CN117144330B

CN117144330B - Preparation method of curved quartz substrate surface metal film layer with oxide transition layer

Info

Publication number: CN117144330B
Application number: CN202310970324.7A
Authority: CN
Inventors: 冯昊; 龚婷; 秦利军; 惠龙飞; 张王乐; 李建国; 胡逸云; 李丹; 房佳斌
Original assignee: Xian Modern Chemistry Research Institute
Current assignee: Xian Modern Chemistry Research Institute
Priority date: 2023-08-03
Filing date: 2023-08-03
Publication date: 2025-11-11
Anticipated expiration: 2043-08-03
Also published as: CN117144330A

Abstract

This invention provides a method for preparing a metal film on a curved quartz substrate with an oxide transition layer. The method employs atomic layer deposition (ALD), first depositing an oxide layer as a transition layer to enhance adhesion on the curved quartz substrate surface, followed by a metal layer as a conductive layer. The deposited transition and conductive layers are then annealed to form the metal film. The oxide in the transition layer is _Al₂O₃ or _TiO₂ ; the metal in the conductive layer is Pt or Ru. This invention solves the problem of inhomogeneity in films prepared by _magnetron sputtering, achieving a non-uniformity of less than 5% in the latitudinal and longitudinal directions of the metal film on the inner wall of a hemispherical harmonic oscillator in ALD. The hemispherical harmonic oscillator of this invention has a low specific surface area and aspect ratio, facilitating mass production of ALD films.

Description

Preparation method of curved quartz substrate surface metal film layer with oxide transition layer

Technical Field

The invention belongs to the technical field of inertial navigation hemispherical resonator gyroscopes, relates to preparation of a metal film layer, and in particular relates to a preparation method of a metal film layer on the surface of a curved quartz substrate with an oxide transition layer.

Background

The hemispherical resonator gyroscope has the advantages of simple structure, small volume, high precision, long service life, stable physical characteristics and the like, and has wide application prospect in the fields of weapon equipment, deep space exploration, satellite communication, inertial navigation systems, navigation telescope and the like.

The core component of the hemispherical resonator gyro consists of an electrostatic excitation cover, a hemispherical resonator and a sensitive reading base 3, which are all processed by quartz glass materials, wherein the hemispherical resonator is the most core sensitive detection element. In order to control the vibration of hemispherical resonators and to obtain accurate vibration signals, it is often necessary to subject the surface of the insulated resonator to a metallization process to render it conductive. However, the hemispherical resonator is in a hemispherical shell shape, so that the surface structure is complex, and the difficulty of plating a high-uniformity and high-precision film on the surface of the hemispherical resonator is very high. In addition, the phenomenon that the plated metal film falls off from the surface of the harmonic oscillator is easily caused by factors such as mismatch of thermal expansion coefficients between quartz materials and metal films of the hemispherical resonator gyroscope.

The method for metallizing and coating the surface of the hemispherical harmonic oscillator is mainly based on magnetron sputtering. The technology adopts the film plating principle that high-energy Ar ions are adopted to bombard the surface of the target material, so that atoms of the target material are deposited on a substrate in a sputtering mode to form a film. The technology has the advantages of abundant selectable metal material types and high deposition efficiency, but the magnetron sputtering is not completely suitable for surface coating of the substrate with the curved surface special-shaped structure and ultrahigh requirement on the quality of the film. The different axial and radial distances from the target to the spherical substrate will cause different thicknesses of the deposited film at different positions of the curved surface under the condition of consistent sputtering rate, resulting in poor uniformity. If the non-uniformity of the Cr/Au thin film prepared on the hemispherical resonator by magnetron sputtering at present reaches more than 20%, the Q value loss of the hemispherical resonator after coating is up to 50%. Magnetron sputtering belongs to physical vapor deposition, and a film layer and a substrate are combined through Van der Waals force, so that the bonding force is weak. After the Cr/Au film is subjected to a high-temperature annealing process, the oxidation of the Cr film can be accelerated, cr ₂O₃ is caused to rapidly migrate to the surface of the Au film to damage the structure of the Au conductive layer, the conductivity is reduced, the binding force of the Au film is reduced, and the Au film is seriously detached from the quartz surface to reduce the quality factor of the harmonic oscillator.

