Preparation method of metal film layer on surface of quartz substrate based on metal transition layer

Abstract

The application provides a preparation method of a metal film layer on a quartz substrate surface based on a metal transition layer, which comprises the following steps: depositing a non-noble metal layer on the surface of a curved quartz substrate as a transition layer for enhancing the bonding force, and then depositing a noble metal layer as a conductive layer, so as to form a metal film layer on the quartz substrate surface based on the metal transition layer. The metal film layer prepared by the method has strong bottom surface bonding force and good uniformity. The non-uniformity of the transition layer is less than 4%, the non-uniformity of the conductive layer is less than 5%, and the resistance of the conductive layer is less than 50Ω. The tensile strength between the entire film layer prepared by the PE-ALD and the curved quartz substrate is greater than 10MPa. The plasma source of the PE-ALD can reduce the reaction temperature of the metal film, remove the surface pollutants and the surface oxides, and improve the bonding force between the multilayer films.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of inertial navigation hemispherical resonator gyroscopes, and relates to metal film layer preparation, in particular to a preparation method of a metal film layer on a quartz substrate surface based on a metal transition layer. BACKGROUND

[0002] The hemispherical resonator gyroscope has broad application prospects in the fields of weapon equipment, deep space exploration, satellite communication, inertial navigation system, navigation, and astronomical telescope, due to its simple structure, small size, high precision, long service life, stable physical characteristics, and other advantages.

[0003] The core components of the hemispherical resonator gyroscope are composed of an electrostatic excitation cover, a hemispherical resonator, and a sensitive reading base, all of which are made of quartz glass material. The hemispherical resonator is the most critical sensitive detection element. In order to control the vibration of the hemispherical resonator and obtain accurate vibration signals, the surface of the insulating resonator usually needs to be treated by a metalizing plating process to make it conductive. However, due to the hemispherical shape of the hemispherical resonator, the surface structure is complex, and it is very difficult to plate a high uniformity and high precision thin film on its surface. In addition, factors such as the mismatch of the thermal expansion coefficients between the quartz material of the hemispherical resonator gyroscope and the metal thin film can easily cause the plated metal thin film to fall off from the surface of the resonator.

[0004] The current domestic reported hemispherical resonator surface metalizing plating method mainly uses magnetron sputtering. The plating principle of this technology is to use high-energy Ar ion bombardment on the surface of the target material to make the atoms of the target material deposit on the substrate in a sputtering manner to form a thin film. This technology has a wide range of metal materials to choose from and high deposition efficiency, but magnetron sputtering is not completely suitable for plating on the surface of a curved and shaped structure substrate with ultra-high requirements for film quality. The distance from the target to the axial and radial direction of the spherical substrate is different, and under the condition of consistent sputtering rate, it will cause the thickness of the deposited thin film at different positions on the curved surface to be different, resulting in poor uniformity. For example, the current Cr / Au thin film prepared on the hemispherical resonator by magnetron sputtering has a non-uniformity of more than 20%, and the Q value loss of the hemispherical resonator after plating is as high as 50%. Magnetron sputtering is a kind of physical vapor deposition, and the film layer and the substrate are combined by Van der Waals force, which has weak binding force. After the Cr / Au thin film undergoes a high-temperature annealing process, the oxidation of the Cr film will be accelerated, causing Cr2O3 to quickly migrate to the surface of the Au film, destroying the structure of the Au conductive layer, causing the conductive performance to decrease, and leading to the decrease of the binding force of the Au film, thus causing the Au film to fall off from the quartz surface and reduce the quality factor of the resonator.

[0005] Hemispherical resonator surface metalizing plating is a key technology for developing navigation-level hemispherical resonator gyroscopes, and it is urgent to solve the problems of non-uniformity and low binding force of the thin film prepared by the existing plating technology to help the development of high-quality factor hemispherical resonator gyroscopes in China. SUMMARY

[0006] In view of the deficiencies in the prior art, the present application aims to provide a preparation method of a metal film layer on a quartz substrate surface based on a metal transition layer, to solve the technical problem of non-uniformity and low bonding force of the thin film prepared by the magnetron sputtering method in the prior art.

[0007] To solve the above technical problems, the present application adopts the following technical solutions:

[0008] A preparation method of a metal film layer on a quartz substrate surface based on a metal transition layer, which adopts the plasma-enhanced atomic layer deposition method to first deposit a layer of non-noble metal as a transition layer for enhancing the bonding force on the surface of a curved quartz substrate, and then deposit a layer of noble metal as a conductive layer, to form the metal film layer on the quartz substrate surface based on the metal transition layer.

[0009] The non-noble metal of the transition layer is Mo, W or Ti.

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

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

[0012] The transition layer and the conductive layer are prepared in the same plasma-enhanced atomic layer deposition reactor and device.

