CN117434096A - Quasi-in-situ SEM (scanning electron microscope) observation method for copper ion electrodeposition nucleation growth behavior - Google Patents
Quasi-in-situ SEM (scanning electron microscope) observation method for copper ion electrodeposition nucleation growth behavior Download PDFInfo
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- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 title claims abstract description 57
- 229910001431 copper ion Inorganic materials 0.000 title claims abstract description 57
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 51
- 238000000034 method Methods 0.000 title claims abstract description 39
- 230000006911 nucleation Effects 0.000 title claims abstract description 32
- 238000010899 nucleation Methods 0.000 title claims abstract description 32
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 25
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 95
- 239000010936 titanium Substances 0.000 claims abstract description 95
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 95
- 238000000151 deposition Methods 0.000 claims abstract description 69
- 230000008021 deposition Effects 0.000 claims abstract description 66
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052802 copper Inorganic materials 0.000 claims abstract description 34
- 239000010949 copper Substances 0.000 claims abstract description 34
- 238000004381 surface treatment Methods 0.000 claims abstract description 9
- 238000012545 processing Methods 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 20
- 239000013078 crystal Substances 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000009987 spinning Methods 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 238000005260 corrosion Methods 0.000 claims description 8
- 230000007797 corrosion Effects 0.000 claims description 8
- 238000005498 polishing Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000009825 accumulation Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- 238000005520 cutting process Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000003792 electrolyte Substances 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
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- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
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- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
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- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
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Abstract
The invention discloses a quasi-in-situ SEM (scanning electron microscope) observation method for copper ion electrodeposition nucleation growth behaviors, and belongs to the field of observation and characterization of copper ion electrodeposition nucleation growth morphology. The method comprises the steps of firstly preparing a titanium cathode sample and carrying out surface treatment, then processing characteristic marks on a surface to be deposited of the titanium cathode sample, and then observing the surface morphology of a copper deposition layer under different accumulated deposition time in situ. Since the conventional SEM equipment cannot perform the electrodeposition experiment, the research of the nucleation growth behavior of the copper ion electrodeposited copper foil process by adopting the in-situ SEM technology is limited. The method can track the microscopic morphology of the copper deposition layer at the same position on the surface of the titanium cathode under different deposition times, analyze the influence of the grain size of the titanium cathode on the copper ion electrodeposition nucleation growth behavior, lay theoretical and technical guidance for the grain size regulation of the titanium cathode for producing electrolytic copper foil, and has simple and controllable process, low technical requirement on sample preparation and high experiment success rate.
Description
Technical Field
The invention relates to the technical field of metal material sample preparation and electrodeposition morphology observation and characterization, in particular to a quasi-in-situ SEM observation method for copper ion electrodeposition nucleation growth behaviors.
Background
When copper ions are electrodeposited on the titanium roller, copper atoms preferentially enter ready lattice positions on the surface of the titanium roller under the action of a force field on the surface of a titanium substrate in an initial period of time after being electrified, and a deposition layer formed by lattices can be completely consistent with the crystal orientation of the surface of the titanium roller. This deposition inherits the phenomenon of matrix lattice growth, known as epitaxial growth. On the microscopic level, the lattice size, arrangement mode, grain size, grain geometry and the like of the surface of the cathode roller determine the electrochemical properties of the surface of the cathode roller, and further influence the crystallization state and crystal arrangement growth of the initial deposition layer of copper ions. Therefore, the essence of the electrolytic copper foil generation is that copper ions continue to be electrodeposited on a cathode roller titanium material lattice, the microstructure and the surface state of the surface of the cathode roller titanium material directly influence the nucleation and growth process of copper ion electrodeposition, the nucleation and growth behaviors of the copper ions on the cathode titanium material in the process of preparing the copper foil by electrodeposition are researched, and the influence of the structural characteristics of the cathode titanium material on the structural genetic characteristics of a copper initial deposition layer is revealed and is the basis of the structural regulation of the cathode titanium material. However, because of challenges in quasi-in-situ observation technology in the electrodeposition process, the lack of the corresponding relation between the microstructure of the cathode titanium material and the evolution behavior of copper ion electrodeposition nucleation growth restricts the development of intermetallic electric crystallization epitaxial growth theory and the research of improving the quality of the copper foil based on the regulation and control of the microstructure of the cathode titanium material.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a quasi-in-situ SEM observation method for the nucleation growth behavior of copper ions on a titanium cathode, which can obtain the morphology of titanium grains in the same area and the evolution process of an initial deposition layer for forming and growing copper crystal nuclei at corresponding positions, and can be used for revealing the influence of the grain structure characteristics of the cathode titanium on the nucleation growth behavior of copper ions.