The metallized coating on the surface of the hemispherical resonator is a key technology for developing a navigation-grade hemispherical resonator gyro, and the problems of uneven film preparation and low binding force of the traditional coating technology are urgently needed to be solved, so that the development of the hemispherical resonator gyro with high quality factor in China is assisted.

Disclosure of Invention

Aiming at the defects existing in the prior art, the invention aims to provide a preparation method of a metal film layer on the surface of a curved quartz substrate with an oxide transition layer, which solves the technical problems of uneven film and low binding force in the preparation of a magnetron sputtering method in the prior art.

In order to solve the technical problems, the invention adopts the following technical scheme:

The preparation method of the metal film layer on the surface of the curved quartz substrate with the oxide transition layer comprises the steps of adopting an atomic layer deposition method, firstly depositing a layer of oxide on the surface of the curved quartz substrate to serve as the transition layer for enhancing the binding force, and then depositing a layer of metal to serve as the conductive layer;

the oxide of the transition layer is Al ₂O₃ or TiO ₂;

the metal of the conductive layer is Pt or Ru.

The invention also has the following technical characteristics:

Preferably, the thickness of the transition layer is 1-10 nm, and the thickness of the conductive layer is 5-30 nm.

Preferably, the curved quartz substrate is a hemispherical resonator in a hemispherical resonator gyroscope.

Preferably, the precursor of atomic layer deposition corresponding to Al ₂O₃ is trimethylaluminum and oxygen, and the precursor of atomic layer deposition corresponding to TiO ₂ is titanium tetraisopropoxide and oxygen.

Preferably, the precursors for atomic layer deposition corresponding to Pt are trimethylcyclopentadienyl platinum and ozone, and the precursors for atomic layer deposition corresponding to Ru are bis (cyclopentadienyl) ruthenium and oxygen.

Preferably, the annealing temperature is 500-550 ℃.

Preferably, the atomic layer deposition cycle number of the oxide is 50.

More preferably, the atomic layer deposition time sequence of the oxide of the transition layer is that the solid precursor corresponding to the oxide is injected for 10-30 seconds, the purging time is 30 seconds, the gas precursor corresponding to the oxide is injected for 10 seconds, and the purging time is 30 seconds.

Preferably, the number of cycles of atomic layer deposition of the metal is 100-500.

More preferably, the atomic layer deposition time sequence of the metal of the conductive layer is that the solid precursor corresponding to the metal is injected for 15-20 seconds, the purging time is 40 seconds, the solid precursor corresponding to the metal is injected for 30 seconds, and the purging time is 40 seconds.

Compared with the prior art, the invention has the following technical effects:

(I) The invention can solve the problem of non-uniformity of the film prepared by magnetron sputtering, and the non-uniformity of the metal film layer prepared by atomic layer deposition in the latitude and longitude directions of the inner wall of the hemispherical resonator is less than 5%.

In the invention, (II) after the Cr/Au film is subjected to a high-temperature annealing process, the conductivity is reduced, and the binding force of the Cr/Au film is reduced, so that the Au film is seriously detached from the quartz surface, and the quality factor of the harmonic oscillator is reduced. The atomic layer deposition is to generate a new chemical bond on the surface of the quartz substrate by chemical reaction, the bonding force of the chemical bond is strong, oxide can not be diffused to the surface of the metal film in the annealing process, and the conductivity and the bonding force are reduced. The resistance of the metal film prepared by atomic layer deposition is less than 30Ω, and the bonding force between the annealed metal film and the quartz substrate is more than 100N.

And (III) the hemispherical harmonic oscillator has low specific surface area and depth ratio, and is easy to realize batch preparation of atomic layer deposition coating.

Drawings

FIG. 1 is a graph showing the variation of ALD Pt cycle number with Pt film thickness.

FIG. 2 is a graph showing the dependence of ALD Pt cycle number on the resistance of Pt film.

FIG. 3 shows the result of 200cPt/50cAl ₂O₃ thin film planar scanning electron microscope.

