WO2021082373A1

WO2021082373A1 - Compound semiconductor flexible carbon-based film and preparation method therefor

Info

Publication number: WO2021082373A1
Application number: PCT/CN2020/087048
Authority: WO
Inventors: 刘萍
Original assignee: 深圳丹邦科技股份有限公司
Priority date: 2019-10-30
Filing date: 2020-04-26
Publication date: 2021-05-06
Also published as: CN110862076A; CN110862076B

Abstract

A compound semiconductor flexible carbon-based film and a preparation method therefor, the method comprising the following steps: S1. hybridizing an anhydride containing a phenyl group with a diamine to obtain a thermoplastic polyimide resin precursor; S2. using the thermoplastic polyimide resin precursor to prepare a polyimide thin film; S3. carbonizing the polyimide thin film with black lead, and doping the polyimide thin film with nano-metal for ion implantation and ion exchange, wherein nano-monoclinic crystals in the film are phase-changed into tetragonal crystals and are changed from single crystals into superlattices; and S4. carrying out a high-temperature annealing treatment on the material obtained in step S3 to form an ultra-flexible ultra-thin compound semiconductor film. The foregoing technical solution provides a compound semiconductor material that has a high-performance, is ultra-flexible, and has ultra-thin microstructures.

Description

Compound semiconductor flexible carbon-based film and preparation method thereof

Technical field

The invention relates to the field of compound semiconductor materials, in particular to a compound semiconductor flexible carbon-based film and a preparation method thereof.

Background technique

With the development of new technologies, one of the most significant contributions to mankind in the last century was the nuclear reactor in 1942, which solved the energy problem of today’s society. The second one should be the transistor invented by Bell Labs in the United States, which brought prosperity to mankind. In the electronic age, the third is that in the 1960s, American physicist Charles Hardtowns invented the highly coherent microwave speed. Charles Hardtowns and AL Shawlow extended the principle of micron amplifiers to optical frequencies. TH Theodore Memann developed the first ruby laser, RN Hall developed a gallium arsenide semiconductor laser, and then South African scientists developed a digital laser. It is the above-mentioned scientists who have brought the current information society to human society. In today's information society era, the cornerstone of supporting software, programs and Internet of Things communications should be integrated circuits (IC chips). In addition, heterojunction integrated circuits, heterojunctions are structured by PN into the same semiconductor material, wide band gap, P-type and N-type A layer of narrow band gap material is inserted between the type semiconductor materials. The band gap difference forms a potential barrier, which restricts the recombination of electrons and holes to the active area, and the refractive index optical field is effectively restricted in the active area. In the silicon era of the last century, integrated circuits had a Moore's law, that is, the number of integrated circuit IC chips doubled every 18 months, and the output reached the extreme value. That is, in 2016, Moore's Law officially came to an end. On the eve of the end, Intel USA The first development of the 14-nanometer chip contains 1.3 billion transistors, so when Moore's Law ends, the inevitable trend is to find new materials to replace silicon materials. The most popular one is compound semiconductor materials.

Compound semiconductor integrated circuits have ultra-high and low speed, low power consumption, multi-function, anti-radiation, higher working frequency, working speed, superior material characteristics in the integrated circuit manufacturing process, high electron mobility and electron drift speed, resistivity Very high, easy to achieve self-isolation in the substrate circuit process, process simplification, wide band gap, can work in the high temperature area, very suitable for microwave circuits and millimeter wave integrated circuits.

Compound semiconductor applications have interdisciplinary nature and are widely used in military fields, intelligent weapons, aerospace, radar, communications, smart phones, optical fiber communications, semiconductor lighting, smart grids, power electronics, microwave radio frequency, optoelectronics, high-speed rail transit , New energy vehicles, unmanned aircraft, large workstations, and direct broadcast communication satellites all have broad application prospects and are key new materials supporting the development of information energy transportation, national defense and other industries.

The disclosure of the above background technical content is only used to assist the understanding of the inventive concept and technical solution of the present invention. It does not necessarily belong to the prior art of the patent application. There is no clear evidence that the above content has been published on the filing date of the patent application. Under the circumstances, the above-mentioned background technology should not be used to evaluate the novelty and inventiveness of this application.

