阅读说明：本技术 一种石墨烯电极谐振子及其制造方法 (Graphene electrode harmonic oscillator and manufacturing method thereof ) 是由 王飞 卢广锋 王凡 于 2020-05-19 设计创作，主要内容包括：本发明提出一种石墨烯电极谐振子的制造方法,包括：1)在管式炉中,将谐振子安置于石英管中,并将充入惰性气体来清除石英管中的空气；2)加热至1000～1200℃保持30～60分钟；3)反应结束时,在惰性气体下系统冷却至室温。本发明还提出一种石墨烯电极谐振子,包括：谐振子石英壳体层和谐振子石墨烯电极层,谐振子石墨烯电极层附着在谐振子石英壳体层内侧。本发明提出的石墨烯镀膜谐振子电导率高,电容效应好,电荷存储多,交换效率高,可以降低谐振子驱动电压。(The invention provides a method for manufacturing a graphene electrode harmonic oscillator, which comprises the following steps: 1) in a tube furnace, arranging a harmonic oscillator in a quartz tube, and filling inert gas to remove air in the quartz tube; 2) heating to 1000-1200 ℃ and keeping for 30-60 minutes; 3) at the end of the reaction, the system was cooled to room temperature under an inert gas. The invention also provides a graphene electrode harmonic oscillator, which comprises: the harmonic oscillator quartz shell layer and the harmonic oscillator graphene electrode layer are attached to the inner side of the harmonic oscillator quartz shell layer. The graphene coated harmonic oscillator provided by the invention has the advantages of high conductivity, good capacitance effect, more charge storage and high exchange efficiency, and can reduce the driving voltage of the harmonic oscillator.)

1. A method for manufacturing a graphene electrode harmonic oscillator is characterized by comprising the following steps:

1) in a tube furnace, arranging a harmonic oscillator in a quartz tube, and filling inert gas to remove air in the quartz tube;

2) heating to 1000-1200 ℃ and keeping for 30-60 minutes;

3) at the end of the reaction, the system was cooled to room temperature under an inert gas.

2. The method for manufacturing a graphene electrode harmonic oscillator according to claim 1,

the conditions of the inert gas in steps 1) and 3) are adjusted according to the volume of the tube furnace.

3. The method for manufacturing a graphene electrode harmonic oscillator according to claim 2,

in step 1), the inert gas condition is 1000 sccm;

in step 2), the inert gas condition was 200/20 sccm;

in step 3), the inert gas condition was 200/20 sccm.

4. The method for manufacturing a graphene electrode harmonic oscillator according to claim 2, further comprising:

the substrate of the resonator is subjected to a hydroxylation pretreatment prior to the tube furnace reaction.

5. The method for manufacturing a graphene electrode harmonic oscillator according to claim 4, further comprising:

high-temperature oxidative cracking is carried out on the surface of the substrate by using methanol, or direct high-temperature pretreatment is carried out by using water vapor.

6. A graphene electrode harmonic oscillator, comprising:

the harmonic oscillator quartz shell layer and the harmonic oscillator graphene electrode layer are attached to the inner side of the harmonic oscillator quartz shell layer.

7. The graphene electrode harmonic oscillator of claim 6, wherein the harmonic oscillator is manufactured by a method comprising:

1) in a tube furnace, arranging a harmonic oscillator in a quartz tube, and flushing inert gas to remove air in the quartz tube;

2) heating to 1000-1200 ℃ and keeping for 30-60 minutes;

3) at the end of the reaction, the system was cooled to room temperature under an inert gas.

8. The graphene electrode harmonic oscillator according to claim 6,

the conditions of the inert gas in steps 1) and 3) are adjusted according to the volume of the tube furnace.

9. The graphene electrode harmonic oscillator according to claim 7,

in step 1), the inert gas condition is 1000 sccm;

in step 2), the inert gas condition was 200/20 sccm;

in step 3), the inert gas condition was 200/20 sccm.