In order to achieve the above purpose, the invention adopts the following specific scheme:
a quasi-in-situ SEM observation method for copper ion electrodeposition nucleation growth behavior on a titanium cathode tracks the morphology evolution of a copper deposition layer at the same position of a titanium cathode sample under different deposition times, and specifically comprises the following steps:
(1) Preparation of titanium cathode samples
Introducing argon into the heat treatment furnace as protective gas, heating the furnace to a target temperature of 500-600 ℃, and after the furnace temperature is reached, placing the original sample of the spinning cathode roller titanium material into the furnace for heat treatment to obtain a recrystallized titanium cathode sample;
(2) Surface treatment of titanium cathode sample
Carrying out surface treatment on the surface to be deposited of each titanium cathode sample so that the grain boundary characteristics of the surface to be deposited are displayed;
(3) Processing of feature markers
Processing a characteristic mark on a surface to be deposited of the surface-treated titanium cathode sample, and taking a picture to record the overall view of the characteristic mark;
(4) Recording SEM morphology of titanium surface grains in target area
Selecting a clean area near the feature mark as a target area, and photographing and recording the SEM morphology of crystal grains on the surface of the sample in the target area;
(5) Electrodeposition of copper ions
Carrying out electrodeposition of copper ions under a direct current condition by adopting an electrolytic tank to obtain an electrodeposition sample;
(6) SEM observation of copper deposit
Transferring the electrodeposited sample to a scanning electron microscope, firstly finding a characteristic mark in an SEM visual field, adjusting the inclination angle of the characteristic mark in a picture to correspond to that before deposition, keeping the position of the sample motionless after finding the same target area before deposition, and photographing step by step from low power to high power; then adjusting the target area to the actual required magnification, and recording the SEM morphology of the copper ion deposition surface;
(7) SEM observation of copper deposit layer at different cumulative deposition times
Repeating the steps (5) - (6), accumulating the copper ion deposition time, shooting the surface morphology of the copper deposition layer under different accumulation deposition time, and sequentially obtaining the quasi-in-situ SEM morphology of the copper electrodeposition nucleation growth process of the same target area and different accumulation deposition time.
Further, in the step (1), the original sample of the spinning cathode roller titanium material is a small titanium sheet cut from a titanium cylinder by wire cutting, and the titanium cylinder is obtained by integral spinning and forming by using industrial pure titanium TA 1.
Further, in the step (2), the titanium cathode sample is subjected to surface treatment by mechanical grinding, electrolytic polishing and chemical etching in sequence, wherein the chemical etching time is 120 s.
Further, in step (3), the depth of the feature mark is greater than the final thickness of the copper deposit.
Further, in the step (4), several SEM morphology images with the magnification of 50-1000 times are obtained by photographing.
Further, in the step (5), the electrolyte comprises copper ions, sulfuric acid, gelatin and SPS, wherein the concentration of the copper ions is 100 g/L, the concentration of the sulfuric acid is 95 g/L, the concentration of the gelatin is 5mg/L, and the concentration of the SPS is 0.3 mg/L.
Taking a titanium cathode sample as a cathode, taking an iridium-plated titanium material as an anode, wherein the electrode spacing between the anode and the cathode is 6 cm, and bonding the back surface and the side surface of the cathode plate by using insulating glue;
the deposition current density was constant at 16.7.+ -. 0.1A/dm 2 The method comprises the steps of carrying out a first treatment on the surface of the And after the deposition is finished, immediately cleaning the copper deposition surface by deionized water, tearing off the insulating adhesive, and washing and drying by alcohol.
Further, in the electrodeposition process, the constant temperature water bath is utilized to keep the temperature of the electrolytic bath at 50 ℃.
Further, the electrodeposition is accompanied by low-speed magnetic stirring.
Further, the first electrodeposition adopts a transient power-off mode to control the deposition time.