Summary of the invention

The main purpose of the present invention is to provide a compound semiconductor flexible carbon-based film and a preparation method thereof to obtain a high-performance compound semiconductor film.

In order to achieve the above objectives, the present invention adopts the following technical solutions:

A method for preparing a compound semiconductor flexible carbon-based film includes the following steps:

S1, hybridizing an anhydride containing a phenyl group with a diamine to obtain a thermoplastic polyimide resin precursor;

S2. Using the thermoplastic polyimide resin precursor to prepare a polyimide film;

S3. Carbonizing the polyimide film with black lead, and doping the polyimide film with nano-metal, performing ion implantation and ion exchange, wherein the nano-monoclinic crystal in the film is transformed into a tetragonal crystal, and Single crystal becomes superlattice;

S4. Perform high-temperature annealing treatment on the material obtained in step S3 to form an ultra-flexible ultra-thin compound semiconductor film.

further:

Step S1 includes:

The volume of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) is 30-60 parts, 4,4'-diaminodiphenyl ether (4,4'-ODA) 30-60 parts by volume and 7-14 parts by volume of diaminodianthracene ether are dissolved in N,N-dimethylformamide (DMF), and then 3,3',4,4'-benzophenone is added 30-60 parts by volume of tetraacid dianhydride (BTDA), then add 20-40 parts by volume of pyromellitic dianhydride (PMDA), and add 3,3',4,4' after a period of reaction -Benzophenone tetracarboxylic dianhydride (BTDA) and/or pyromellitic dianhydride (PMDA) to obtain a polyimide resin precursor with thermoplasticity, heat resistance and freedom.

In step S1, the total number of moles of 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) and pyromellitic dianhydride (PMDA) is approximately equal to 2,2-bis[ The total number of moles of 4-(4-aminophenoxy)phenyl]propane (BAPP), 4,4'-diaminodiphenyl ether (4,4'-ODA) and diaminodianthracene ether.

In step S2, gel synthesis is performed using diaminodianthracene ether and the thermoplastic polyimide resin precursor, and a blowout spraying method is used to uniformly form a film to obtain a heteromorphic hybrid polyimide film.

In step S2, gel synthesis is performed at a temperature above -100°C. Preferably, the molecular weight of the diaminodianthracene ether after hybridization exceeds 1 million or more.

In step S3, during the dehydrogenation and denitrification during the blackening process, the nano metal is mixed with the protective gas under a pressure of 50 Kpa.

The nano metal is selected from Al, Ga, In, and Ge, preferably from Ga, In, and Ge, with a particle size of 1000 nm or less, preferably 400 nm or less.

In step S3, a continuous carbonization and black lead furnace is used. During the process, the polyimide film is passed through the preheating zone, the heating and constant temperature heating zone, and the cooling zone, so that the ion implantation and ion exchange time meet the set requirements.

In step S4, an annealing process is carried out at a temperature not lower than 3200°C to expand the base film material, deoxidize and replace, transform the crystal phase transition, and meet the requirements of high superlattice orientation.

A compound semiconductor flexible carbon-based film is a flexible carbon-based film prepared by using the method for preparing a flexible carbon-based film.

The present invention has the following beneficial effects:

The method for preparing a compound semiconductor flexible carbon-based film provided by the present invention hybridizes an anhydride containing a phenyl group with a diamine to obtain a thermoplastic polyimide resin precursor, and prepares a polyimide film from the precursor, preferably by chemical spraying , The use of double-inclined heteromorphic hybrid polyimide, with high heat resistance and freedom, to prepare high-density thick film; the obtained polyimide film is carbonized and black leaded high temperature treatment, and through doping Nano-metal materials, through ion implantation and ion exchange, transform nano-monoclinic crystals into tetragonal crystals; further use high-temperature annealing process, base film material expansion, deoxidation replacement, liquid crystal phase transition of metal nano-elements, and also reduce the defect grain boundaries , To ensure that the layered plane direction is aligned with the vertical direction, with higher orientation, can make the superlattice reach more than 87% orientation, thereby optimizing the van der waals force of the substrate; finally, the band gap can be obtained as 2.3 EV, carrier concentration is 1.6×10 ²⁰ cm ^-3 , resistivity is 2.310E-04 (Ω·m/cm), with high temperature, high pressure, high frequency performance, wide width 920～1200mm, super flexible, super Thin-layer microstructured compound semiconductor material CCX.