FIG. 4 shows the grazing incidence X-ray diffraction results of a 200cPt/50cAl ₂O₃ film.

FIG. 5 is a full spectrum of X-ray photoelectron spectroscopy (a) and a fine scan spectrum of Pt 4f (b) for a 200cPt/50cAl ₂O₃ film.

FIG. 6 shows the results of a bonding force test of 200cPt/50cAl ₂O₃ thin films to a quartz substrate before and after annealing.

FIG. 7 shows the results of a bonding force test of 200cPt/25cAl ₂O₃ film to a quartz substrate before and after annealing.

Fig. 8 is a schematic diagram of a simulated metal hemisphere structure before (a) and after (B) attachment of a silicon wafer.

FIG. 9 is a FIB-TEM and high magnification TEM photograph of a hemispherical resonator surface 200cPt/50cAl ₂O₃ thin film cross section.

FIG. 10 shows a hemispherical resonator surface 200cPt/50cAl ₂O₃ film cross-section HAADF-STEM, EDX mapping, and line scanning.

Fig. 11 is a result of simulating thickness variation of the inner wall Pt film of the metal hemispheres 1 (a) and 2 (b) in terms of latitude and longitude.

Fig. 12 is a graph showing the results of simulating the resistance change of the inner wall Pt film of the metal hemispheres 1 (a) and 2 (b) in terms of latitude and longitude.

FIG. 13 shows the grazing incidence X-ray diffraction results of 150cPt/50cTiO ₂ films.

Fig. 14 is a graph showing the results of simulating thickness and resistance changes of the metal hemispherical inner wall Pt thin film in the latitude and longitude directions.

FIG. 15 is a test of the bonding force of 150cPt/50cTiO ₂ films to quartz substrates.

Fig. 16 is a graph showing the results of simulating thickness and resistance changes of the metal hemispherical inner wall Pt thin film in the latitude and longitude directions.

FIG. 17 is a test of the bonding force of 200cRu/50cAl ₂O₃ films to quartz substrates.

Fig. 18 is a graph showing the results of simulating the thickness and resistance change of the metal hemispherical inner wall Pt thin film in the latitude and longitude directions.

Fig. 19 is a graph showing the results of simulating thickness and resistance changes of the metal hemispherical inner wall Pt thin film in the latitude and longitude directions.

Fig. 20 is a graph showing the results of simulating the thickness and resistance change of the Pd film on the inner wall of the metal hemisphere in the latitude and longitude directions.

The following examples illustrate the invention in further detail.

Detailed Description

All materials and equipment used in the present invention are known in the art, unless otherwise specified.

The hemispherical resonator gyroscope has wide application prospect in the field of high-precision navigation. The surface of a hemispherical resonator of a core component of the hemispherical resonator gyro needs to be plated with a metal film to be conductive. Atomic layer deposition belongs to a high-precision micro-nano processing manufacturing technology, and can form a film layer with controllable and uniform thickness on the surface of a three-dimensional structure. The precursor for atomic layer deposition generates a new chemical bond through chemical reaction with a silicon-oxygen bond on the surface of a hemispherical resonator made of quartz material, and the film is deposited on the surface of a substrate, wherein the bonding force of the chemical bond is far greater than Van der Waals force. In addition, the atomic layer deposition is used for preparing the oxide with extremely thin thickness as a transition layer, so that the quality factor of the harmonic oscillator is not reduced, and the absorption of water molecules to the surface of the harmonic oscillator is inhibited to increase loss. The hemispherical harmonic oscillator has low specific surface area and depth ratio, and is easy to realize the mass preparation of atomic layer deposition coating. Therefore, the metal film prepared by atomic layer deposition has the technical scheme of application prospect.

In the invention, an elliptical polarization Spectrometer (SE) is adopted to measure the film thickness, a Scanning Electron Microscope (SEM) is adopted to observe the film morphology, a focused ion beam-transmission electron microscope (FIB-TEM) is adopted to observe the film microstructure, X-ray photoelectron spectroscopy (XPS) is adopted to analyze the film composition, grazing incidence X-ray diffraction (GIXRD) is adopted to analyze the phase structure of the film, an electronic universal tester is adopted to test the binding force between the film and a quartz substrate, and a four-probe resistance meter is adopted to test the film resistance.