Further, in the step (7), repeating the steps (5) - (6) three times, wherein the accumulated deposition time of the three times is 3s, 10s and 30s respectively.
The beneficial effects are that:
1) The quasi-in-situ SEM observation method designed by the invention can intuitively track nucleation growth behaviors of the copper ion electrodeposition process at fixed points, breaks through the problem that the characteristic of the grain structure of the titanium cathode and the evolution of the characteristic of the initial deposition structure of the copper ion cannot establish an intuitive corresponding relation, introduces the growth process of depositing copper ions in the same area on the titanium cathode in detail, reveals the influence of the characteristic of the grain of the titanium cathode on the nucleation growth behaviors of the copper ion electrodeposition, and provides theoretical basis for promoting the design and preparation of the titanium cathode for the electrolytic copper foil.
2) And the feature marks are processed on the surface to be deposited of the titanium cathode sample by adopting tools such as a diamond cutter or a Vickers hardness tester, and the like, so that the same target area can be rapidly and accurately positioned and tracked. In addition, the depth of the feature mark is ensured to be larger than the final thickness of the copper deposition layer to be observed, and the situation that the mark position cannot be tracked after multiple deposition coverage is avoided.
3) And before the electrodeposition experiment, carrying out surface treatment on the titanium cathode by adopting an electrolytic polishing and chemical corrosion method on the titanium sample. The electrolytic polishing can remove the surface stress of the titanium cathode, and avoid the influence of defects such as scratches and the like on electrodeposition; the chemical corrosion makes the appearance characteristics of the crystal grains appear, the evolution process of copper crystal nucleus formation and growth at different crystal grain characteristics is convenient and visual to observe, and the operation is simple.
Drawings
FIG. 1 is a schematic diagram showing the relative positions of a cross-shaped feature mark and a target area on a surface to be deposited of a titanium sample.
FIG. 2 is an SEM image of the "cross" mark of the surface to be deposited of a titanium sample according to example 1 of the present invention.
Fig. 3 is a SEM tissue morphology and a partial magnified high-magnification image of example 1 of the present invention when copper is electrodeposited for 1 s.
Fig. 4 is a SEM tissue morphology and a partial magnified high-magnification image of example 1 of the present invention when copper is electrodeposited for 3 s.
Fig. 5 is a SEM tissue morphology and a partial magnified high-magnification image of example 1 of the present invention when copper is electrodeposited for 10 s.
Fig. 6 is a SEM tissue morphology and a partial magnified high-magnification image of example 1 of the present invention when copper is electrodeposited for 30 s.
Detailed Description
The technical solutions of the present invention will be clearly and completely described below in connection with specific embodiments, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
The invention provides a quasi-in-situ SEM scanning observation method for copper electrodeposition nucleation growth behavior, which comprises the following steps:
(1) Preparing a plurality of titanium cathode samples with different grain sizes: argon is introduced into a vacuum atmosphere tubular resistance furnace as protective gas, the furnace temperature is raised to a target temperature of 500-600 ℃, and after the furnace temperature is reached, the original sample of the spinning cathode roller titanium material is placed into a heat treatment furnace for heat preservation for 60 min, so as to obtain a titanium cathode sample; the original sample of the spinning cathode roller titanium material is a 24 mm multiplied by 12 multiplied by mm multiplied by 4 mm small titanium sheet cut from a titanium cylinder by wire cutting, the titanium cylinder is obtained by integral spinning forming by utilizing industrial pure titanium TA1, the outer diameter of the spinning forming titanium cylinder is 2700-3000 mm, the wall thickness is 20-25 mm, and the spinning deformation is 50-60%;