[0013] Preferably, the thickness of the transition layer is 1-20 nm, and the thickness of the conductive layer is 5-30 nm.

[0014] Preferably, the curved quartz substrate is a hemispherical resonator in a hemispherical resonator gyroscope.

[0015] Preferably, the non-uniformity of the transition layer is less than 4%.

[0016] Preferably, the non-uniformity of the conductive layer is less than 5%.

[0017] Preferably, the resistance of the conductive layer is less than 50Ω.

[0018] Preferably, the tensile strength between the metal film layer on the quartz substrate surface based on the metal transition layer and the curved quartz substrate is greater than 10 MPa.

[0019] Preferably, the atomic layer deposition precursor corresponding to Mo is ethylsilane and molybdenum hexafluoride; the atomic layer deposition precursor corresponding to W is ethylsilane and tungsten hexafluoride; and the atomic layer deposition precursor corresponding to Ti is titanium tetrachloride and plasma 20% H2 / N2.

[0020] Preferably, the atomic layer deposition precursor corresponding to Pt is trimethylmethylcyclopentadienyl platinum and plasma 20% H2 / N2.

[0021] Preferably, the number of atomic layer deposition cycles of the transition layer is 5-50 cycles.

[0022] More preferably, the timing sequence of atomic layer deposition of the transition layer corresponding to Mo or W is: first gas precursor injection time 6 seconds, main valve closed, first gas precursor stays in the reactor for 2-10 seconds, purge time 30 seconds, second gas precursor injection time 6 seconds, main valve closed, second precursor stays in the reactor for 2-10 seconds, purge time 30 seconds.

[0023] More preferably, the timing sequence of atomic layer deposition of the transition layer corresponding to Ti is: titanium tetrachloride precursor injection time 3 seconds, purge time 30 seconds, second plasma 20% H2 / N2 precursor injection time 2 seconds, purge time 30 seconds.

[0024] Preferably, the number of atomic layer deposition cycles of the conductive layer is 100-400 cycles.

[0025] More preferably, the timing sequence of atomic layer deposition of the conductive layer is: first solid precursor injection time 10-30 seconds, purge time 40 seconds, second plasma precursor 20% H2 / N2 injection time 10-60 seconds, purge time 40 seconds.

[0026] Compared with the prior art, the present application has the following technical effects:

[0027] (I) The metal film layer prepared by the present application has strong bottom surface bonding force and good uniformity. The non-uniformity of the transition layer of the present application is less than 4%, the non-uniformity of the conductive layer is less than 5%, and the resistance of the conductive layer is less than 50Ω. The tensile strength between the entire film layer prepared by PE-ALD of the present application and the curved quartz substrate is greater than 10MPa.

[0028] (II) The plasma source of PE-ALD of the present application can reduce the reaction temperature of the metal thin film on the one hand, and can remove the surface pollutants and surface oxides on the other hand, thereby improving the bonding force between the multi-layer thin films.

[0029] (III) The W, Mo, Ti metal layer and the Pt, Ru noble metal layer of the present application are prepared in the same equipment. After the deposition of the first layer of metal layer by the resonator, the resonator is not taken out, and the second layer of noble metal layer is continuously deposited. In this way, the W, Mo, Ti metal of the resonator can be prevented from being oxidized and contaminated by air, the bonding force of the synthesized metal / metal film layer is stronger, and the loss of the resonator is reduced.

[0030] (IV) The half-spherical resonator has low specific surface area and depth ratio, and it is easy to realize batch preparation of atomic layer deposition coating. BRIEF DESCRIPTION OF DRAWINGS

[0031] Figure 1 Thickness profile of 12c Mo thin film in circumferential and radial direction (a) and 300c Pt / 12c Mo thin film in circumferential and radial direction (b) and resistance value (c) for simulating the half-sphere harmonic oscillator inner wall.

[0032] Figure 2 XPS depth profile of 300c Pt / 12c Mo thin film XPS fine scan spectrum depth profile of Pt 4f (B) and Mo 3d (C) for (A).

[0033] Figure 3 GIXRD of 10c Mo, 200c Pt / 10c Mo thin film.

[0034] Figure 4 SEM and AFM results of 12c Mo (a, c), 300c Pt / 12c Mo (b, d) thin film.

[0035] Figure 5 TEM images of 300c Pt / 12c Mo thin film cross section at different magnifications.

[0036] Figure 6 EDS-mapping images of 300c Pt / 12c Mo thin film cross section (a) HAADF-STEM and (b) Pt, (c) Mo, (d) O, (e) Si, (f) Mixing and (g) line scan.

[0037] Figure 7 Adhesion test results of PE-ALD Pt / Mo thin film to quartz substrate.

[0038] Figure 8 XPS depth profile of 400c Pt / 15c Mo thin film XPS fine scan spectrum depth profile of Pt 4f (B) and Mo 3d (C) for (A).