10. The graphene electrode harmonic oscillator of claim 7, further comprising:

the substrate of the resonator is subjected to a hydroxylation pretreatment prior to the tube furnace reaction.

Technical Field

The invention relates to the technical field of coating treatment, in particular to a graphene electrode harmonic oscillator and a manufacturing method thereof.

Background

The Hemispherical Resonator Gyroscope (HRG) is a Coriolis vibration gyroscope, and compared with the traditional mechanical gyroscope, the hemispherical resonator gyroscope has the advantages of no high-speed rotor and movable support in the structure, good stability, high precision, small volume, low noise, high resolution, long service life, high reliability, nuclear radiation resistance and other functions, so that the hemispherical resonator gyroscope is widely applied to weaponry such as aviation, spaceflight, ships, weapons and the like, and is an important component in units such as inertial navigation guidance, carrier attitude stability control, inertial measurement and the like of a modern weapon system.

The core sensitive component of the hemispherical resonance gyroscope is a hemispherical thin shell-shaped harmonic oscillator which is precisely processed by fused quartz glass material with low thermal expansion coefficient and high quality factor (Q) value, so that the hemispherical resonance gyroscope has extremely high dimensional requirement and vibration stability, which is an important dependence on the high precision performance of the hemispherical resonance gyroscope. The harmonic oscillator is affected by factors such as uneven quality, uneven stress, uneven quality factor, uneven thickness of the thin shell and the like in the manufacturing process, so that the Q value of the harmonic oscillator is unstable, and the precision of the gyroscope is affected.

The metalized coating treatment enables the harmonic oscillator electrode to have a conductive function, and a capacitor is formed. The vibration characteristics of the harmonic oscillator are directly influenced by factors such as the thickness, the adhesive force, the uniformity and the like of the electrode film layer. If the film is uneven, the adhesive force is too large or too small, the film has internal stress and the like, the phenomena of reduction of the Q value of the harmonic oscillator and increase of the frequency difference can occur. One of the important processes for determining the uniformity of the thickness of the shell is the uniformity of the metallization treatment of the insulating surface of the harmonic oscillator.

The disadvantages of using a metallized coating film are:

(1) the uniformity of the coating film in the spherical surface is not easy to control;

(2) the mechanical properties of the quartz harmonic oscillator body and the metal electrode are far different, the loss inside the film layer is large, and the Q value is influenced;

(3) the coefficients of expansion of quartz and metal are not matched;

(4) the metal film is unstable in chemical property;

(5) generally, a composite metal film is used, and some metals have lower melting points and are far from quartz, so that the composite metal film is not suitable for high-temperature treatment.

Disclosure of Invention

The invention provides a method for manufacturing a graphene electrode harmonic oscillator aiming at the problems of metal coating, which comprises the following steps: 1) in a tube furnace, arranging a harmonic oscillator in a quartz tube, and filling inert gas to remove air in the quartz tube; 2) heating to 1000-1200 ℃ and keeping for 30-60 minutes; 3) at the end of the reaction, the system was cooled to room temperature under an inert gas.

Optionally, the conditions of the inert gas in steps 1) and 3) are adjusted according to the volume of the tube furnace.

Alternatively, in step 1), the inert gas condition is 1000 sccm;

in step 2), the inert gas condition was 200/20 sccm;

in step 3), the inert gas condition was 200/20 sccm.

Optionally, the substrate of the resonator is subjected to a hydroxylation pretreatment prior to the tube furnace reaction.

Alternatively, methanol is used for high-temperature oxidative cracking on the surface of the substrate, or direct steam high-temperature pretreatment is carried out.

The invention also provides a graphene electrode harmonic oscillator, which comprises: the harmonic oscillator quartz shell layer and the harmonic oscillator graphene electrode layer are attached to the inner side of the harmonic oscillator quartz shell layer.

