Method for preparing a curved quartz substrate surface metal film layer with an oxide transition layer

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. The inhomogeneity of the metal film prepared by ALD in the latitudinal and longitudinal directions of the inner wall of a hemispherical harmonic oscillator is less than 5%. The hemispherical harmonic oscillator of this invention has a low specific surface area and aspect ratio, making it easy to achieve mass production of ALD films.

Description

Technical Field

[0001] This invention belongs to the field of inertial navigation hemispherical resonant gyroscope technology, and relates to the preparation of metal film layers, specifically to a method for preparing a metal film layer on the surface of a curved quartz substrate with an oxide transition layer. Background Technology

[0002] Due to their advantages such as simple structure, small size, high precision, long life and stable physical characteristics, hemispherical resonant gyroscopes have broad application prospects in fields such as weaponry, deep space exploration, satellite communication, inertial navigation systems, navigation and astronomical telescopes.

[0003] The core components of a hemispherical resonator gyroscope consist of three parts: an electrostatic excitation cover, a hemispherical resonator, and a sensitive readout base, all made of quartz glass. The hemispherical resonator is the most crucial sensing element. To control the vibration of the hemispherical resonator and obtain a precise vibration signal, the insulating resonator surface is typically metallized to make it conductive. However, due to the hemispherical resonator's complex surface structure, depositing a highly uniform and precise thin film on its surface is extremely difficult. Furthermore, factors such as the mismatch in thermal expansion coefficients between the quartz material and the metal thin film can easily cause the deposited metal film to detach from the resonator surface.

[0004] Currently, the most publicly reported methods for metallizing hemispherical harmonic oscillators in China are magnetron sputtering. This technique involves bombarding the target surface with high-energy Ar ions, causing the target atoms to be deposited onto the substrate via sputtering to form a thin film. While this technique offers a wide range of selectable metal materials and high deposition efficiency, magnetron sputtering is not entirely suitable for coating curved or irregularly shaped substrates where extremely high film quality is required. The varying axial and radial distances from the target to the spherical substrate, even at a consistent sputtering rate, will result in different film thicknesses at different locations on the curved surface, leading to poor uniformity. For example, the non-uniformity of Cr / Au films prepared on hemispherical harmonic oscillators using magnetron sputtering exceeds 20%, and the Q-value loss of the hemispherical harmonic oscillator after coating can reach as high as 50%. Magnetron sputtering is a physical vapor deposition method, where the film and substrate are bonded by van der Waals forces, resulting in relatively weak adhesion. After high-temperature annealing, the oxidation of Cr film is accelerated, causing Cr2O3 to migrate rapidly to the surface of Au film, damaging the structure of Au conductive layer, resulting in decreased conductivity, reduced adhesion of Au film, and severe detachment of Au film from quartz surface, thus reducing the quality factor of resonator.

[0005] Metallization coating on the surface of hemispherical resonators is a key technology for developing navigation-grade hemispherical resonator gyroscopes. There is an urgent need to solve the problems of uneven thin film preparation and low adhesion in existing coating technologies, so as to help develop high-quality factor hemispherical resonator gyroscopes in my country. Summary of the Invention

[0006] To address the shortcomings of existing technologies, the present invention aims to provide a method for preparing a metal film layer on a curved quartz substrate with an oxide transition layer, thereby solving the technical problems of uneven film and low adhesion in the existing magnetron sputtering method.

[0007] To solve the above-mentioned technical problems, the present invention adopts the following technical solution:

[0008] A method for preparing a metal film on the surface of a curved quartz substrate with an oxide transition layer is disclosed. The method employs atomic layer deposition (ALD) to first deposit an oxide layer as a transition layer to enhance adhesion on the surface of the curved quartz substrate, and then deposit a metal layer as a conductive layer. The deposited transition layer and conductive layer are annealed to form the metal film.

[0009] The oxide of the transition layer is Al2O3 or TiO2;

[0010] The metal of the conductive layer is Pt or Ru.

[0011] The present invention also has the following technical features:

[0012] Preferably, the thickness of the transition layer is 1–10 nm; and the thickness of the conductive layer is 5–30 nm.