The following specific embodiments of the present application are provided, and it should be noted that the present application is not limited to the following specific embodiments, and all equivalent changes made on the basis of the technical scheme of the present application fall within the protection scope of the present application.

Examples 1 to 6:

The embodiment provides a preparation method of a curved quartz substrate surface metal film layer with an oxide transition layer, namely, an atomic layer deposition is adopted to prepare a hemispherical resonator Pt/Al ₂O₃ film layer with a circulation cycle number, and the method comprises the following steps:

In the first step, a silicon wafer and a quartz wafer (20 mm. Times.20 mm. Times.2 mm) are placed in an atomic layer deposition reactor, the reactor temperature is 200 ℃, the pressure is 1Torr, the carrier gas flow rate is 100ml/min, and Al ₂O₃ precursor Trimethylaluminum (TMA) and oxygen (O ₂),O₂ flow rate is 40 ml/min) are deposited.

In the second step, the timing of depositing the Al ₂O₃ film is that TMA injection time is 10 seconds, purging time is 30 seconds, O ₂ injection time is 10 seconds, purging time is 30 seconds, and the cycle number is 50.

In a third step, trimethylmethylcyclopentadienyl platinum (MeCpPtMe ₃) and O ₃,MeCpPtMe₃, the Pt film precursor, the carrier gas carrying the MeCpPtMe ₃ precursor, is heated to 50 ℃, and the flow of O ₃ is 40ml/min.

Fourth, the deposition Pt film time sequence is that the injection time of MeCpPtMe ₃ is 20 seconds, the purge time is 40 seconds, the injection time of O ₃ is 30 seconds, the purge time is 40 seconds, and the cycle number is 100, 150, 180, 200, 250 and 500 respectively.

And fifthly, annealing the Pt/Al ₂O₃ film layer by adopting a high-temperature furnace, wherein the annealing temperature is 550 ℃, and the annealing time is 4 hours.

Thickness measurements were made on 100, 150, 180, 200, 250, 500 cycle Pt films grown on silicon wafers deposited with 50 cycle Al ₂O₃ substrates, and the results are shown in fig. 1. From FIG. 1, it is seen that the Pt film thickness increases linearly with increasing number of periods of Pt, and the average growth rate of Pt is equal to or higher thanCycle. Is affected by the nucleation delay of the metal Pt film on the Al ₂O₃, and the growth rate of Pt is lower at 100 cyclesCycle.

The Pt thin films of the above different cycles were subjected to resistance test, and the results are shown in fig. 2. As shown in FIG. 2, when the number of Pt cycles is 100, the resistance value is 148 omega, and when the number of Pt cycles is greater than 150, the resistance value is smaller than 20 omega and is close to the resistance of the bulk metal Pt.

The morphology of the 200cPt/50cAl ₂O₃ thin film plane on the silicon wafer was observed by Scanning Electron Microscopy (SEM), and the results are shown in FIG. 3. It can be seen from FIG. 3 that the Pt nanoparticles are uniformly distributed on the surface of the 200cPt/50cAl ₂O₃ film.

FIG. 4 is a graph of the results of a 200cPt/50cAl ₂O₃ thin film grazing incidence X-ray diffraction (GIXRD). Diffraction peaks for the (111), (200), (220), and (311) crystal planes of the metallic Pt appear in the GIXRD spectrum of fig. 4. Al ₂O₃ is an amorphous film with no corresponding diffraction peaks.

The composition of the surface of the 200cPt/50cAl ₂O₃ film was analyzed by X-ray photoelectron spectroscopy (XPS), and the results are shown in FIG. 5. It is seen from fig. 5 (a) that the film surface contains Pt, O, C elements, which are mainly from surface contaminated carbon and adsorbed oxygen. The contaminated layer on the surface of the 200cPt/50cAl ₂O₃ film was etched for 30 seconds, and the binding energy of Pt 4f _5/2 and Pt 4f _7/2 was located at 74.7eV and 71.4eV as seen from the fine scan spectrum of Pt element (b) in fig. 5, indicating that the Pt film was composed of elemental Pt.