The compound semiconductor CCX flexible carbon-based film obtained in the present invention has no wrinkles and is super-elastic. After experimental tests, it can be folded more than 8000 times under the limit of 10% elongation, bends more than 100,000 cycles at 180°C, and has a flux concentration of 1.6 ×10 ²⁰ cm ^-3 , 30μm thick thermal conductivity K value of 1488W/m ^-1 k ^-1 .

Description of the drawings

Fig. 1 is a flow chart of the carbonization process in an embodiment of the present invention.

Fig. 2 is a schematic diagram of a side cross-sectional structure of a carbonization furnace in an embodiment of the present invention.

Fig. 3 is a schematic diagram of a cross-sectional structure of a carbonization furnace in an embodiment of the present invention.

Detailed ways

The embodiments of the present invention will be described in detail below. It should be emphasized that the following description is only exemplary, and is not intended to limit the scope of the present invention and its application.

In one embodiment, a method for preparing a compound semiconductor flexible carbon-based film includes the following steps:

The method for preparing a flexible carbon-based film provided by the present invention hybridizes an anhydride containing a phenyl group with a diamine to obtain a thermoplastic polyimide resin precursor, and prepares a high-density polyimide film from the precursor, preferably by chemical spraying , The use of double-inclined heteromorphic hybrid polyimide, with high heat resistance and freedom, to prepare high-density thick film; the obtained polyimide film is carbonized and black leaded high-temperature treatment, and through doping Nano metal materials, through ion implantation and ion exchange, transform nano monoclinic crystals into tetragonal crystals; and optimize the use of high temperature annealing process, base film material expansion, deoxidation replacement, liquid crystal phase transition of metal nano elements, and also reduce defect crystals The boundary ensures that the layered plane direction is aligned with the vertical direction, and has higher orientation, which can make the superlattice reach more than 87% orientation, thereby optimizing the van derwaals force of the substrate. After experimental testing, the preparation method of the present invention can obtain a band gap of 2.3EV, a carrier concentration of 1.6×10 ²⁰ cm ^-3 , and a resistivity of 2.310E-04 (Ω·m/cm). It has high temperature and high pressure. , High-frequency performance, large width 920～1200mm, ultra-flexible, ultra-thin layer microstructure compound semiconductor material CCX.

In a preferred embodiment, step S1 includes:

In a more preferred embodiment, in step S1, the total moles of 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) and pyromellitic dianhydride (PMDA) Roughly equal to 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), 4,4'-diaminodiphenyl ether (4,4'-ODA) and diaminodianthracene The total number of moles of ether.

In a preferred embodiment, in step S2, diaminodianthracene ether and the thermoplastic polyimide resin precursor are used for gel synthesis, and the blowout spraying method is used to form a uniform film to obtain a heteromorphic hybrid polyamide. Imine film.

In a more preferred embodiment, in step S2, gel synthesis is performed at a temperature above -100°C. Preferably, the molecular weight of the diaminodianthracene ether after hybridization exceeds 1 million or more.

In a preferred embodiment, in step S3, during dehydrogenation and denitrification in the black-leadization process, the nano metal is mixed with the protective gas under a pressure of 50 Kpa.

Preferably, two or more of the three protective gases N, Ar, and Ne are mixed and used during the carbonization black leading treatment, more preferably 50% of each of N and Ar are mixed during the carbonization process, and more preferably mixed during the black leading treatment Use 50% each of Ar and Ne. This design is very helpful in anti-oxidation. When carbonizing black lead, the mixed shielding gas effectively protects the surface from oxidation and air pressure. For black lead, high-purity neon gas can also be selected.