(2) Surface treatment of titanium cathode sample: sequentially carrying out mechanical grinding, electrolytic polishing and chemical corrosion treatment on the surface to be deposited of the cathode titanium sample after heat treatment, wherein the chemical corrosion time is 120 s, so that the grain boundary characteristics of the titanium cathode sample are displayed;
(3) Processing of characteristic marks: machining a characteristic mark on the surface to be deposited of the titanium cathode by using a diamond cutter or a Vickers hardness tester and other tools, wherein the depth of the characteristic mark is larger than the final thickness of the copper deposition layer to be observed; shooting a low-power (50-1000 times) picture to record the overall position of the feature mark, so as to facilitate the subsequent positioning of target areas of electrodeposited samples with different time;
(4) SEM observation of grain characteristics on the surface of the titanium material: selecting a clean area near the feature mark as a target area, and photographing and recording the SEM morphology of crystal grains on the surface of the sample in the target area;
(5) Copper ion electrodeposition experiments: and carrying out an electrodeposition experiment of copper ions under a direct current condition by adopting an electrolytic tank. The electrolyte composition is copper ion concentration 100 g/L, sulfuric acid concentration 95 g/L, gelatin concentration 5mg/L, SPS concentration 0.3 mg/L. Titanium cathode samples with different grain sizes are used as cathodes, iridium-plated titanium materials are used as anodes, the distance between the cathodes and the anodes is fixed to be 6 cm, and the back surface and the side surface of the cathode plate are bonded by insulating glue to prevent the interference surface from contacting with current and reducing current efficiency. The constant temperature water bath kettle is used for heat preservation at 50 ℃, and the deposition current density is constant at 16.7+/-0.1A/dm 2 When the electrodeposition is carried out, slight magnetic stirring is carried out, after the deposition is finished, deionized water is immediately used for cleaning the copper deposition surface, insulating glue is torn off, and alcohol is used for washing and drying; it should be noted that, the first electrodeposition adopts an instantaneous power-off mode to control the deposition time so as to obtain the deposition characteristics of the copper ions at the earliest stage;
(6) SEM observation of copper deposit: transferring an electrodeposited sample into a Scanning Electron Microscope (SEM), firstly finding a characteristic mark in an SEM visual field, adjusting the inclination angle of the characteristic mark in a picture to correspond to that before deposition, after finding a cleaner area near the characteristic mark selected by the target area which is the same as that before deposition as a target area, keeping the position of the sample, photographing step by step from low power to high power so as to position the area in different deposition time, then adjusting the target area to the actual required magnification, and recording the morphology of the copper ion deposition surface SEM;
(7) SEM observation of the surface morphology of the copper deposit layer at different deposition times: repeating the steps (5) - (6), accumulating copper ion deposition time, shooting the surface morphology of the sample copper deposition layer with different accumulated deposition time, and sequentially obtaining quasi-in-situ SEM observation of the copper electrodeposition nucleation growth process with different accumulated deposition time in the same target area.
In the step (4), the equipment model used for SEM observation of the grain characteristics of the surface of the titanium material is JSM-7800, the scanning voltage is 20.0. 20.0 kV, and when the SEM image is acquired for the first time after the target area is selected, the image with the size of 50 times to 1000 times is ensured, so that the accurate positioning of the same target area of samples with different accumulated deposition time can be conveniently carried out.
The present invention will be described in further detail with reference to the accompanying drawings and examples.
First, the source of the original sample, which is a plurality of titanium pieces cut from a cathode roll cylinder manufactured by integral spin forming using commercially pure titanium TA1, with a size of 24 mm (tangential) ×12mm (axial) ×4 mm (radial), by wire cutting will be described in the following examples.