[0013] Preferably, the curved quartz substrate is a hemispherical harmonic oscillator in a hemispherical resonant gyroscope.

[0014] Preferably, the precursors for atomic layer deposition of Al2O3 are trimethylaluminum and oxygen; the precursors for atomic layer deposition of TiO2 are tetraisopropoxide titanium and oxygen.

[0015] Preferably, the precursors for atomic layer deposition of Pt are trimethylmethylcyclopentadienylplatinum and ozone; the precursors for atomic layer deposition of Ru are bis(cyclopentadienyl)ruthenium and oxygen.

[0016] Preferably, the annealing temperature is 500–550°C.

[0017] Preferably, the number of atomic layer deposition cycles of the oxide is 50 cycles.

[0018] More preferably, the atomic layer deposition sequence of the oxide in the transition layer is as follows: the solid precursor injection time corresponding to the oxide is 10-30 seconds, the purging time is 30 seconds, the gas precursor injection time corresponding to the oxide is 10 seconds, and the purging time is 30 seconds.

[0019] Preferably, the number of atomic layer deposition cycles of the metal is 100 to 500 cycles.

[0020] More preferably, the timing of atomic layer deposition of the metal in the conductive layer is as follows: the solid precursor implantation time corresponding to the metal is 15-20 seconds, the purge time is 40 seconds, the solid precursor implantation time corresponding to the metal is 30 seconds, and the purge time is 40 seconds.

[0021] Compared with the prior art, the present invention has the following technical effects:

[0022] (I) The present invention can solve the problem of unevenness of thin films prepared by magnetron sputtering, and the unevenness of metal films prepared by atomic layer deposition in the latitude and longitude directions of the inner wall of the hemispherical harmonic oscillator is less than 5%.

[0023] (II) In this invention, the conductivity of the Cr / Au thin film decreases after high-temperature annealing, and the adhesion of the Cr / Au thin film weakens, leading to severe detachment of the Au film from the quartz surface and a reduction in the quality factor of the resonator. Atomic layer deposition (ALD) involves a chemical reaction on the quartz substrate surface to generate new chemical bonds. These bonds are strong, and during annealing, oxides do not diffuse to the metal thin film surface, thus reducing conductivity and adhesion. The metal thin film prepared by ALD has a resistance of less than 30Ω, and after annealing, its adhesion to the quartz substrate is greater than 100N.

[0024] (III) The hemispherical harmonic oscillator of the present invention has a low specific surface area and depth ratio, making it easy to achieve mass production of atomic layer deposition coatings. Attached Figure Description

[0025] Figure 1 This is a graph showing the trend of the number of Pt cycles in ALD as a function of Pt film thickness.

[0026] Figure 2 This is a graph showing the trend of the number of Pt cycles in ALD as a function of the Pt thin film resistance.

[0027] Figure 3 The results are from a planar scanning electron microscope (SEM) of a 200cPt / 50cAl2O3 thin film.

[0028] Figure 4 Grazing incidence X-ray diffraction results for 200cPt / 50cAl2O3 thin films.

[0029] Figure 5 The full X-ray photoelectron spectroscopy (XPS) spectrum of the 200cPt / 50cAl2O3 thin film (a) and the fine scan spectrum of Pt 4f (b).

[0030] Figure 6 The results show the adhesion test between the 200cPt / 50cAl2O3 thin film and the quartz substrate before and after annealing.

[0031] Figure 7 The results show the adhesion test between the 200cPt / 25cAl2O3 film and the quartz substrate before and after annealing.

[0032] Figure 8 Schematic diagrams of simulated metal hemispherical structures before (A) and after (B) silicon wafer bonding.

[0033] Figure 9 FIB-TEM and high-magnification TEM images of the cross-section of the 200cPt / 50cAl2O3 thin film on the surface of a hemispherical harmonic oscillator.

[0034] Figure 10 HAADF-STEM, EDX mapping, and line scanning of the cross-section of the 200cPt / 50cAl2O3 thin film on the surface of the hemispherical harmonic oscillator.

[0035] Figure 11 The results were used to simulate the thickness variation of the Pt film on the inner wall of the metal hemispheres 1(a) and 2(b) along the latitude and longitude.