In a preferred embodiment, the nano metal is selected from Al, Ga, In, and Ge, preferably from Ga, In, and Ge, with a particle size of 1000 nm or less, preferably 400 nm or less.

In a preferred embodiment, in step S3, a continuous carbonization and black lead furnace is used. During the process, the polyimide film is passed through the preheating zone, the heating zone and the constant temperature heating zone, and the cooling zone for ion implantation and ion exchange. The time reaches the set requirement.

In a preferred embodiment, in step S4, an annealing process is performed at a temperature not lower than 3200° C. to expand the base film material, deoxidize and replace, transform the crystal phase transition, and meet the requirements of high superlattice orientation.

In another embodiment, a compound semiconductor flexible carbon-based film is a flexible carbon-based film prepared by using the flexible carbon-based film preparation method of any one of the foregoing embodiments. The compound semiconductor CCX flexible carbon-based film obtained by the present invention is super-elastic. After product testing, it can be folded more than 8,000 times under the limit of 10% elongation, bent more than 100,000 cycles at 180°C, and has a flux concentration of 1.6×10 ^The thermal conductivity of 20 cm ^-3 and 30 μm thick has a K value of 1488W/m ^-1 k ^-1 .

The features and advantages of specific embodiments of the present invention are further described below.

The preparation method of the flexible carbon-based film of this specific embodiment includes the following steps:

In step S1, an anhydride containing a phenyl group is hybridized with a diamine to obtain a thermoplastic polyimide resin precursor.

Preferably, it comprises: 30-60 parts by volume of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), 4,4'-diaminodiphenyl ether (4, 4'-ODA) 30-60 parts by volume and diaminodianthracene ether (also called heterodiamine, structural formula is

) Dissolve 7-14 parts by volume in N,N-dimethylformamide (DMF), and add 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) by volume 30～ 60 parts, and then add 20-40 parts by volume of pyromellitic dianhydride (PMDA), and add 3,3',4,4'-benzophenone dianhydride (BTDA) after a period of reaction ) And/or pyromellitic diacid dianhydride (PMDA), the supplementary amount is one-third of each, added every 45 minutes on average to make the reaction more thorough and the viscosity more uniform, and also make 3,3 The total number of moles of',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) and pyromellitic dianhydride (PMDA) is roughly equal to 2,2-bis[4-(4-aminophenoxy) (Base) phenyl] propane (BAPP), 4,4'-diaminodiphenyl ether (4,4'-ODA) and the total number of moles of diaminodianthracene ether, resulting in thermoplasticity, heat resistance and freedom The precursor of polyimide resin.

For details, reference may also be made to the method disclosed in the applicant's prior patent application 201910055344.5.

In step S2, diaminodianthracene ether and the thermoplastic polyimide resin precursor are used for gel synthesis, and a blowout spraying method is used to form a uniform film. Wherein, the heteromorphic diamine (diaminodianthracene ether) has a hybridization molecular weight of more than 1 million, gel synthesis is performed at a temperature of -100°C or more, and a uniform film is formed by a blowout spraying method. Among them, the solvent is volatilized by the blowout device, and the water is isolated to prepare a high-density polyimide thick film. The specific method can refer to the method disclosed in the applicant's prior patent application 201910055344.5.

In step S3, the polyimide film is carbonized with black lead, and the polyimide film is doped with nano-metal, and ion implantation and ion exchange are performed, wherein the nano-monoclinic crystals in the film are transformed into tetragonal crystals. And from single crystal to superlattice. Specifically, a fully automatic continuous carbonization and black lead furnace is used. During the process, the polyimide film is passed through the preheating zone, heating and constant temperature heating zone, and cooling zone, so that the ion implantation and ion exchange time meet the set process requirements , Through the heat source, protective gas, temperature, time, speed control, orderly cycle operation. Refer to Figure 1, Figure 2 and Figure 3 for the processing process and furnace equipment of this step. The design of the heating treatment can adopt the specific method of carbonizing and graphitizing the polyimide film disclosed in the applicant's prior patent application publication number CN106829930A. As shown in Figure 2, a carbonization furnace includes a furnace body 1, a heater 2, a machine leg 3, a machined part 4, an automatic feed port 5, an automatic discharge port 6, and the furnace body 1 ranges from an automatic feed port 5 to The direction of the automatic discharge port 6 is sequentially provided with a low temperature zone, a medium temperature zone and a high temperature zone. As shown in FIG. 2, the furnace body 1 of the carbonization furnace includes a furnace shell 7 with an insulation layer 8 inside the furnace shell 7 and a gas protection space 9.