And using an electronic universal tester, and carrying out binding force test on the 200cPt/50cAl ₂O₃ film and the quartz substrate before and after annealing according to a pulling-off method described in GB5210-2006 standard. FIG. 6 is a graph showing the results of a bond test of a 200cPt/50cAl ₂O₃ film before and after annealing, showing that the 200cPt/50cAl ₂O₃ film is detached from the quartz surface only when the film is 308N, indicating that the maximum bonding force between the ALD-prepared 200cPt/50cAl ₂O₃ film and the quartz substrate is 308N, the bonding force between the annealed 200cPt/50cAl ₂O₃ film and the quartz substrate is reduced, and detachment from the quartz substrate surface when the film is 115N may be caused by new stress in the film interface after annealing, resulting in reduced bonding force.

Example 7:

The embodiment provides a preparation method of a metal film layer on the surface of a curved quartz substrate with an oxide transition layer, namely, an atomic layer deposition is adopted to prepare a hemispherical resonator Pt/Al ₂O₃ film layer, other conditions are unchanged on the basis of the embodiment 1 to the embodiment 6, the cycle number of deposited Al ₂O₃ is 25, and the cycle number of deposited Pt is 200.

And using an electronic universal tester, and carrying out binding force test on the 200cPt/25cAl ₂O₃ film and the quartz substrate before and after annealing according to a pulling-off method described in GB5210-2006 standard. FIG. 7 is a graph showing the results of the bonding force test before and after annealing of the 200cPt/25cAl ₂O₃ film, which shows that the bonding force before and after annealing of the 200cPt/50cAl ₂O₃,200cPt/25cAl₂O₃ film is 264N and 106N respectively, which is lower than that of the 200cPt/50cAl ₂O₃ film, and shows that the Al ₂O₃ with the thickness of 50 cycles has stronger interaction with the metal Pt and higher bonding force.

Example 8:

The embodiment provides a preparation method of a metal film layer on the surface of a curved quartz substrate with an oxide transition layer, namely, an atomic layer deposition is adopted to prepare a hemispherical resonator Pt/Al ₂O₃ film layer, other conditions are unchanged on the basis of the embodiment 1 to the embodiment 6, and the substrate is a quartz hemispherical resonator and a simulated metal hemisphere attached with a silicon wafer. The schematic diagrams of the simulated metal hemispheres before and after the silicon wafers are shown as A in fig. 8 and B in fig. 8, the size of the simulated metal hemispheres is the same as that of an actual quartz hemispheric harmonic oscillator, 2 and 4 silicon wafers are attached to the latitude and longitude of the inner wall of the sphere, and the total number of the silicon wafers is 8, so that the thickness of the film is tested, and the uniformity of the film thickness of the film in the latitude and longitude directions is represented.

The number of cycles of depositing Al ₂O₃ on the quartz hemisphere harmonic oscillator and the simulated metal hemisphere with silicon wafer is 50, and the number of cycles of depositing Pt is 200. The hemispherical resonator of the 200cPt/50cAl ₂O₃ film deposited was sampled using a Focused Ion Beam (FIB), and the microstructure of the 200cPt/50cAl ₂O₃ film was observed by TEM, and the results are shown in fig. 9. As seen from FIG. 9 (a), the film thickness of 200cPt/50cAl ₂O₃ was uniform, and the average thickness was 28.3nm. As shown in FIG. 9 (b), the film layers of Pt and Al ₂O₃ are seen after the 200cPt/50cAl ₂O₃ film is enlarged, the average thickness is 22.3nm to 5.7nm respectively, and the growth rates of Pt and Al ₂O₃ can be calculated to be equal to or greater than that of the film layersCycle. In EDX-mapping analysis of 200cPt/50cAl ₂O₃ film cross section, it is seen from FIG. 10 that the film contains Pt, al and O elements and is uniformly distributed, and in addition, the existence of Al and O elements in the Pt film layer can be observed, which means that the Al ₂O₃ film has diffusion in the Pt film layer, and the mutual permeation of Pt, al and O elements in a certain area can be seen in line scanning, and the Si element also has diffusion in the Al ₂O₃ film. The results show that atomic layer deposition is a bottom-up film synthesis technology, and Pt and Al atomic layers synthesized by chemical reaction on the surface can be mutually diffused to form PtAlO mixture interfaces, and the interfaces are favorable for improving the binding force.