[0036] Figure 12 The results were used to simulate the resistance changes of the Pt thin film on the inner wall of the metal hemispheres 1(a) and 2(b) at latitude and longitude.

[0037] Figure 13 The results are from grazing incidence X-ray diffraction of a 150cPt / 50cTiO2 thin film.

[0038] Figure 14 The results were used to simulate the thickness and resistance variations of the Pt thin film on the inner wall of a metallic hemisphere in the latitudinal and longitudinal directions.

[0039] Figure 15 The adhesion between the 150cPt / 50cTiO2 thin film and the quartz substrate was tested.

[0040] Figure 16 The results were used to simulate the thickness and resistance variations of the Pt thin film on the inner wall of a metallic hemisphere in the latitudinal and longitudinal directions.

[0041] Figure 17 The adhesion between the 200cRu / 50cAl2O3 thin film and the quartz substrate was tested.

[0042] Figure 18 The results were used to simulate the thickness and resistance variations of the Pt thin film on the inner wall of a metallic hemisphere in the latitudinal and longitudinal directions.

[0043] Figure 19 The results were used to simulate the thickness and resistance variations of the Pt thin film on the inner wall of a metallic hemisphere in the latitudinal and longitudinal directions.

[0044] Figure 20 The results were used to simulate the thickness and resistance variations of the Pd thin film on the inner wall of a metal hemisphere in the latitudinal and longitudinal directions.

[0045] The specific content of the present invention will be further explained in detail below with reference to the embodiments. Detailed Implementation

[0046] It should be noted that, unless otherwise specified, all materials and devices used in this invention are those known in the art.

[0047] Hemispherical resonator gyroscopes have broad application prospects in high-precision navigation. The core component of a hemispherical resonator gyroscope, the hemispherical harmonic oscillator, requires a metal film to be deposited on its surface to make it conductive. Atomic layer deposition (ALD) is a high-precision micro-nano fabrication technology capable of forming a film with controllable and uniform thickness on three-dimensional structural surfaces. The precursor for ALD reacts chemically with the silicon-oxygen bonds on the surface of the quartz hemispherical resonator to generate new chemical bonds, depositing the film onto the substrate surface. The bonding force of these chemical bonds is much greater than that of van der Waals forces. Furthermore, ALD prepares an extremely thin oxide layer as a transition layer, which does not reduce the quality factor of the resonator and also inhibits water molecule adsorption onto the resonator surface, thus reducing losses. The hemispherical resonator has a low specific surface area and aspect ratio, making it easy to mass-produce ALD films. Therefore, metal films prepared by ALD are a promising technological solution.

[0048] In this invention, an elliptic polarization spectrometer (SE) is used to measure the film thickness; a scanning electron microscope (SEM) is used to observe the film morphology; a focused ion beam transmission electron microscope (FIB-TEM) is used to observe the film microstructure; X-ray photoelectron spectroscopy (XPS) is used to analyze the film composition; grazing incidence X-ray diffraction (GIXRD) is used to analyze the phase structure of the film; an electronic universal testing machine is used to test the adhesion between the film and the quartz substrate; and a four-probe resistor meter is used to test the film resistance.

[0049] The following are specific embodiments of the present invention. It should be noted that the present invention is not limited to the following specific embodiments. All equivalent modifications made based on the technical solutions of this application fall within the protection scope of the present invention.

[0050] Examples 1 to 6:

[0051] This embodiment provides a method for preparing a metal film on a curved quartz substrate with an oxide transition layer, specifically, a Pt / Al2O3 film for a hemispherical harmonic oscillator with a certain number of cycles is prepared by atomic layer deposition. The method includes the following steps:

[0052] The first step involves placing silicon wafers and quartz wafers (20mm×20mm×2mm) into an atomic layer deposition reactor. The reactor temperature is 200℃, the pressure is 1 Torr, and the carrier gas flow rate is 100ml / min. The Al2O3 precursor trimethylaluminum (TMA) and oxygen (O2) are deposited at an O2 flow rate of 40ml / min.