In step S3, for the doped nano-metal, specifically during dehydrogenation and denitrification in the black-leadization process, the nano-metal is mixed with the protective gas at a pressure of 50 Kpa. The nano metal is selected from Al, Ga, In, and Ge, preferably from Ga, In, and Ge. The particle size of the nano metal is 1000 nm or less, preferably 400 nm. For ion implantation and ion exchange, when black lead is formed, the base film begins to expand at 2800°C, monocrystalline and monoclinic crystal phase change, the carbon element lattice is complete, and the above-mentioned nano metal is injected during deoxidation. The nano metal element changes from transition The element phase changes into a tetragonal lattice, and at the same time it changes from a single crystal to a superlattice.

In step S4, in order to reduce the defect grain boundaries and transition from one axis to two axes, an extremely high temperature of 3200°C is used for annealing process, through cyclic expansion, deoxidation and replacement, transformation of crystal phase transformation, so that the layered plane direction is aligned with the vertical direction. In order to achieve high orientation requirements, the superlattice can reach 87% or more orientation, thereby optimizing van der waals force, so that the flexible carbon-based film can reach ^{a K value of 1900±100W/m -1} k ^-1 , without wrinkles and super Elastic, fold more than 8000 times at the limit of 10% elongation, and bend more than 100,000 cycles at 180℃.

The semiconductor carrier concentration of the flexible carbon-based film of the present invention reaches 1.6×10 ²⁰ , and has high thermal conductivity, at least partly due to the high concentration, the core vibration of the particles in the crystal lattice, the scaling of the crystal domain size, and the formation of interface boundary holes, It has a high degree of crystallinity, and it reduces the defect grain boundaries. The thermal conductivity K value of 30μm thick is 1488W/m ^-1 k ^-1 , and the strain is very limited, within the range of 0.2% to 0.4%, and finally achieves super flexible performance.

It is particularly preferable to use an annealing process with an extremely high temperature of not less than 3200°C to eliminate the defect grain boundaries. The defects refer to the oxygen-containing functional groups on the surface of the compound semiconductor CCX base film, and there are no defects in the _{nano-cavities and SP 3 carbon bonds.} The crystals in the superelastic carbon-carbon-hybrid olefin sheet can be folded to adapt to the large elongation under external tension, and can provide sufficient bending freedom. At the same time, the high temperature annealing reduces the phonon scattering center and the lattice structure. Defects and defects in the functional groups of carbon-carbon-X based membranes. The invention can be used to provide high-performance compound semiconductor materials and equipment, with good application prospects and high application value.

The above content is a further detailed description of the present invention in combination with specific/preferred embodiments, and it cannot be considered that the specific implementation of the present invention is limited to these descriptions. For those of ordinary skill in the technical field to which the present invention belongs, without departing from the concept of the present invention, they can also make several substitutions or modifications to the described embodiments, and these substitutions or modifications should be regarded as It belongs to the protection scope of the present invention. In the description of this specification, reference to the description of the terms "one embodiment", "some embodiments", "preferred embodiment", "examples", "specific examples", or "some examples" etc. means to incorporate the implementation The specific features, structures, materials or characteristics described in the examples or examples are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the described specific features, structures, materials or characteristics may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art can combine and combine the different embodiments or examples and the features of the different embodiments or examples described in this specification without contradicting each other. Although the embodiments of the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the scope defined by the appended claims. In addition, the scope of the present invention is not intended to be limited to the specific embodiments of the processes, machines, manufacturing, material composition, means, methods, and steps described in the specification. A person of ordinary skill in the art will readily understand that the above-mentioned disclosures, processes, machines, processes, machines, and machines that currently exist or will be developed later that perform substantially the same functions as the corresponding embodiments described herein or obtain substantially the same results as the embodiments described herein can be used. Manufacturing, material composition, means, method, or step. Therefore, the appended claims intend to include these processes, machines, manufacturing, material compositions, means, methods, or steps within their scope.