[0039] Figure 9 XPS depth profile of 200c Pt / 15c W thin film XPS fine scan spectrum depth profile of Pt 4f (B) and W 4f (C) for (A).

[0040] Figure 10 TEM images of 200c Pt / 15c W thin film cross section.

[0041] Figure 11 EDS-mapping images of 200c Pt / 15c W thin film cross section (a) HAADF and (b) Pt, (c) W, (d) O elements.

[0042] Figure 12The results of the bonding force test of the PE-ALD film and the quartz substrate.

[0043] Figure 13 The thickness distribution (a) and the resistance value (c) of the 200cPt / 30cTi film in the circumferential and radial directions.

[0044] Figure 14 The HAADF (a) and the EDS-mapping (b) of the Pt, (c) the Ti, and (d) the O elements of the cross section of the 200cPt / 30cTi film.

[0045] Figure 15 The results of the bonding force test of the PE-ALD film and the quartz substrate.

[0046] The specific content of the present application is further explained in detail in combination with the following examples. DETAILED DESCRIPTION

[0047] It should be noted that all the materials and equipment in the present application are known in the art without special instructions.

[0048] The hemispherical resonator gyro has a broad application prospect in the field of high-precision navigation. The hemispherical resonator gyro needs to be plated with a metal film on the surface of the hemispherical resonator to make it conductive. PE-ALD can improve the uniformity and control precision of the film on the surface of the resonator, reduce the resonator loss, and reduce the frequency difference. The metal / metal film layer prepared by PE-ALD technology has high bonding force and good conductivity. The specific surface area and depth ratio of the hemispherical resonator are low, and the batch production of atomic layer deposition plating film can be easily realized.

[0049] The present application provides a kind of hemispherical resonator plasma enhanced-atomic layer deposition (PE-ALD) metal film layer preparation method. ALD belongs to a kind of high-precision micro-nano processing manufacturing technology, can form thickness controllable, uniform film on the surface of three-dimensional structure. The preparation of PE-ALD metal film layer: first, a layer of metal transition layer is deposited on the surface of the resonator, the resonator is continuously deposited with a layer of noble metal conductive layer, and the two metal film layers are prepared in the same PE-ALD reactor and device. The metal transition layer and the conductive layer diffuse into each other to form an alloy, which enhances the bonding force of the transition layer and the conductive layer.

[0050] In the present application, the film thickness is measured by an ellipsometer (SE), the film morphology is observed by an atomic force microscope (AFM), the film microstructure is observed by a focused ion beam-transmission electron microscope (FIB-TEM), the film composition is analyzed by an X-ray photoelectron spectrometer (XPS), the film phase structure is analyzed by a grazing incidence X-ray diffractometer (GIXRD), the film and quartz substrate adhesion is tested by an electronic universal testing machine, and the film resistance is tested by a four-probe resistance meter.

[0051] The following gives specific embodiments of the present application, and it is to be noted that the present application is not limited to the following specific embodiments, and any equivalent changes made on the basis of the technical solutions of the present application all fall within the protection scope of the present application.

[0052] Embodiment 1

[0053] The present embodiment gives a preparation method of a metal film layer on a quartz substrate surface based on a metal transition layer, and specifically, the present embodiment uses PE-ALD to prepare a hemispherical resonator 300cPt / 12cMo film layer, and the method specifically comprises the following steps:

[0054] In the first step, the hemispherical resonator, a quartz piece (20mm×20mm×2mm) for testing, a simulated hemispherical resonator, and a silicon piece are placed in a PE-ALD reactor, the reactor temperature is 200℃, and the reaction pressure is 1Torr.

[0055] In the second step, the Mo precursor is disilane (Si2H6) and molybdenum hexafluoride (MoF6), the Si2H6 injection time is 6 seconds, the main valve is closed, the Si2H6 stays in the reactor for 2 seconds, the purging time is 30 seconds, the MoF6 injection time is 6 seconds, the main valve is closed, the MoF6 stays in the reactor for 2 seconds, the purging time is 30 seconds, and the cycle number is 12.

[0056] In the third step, all sample pieces continue to deposit a Pt thin film in situ. The Pt thin film precursor is trimethylmethylcyclopentadienyl platinum (MeCpPtMe3) and 20% H2 / N2 plasma, the MeCpPtMe3 is heated to 50℃, the carrier gas carrying the MeCpPtMe3 precursor is 40ml / min, the 20% H2 / N2 mixed gas flow is 30ml / min, and the radio frequency plasma generator power is 300W.

[0057] In the fourth step, the Pt thin film deposition timing is as follows: the MeCpPtMe3 injection time is 10 seconds, the purging time is 40 seconds, the 20% H2 / N2 plasma injection time is 10 seconds, the purging time is 40 seconds, and the cycle number is 300.

