used for accurately finishing surface adsorption to prepare materials, and the uniformity of dielectric constant is improved.
Further, in the course of resin infiltration, the entire resin infiltration was performed under isostatic pressure at 10 atmospheres. The dielectric constant of the mode is slightly larger, but the pressure resistance is stronger; the pressure resistance varies from 5MPa to 50 MPa.
Furthermore, the aerogel plus nanosphere structure has two preparation modes, the first mode of preparing the gel microsphere structure is:
s1, preparing tertiary butanol gel injection molding premix by taking tertiary butanol, acrylamide and N, N' -methylene bisacrylamide as raw materials; the mass ratio of the raw materials of the tertiary butanol premix is 85-80:15-20:1-0.5, the mass fraction of ammonium persulfate in the initiator is 20-50 wt%, and the mass fraction of tetramethyl ethylenediamine in the catalyst is 2-5 wt%;
s2, adding the tertiary butanol premix into diluted silica sol, adding nano hollow microspheres, an initiator and a catalyst, and performing gel casting; the addition amount of the initiator is 1wt percent to 3wt percent, and the addition amount of the catalyst is 0.1wt percent to 0.5wt percent; the gel temperature is 30-60 ℃ and the gel time is 0.5-2 h;
s3, drying the demoulded sample, and calcining at a high temperature to obtain the product; the calcination temperature is 1200-1400 ℃, the temperature rising rate is 2-5 ℃/min, and the heat preservation is carried out for 1-4h;
and mullite fiber with diameter of 10-30nm and content of 1.5-2.5 wt% can be added in the step S2;
the second way to prepare the gel microsphere structure is:
adding deionized water, an absolute ethyl alcohol solvent, formamide, an ethylene glycol drying control additive and nano hollow microspheres into a silicon source, and simultaneously adding nano mullite fibers with the diameter of 10-30nm and the content of 1.5% -2.5%; keeping the temperature in a 60 ℃ constant-temperature water bath for 2 hours, dripping ammonia water with the mass fraction of 1.5%, adjusting the PH value to 3.0-3.5, standing and aging to obtain a gel microsphere structure; wherein the silicon source is ethyl orthosilicate; ethyl orthosilicate, deionized water, absolute ethanol, ammonia water=1:3.5:8:8.5; the prepared structure is a gel microsphere structure with a dielectric constant of 1.12.
Furthermore, the nano microsphere adopts a hollow microsphere with the diameter of 30nm-100nm, and the preparation method comprises the following steps:
s1, adding 30-50 parts by weight of mullite, 20-30 parts by weight of alumina, 10-20 parts by weight of silicon dioxide, 1-3 parts by weight of magnesium oxide and 1-3 parts by weight of zinc oxide into a ball mill, and uniformly ball-milling at a rotating speed of 300-600rpm to obtain mixed powder;
s2, adding 10-20 parts by weight of mixed powder into 40-60 parts by weight of deionized water, adding 0.1-0.5 part by weight of sodium dodecyl benzene sulfonate, uniformly stirring to obtain slurry, and pumping the slurry into a centrifugal spray dryer for spray granulation to obtain a granulating substance;
s3, sintering the pelleting material at 900-1000 ℃ for 50-80min, and then sintering the pelleting material at 400-1500 ℃ for 40-80min to obtain a precursor;
s4, uniformly dispersing 15 parts by weight of precursor in 40-70 parts by weight of deionized water, adding 0.5-1 part by weight of ethyl silane coupling agent, uniformly stirring at 200-700rpm, filtering, and drying to obtain the modified nano inorganic mullite alumina hollow microsphere.
The particle size and wall thickness of the hollow microsphere are controlled by the change of each component such as mullite.
The hollow microspheres with nanometer particle size can also avoid the problem of too low flatness of the metal plating layer caused by rough side surfaces of the through holes of the substrate.
The 5G wave-transparent substrate and the preparation method thereof have the beneficial effects that: according to the application, the hollow nano-microspheres are restrained by the aerogel, so that the uniform distribution of the nano-microspheres is completed, and the nano-microspheres are easier to stir uniformly under the condition of low viscosity, so that the material consistency of a matrix is realized. In addition, by introducing the aerogel structure, the hollow matrix layer is formed under a specific state, so that the dielectric constant is further reduced, the matrix weight is reduced, and the resin usage amount is reduced. In addition, the application realizes the regulation and control of the dielectric constant by introducing an ultraviolet curing mode.