Claims

A method for preparing a compound semiconductor flexible carbon-based film, which is characterized in that it comprises the following steps:

S1, hybridizing an anhydride containing a phenyl group with a diamine to obtain a thermoplastic polyimide resin precursor;

S2. Using the thermoplastic polyimide resin precursor to prepare a polyimide film;

S3. The polyimide film is carbonized with black lead, and the polyimide film is doped with nano-metal, and ion implantation and ion exchange are carried out. Among them, the nano-monoclinic crystal in the film is transformed into a tetragonal crystal, and From single crystal to superlattice;

S4. Perform high-temperature annealing treatment on the material obtained in step S3 to form an ultra-flexible ultra-thin compound semiconductor film.
The method for preparing a flexible carbon-based film according to claim 1, wherein step S1 comprises:

The volume of 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP) is 30-60 parts, 4,4'-diaminodiphenyl ether (4,4'-ODA) 30-60 parts by volume and 7-14 parts by volume of diaminodianthracene ether are dissolved in N,N-dimethylformamide (DMF), and then 3,3',4,4'-benzophenone is added 30-60 parts by volume of tetraacid dianhydride (BTDA), then add 20-40 parts by volume of pyromellitic dianhydride (PMDA), and add 3,3',4,4' after a period of reaction -Benzophenone tetracarboxylic dianhydride (BTDA) and/or pyromellitic dianhydride (PMDA) to obtain a polyimide resin precursor with thermoplasticity, heat resistance and freedom.
The method for preparing a flexible carbon-based film according to claim 2, wherein in step S1, 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA) and pyromellitic acid The total number of moles of diacid dianhydride (PMDA) is roughly equal to 2,2-bis[4-(4-aminophenoxy)phenyl]propane (BAPP), 4,4'-diaminodiphenyl ether (4 ,4'-ODA) and the total number of moles of diaminodianthracene ether.
The method for preparing a flexible carbon-based film according to claim 1, wherein in step S2, diaminodianthracene ether and the thermoplastic polyimide resin precursor are used for gel synthesis, and blowout spraying is used. The method uniformly forms a film to obtain a heteromorphic hybrid polyimide film.
The method for preparing a flexible carbon-based film according to claim 4, characterized in that, in step S2, gel synthesis is performed at a temperature above -100°C. Preferably, the molecular weight of the diaminodianthracene ether after hybridization exceeds 1 million.
The method for preparing a flexible carbon-based film according to any one of claims 1 to 5, characterized in that, in step S3, during the dehydrogenation and denitrification in the black leading process, under 50Kpa pressure, the nano metal will be protected Gas incorporation.
The method for preparing a flexible carbon-based film according to any one of claims 1 to 6, wherein the nano metal is selected from Al, Ga, In, and Ge, preferably from Ga, In, and Ge, with a particle size of 1000 nm or less , Preferably 400nm or less.
The method for preparing a flexible carbon-based film according to any one of claims 1 to 7, characterized in that, in step S3, a continuous carbonization and black lead furnace is used, and the polyimide film is preheated during the process. Zone, heating and constant temperature heating zone, and cooling zone, so that the ion implantation and ion exchange time can meet the set requirements.
The method for preparing a flexible carbon-based film according to any one of claims 1 to 8, characterized in that, in step S4, an annealing process is performed at a temperature not lower than 3200°C to expand the base film material, deoxidize and replace, and transform crystals. The phase change meets the high orientation requirements of the superlattice.
A compound semiconductor flexible carbon-based film, which is characterized in that it is a flexible carbon-based film prepared by the method for preparing a flexible carbon-based film according to claim 1.