[0058] The thicknesses of 12cMo and 300cPt / 12cMo films grown by PE-ALD in the circumferential and radial directions on the inner wall of a simulated hemispherical harmonic oscillator were measured using an ellipsometry. The resistivity of the 300cPt / 12cMo film grown by PE-ALD in the circumferential and radial directions on the inner wall of the simulated hemispherical harmonic oscillator was then measured using a four-probe resistor meter. The results are as follows: Figure 1 As shown in a~c in the diagram. From Figure 1 From a to c, we can see that the average thickness of 12cMo on the Si wafer surface is The non-uniformity is 3.5%, and the average thickness of 300cPt on the surface of the 12cMo film is... The non-uniformity of 4.0% indicates that the uniformity of Mo and Pt deposited by PE-ALD is better than that of magnetron sputtering. The average resistance of 300cPt on the surface of the Mo film is 31.3Ω, which is higher than the resistance of Pt with Al2O3 as the transition layer by 10Ω. This may be because the Mo metal particles diffuse to the surface of the Pt metal, increasing the resistance of the Pt film.

[0059] XPS depth profiling was performed on the deposited 300cPt / 12cMo thin film to analyze the chemical environment of Pt and Mo elements at different film depths. The results are as follows: Figure 2 As shown in A to C in the figure. The depth analysis results of the 300cPt / 12cMo thin film show that during the etching time of 0–500 s, only a Pt film layer exists, and the Pt element is uniformly distributed. With increasing etching time, Mo, C, O, and Si elements appear, and Pt, Mo, and Si elements interdiffusion occurs within the etching time range of 700 s–1200 s. The XPS fine scan spectra of Pt and Mo elements at etching times of 0 s, 400 s, 800 s, 1200 s, 1600 s, and 2000 s are analyzed, and the results are as follows: Figure 2 The values ​​B through C are shown in the diagram. The Pt4f of the Pt element... 7 / 2 and Pt4f 5 / 2 The binding energies of the energy levels are 71.0 eV and 74.4 eV, respectively, belonging to the metallic state of Pt. With increasing etching depth, Pt4f... 7 / 2 The binding energy increased to 71.4 eV, indicating the formation of partially oxidized PtO. Mo elements were present in Mo3d before etching. 3 / 2 and Mo3d 5 / 2 The binding energies are 236.7 eV and 233.6 eV, significantly higher than the binding energies of zero-valent Mo (228.0 eV and 231.0 eV), classifying them as MoO3 compounds. With increasing etching time, more valence states of Mo appeared, corresponding to Mo3d... 5 / 2 The binding energies are 228.9 eV and 229.8 eV, respectively, belonging to MoO and MoO2 compounds. When the etching time is further increased to 1200 s, Mo3d... 5 / 2 The binding energy is 228.0 eV, which belongs to the metallic state of Mo.

[0060] Figure 3 GIXRD patterns of 12cMo, 300cPt / 12cMo films are shown. From Figure 3 it can be seen that Mo diffraction peaks do not appear in 12cMo film, which may be due to the small particle size of Mo, and Mo metal diffraction peaks are not detected. The characteristic diffraction peaks of Pt metal (111), (200), (220), (311), (222) crystal planes appear in 300cPt / 12cMo film.

[0061] The morphology and roughness of 12cMo, 300cPt / 12cMo films are observed by scanning electron microscopy (SEM) and atomic force microscopy (AFM), and the results are shown in Figure 4 From a to b in Figure 4 it can be seen that the Mo film surface particles are highly uniform in dispersion, and the Pt film particles deposited on the Mo surface are also very uniform and dense. Figure 4 The AFM pictures in c to d in indicate that 12cMo and 300cPt / 12cMo films are uniform and dense, and the roughness is small, which is 0.64 nm and 0.99 nm, respectively.

[0062] Figure 5 The cross-sectional microstructure of 300cPt / 12cMo film layer is observed by focused ion beam-transmission electron microscopy (FIB-TEM), and the results are shown in Figure 5 From the TEM picture in A in Figure 5 it can be seen that the film is composed of two layers of film layers, which are Pt and Mo. From B in it can be seen that the average thickness of Pt film layer is 17.3 nm, and the average growth rate is The average thickness of the next Mo film layer is 14.0 nm, and the average growth rate is From this, it can be seen that the average growth rates of Pt and Mo are the same as the reported values, and the thicknesses of 300cPt and 12cMo films are also basically consistent with the test results of ellipsometer. From C in Figure 5 it can be seen that the interfaces of Pt and Mo, Mo and Si substrate in Pt / Mo composite film are not clear, which indicates that Pt and Mo diffuse with each other, and Mo and Si diffuse with each other, which can effectively form a film layer with high bonding force.