Optionally, the harmonic oscillator is manufactured by the following method: 1) in a tube furnace, arranging a harmonic oscillator in a quartz tube, and filling inert gas to remove air in the quartz tube; 2) heating to 1000-1200 ℃ and keeping for 30-60 minutes; 3) at the end of the reaction, the system was cooled to room temperature under an inert gas.

Optionally, the conditions of the inert gas in steps 1) and 3) are adjusted according to the volume of the tube furnace.

Alternatively, in step 1), the inert gas condition is 1000 sccm;

in step 2), the inert gas condition was 200/20 sccm;

in step 3), the inert gas condition was 200/20 sccm.

Optionally, the substrate of the resonator is subjected to a hydroxylation pretreatment prior to the tube furnace reaction.

The invention has the beneficial effects that: the graphene has stable physical and chemical properties, excellent electrical properties and mechanical strength, and is very suitable for capacitor electrode materials; the expansion coefficients of the graphene and quartz glass which is used as a resonator body material are close, so that the internal stress in the coating process is reduced, and the problem that the expansion coefficients of a metal coating and the quartz glass are not matched is solved; the novel graphene coated harmonic oscillator has high conductivity, good capacitance effect, more charge storage and high exchange efficiency, and can reduce the driving voltage of the harmonic oscillator; the graphene layer prepared by the CVD method is high in surface uniformity, the thickness of the obtained harmonic oscillator thin wall is uniform, and the precision of the hemispherical resonator gyro is improved.

Drawings

In order that the invention may be more readily understood, it will be described in more detail with reference to specific embodiments thereof that are illustrated in the accompanying drawings. These drawings depict only typical embodiments of the invention and are not therefore to be considered to limit the scope of the invention.

Fig. 1 is a schematic flow chart of CVD graphene growth.

Fig. 2 is a perspective view of a graphene electrode harmonic oscillator manufactured by the method of the present invention.

Fig. 3 is a cross-sectional view of a graphene electrode harmonic oscillator manufactured by the method of the present invention.

Reference numerals

1-carbon source (in erlenmeyer flask); 2-a tube furnace; 3-harmonic oscillator; 3-1 harmonic oscillator quartz shell layer; 3-2 harmonic oscillator graphene electrode layers.

Detailed Description

Embodiments of the present invention will now be described with reference to the drawings, wherein like parts are designated by like reference numerals. The embodiments described below and the technical features of the embodiments may be combined with each other without conflict.

The method of the present invention may be performed in other places where plating of electrodes is required, or in other parts of the hemispherical resonator gyroscope where plating of electrodes is required. The present invention will be described below by taking a hemispherical resonator gyro as an example.

The invention provides a novel hemispherical resonator gyroscope based on graphene grown by a surface CVD method, and a uniform novel graphene electrode resonator is formed. Graphene is a very potential harmonic oscillator coating material. Mainly for the following reasons:

(1) the graphene has extremely high conductivity 10⁴～10⁶And (5) S/m. (monolayer CVD graphene is only 0.334nm thick, but also has a lower density than metal).

(2) Due to the extremely large specific surface area (the theoretical specific surface area is up to 2675 m)²And/g), the graphene can form a complete single-layer structure electric double layer on the surface of the harmonic oscillator.

(3) The carrier mobility of the graphene can exceed 20000cm²and/Vs, the carrier in the graphene can be an electron or a hole, the movement speed of the electron in the graphene is close to the speed of light, and the mobility is less influenced by temperature.

(4) The mechanical strength is high: graphene is the highest material known at present, the strength of the graphene is 100 times higher than that of steel, and the Young modulus of the graphene is up to 1 TPa.

(5) Good thermal conductivity: the graphene has very good heat conduction performance, and the theoretical conduction coefficient of the defect-free single-layer graphene can reach 5000W/m K.

(6) Coefficient of thermal expansion matched to quartz glass: the thermal expansion coefficient of the graphene is much lower than that of a metal film, and is closer to that of a harmonic oscillator bulk material.