[0053] The second step, the timing of Al2O3 film deposition: TMA injection time 10 seconds, purge time 30 seconds, O2 injection time 10 seconds, purge time 30 seconds, 50 cycles.

[0054] The third step involves depositing the Pt thin film precursor trimethylmethylcyclopentadienylplatinum (MeCpPtMe3) and O3. The MeCpPtMe3 is heated to 50°C, and the carrier gas carrying the MeCpPtMe3 precursor is 40 ml / min, while the O3 flow rate is 40 ml / min.

[0055] Step 4, Pt film deposition timing: MeCpPtMe3 implantation time 20 seconds, purge time 40 seconds, O3 implantation time 30 seconds, purge time 40 seconds, with cycle numbers of 100, 150, 180, 200, 250, and 500 respectively.

[0056] The fifth step involves annealing the Pt / Al2O3 film in a high-temperature furnace at 550°C for 4 hours.

[0057] The thicknesses of Pt films with 100, 150, 180, 200, 250, and 500 periods grown on silicon wafers with 50-period Al2O3 deposition were measured, and the results are as follows: Figure 1 As shown. From Figure 1 We observed that the Pt film thickness increased linearly with the increase of the number of Pt cycles, and the average growth rate of Pt... / cycle. Due to the delayed nucleation of Pt thin films on Al2O3, the growth rate of Pt is relatively low at 100 cycles. / cycle.

[0058] Resistance tests were performed on Pt thin films with different period numbers, and the results are as follows: Figure 2 As shown. From Figure 2 It can be seen that when the number of Pt cycles is 100, the resistance value is ~148Ω. When the number of Pt cycles is greater than 150, the resistance value is less than ~20Ω, which is close to the resistance of bulk metal Pt.

[0059] The morphology of the 200cPt / 50cAl2O3 thin film on a silicon wafer was observed using scanning electron microscopy (SEM), and the results are as follows: Figure 3 As shown. From Figure 3 Pt nanoparticles are uniformly distributed on the surface of the 200cPt / 50cAl2O3 thin film.

[0060] Figure 4 These are the results of grazing incidence X-ray diffraction (GIXRD) of a 200cPt / 50cAl2O3 thin film. Figure 4The GIXRD spectrum showed diffraction peaks of the (111), (200), (220), and (311) crystal planes of metallic Pt. Al2O3 is an amorphous thin film and does not have corresponding diffraction peaks.

[0061] The composition of the 200cPt / 50cAl2O3 thin film surface was analyzed by X-ray photoelectron spectroscopy (XPS), and the results are as follows: Figure 5 As shown. From Figure 5 (a) shows that the film surface contains Pt, O, and C elements, with C and O mainly originating from surface contaminant carbon and adsorbed oxygen. The contaminant layer on the 200cPt / 50cAl2O3 film surface was etched for 30 seconds. Figure 5 The fine scan spectrum of Pt element in (b) shows that Pt 4f 5 / 2 and Pt 4f 7 / 2 The binding energies are located at 74.7 eV and 71.4 eV, indicating that the Pt film is composed of elemental Pt.

[0062] The adhesion between 200cPt / 50cAl2O3 films and quartz substrates before and after annealing was tested using an electronic universal testing machine according to the pull-out method described in GB5210-2006 standard. Figure 6 The results show the adhesion test results of the 200cPt / 50cAl2O3 film before and after annealing. It can be seen that the 200cPt / 50cAl2O3 film can only detach from the quartz surface at 308N, indicating that the maximum adhesion between the 200cPt / 50cAl2O3 film prepared by ALD and the quartz substrate is 308N. After annealing, the adhesion between the 200cPt / 50cAl2O3 film and the quartz substrate decreases, and it detaches from the quartz substrate surface at 115N. This may be because new stress is generated in the film interface after annealing, leading to a decrease in adhesion.

[0063] Example 7:

[0064] This embodiment provides a method for preparing a metal film on a curved quartz substrate with an oxide transition layer, namely, preparing a Pt / Al2O3 film for a hemispherical harmonic oscillator by atomic layer deposition. This method is based on Examples 1 to 6, with other conditions remaining unchanged, except that the number of Al2O3 deposition cycles is 25 and the number of Pt deposition cycles is 200.