[0063] Figure 6 a to g are high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) characterization and energy dispersive spectroscopy-element distribution (EDS-mapping) characterization of Pt, Mo, O elements of 300cPt / 12cMo film. Figure 6 a again proves that 300cPt / 12cMo film is composed of Pt and Mo, and Pt metal can also be clearly seen to diffuse into Mo film layer. From Figure 6It can be seen from b-f that the elements of Pt, Mo and O are uniformly distributed in the whole film layer. Figure 6 It can be seen from g that the elements of Pt, Mo, O and Si exist in 20-35 nm in the total film of 300cPt / 12cMo, which is consistent with the result of XPS depth analysis in A. Figure 2 The result of XPS depth analysis in A is consistent.

[0064] Examples 2 to 6:

[0065] This embodiment provides a preparation method of a metal film layer on a quartz substrate surface based on a metal transition layer. Specifically, this embodiment uses PE-ALD to prepare Pt / 12cMo film layers of different cycle periods of hemispherical resonators. The method keeps other conditions unchanged as in Example 1, and adjusts the cycle number of ALD Mo to deposit 5c, 10c, 15c, 18c and 20c metal Mo, respectively. 300cPt / 5cMo, 300cPt / 10cMo, 300cPt / 12cMo, 300cPt / 15cMo, 300cPt / 18cMo and 300cPt / 20cMo thin films are prepared.

[0066] The adhesion of 300cPt / 5cMo, 300cPt / 10cMo, 300cPt / 12cMo, 300cPt / 15cMo, 300cPt / 18cMo and 300cPt / 20cMo thin films to the quartz substrate is tested by using an electronic universal testing machine according to the pull-off method described in GB5210-2006 standard. It can be seen from Figure 7 that the tensile strength of the quartz substrate is about 8.8 MPa, and the tensile strength of 300cPt / 5cMo to the quartz substrate is about 8.9 MPa, which is basically equivalent to the cohesive force of the quartz material itself. As the cycle number of the metal Mo transition layer increases from 10 to 15, the tensile strength remains in the range of 7.1-8.0 MPa, which is slightly lower than that of the quartz substrate. When the cycle number of the Mo transition layer continues to increase to 18 and 20 cycles, the tensile strength of the thin film decreases significantly to about 4 MPa. It is possible that when the thickness of the Mo film increases to a certain extent, a certain tensile stress is generated, which destroys the strength of the film.

[0067] Example 7:

[0068] This embodiment provides a preparation method of a metal film layer on a quartz substrate surface based on a metal transition layer. Specifically, this embodiment uses PE-ALD to prepare 400cPt / 15cMo film layers of hemispherical resonators, which specifically includes the following steps:

[0069] Firstly, the hemispherical resonator, the quartz piece (20mm×20mm×2mm) for testing, the simulated hemispherical resonator and the silicon piece are placed in the PE-ALD reactor, the reactor temperature is 200℃, and the reaction pressure is 1 Torr.

[0070] The second step involves depositing Mo precursors of silane (Si2H6) and molybdenum hexafluoride (MoF6). The Si2H6 injection time is 6 seconds, the main valve is closed, the Si2H6 stays in the reactor for 2 seconds, and the purging time is 30 seconds. The MoF6 injection time is 6 seconds, the main valve is closed, the MoF6 stays in the reactor for 2 seconds, and the purging time is 30 seconds. The number of cycles is 15.

[0071] In the third step, all sample specimens continued to have Pt thin films deposited in situ. The Pt film deposition precursor was trimethylmethylcyclopentadienylplatinum (MeCpPtMe3), and the plasma was 20% H2 / N2. MeCpPtMe3 was heated to 50°C, the carrier gas carrying the MeCpPtMe3 precursor was 40 ml / min, the flow rate of the 20% H2 / N2 mixed gas was 30 ml / min, and the power of the radio frequency plasma generator was 300 W.

[0072] Step 4, Pt film deposition timing: MeCpPtMe3 injection time 10 seconds, purge time 40 seconds, plasma 20% H2 / N2 injection time 10 seconds, purge time 40 seconds, number of cycles 400.

[0073] XPS depth profiling was performed on the deposited 400cPt / 15cMo thin film to analyze the chemical environment of Pt and Mo elements at different film depths. The results are as follows: Figure 8 As shown in A to C in the figure. The results of depth analysis of the 400cPt / 15cMo thin film. Figure 8 As shown in Figure A, only a Pt film layer exists within the etching time of 0–700 s, and the Pt element is uniformly distributed. With increasing etching time, Mo, C, O, and Si elements appear. Due to the relatively thick 400 cPt / 15 cMo film, an etching time of 2000 s did not etch the film to the silicon substrate, and the atomic percentage of Si was less than 30%. The XPS fine scan spectra of Pt and Mo elements at etching times of 0 s, 400 s, 800 s, 1200 s, 1600 s, and 2000 s are analyzed, and the results are as follows: Figure 8 The values ​​B through C are shown in the diagram. The Pt4f of the Pt element... 7 / 2 and Pt4f 5 / 2 The binding energies of the energy levels are 71.3 eV and 74.7 eV, respectively, belonging to the metallic state of Pt. With increasing etching depth, Pt4f... 7 / 2 The binding energy increased to 71.9 eV, indicating the formation of partially oxidized PtO. Mo elements were present in Mo3d prior to etching. 3 / 2 and Mo3d 5 / 2 The binding energies are 232.8 eV and 229.5 eV, higher than the binding energies of zero-valent Mo (228.0 eV and 231.0 eV), classifying them as MoO2 compounds. With increasing etching time, the corresponding Mo3d... 5 / 2The binding energy is reduced to 227.9 eV, which is attributed to metallic Mo, indicating that 15cMo contains more elemental Mo.