Drawings
The application will be described in further detail with reference to the accompanying drawings and detailed description.
FIG. 1 is a schematic view of a surface-coated substrate structure;
FIG. 2 is a schematic view of the structure of a bulk coated substrate;
FIG. 3 is a graph of dielectric constant for different epoxy loadings;
FIG. 4 is a graph of dielectric constants of various particle size aerogel+nanospheres prepared phenolic resin substrates;
FIG. 5 is a graph of dielectric constant for different BT resin loadings;
FIG. 6 is a graph of dielectric constant for various PTFE matrix loadings.
Detailed Description
The application will be described in detail hereinafter with reference to the drawings in conjunction with embodiments. It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other.
Example 1
According to one aspect of the application, there is provided a 5G wave-transparent substrate and a preparation method thereof, comprising the steps of:
firstly, prefabricating a silica aerogel+nanoparticle structure: adding deionized water, an absolute ethyl alcohol solvent, formamide, an ethylene glycol drying control additive and nano hollow microspheres into a silicon source, and simultaneously adding nano mullite fibers with the diameter of 10-30nm and the content of 1.5% -2.5%; keeping the temperature in a 60 ℃ constant-temperature water bath for 2 hours, dripping ammonia water with the mass fraction of 1.5%, adjusting the pH value to 3.0-3.5, standing and aging to obtain a gel microsphere structure; wherein the silicon source is ethyl orthosilicate; ethyl orthosilicate, deionized water, absolute ethanol, ammonia water=1:3.5:8:8.5; the prepared structure is a gel microsphere structure with a dielectric constant of 1.12.
Then, different resin precursors are prepared according to different resin materials, and are combined with gel microspheres to form a substrate.
(1) Preparation of epoxy resin substrate:
10 parts of methyl hexahydrophthalic anhydride and 50 parts of bisphenol A epoxy resin are taken as main materials, the materials are stirred and heated to 80 ℃ to form a resin precursor, then the precursor is injected into a mould in which gel microspheres are placed according to the weight ratio of the precursor to the gel microspheres of 3:1, and the metamaterial dielectric substrate is formed by hot pressing, wherein the hot pressing temperature is 180 ℃, and the hot pressing pressure is 45MPa.
At 30% loading, 11×10 5 A low dielectric constant of 1.77 was obtained under HZ conditions. As shown in fig. 3, the smaller the resin amount, the lower the dielectric constant at different epoxy resin loading.
(2) Preparation of phenolic resin substrate:
15 parts of phenolic resin, 25 parts of phosphorus-containing active ester compound, 10 parts of reinforcing agent, 0.5 part of curing accelerator and 40 parts of acetone are added into a glue mixing kettle, the solid content of glue solution is controlled to be 65%, and the glue solution is uniformly stirred and cured for 8 hours to prepare a resin precursor; injecting the precursor into a mold with gel microspheres placed therein, standing for 30min to form an overlapped layer, baking at 155 ℃ for 5min, and then baking at 200 ℃ for 2h to form a resin substrate.
As shown in fig. 4, the dielectric constants of the phenolic resin substrates prepared from the gel microspheres with different particle sizes, wherein 100nm cannot have proper aerogel structure constraint due to larger particle size, and the distribution uniformity is poor, and the dielectric constants are worse than those of 70nm microsphere substrates uniformly constrained by aerogel structure although the air occupies relatively large space. At 11×10 5 A low dielectric constant of 1.99 was obtained under HZ conditions.
(3) Preparation of BT resin substrate:
(1) firstly, preparing modified polyphenyl ether, weighing 15 parts of high-brominated epoxy resin, 20 parts of phenolic epoxy resin, 50 parts of polyphenyl ether, 3 parts of methyltetrahydrophthalic anhydride and 4 parts of 2-methylimidazole, placing the materials into a reaction kettle for reaction, weighing 2 parts of trichloromethane, adding the materials into the reaction kettle, uniformly stirring, and cooling to 23 ℃; preparing modified cyanate resin, weighing 15 parts of epoxy resin and 3 parts of diaminodiphenyl sulfone, putting into a reaction kettle, heating, weighing 45 parts of cyanate resin, putting into the reaction kettle, uniformly stirring until resin components are completely melted, presenting a transparent state, finally weighing 5 parts of polyetherimide resin, putting into the reaction kettle, heating to 280 ℃, uniformly stirring, and cooling to 55 ℃; finally, mixing the modified polyphenyl ether and the modified cyanate resin, and stirring for 25min to obtain the adhesive.