[0065] The adhesion between 200cPt / 25cAl2O3 films and quartz substrates before and after annealing was tested using an electronic universal testing machine according to the pull-out method described in GB5210-2006 standard. Figure 7The results show the adhesion test results of the 200cPt / 25cAl2O3 film before and after annealing. It can be seen that compared with 200cPt / 50cAl2O3, the adhesion of the 200cPt / 25cAl2O3 film before and after annealing is 264N and 106N respectively, which is lower than that of the 200cPt / 50cAl2O3 film. This indicates that the 50-cycle-thickness Al2O3 interacts strongly with metallic Pt and has a higher adhesion.

[0066] Example 8:

[0067] This embodiment presents a method for preparing a metal film on a curved quartz substrate with an oxide transition layer. Specifically, it describes the preparation of a Pt / Al₂O₃ film on a hemispherical resonator using atomic layer deposition. This method is based on Examples 1 to 6, with other conditions remaining unchanged. The substrate is a quartz hemispherical resonator and a simulated metal hemisphere with a silicon wafer attached. Schematic diagrams of the simulated metal hemisphere before and after silicon wafer attachment are shown below. Figure 8 A and Figure 8 As shown in B, the simulated metal hemisphere has the same dimensions as the actual quartz hemisphere harmonic oscillator. Two and four silicon wafers are attached to the latitude and longitude of the inner wall of the sphere, respectively, for a total of eight silicon wafers, which are used to test the film thickness and characterize the uniformity of the film thickness in the latitude and longitude directions.

[0068] In a quartz hemispherical resonator and a simulated metal hemisphere with a silicon wafer, the number of Al2O3 deposition cycles was 50, and the number of Pt deposition cycles was 200. A hemispherical resonator with a 200cPt / 50cAl2O3 film was prepared using focused ion beam (FIB), and the microstructure of the 200cPt / 50cAl2O3 film was observed by TEM. The results are as follows. Figure 9 As shown. From Figure 9 As shown in (a), the 200cPt / 50cAl2O3 film has a uniform thickness with an average thickness of ~28.3 nm. Figure 9 As shown in (b), the 200cPt / 50cAl2O3 thin film, when magnified, shows that the average thicknesses of the Pt and Al2O3 layers are ~22.3 nm and ~5.7 nm, respectively. The growth rates of both Pt and Al2O3 can be calculated to be ~ / cycle. EDX-mapping analysis of the cross-section of a 200cPt / 50cAl2O3 thin film was performed from... Figure 10The results show that the film contains Pt, Al, and O elements and is uniformly distributed. Furthermore, Al and O elements are observed within the Pt layer, indicating diffusion of Al₂O₃ within the Pt layer. Line scanning also reveals interpenetration of Pt, Al, and O elements in certain regions, and Si elements also diffuse into the Al₂O₃ film. These results demonstrate that atomic layer deposition (ALD) is a bottom-up thin film synthesis technique. The Pt and Al atomic layers synthesized through surface chemical reactions interdiffusion form a PtAlO₂ mixture interface, which is beneficial for improving adhesion.

[0069] Figure 11 It is a simulated metallic hemispherical harmonic 1 ( Figure 11 (a) and 2 ( Figure 11 (b) The thickness of the Pt film on the inner wall in terms of latitude and longitude. From Figure 11 (a) and Figure 11 As shown in (b), the average thickness of the Pt thin film in the simulated metallic hemispheres 1 and 2 is and The non-uniformity was 1.6% and 2.0%, respectively, with the film uniformity being significantly better than that of magnetron sputtering. From Figure 12 (a) and Figure 12 As shown in (b), the average resistance of the Pt thin film in the simulated metal hemispheres 1 and 2 is 8.9Ω and 8.6Ω, respectively, which is much lower than that of the Cr / Au thin film system prepared by commonly used magnetron sputtering.