(7) Graphene can be heated to 3000 ℃ for graphitization in an oxygen-free environment, and the tolerance temperature of the graphene is far higher than that of quartz, so that processes such as high-temperature annealing, high-temperature hot pressing and the like can be implemented.

The method for manufacturing the novel hemispherical gyroscope harmonic oscillator based on graphene grown by the surface CVD method according to the present invention is described below with reference to fig. 1, and the method according to the present invention includes steps S1-S3.

And S1, cleaning the harmonic oscillator.

Preferably, RCA (radio Corporation of America) wet chemical cleaning process is adopted, which specifically comprises the following steps:

s1-1, immersing the harmonic oscillator in acetone, heating to 50 ℃, and ultrasonically cleaning for 20-30 minutes.

And S1-2, washing the residual acetone on the harmonic oscillator with alcohol, and then carrying out ultrasonic treatment in the alcohol for 10 minutes.

S1-3, taking out the harmonic oscillator, washing the harmonic oscillator with deionized water, and adding the harmonic oscillator into the mixed solution (concentrated H)₂SO₄/H₂O₂7/3) for more than 4 hours.

S1-4, taking out the harmonic oscillator, washing the harmonic oscillator clean by using deionized water, and drying the harmonic oscillator by using high-purity nitrogen for later use.

S2, subjecting the substrate of the resonator to a hydroxylation pretreatment. Specifically, methanol can be used for high-temperature oxidative cracking on the surface of the substrate, or direct water vapor high-temperature pretreatment is carried out.

The hydroxylation pretreatment can hydroxylate the silicon oxide substrate, weaken the combination between the edge of the graphene and the substrate at the later stage, inhibit the secondary nucleation of the graphene, realize the dominant growth of primary nuclei of the graphene and then form the ultra-uniform graphene single-layer film. The hydroxylation pretreatment is carried out on the substrate of the harmonic oscillator, so that the growth quality of graphene is better (the surface is uniform, the surface width is complete, and the thickness is consistent).

S3, growing the graphene film by a surface CVD method. As shown in fig. 1, the growth of CVD graphene may be performed in a tube furnace 2 using one or several carbon sources 1 of acetone, ethanol, methane and methanol as carbon precursors. Using Ar (or other inert gas) and H₂The liquid precursor is delivered to the heated tube furnace 2 through a bubbler.

S3-1, in the tube furnace 2, a resonator was placed at the center of the quartz tube, and Ar gas (or other inert gas) of 1000sccm (which can be adjusted to an optimum value by calculation and experience based on the volume of the tube furnace) (standard state cubic centimeters per minute) was charged into the system to remove air remaining in the quartz tube.

S3-2, Ar/H at 200/20sccm₂And heating the system to 1000-1200 ℃ in a gas environment and keeping the temperature for 30-60 minutes. Ar and H₂The flow passes through the erlenmeyer flask 1, bubbling the liquid carbon precursor into the reaction chamber (tube furnace).

S3-3, at the end of the reaction, the flask 1 was closed and Ar/H at 200/20sccm (which can be adjusted to obtain the optimum value based on the volume calculation and experience of the tube furnace)₂The system was cooled to room temperature under gas. And obtaining the uniformly-grown hemispherical gyroscope novel graphene electrode harmonic oscillator.

As shown in fig. 2-3, the present application also proposes a graphene electrode harmonic oscillator, where the harmonic oscillator 3 includes a harmonic oscillator quartz shell layer 3-1 and a harmonic oscillator graphene electrode layer 3-2. The harmonic oscillator graphene electrode layer 3-2 is attached to the inner side of the harmonic oscillator quartz shell layer 3-1.

The above-described embodiments are merely preferred embodiments of the present invention, and general changes and substitutions by those skilled in the art within the technical scope of the present invention are included in the protection scope of the present invention.