Fig. 11 is a graph simulating the thickness of inner wall Pt films of metal hemispheres 1 (fig. 11 (a)) and 2 (fig. 11 (b)) in terms of latitude and longitude. As seen from (a) in FIG. 11 and (b) in FIG. 11, the average thickness of Pt film simulating the metal hemispheres 1 and 2 wasAndThe non-uniformity is 1.6% and 2.0%, respectively, and the film uniformity is significantly better than magnetron sputtering. As seen from FIG. 12 (a) and FIG. 12 (b), the average resistances of Pt thin films simulating metal hemispheres 1 and 2 were 8.9Ω and 8.6Ω, respectively, which are far lower than those of the Cr/Au thin film systems produced by conventional magnetron sputtering.

Example 9:

the embodiment provides a preparation method of a metal film layer on the surface of a curved quartz substrate with an oxide transition layer, namely, an atomic layer deposition is adopted to prepare a hemispherical resonator Pt/TiO ₂ film layer, and the method comprises the following steps:

Firstly, placing a hemispherical resonator, a simulated metal hemispherical attached to a silicon wafer and a cospecies silicon wafer in an atomic layer deposition reactor, wherein the temperature of the reactor is 200 ℃, the pressure is 1Torr, the carrier gas flow is 100ml/min, the deposited TiO ₂ precursor titanium tetraisopropoxide (Ti (OPr) ₄) and oxygen (O ₂),Ti(OPr)₄) are heated to 50 ℃, the carrier gas flow for purging Ti (OPr) ₄ is 40ml/min, and the O ₂ flow is 40ml/min.

In the second step, the Ti (OPr) ₄ film is deposited at a timing of 30 seconds for Ti (OPr) ₄ injection time, 30 seconds for purge time, 10 seconds for O ₂ injection time, 30 seconds for purge time, and 50 cycle periods.

Fourth, the deposition Pt film time sequence is that the injection time of MeCpPtMe ₃ is 20 seconds, the purge time is 40 seconds, the injection time of O ₃ is 30 seconds, the purge time is 40 seconds, and the cycle number is 150.

And fifthly, annealing the 150cPt/50cTiO ₂ film layer by adopting an annealing device, wherein the annealing temperature is 500 ℃ and the annealing time is 4 hours.

FIG. 13 is a grazing incidence X-ray diffraction (GIXRD) result for a 150cPt/50TiO ₂ film. Diffraction peaks for the (111), (200), (220), and (311) crystal planes of the metal Pt appear in the GIXRD spectrum of fig. 13. Fig. 14 is a graph simulating thickness and resistance values of a metallic hemispherical inner wall Pt film in terms of latitude and longitude. As seen from FIG. 14, the average thickness of the simulated metal hemisphere Pt film isThe unevenness was 3.5%. As shown in FIG. 15, the electronic universal tester tests that the binding force between the 150cPt/50TiO ₂ film and the quartz substrate is 230N at the maximum.

Example 10:

The embodiment provides a preparation method of a metal film layer on the surface of a curved quartz substrate with an oxide transition layer, namely, an atomic layer deposition is adopted to prepare a hemispherical resonator Ru/Al ₂O₃ film layer, and the method comprises the following steps:

Firstly, a quartz hemispherical resonator, a simulated metal hemisphere of a silicon wafer, a silicon wafer and a quartz wafer (20 mm multiplied by 2 mm) are placed in an atomic layer deposition reactor, the reactor temperature is 300 ℃, the pressure is 1Torr, the carrier gas flow is 100ml/min, and the Al ₂O₃ precursor Trimethylaluminum (TMA) and oxygen (O ₂),O₂ flow is 40 ml/min) are deposited.