[0070] Example 9:

[0071] This embodiment provides a method for preparing a metal film on a curved quartz substrate with an oxide transition layer, specifically, a Pt / TiO2 film for a hemispherical harmonic oscillator is prepared by atomic layer deposition. The method includes the following steps:

[0072] The first step involves placing a hemispherical resonator, a simulated metal hemisphere with attached silicon wafers, and a sample silicon wafer into an atomic layer deposition reactor. The reactor temperature is 200℃, the pressure is 1 Torr, and the carrier gas flow rate is 100 ml / min. TiO2 precursor titanium tetraisopropoxide (Ti(OPr)4) and oxygen (O2) are deposited. Ti(OPr)4 is heated to 50℃, and the carrier gas flow rate for purging Ti(OPr)4 is 40 ml / min, and the O2 flow rate is 40 ml / min.

[0073] The second step, the timing of depositing Ti(OPr)4 thin film: Ti(OPr)4 implantation time 30 seconds, purge time 30 seconds, O2 implantation time 10 seconds, purge time 30 seconds, number of cycles 50.

[0074] The third step involves depositing the Pt thin film precursor trimethylmethylcyclopentadienylplatinum (MeCpPtMe3) and O3. The MeCpPtMe3 is heated to 50°C, and the carrier gas carrying the MeCpPtMe3 precursor is 40 ml / min, while the O3 flow rate is 40 ml / min.

[0075] Step 4, Pt film deposition timing: MeCpPtMe3 implantation time 20 seconds, purge time 40 seconds, O3 implantation time 30 seconds, purge time 40 seconds, number of cycles 150.

[0076] The fifth step involves annealing the 150cPt / 50cTiO2 film using an annealing apparatus at a temperature of 500℃ for 4 hours.

[0077] Figure 13 These are the results of grazing incidence X-ray diffraction (GIXRD) of a 150cPt / 50TiO2 thin film. Figure 13 The GIXRD spectrum showed diffraction peaks of the (111), (200), (220), and (311) crystal planes of metallic Pt. Figure 14 This simulates the thickness and resistivity of the Pt thin film on the inner wall of a metallic hemisphere at different latitudes and longitudes. From Figure 14 As can be seen from the data, the average thickness of the simulated metallic hemispherical Pt thin film is... The non-uniformity is 3.5%. For example... Figure 15 As shown, the maximum bonding force between the 150cPt / 50TiO2 film and the quartz substrate was measured to be 230N using an electronic universal testing machine.

[0078] Example 10:

[0079] This embodiment provides a method for preparing a metal film on a curved quartz substrate with an oxide transition layer, specifically, a Ru / Al2O3 film for a hemispherical harmonic oscillator is prepared by atomic layer deposition. The method includes the following steps:

[0080] The first step involves placing a quartz hemispherical harmonic oscillator, a simulated metal hemisphere with attached silicon wafers, a silicon wafer, and a quartz wafer (20mm×20mm×2mm) into an atomic layer deposition reactor. The reactor temperature is 300℃, the pressure is 1 Torr, and the carrier gas flow rate is 100ml / min. The Al2O3 precursor trimethylaluminum (TMA) and oxygen (O2) are deposited at an O2 flow rate of 40ml / min.

[0081] The second step, the timing of Al2O3 film deposition: TMA injection time 10 seconds, purge time 30 seconds, O2 injection time 10 seconds, purge time 30 seconds, 50 cycles.

[0082] The third step involves depositing the Ru film precursor bis(cyclopentadiene)ruthenium (RuCp2) and O2. The RuCp2 is heated to 80°C, and the carrier gas carrying the RuCp2 precursor is 40 ml / min.

[0083] Step 4, Ru film deposition timing: RuCp2 injection time 15 seconds, purge time 40 seconds, O2 injection time 30 seconds, purge time 40 seconds, cycle number 200.

[0084] The fifth step involves annealing the Ru / Al2O3 film using an annealing apparatus at a temperature of 500°C for 4 hours.

[0085] Figure 16 This simulates the thickness and resistivity of the Ru thin film on the inner wall of a metallic hemisphere at different latitudes and longitudes. From Figure 16 As can be seen from the data, the average thickness of the simulated metallic hemispherical Ru film is [value missing]. The non-uniformity is 4.3%, and the average resistance is 8.4Ω. For example... Figure 17 As shown, the maximum bonding force between the 200cRu / 50cAl2O3 film and the quartz substrate was measured to be 342N using an electronic universal testing machine.