Example 1
A quasi-in-situ SEM scanning observation method for copper electrodeposition nucleation growth behavior comprises the following steps:
(1) Introducing argon into the vacuum atmosphere tubular resistance furnace as protective gas, heating the furnace to a target temperature of 500 ℃, and then placing the original sample of the spinning cathode roller titanium material into a heat treatment furnace for heat preservation for 60 min to obtain a titanium cathode sample;
(2) Grinding the titanium cathode sample obtained by heat treatment by adopting metallographic sand paper of No. 240, no. 400, no. 500, no. 600, no. 800, no. 1000, no. 2000 and No. 3000 in sequence, and carrying out electrolytic polishing treatment on the sample for 110 seconds at constant current of 2.5A after grinding; cleaning and drying the surface after polishing, and then carrying out chemical corrosion, wherein the volume ratio of corrosive liquid is hydrofluoric acid: nitric acid: water = 1:2:100, the corrosion time is 120 s, so that the grain boundary morphology of the surface of the titanium material is revealed;
(3) Processing a cross scratch mark which is easy to identify on a surface to be deposited of a titanium cathode sample by adopting a diamond cutter, as shown in figure 1;
(4) Fixing a titanium sample on an SEM sample stage according to the direction shown in figure 1, wherein the long side direction of the sample is parallel to the AB side of the sample stage, the scanning voltage is 20.0 kV, SEM observation is carried out on a cleaner area near the feature mark, and the average grain size of the surface of the titanium sample is about 5.6 mu m, so that the result is shown in figure 2;
(5) Taking out the titanium sample, and carrying out an electrodeposited copper foil experiment: and preparing the copper foil by adopting an electrolytic tank to carry out a direct current deposition method. Electrolyte composition: the copper ion concentration is 100 g/L, the sulfuric acid concentration is 95 g/L, the gelatin concentration is 5mg/L, and the SPS concentration is 0.3 mg/L. The titanium sheet sample to be deposited is taken as a cathode, an iridium-coated titanium plate is taken as an anode, the distance between the anode and the cathode is fixed to be 6 cm, the back surface and the side surface of the polar plate are attached by insulating glue, and the deposition area is fixed to be 15 mm multiplied by 12 mm. The constant temperature water bath kettle is utilized to keep the temperature at 50 ℃ and the density is constant at 16.7+/-0.1A/dm 2 The electro-deposition is carried out with slight magnetic stirring, after the deposition time is 1s, the insulating adhesive is torn off, the electro-deposition is carried out with deionized water for a plurality of times, and the electro-deposition is carried out with alcohol washing and then cold air drying;
(6) Placing the deposited sample on a sample stage of a Scanning Electron Microscope (SEM) according to the same lofting mode before depositing the titanium sample, finding the same target area according to the characteristic mark, rotating and finely adjusting the SEM image to enable the long scratches of the sample to have an intersection part with the upper edge line in the visual field of the scanning electron microscope, wherein the area in the visual field comprises a part of the scratch mark and a mark point influence area, and in order to remove the influence of the scratch defect area on the SEM morphology observation, keeping the position of the sample motionless, adjusting the magnification to 1000 times, and carrying out SEM observation of the morphology of the first copper ion deposited tissue, wherein the result is shown in figure 3;
(7) Repeating the steps (5) - (6) to accumulate the deposition time for 3s, and carrying out SEM observation on the morphology of the second copper ion deposition tissue, wherein the result is shown in figure 4;
(8) Repeating the step (7) to accumulate the deposition time for 10s, and carrying out SEM observation on the morphology of the third copper ion deposition tissue, wherein the result is shown in figure 5;
(9) Repeating the step (8) for 30s, and carrying out SEM observation of the morphology of the third copper ion deposition tissue, wherein the result is shown in FIG. 6;
as can be seen from fig. 3, 4, 5, and 6, the method of the present invention can realize SEM tracking of the morphology evolution of copper ion electrodeposited microstructure in the same area of the titanium cathode surface with an average grain size of about 5.6 μm. The results show that copper ions preferentially nucleate at the grain boundaries, and as the deposition time increases, copper deposition particles cluster, cascade, and further expand into the grain boundaries, covering the entire grain. Meanwhile, compared with titanium crystal grains with different sizes in the target area, the size of the titanium crystal grains can influence the electrodepositing nucleation rate of copper ions, the smaller the size of the titanium crystal grains is, the faster the nucleation rate of copper ions is, the shorter the time required for copper particles to expand to a full-coverage state in the crystal is, and further, the copper particles can be fully paved on the whole crystal grains or reach the target deposition thickness in a shorter time.
The above description is only of the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. All equivalent changes or modifications made according to the essence of the present invention should be included in the scope of the present invention.