[0074] Example 8:

[0075] This embodiment gives a preparation method of a metal transition layer based quartz substrate surface metal film layer. Specifically, this embodiment adopts PE-ALD to prepare a hemispherical resonator 200cPt / 15cW film layer, which specifically includes the following steps:

[0076] Firstly, the hemispherical resonator, the quartz piece (20mmx20mmx2mm) for trial, the simulated hemispherical resonator, and the silicon piece are placed in the PE-ALD reactor, the reactor temperature is 200℃, and the reaction pressure is 1Torr.

[0077] Secondly, the W precursor is disilane (Si2H6) and tungsten hexafluoride (WF6), the Si2H6 injection time is 6 seconds, the main valve is closed, the Si2H6 stays in the reactor for 10 seconds, the purging time is 30 seconds, the WF6 injection time is 6 seconds, the main valve is closed, the WF6 stays in the reactor for 10 seconds, the purging time is 30 seconds, and the cycle number is 20.

[0078] Thirdly, all sample test pieces continue to deposit Pt thin film in situ. The Pt thin film precursor is trimethylmethylcyclopentadienyl platinum (MeCpPtMe3) and plasma 20% H2 / N2, the MeCpPtMe3 is heated to 50℃, the carrier gas carrying the MeCpPtMe3 precursor is 40ml / min, the 20% H2 / N2 mixed gas flow is 30ml / min, and the radio frequency plasma generator power is 300W.

[0079] Fourthly, the Pt thin film deposition timing is as follows: the MeCpPtMe3 injection time is 20 seconds, the purging time is 40 seconds, the plasma 20% H2 / N2 injection time is 30 seconds, the purging time is 40 seconds, and the cycle number is 200.

[0080] The deposited 200cPt / 15cW thin film is subjected to XPS analysis, and the results are shown as A-C in Figure 9 From the XPS depth etching full spectrum of A in Figure 9 It is found that the 200cPt / 15cW thin film contains Pt, W, O, and Si elements from the XPS depth etching full spectrum of A in Figure 9 B-C in Figure 9 As can be seen from B in 7 / 2and Pt 4f 5 / 2 The binding energies decreased to 71.1 eV and 74.4 eV, belonging to the metallic state of Pt. When the etching time increased to 1200 s, the Pt 4f XPS peak split into a doublet, indicating that Pt 4f... 7 / 2 The binding energies were 71.1 eV and 72.5 eV, respectively, belonging to Pt and PtO. Further increasing the etching time to 1600 s, XPS only detected PtO. From... Figure 9 As can be seen from C, when the etching time is 0s, the W 4f of element W 7 / 2 and W 4f 5 / 2 The binding energies of the energy levels are 32.6 eV and 34.7 eV, belonging to the metallic state WO2, indicating that the W metal surface is oxidized, and the formed WO2 causes the Pt metal to be oxidized. With increasing etching depth, W4f... 7 / 2 The binding energies of the energy levels are 31.0 eV and 32.6 eV, respectively, belonging to W and WO2. When the etching time reaches 1600 s, only metallic W remains.

[0081] The microstructure of the 200cPt / 15cW film cross-section on the surface of the hemispherical harmonic oscillator was observed using FIB-TEM, and the results are as follows: Figure 10 As shown in a~c in the diagram. From Figure 10 The image 'a' shows that the 200cPt / 15cW thin film consists of two layers of Pt and W films, and the films are uniform and smooth; from Figure 10 In section b, we see that the average thickness of the Pt film is 14.2 nm, and the average growth rate is... The average thickness of the W film is 6.9 nm, and the average growth rate is... The values ​​are consistent with those reported in the literature. From... Figure 10 In the high-magnification image of c, a small amount of W film can be seen to penetrate into the Pt film layer, thereby improving the film adhesion.