Third, the Ru film precursor bis (cyclopentadienyl) ruthenium (RuCp ₂) and O ₂,RuCp₂ were deposited by heating to 80℃with 40ml/min carrier gas carrying RuCp ₂ precursor.

Fourthly, the Ru film deposition time sequence is RuCp ₂, the injection time is 15 seconds, the purging time is 40 seconds, the O ₂ injection time is 30 seconds, the purging time is 40 seconds, and the cycle number is 200.

And fifthly, annealing the Ru/Al ₂O₃ film layer by adopting an annealing device, wherein the annealing temperature is 500 ℃ and the annealing time is 4 hours.

Fig. 16 is a graph simulating thickness and resistance values of the metal hemispherical inner wall Ru thin film in latitude and longitude. As seen from FIG. 16, the average thickness of the simulated metal hemisphere Ru film isThe unevenness was 4.3%, and the average resistance was 8.4. OMEGA. As shown in FIG. 17, the binding force between the 200cRu/50cAl ₂O₃ film and the quartz substrate is measured to be 342N.

Comparative example 1:

This comparative example was used in comparative example 8, which shows a method for preparing a metallic film layer on the surface of a curved quartz substrate with an oxide transition layer, i.e., preparing a hemispherical resonator Pt/NiO film layer by atomic layer deposition, comprising the steps of:

Firstly, placing a simulated metal hemisphere and a quartz plate (20 mm multiplied by 2 mm) attached with a silicon wafer into an atomic layer deposition reactor, wherein the temperature of the reactor is 200 ℃, the pressure is 1Torr, the carrier gas flow is 100ml/min, the deposited NiO precursor is bis (cyclopentadiene) nickel (NiCp ₂) and oxygen (O ₂),NiCp₂ heating temperature is 80 ℃, the carrier gas carrying NiCp ₂ precursor is 40ml/min, and the O ₂ flow is 40ml/min.

In the second step, the time sequence of the NiO film deposition is NiCp ₂, the injection time is 10 seconds, the purging time is 30 seconds, the O ₂ injection time is 10 seconds, the purging time is 30 seconds, and the cycle number is 50.

Fourth, the deposition Pt film time sequence is that the injection time of MeCpPtMe ₃ is 20 seconds, the purge time is 40 seconds, the injection time of O ₃ is 30 seconds, the purge time is 40 seconds, and the cycle number is 200.

And fifthly, annealing the Pt/NiO film layer by adopting a high-temperature furnace, wherein the annealing temperature is 550 ℃, and the annealing time is4 hours.

Fig. 18 is a graph simulating thickness and resistance values of a metallic hemispherical inner wall Pt film in terms of latitude and longitude. As seen in FIG. 18, the average thickness of the simulated metal hemisphere Pt film isThe unevenness was 28.9% and the average resistance was 19Ω, indicating that poor uniformity of the NiO transition layer resulted in increased unevenness of the metal layer Pt film.

Comparative example 2:

this comparative example was used in comparative example 8, which shows a method for preparing a metal film layer on the surface of a curved quartz substrate with an oxide transition layer, namely, a hemispherical resonator Pt/VO ₂ film layer was prepared by atomic layer deposition, comprising the steps of:

Firstly, placing a simulated metal hemisphere and a quartz plate (20 mm multiplied by 2 mm) attached with a silicon wafer into an atomic layer deposition reactor, wherein the temperature of the reactor is 200 ℃, the pressure is 1Torr, the carrier gas flow is 100ml/min, the deposition VO ₂ precursor triisopropoxyvanadium oxide (VO (OC ₃H₇)₃) and oxygen (O ₂),VO(OC₃H₇)₃ heating temperature is 50 ℃), the carrier gas carrying the VO (OC ₃H₇)₃ precursor is 40ml/min, and the O ₂ flow is 40 ml/min).

In the second step, the VO ₂ film is deposited at the timing of VO (OC ₃H₇)₃ injection time of 10 seconds, purge time of 30 seconds, O ₂ injection time of 10 seconds, purge time of 30 seconds and 50 cycle periods.