(2) Coating an adhesive on the gel microsphere structure, finishing the coating of the quantitative adhesive by a scraping plate, adopting a warm isostatic pressing mode, finishing the infiltration of the adhesive at 450 ℃ under the pressure of 100MPa for 10min, and then canceling the pressure and continuously drying for 30min to finish the preparation of the substrate. As shown in FIG. 5, at 30% fill, 11X 10 5 A low dielectric constant of 2.097 was obtained under HZ conditions.
(4) Preparation of Polytetrafluoroethylene (PTFE) substrate:
coating polytetrafluoroethylene emulsion on a gel microsphere structure, placing polytetrafluoroethylene emulsion in a mold, controlling the depth of the gel microsphere structure contacting the emulsion, controlling the overlapping area of the gel emulsion, fully soaking, drying at 100 ℃ for 30min, and calcining at 350 ℃ for 15min to form structures with different matrix ratios, thereby obtaining the PTFE substrate.
As shown in fig. 6, the PTFE substrate itself has a low dielectric constant, so that the variation in dielectric constant is less different in the case of 100% filling than in the case of unfilled aerogel microsphere structure, and the decrease in dielectric constant is more pronounced in the case of insufficient filling. This is a significant reduction in aerogel microsphere structure. At 30% fill, at 11X 10 5 A low dielectric constant of 1.44 was obtained under HZ conditions.
The four numerical precursors are divided into a surface coating type and an integral coating type when the gel microspheres are coated, wherein the surface coating type forms a surface coating type substrate, as shown in figure 1, the dielectric constant is between 1.9 and 2.3, and the compression resistance is 45 to 75 percent of a normal value; and the whole coating type forms a whole coating type substrate, as shown in fig. 2, the dielectric constant is between 2.2 and 3.5, and the compressive capacity is 55 to 85% of the normal value.
Example two
Based on the first embodiment, the preparation mode of the silica aerogel+nanoparticle structure is changed as follows: preparing tertiary butanol gel injection molding premix by taking tertiary butanol, acrylamide and N, N' -methylene bisacrylamide as raw materials; the mass ratio of the raw materials of the tertiary butanol premix is 85-80:15-20:1-0.5, the mass fraction of ammonium persulfate in the initiator is 20-50 wt%, and the mass fraction of tetramethyl ethylenediamine in the catalyst is 2-5 wt%; adding the tertiary butanol premix into diluted silica sol, adding mullite fiber, nano hollow microspheres, initiator and catalyst, and performing gel casting; the addition amount of the initiator is 1wt percent to 3wt percent, and the addition amount of the catalyst is 0.1wt percent to 0.5wt percent; the gel temperature is 30-60 ℃, the gel time is 0.5-2 h, the mullite fiber is nanofiber, the diameter is 10-30nm, and the content is 1.5-2.5 wt%; drying the demoulded sample, and calcining at high temperature to obtain the product; the calcination temperature is 1200-1400 ℃, the temperature rising rate is 2-5 ℃/min, and the heat preservation is carried out for 1-4h.
The remainder is the same as in embodiment one.
Of course, the above description is not intended to limit the application, but rather the application is not limited to the above examples, and variations, modifications, additions or substitutions within the spirit and scope of the application will be within the scope of the application.
Claims (8)
1. The 5G wave-transparent substrate and the preparation method thereof are characterized by comprising the following preparation steps of:
s1, preparing nano hollow microspheres: preparing hollow microspheres with the particle size of 70nm and an aerogel precursor in advance, uniformly mixing the hollow microspheres into the aerogel precursor, and drying to obtain aerogel; the air gap of the aerogel is smaller than 70nm, so that the movement of the hollow microspheres is restrained, and a uniformly distributed nano hollow microsphere structure is formed;
s2, coating a resin matrix or polyimide precursor and PTFE precursor on the nano hollow microsphere structure, finishing surface or whole resin infiltration in a vacuum adsorption mode, and then heating and curing to form a wave-transmitting substrate base material, wherein copper foil can be sintered on the base material, and drilling treatment can be carried out to form the wave-transmitting substrate.