[0082] Figure 11 a to d in the figure represent the HAADF-STEM and EDS-mapping characterization of the 200cPt / 15cW thin film and the Pt, W, and O elements. Figure 11 The 'a' in the figure indicates that the brighter areas in the 200cPt / 15cW film are Pt, and the darker areas are W. From... Figure 11 From b to c, it can be seen that Pt and W elements are uniformly distributed throughout the film. Figure 11 The absence of significant amounts of oxygen (O) in d indicates that the W film was not completely oxidized and that metallic W is present. This is consistent with... Figure 9 The result for C is consistent with the previous one.

[0083] Examples 9 to 12:

[0084] The embodiment provides a preparation method of a metal film layer on a quartz substrate surface based on a metal transition layer. Specifically, the embodiment adopts PE-ALD to prepare Pt / 15cW film layers with different cycle numbers of hemispherical resonators. The method keeps other conditions of the embodiment 8 unchanged, adjusts the ALDW cycle number, and respectively deposits 5c, 10c, 20c and 30c metal W. The 200cPt / 5cW, 200cPt / 10cW, 200cPt / 20cW and 200cPt / 30cW thin films are prepared.

[0085] An electronic universal testing machine is used to test the binding force of the 200cPt, 200cPt / 5cW, 200cPt / 10cW, 200cPt / 15cW, 200cPt / 20cW and 200cPt / 30cW thin films and the quartz substrate. The results are shown in the following table. Figure 12 Figure 12 It can be seen from the table that the tensile strength of the quartz substrate is about 8.8 MPa, and the binding strength of the 200cPt thin film and the quartz substrate is very weak, about 3 MPa. After setting the 5cW transition layer, the tensile strength of the 200cPt thin film and the quartz substrate is obviously improved, and is enhanced to about 7 MPa. With the increase of the cycle number of W, the tensile strength of the 200cPt thin film and the quartz substrate continues to increase, and the tensile strength of the 15cW thin film reaches about 9.9 MPa. However, when the cycle number of W is further increased to 20 and 30, the tensile strength of the 200cPt thin film and the quartz substrate is reduced to about 4 MPa. When more metal W penetrates into the Pt thin film, the Pt lattice mismatch is caused, the stress of the Pt thin film is increased, and the mechanical properties of the Pt / W thin film are greatly changed.

[0086] Embodiment 13

[0087] The embodiment provides a preparation method of a metal film layer on a quartz substrate surface based on a metal transition layer. Specifically, the embodiment adopts PE-ALD to prepare 200cPt / 10cTi film layers of hemispherical resonators. The method specifically includes the following steps.

[0088] In the first step, the hemispherical resonator, the quartz piece (20mmx20mmx2mm) for assisting test, the simulated hemispherical resonator and the silicon piece are placed in the PE-ALD reactor, the reactor temperature is 150 DEG C, and the reaction pressure is 1 Torr.

[0089] ​The second step, the Ti precursor is titanium tetrachloride (TiCl4) and plasma 20% H2 / N2. The TiCl4 heating temperature is 35°C, the N2 flow rate for purging TiCl4 is 20 ml / min. The 20% H2 / N2 mixed gas is used as the plasma source, the H2 flow rate is 30 ml / min, and the radio frequency plasma generator power is 300 W. The TiCl4 injection time is 3 seconds, the purging time is 30 seconds, the 20% H2 / N2 injection time is 2 seconds, the purging time is 30 seconds, and the cycle number is 20.

[0090] The third step, all sample pieces continue to deposit Pt thin film in situ. The Pt thin film precursor is trimethylmethylcyclopentadienyl platinum (MeCpPtMe3) and plasma 20% H2 / N2, the MeCpPtMe3 heating temperature is 50°C, the carrier gas for carrying the MeCpPtMe3 precursor is 40 ml / min, the 20% H2 / N2 mixed gas flow rate is 30 ml / min, and the radio frequency plasma generator power is 300 W.

[0091] The fourth step, the Pt thin film deposition timing: the MeCpPtMe3 injection time is 30 seconds, the purging time is 40 seconds, the 20% H2 / N2 injection time is 60 seconds, the purging time is 40 seconds, the cycle number is 200.

[0092] The thicknesses of the 30cTi, 200cPt / 30cTi thin films grown on the inner wall of the simulated hemispherical resonator by PE-ALD in the circumferential and radial directions were tested by an ellipsometer, and the resistances of the 200cPt / 30cTi thin films grown on the inner wall of the simulated hemispherical resonator by PE-ALD in the circumferential and radial directions were tested by a four-probe resistance meter, and the results are shown in Figs. 6a-6c. Figure 13 As shown in Figs. 6a-6c, the average thickness of the 30cTi on the surface of the Si wafer is 30.2 nm, the average growth rate is 1.01 nm / cycle, and the non-uniformity is 2.8%. Figure 13 As shown in Figs. 6a-6c, the average thickness of the 30cTi on the surface of the Si wafer is 30.2 nm, the average growth rate is 1.01 nm / cycle, and the non-uniformity is 2.8%. The average growth rate is 1.01 nm / cycle The average thickness of the 200cPt on the surface of the 12cMo thin film is 20.2 nm, the average growth rate is 0.81 nm / cycle, and the non-uniformity is 3.1%. The average growth rate is 0.81 nm / cycle The average thickness of the 200cPt on the surface of the 12cMo thin film is 20.2 nm, the average growth rate is 0.81 nm / cycle, and the non-uniformity is 3.1%. The average resistance of the 200cPt on the surface of the 30cTi thin film is 32.5 Ω, which is higher than the resistance of Pt with Al2O3 as the transition layer, which is 10 Ω. It is possible that Ti metal particles diffuse to the surface of the Pt metal, increasing the resistance of the Pt thin film.