[0086] Comparative Example 1:

[0087] This comparative example is used to compare with Example 8. This comparative example provides a method for preparing a metal film on the surface of a curved quartz substrate with an oxide transition layer, namely, preparing a hemispherical harmonic oscillator Pt / NiO film using atomic layer deposition. The method includes the following steps:

[0088] The first step involves placing a simulated metal hemisphere with a silicon wafer and a quartz plate (20mm×20mm×2mm) inside an atomic layer deposition reactor. The reactor temperature is 200℃, the pressure is 1 Torr, and the carrier gas flow rate is 100ml / min. NiO precursor bis(cyclopentadiene)nickel (NiCp2) and oxygen (O2) are deposited. The NiCp2 heating temperature is 80℃, the carrier gas carrying the NiCp2 precursor is 40ml / min, and the O2 flow rate is 40ml / min.

[0089] The second step, the timing of NiO film deposition: NiCp2 implantation time 10 seconds, purge time 30 seconds, O2 implantation time 10 seconds, purge time 30 seconds, 50 cycles.

[0090] The third step involves depositing the Pt thin film precursor trimethylmethylcyclopentadienylplatinum (MeCpPtMe3) and O3. The MeCpPtMe3 is heated to 50°C, and the carrier gas carrying the MeCpPtMe3 precursor is 40 ml / min, while the O3 flow rate is 40 ml / min.

[0091] Step 4, Pt film deposition timing: MeCpPtMe3 implantation time 20 seconds, purge time 40 seconds, O3 implantation time 30 seconds, purge time 40 seconds, cycle number 200.

[0092] The fifth step is to anneal the Pt / NiO film in a high-temperature furnace at a temperature of 550°C for 4 hours.

[0093] Figure 18 This simulates the thickness and resistivity of the Pt thin film on the inner wall of a metallic hemisphere at different latitudes and longitudes. From Figure 18 As can be seen from the data, the average thickness of the simulated metallic hemispherical Pt thin film is... The non-uniformity was 28.9% and the average resistance was 19Ω, indicating that the poor uniformity of the NiO transition layer led to an increase in the non-uniformity of the Pt metal film.

[0094] Comparative Example 2:

[0095] This comparative example is used to compare with Example 8. This comparative example provides a method for preparing a metal film layer on the surface of a curved quartz substrate with an oxide transition layer, namely, preparing a Pt / VO2 film layer for a hemispherical harmonic oscillator by atomic layer deposition. The method includes the following steps:

[0096] The first step involves placing a simulated metal hemisphere with a silicon wafer and a quartz wafer (20mm×20mm×2mm) into an atomic layer deposition reactor. The reactor temperature is 200℃, the pressure is 1 Torr, the carrier gas flow rate is 100ml / min, and the VO2 precursor triisopropoxyvanadium oxide (VO(OC3H7)3) and oxygen (O2) are deposited. The VO(OC3H7)3 is heated to 50℃, the carrier gas carrying the VO(OC3H7)3 precursor is 40ml / min, and the O2 flow rate is 40ml / min.

[0097] The second step, the timing of VO2 film deposition: VO(OC3H7)3 injection time 10 seconds, purge time 30 seconds, O2 injection time 10 seconds, purge time 30 seconds, number of cycles 50.

[0098] The third step involves depositing the Pt thin film precursor trimethylmethylcyclopentadienylplatinum (MeCpPtMe3) and O3. The MeCpPtMe3 is heated to 50°C, and the carrier gas carrying the MeCpPtMe3 precursor is 40 ml / min, while the O3 flow rate is 40 ml / min.

[0099] Step 4, Pt film deposition timing: MeCpPtMe3 implantation time 20 seconds, purge time 40 seconds, O3 implantation time 30 seconds, purge time 40 seconds, cycle number 200.

[0100] The fifth step involves annealing the Pt / VO2 film in a high-temperature furnace at 550°C for 4 hours.