Claims (10)
1. A quasi-in-situ SEM observation method for copper ion electrodeposition nucleation growth behavior, which is characterized by comprising the following steps:
(1) Preparation of titanium cathode samples
Introducing argon into the heat treatment furnace as protective gas, heating the furnace to a target temperature of 500-600 ℃, and after the furnace temperature is reached, placing the original sample of the spinning cathode roller titanium material into the furnace for heat treatment to obtain a recrystallized titanium cathode sample;
(2) Surface treatment of titanium cathode sample
Carrying out surface treatment on the surface to be deposited of each titanium cathode sample so that the grain boundary characteristics of the surface to be deposited are displayed;
(3) Processing of feature markers
Processing a characteristic mark on a surface to be deposited of the surface-treated titanium cathode sample, and taking a picture to record the overall view of the characteristic mark;
(4) Recording SEM morphology of titanium surface grains in target area
Selecting a clean area near the feature mark as a target area, and photographing and recording the SEM morphology of crystal grains on the surface of the sample in the target area;
(5) Electrodeposition of copper ions
Carrying out electrodeposition of copper ions under a direct current condition by adopting an electrolytic tank to obtain an electrodeposition sample;
(6) SEM observation of copper deposit
Transferring the electrodeposited sample to a scanning electron microscope, firstly finding a characteristic mark in an SEM visual field, adjusting the inclination angle of the characteristic mark in a picture to correspond to that before deposition, keeping the position of the sample motionless after finding the same target area before deposition, and photographing step by step from low power to high power; then adjusting the target area to the actual required magnification, and recording the SEM morphology of the copper ion deposition surface;
(7) SEM observation of copper deposit layer at different cumulative deposition times
Repeating the steps (5) - (6), accumulating the copper ion deposition time, shooting the surface morphology of the copper deposition layer under different accumulation deposition time, and sequentially obtaining the quasi-in-situ SEM morphology of the copper electrodeposition nucleation growth process of the same target area and different accumulation deposition time.
2. A method of quasi-in-situ SEM observation of nucleation growth behaviour of copper ion electrodeposition according to claim 1, wherein: in the step (1), the original sample of the spinning cathode roller titanium material is a small titanium sheet cut from a titanium cylinder by wire cutting, and the titanium cylinder is obtained by integral spinning and forming by using industrial pure titanium TA 1.
3. A method of quasi-in-situ SEM observation of nucleation growth behaviour of copper ion electrodeposition according to claim 1, wherein: in the step (2), the surface treatment is sequentially carried out on the titanium cathode sample through mechanical grinding, electrolytic polishing and chemical corrosion, wherein the chemical corrosion time is 120 s.
4. A method of quasi-in-situ SEM observation of nucleation growth behaviour of copper ion electrodeposition according to claim 1, wherein: in step (3), the depth of the feature marks is greater than the final thickness of the copper deposit.
5. A method of quasi-in-situ SEM observation of nucleation growth behaviour of copper ion electrodeposition according to claim 1, wherein: in the step (4), a plurality of SEM morphology images with the magnification of 50-1000 times are obtained through photographing.
6. A method of quasi-in-situ SEM observation of nucleation growth behaviour of copper ion electrodeposition according to claim 1, wherein: in the step (5), the electrolyte comprises copper ions, sulfuric acid, gelatin and SPS, wherein the concentration of the copper ions is 100 g/L, the concentration of the sulfuric acid is 95 g/L, the concentration of the gelatin is 5mg/L, and the concentration of the SPS is 0.3 mg/L;
taking a titanium cathode sample as a cathode, taking an iridium-plated titanium material as an anode, wherein the electrode spacing between the anode and the cathode is 6 cm, and bonding the back surface and the side surface of the cathode plate by using insulating glue;
the deposition current density was constant at 16.7.+ -. 0.1A/dm 2 The method comprises the steps of carrying out a first treatment on the surface of the And after the deposition is finished, immediately cleaning the copper deposition surface by deionized water, tearing off the insulating adhesive, and washing and drying by alcohol.
7. A method of quasi-in-situ SEM observation of nucleation growth behavior of copper ion electrodeposition according to claim 6, wherein: in the electrodeposition process, the constant temperature water bath kettle is utilized to keep the temperature of the electrolytic bath at 50 ℃.
8. A method of quasi-in-situ SEM observation of nucleation growth behavior of copper ion electrodeposition according to claim 6, wherein: the electrodeposition is accompanied by low-speed magnetic stirring.
9. A method of quasi-in-situ SEM observation of nucleation growth behavior of copper ion electrodeposition according to claim 6, wherein: the first electrodeposition adopts a mode of instantaneous power off to control the deposition time.
10. A method of quasi-in-situ SEM observation of nucleation growth behaviour of copper ion electrodeposition according to claim 1, wherein: in the step (7), repeating the steps (5) - (6) for three times, wherein the accumulated deposition time of the three times is 3s, 10s and 30s respectively.
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