[0093] Figure 14 Figs. 6a-6d are HAADF-STEM and EDS-mapping of the Pt, Ti, and O elements of the 200cPt / 30cTi thin film. Figure 14 Fig. 6a shows that the brighter area in the 200cPt / 30cTi thin film is Pt, and the darker area is Ti. Figure 14Pt, Ti elements are uniformly distributed in the whole film layer, from Figure 14 O element is not seen in d, indicating that Ti film is not completely oxidized.

[0094] Examples 14 to 18:

[0095] This example gives a preparation method of metal film layer on quartz substrate surface based on metal transition layer. Specifically, this example uses PE-ALD to prepare Pt / 10cTi film layer with different cycle numbers of hemispherical resonator, which keeps other conditions unchanged in Example 13, adjusts the cycle number of PE-ALD Ti, and respectively deposits 10c, 20c, 35c, 40c and 50c metal Ti. 200cPt / 10cTi, 200cPt / 20cTi, 200cPt / 35cTi, 200cPt / 40cTi and 200cPt / 50cTi films are prepared.

[0096] The binding force test of 200cPt, 200cPt / 10cTi, 200cPt / 20cTi, 200cPt / 35cTi, 200cPt / 40cTi and 200cPt / 50cTi films and quartz substrate is carried out by using electronic universal testing machine, and the results are shown in Figure 15 From Figure 15 , it can be seen that the tensile strength of quartz substrate is ~ 8.8 MPa, and the binding strength of 200cPt film and quartz substrate is very weak, which is 3 MPa. After setting 10cTi transition layer, the tensile strength of 200cPt film and quartz substrate is obviously improved, which is enhanced to ~ 5.7 MPa. With the increase of cycle number of Ti, the tensile strength of 200cPt film and quartz substrate continues to increase, and when the cycle number of Ti is 30c, the tensile strength of the film reaches ~ 10.1 MPa. However, when the cycle number of Ti is further increased to 35 and 40, the tensile strength of 200cPt film and quartz substrate decreases to ~ 8.2 MPa. When the cycle number of Ti is further increased to 50, the tensile strength of 200cPt film and quartz substrate decreases to ~ 4.3 MPa. It is possible that the internal stress of Ti film increases after the increase of Ti transition layer, which leads to the easy falling of Ti film from the quartz surface.

Claims

1. A method for preparing a metal film layer on a quartz substrate surface based on a metal transition layer, characterized in that, The method adopts plasma enhanced-atomic layer deposition method to deposit a non-noble metal layer as a transition layer for enhancing the binding force on the surface of a curved quartz substrate, and then deposit a noble metal layer as a conductive layer, thereby forming a metal film layer on the surface of the quartz substrate based on the metal transition layer; The non-noble metal of the transition layer is Mo or W; The noble metal of the conductive layer is Pt, Ir or Ru; The transition layer and the conductive layer are prepared in the same plasma enhanced-atomic layer deposition reactor and device; The thickness of the transition layer is 1-20 nm; and the thickness of the conductive layer is 5-30 nm; The non-uniformity of the transition layer is less than 4%; The non-uniformity of the conductive layer is less than 5%; The resistance of the conductive layer is less than 50 Ω; The tensile strength between the metal film layer on the surface of the quartz substrate based on the metal transition layer and the curved quartz substrate is greater than 10 MPa.

2. The method for preparing a metal film layer on a quartz substrate surface based on a metal transition layer according to claim 1, wherein The curved quartz substrate is a hemispherical resonator in a hemispherical resonator gyro.

3. The method for preparing a metal film layer on a quartz substrate surface based on a metal transition layer according to claim 1, wherein the metal transition layer is formed by sputtering a metal target in an atmosphere of argon gas and oxygen gas. The number of atomic layer deposition cycles of the transition layer is 5-50 cycles.

4. The method for preparing a metal film layer on a quartz substrate surface based on a metal transition layer according to claim 1, wherein the metal transition layer is formed by sputtering a metal target in an atmosphere of argon gas and oxygen gas. The number of atomic layer deposition cycles of the conductive layer is 100-400 cycles.

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