And fifthly, annealing the Pt/VO ₂ film layer by adopting a high-temperature furnace, wherein the annealing temperature is 550 ℃, and the annealing time is 4 hours.

Fig. 19 is a graph simulating thickness and resistance values of a metallic hemispherical inner wall Pt film in terms of latitude and longitude. As seen in FIG. 19, the average thickness of the simulated metal hemisphere Pt film isThe unevenness was 39.8% and the average resistance was 25Ω, indicating that poor uniformity of the VO ₂ transition layer resulted in increased unevenness of the metal layer Pt film.

Comparative example 3:

This comparative example was used in comparative example 8, which shows a method for preparing a metal film layer on the surface of a curved quartz substrate with an oxide transition layer, namely, a hemispherical resonator Pd/Al ₂O₃ film layer is prepared by atomic layer deposition, and the method comprises the following steps:

Firstly, placing a simulated metal hemisphere and a quartz plate (20 mm multiplied by 2 mm) attached with a silicon wafer into an atomic layer deposition reactor, wherein the temperature of the reactor is 200 ℃, the pressure is 1Torr, the carrier gas flow rate is 100ml/min, and the deposition Al ₂O₃ precursor Trimethylaluminum (TMA) and oxygen (O ₂),O₂ flow rate is 40 ml/min).

Third, pd film precursor hexafluoroacetylacetonate (Pd (hfac) ₆) and formaldehyde (HCHO) are deposited, pd (hfac) ₆ is heated to 60 ℃, and carrier gas carrying Pd (hfac) ₆ precursor is 80ml/min.

Fourth, pd film deposition time sequence, namely Pd (hfac) ₆ injection time 20 seconds, purging time 40 seconds, HCHO injection time 30 seconds, purging time 40 seconds, and cycle number 200 respectively.

And fifthly, annealing the Pd/Al ₂O₃ film layer by adopting a high-temperature furnace, wherein the annealing temperature is 550 ℃, and the annealing time is 4 hours.

Fig. 20 is a graph simulating the thickness and resistance values of the metal hemispherical inner wall Pd film in terms of latitude and longitude. As seen from FIG. 20, the average thickness of the Pd film in the simulated metal hemisphere isThe unevenness is 56.3%, the average resistance is 56 omega, which indicates that the Pd film of the metal layer is uneven and the resistance is too high to meet the use requirement.

Claims

1. A preparation method of a metal film layer on the surface of a curved quartz substrate with an oxide transition layer is characterized in that an atomic layer deposition method is adopted, a layer of oxide is deposited on the surface of the curved quartz substrate as a transition layer for enhancing the binding force, and a layer of metal is deposited as a conductive layer;

the curved quartz substrate is a hemispherical harmonic oscillator in the hemispherical resonance gyroscope;

The transition layer is formed by an atomic layer deposited precursor corresponding to Al ₂O₃ or TiO ₂;Al₂O₃ and a precursor corresponding to TiO ₂, wherein the atomic layer deposited precursor is trimethylaluminum and oxygen;

The metal of the conductive layer is Pt or Ru, precursors of atomic layer deposition corresponding to Pt are trimethyl methyl cyclopentadienyl platinum and ozone, and precursors of atomic layer deposition corresponding to Ru are bis (cyclopentadiene) ruthenium and oxygen;

The thickness of the transition layer is 1-10 nm, the cycle number of atomic layer deposition of the oxide is 50, and the time sequence of atomic layer deposition of the oxide of the transition layer is that the solid precursor corresponding to the oxide is injected for 10-30 seconds, the purging time is 30 seconds, the gas precursor corresponding to the oxide is injected for 10 seconds, and the purging time is 30 seconds;

The thickness of the conductive layer is 5-30 nm, the cycle number of the atomic layer deposition of the metal is 100-500, and the time sequence of the atomic layer deposition of the metal of the conductive layer is 15-20 seconds of solid precursor injection time corresponding to the metal, 40 seconds of purging time, 30 seconds of solid precursor injection time corresponding to the metal and 40 seconds of purging time;

the annealing temperature is 500-550 ℃.