2. The 5G wave-transparent substrate and the preparation method thereof according to claim 1, wherein: the hollow microsphere is one of mullite microsphere, silicon dioxide microsphere and aluminum oxide microsphere; the hollow microsphere is preferably modified by a surface silane coupling agent, and is more suitable for adsorption and uniformity of aerogel precursors.
3. The 5G wave-transparent substrate and the preparation method thereof according to claim 1, wherein: the particle size in the hollow microsphere shell is smaller than 50nm, the free path of air is restrained, and the heat energy generation caused by Brownian motion is reduced.
4. The 5G wave-transparent substrate and the preparation method thereof according to claim 1, wherein: the aerogel is mullite fiber reinforced structural aerogel, and the compressive capacity of the aerogel is improved.
5. The 5G wave-transparent substrate and the preparation method thereof according to claim 1, wherein: the resin matrix is polyimide resin, epoxy resin and phenolic resin.
6. The 5G wave-transparent substrate and the preparation method thereof according to claim 1, wherein: in the resin infiltration process, the entire resin infiltration was performed under isostatic pressure at 10 atmospheres.
7. The 5G wave-transparent substrate and the preparation method thereof according to claim 1, wherein: the aerogel and nano microsphere structure has two preparation modes, and the first mode for preparing the gel microsphere structure is as follows:
s1, preparing tertiary butanol gel injection molding premix by taking tertiary butanol, acrylamide and N, N' -methylene bisacrylamide as raw materials; the mass ratio of the raw materials of the tertiary butanol premix is 85-80:15-20:1-0.5, the mass fraction of ammonium persulfate in the initiator is 20-50 wt%, and the mass fraction of tetramethyl ethylenediamine in the catalyst is 2-5 wt%;
s2, adding the tertiary butanol premix into diluted silica sol, adding nano hollow microspheres, an initiator and a catalyst, and performing gel casting; the addition amount of the initiator is 1wt percent to 3wt percent, and the addition amount of the catalyst is 0.1wt percent to 0.5wt percent; the gel temperature is 30-60 ℃ and the gel time is 0.5-2 h;
s3, drying the demoulded sample, and calcining at a high temperature to obtain the product; the calcination temperature is 1200-1400 ℃, the temperature rising rate is 2-5 ℃/min, and the heat preservation is carried out for 1-4h;
and mullite fiber with diameter of 10-30nm and content of 1.5-2.5 wt% can be added in the step S2;
the second way to prepare the gel microsphere structure is:
adding deionized water, an absolute ethyl alcohol solvent, formamide, an ethylene glycol drying control additive and nano hollow microspheres into a silicon source, and simultaneously adding nano mullite fibers with the diameter of 10-30nm and the content of 1.5% -2.5%; keeping the temperature in a 60 ℃ constant-temperature water bath for 2 hours, dripping ammonia water with the mass fraction of 1.5%, adjusting the PH value to 3.0-3.5, standing and aging to obtain a gel microsphere structure; wherein the silicon source is ethyl orthosilicate; ethyl orthosilicate, deionized water, absolute ethanol, ammonia water=1:3.5:8:8.5; the prepared structure is a gel microsphere structure with a dielectric constant of 1.12.
8. The 5G wave-transparent substrate and the preparation method thereof according to claim 7, wherein: the nanometer microsphere adopts a hollow microsphere with the diameter of 30nm-100nm, and the preparation method comprises the following steps:
s1, adding 30-50 parts by weight of mullite, 20-30 parts by weight of alumina, 10-20 parts by weight of silicon dioxide, 1-3 parts by weight of magnesium oxide and 1-3 parts by weight of zinc oxide into a ball mill, and uniformly ball-milling at a rotating speed of 300-600rpm to obtain mixed powder;
s2, adding 10-20 parts by weight of mixed powder into 40-60 parts by weight of deionized water, adding 0.1-0.5 part by weight of sodium dodecyl benzene sulfonate, uniformly stirring to obtain slurry, and pumping the slurry into a centrifugal spray dryer for spray granulation to obtain a granulating substance;
s3, sintering the pelleting material at 900-1000 ℃ for 50-80min, and then sintering the pelleting material at 400-1500 ℃ for 40-80min to obtain a precursor;
s4, uniformly dispersing 15 parts by weight of precursor in 40-70 parts by weight of deionized water, adding 0.5-1 part by weight of ethyl silane coupling agent, uniformly stirring at 200-700rpm, filtering, and drying to obtain the modified nano inorganic mullite alumina hollow microsphere.
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