[0101] Figure 19 This simulates the thickness and resistivity of the Pt thin film on the inner wall of a metallic hemisphere at different latitudes and longitudes. From Figure 19 As can be seen from the data, the average thickness of the simulated metallic hemispherical Pt thin film is... The non-uniformity was 39.8% and the average resistance was 25Ω, indicating that the poor uniformity of the VO2 transition layer led to an increase in the non-uniformity of the Pt metal film.

[0102] Comparative Example 3:

[0103] This comparative example is used to compare with Example 8. This comparative example provides a method for preparing a metal film on the surface of a curved quartz substrate with an oxide transition layer, namely, preparing a Pd / Al2O3 film for a hemispherical harmonic oscillator by atomic layer deposition. The method includes the following steps:

[0104] The first step involves placing a simulated metal hemisphere with a silicon wafer attached and a quartz wafer (20mm×20mm×2mm) inside an atomic layer deposition reactor. The reactor temperature is 200℃, the pressure is 1 Torr, and the carrier gas flow rate is 100ml / min. The Al2O3 precursor trimethylaluminum (TMA) and oxygen (O2) are deposited at an O2 flow rate of 40ml / min.

[0105] The second step, the timing of Al2O3 film deposition: TMA injection time 10 seconds, purge time 30 seconds, O2 injection time 10 seconds, purge time 30 seconds, 50 cycles.

[0106] The third step involves depositing the Pd thin film precursors palladium hexafluoroacetylacetone (Pd(hfac)6) and formaldehyde (HCHO). Pd(hfac)6 is heated to 60°C, and the carrier gas carrying the Pd(hfac)6 precursor is supplied at a flow rate of 80 ml / min.

[0107] Step 4, Pd film deposition timing: Pd(hfac)6 implantation time 20 seconds, purge time 40 seconds, HCHO implantation time 30 seconds, purge time 40 seconds, and the number of cycles is 200 for each.

[0108] The fifth step involves annealing the Pd / Al2O3 film in a high-temperature furnace at 550°C for 4 hours.

[0109] Figure 20 This simulates the thickness and resistivity of the Pd thin film on the inner wall of a metallic hemisphere at different latitudes and longitudes. From Figure 20 As can be seen from the data, the average thickness of the simulated metallic hemispherical Pd thin film is [data missing]. The non-uniformity is 56.3% and the average resistance is 56Ω, indicating that the Pd metal film is non-uniform and has too high a resistance, which does not meet the requirements for use.

Claims

1. A method for preparing a metal film layer on the surface of a curved quartz substrate with an oxide transition layer, characterized in that, This method employs atomic layer deposition, first depositing an oxide layer as a transition layer to enhance adhesion on the surface of a curved quartz substrate, and then depositing a metal layer as a conductive layer; the deposited transition layer and conductive layer are annealed to form a metal film layer. The curved quartz substrate is the hemispherical harmonic oscillator in a hemispherical resonant gyroscope; The oxide of the transition layer is Al2O3 or TiO2; the precursor for the atomic layer deposition corresponding to Al2O3 is trimethylaluminum and oxygen; The precursors for atomic layer deposition of TiO2 are titanium tetraisopropoxide and oxygen. The conductive layer is made of Pt or Ru; the precursor for atomic layer deposition of Pt is trimethylmethylcyclopentadienylplatinum and ozone; the precursor for atomic layer deposition of Ru is bis(cyclopentadienyl)ruthenium and oxygen. The thickness of the transition layer is 1-10 nm; the number of atomic layer deposition cycles of the oxide is 50 cycles; the timing of the atomic layer deposition of the oxide in the transition layer is as follows: the solid precursor injection time corresponding to the oxide is 10-30 seconds, the purge time is 30 seconds, the gas precursor injection time corresponding to the oxide is 10 seconds, and the purge time is 30 seconds. The thickness of the conductive layer is 5-30 nm; the number of atomic layer deposition cycles of the metal is 100-500 cycles; the timing of the atomic layer deposition of the metal in the conductive layer is as follows: the solid precursor implantation time corresponding to the metal is 15-20 seconds, the purge time is 40 seconds, the solid precursor implantation time corresponding to the metal is 30 seconds, and the purge time is 40 seconds. The annealing temperature is 500–550°C.

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