CN113526459A - Surface planarization method for micro-scale 3D printing copper/nickel heterogeneous microstructure - Google Patents
Surface planarization method for micro-scale 3D printing copper/nickel heterogeneous microstructure Download PDFInfo
- Publication number
- CN113526459A CN113526459A CN202110809582.8A CN202110809582A CN113526459A CN 113526459 A CN113526459 A CN 113526459A CN 202110809582 A CN202110809582 A CN 202110809582A CN 113526459 A CN113526459 A CN 113526459A
- Authority
- CN
- China
- Prior art keywords
- copper
- nickel
- micro
- heterogeneous microstructure
- sodium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C1/00—Manufacture or treatment of devices or systems in or on a substrate
- B81C1/00436—Shaping materials, i.e. techniques for structuring the substrate or the layers on the substrate
- B81C1/00555—Achieving a desired geometry, i.e. controlling etch rates, anisotropy or selectivity
- B81C1/00611—Processes for the planarisation of structures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C2201/00—Manufacture or treatment of microstructural devices or systems
- B81C2201/01—Manufacture or treatment of microstructural devices or systems in or on a substrate
- B81C2201/0101—Shaping material; Structuring the bulk substrate or layers on the substrate; Film patterning
- B81C2201/0118—Processes for the planarization of structures
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C2201/00—Manufacture or treatment of microstructural devices or systems
- B81C2201/01—Manufacture or treatment of microstructural devices or systems in or on a substrate
- B81C2201/0101—Shaping material; Structuring the bulk substrate or layers on the substrate; Film patterning
- B81C2201/0118—Processes for the planarization of structures
- B81C2201/0119—Processes for the planarization of structures involving only addition of materials, i.e. additive planarization
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B81—MICROSTRUCTURAL TECHNOLOGY
- B81C—PROCESSES OR APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OR TREATMENT OF MICROSTRUCTURAL DEVICES OR SYSTEMS
- B81C2201/00—Manufacture or treatment of microstructural devices or systems
- B81C2201/01—Manufacture or treatment of microstructural devices or systems in or on a substrate
- B81C2201/0101—Shaping material; Structuring the bulk substrate or layers on the substrate; Film patterning
- B81C2201/0118—Processes for the planarization of structures
- B81C2201/0125—Blanket removal, e.g. polishing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/25—Process efficiency
Landscapes
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Geometry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- ing And Chemical Polishing (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
The invention discloses a surface flattening method for a micro-scale 3D printing copper/nickel heterogeneous microstructure, which is applied to the field of micro-electro-mechanical system manufacturing and aims at solving the problems that the surface flatness and the surface integrity obtained by the existing pure mechanical flattening methods such as milling, grinding and the like are not high and the ultra-precise micro-scale 3D printing manufacturing requirements of micro-electro-mechanical systems cannot be met; firstly, carrying out rough planarization on the surface of a copper/nickel heterogeneous microstructure by adopting mechanical grinding, then carrying out fine planarization on the surface of the copper/nickel heterogeneous microstructure subjected to mechanical grinding by adopting chemical mechanical polishing, and regulating and controlling the removal rate selection ratio of copper and nickel materials by regulating the content of a metal oxidant in a polishing solution to obtain the constant-speed removal of copper and nickel so as to realize the planarization of the surface of the copper/nickel heterogeneous microstructure; the method can efficiently realize the surface planarization of the copper/nickel heterogeneous microstructure, obtain a high-integrity surface, and break through the key common technology of the planarization, which restricts the micro-scale 3D printing precision and quality based on electrochemical deposition.
Description
Technical Field
The invention belongs to the field of manufacturing of micro-electro-mechanical systems, and particularly relates to a surface planarization method for a micro-scale 3D printed copper/nickel heterogeneous microstructure.
Background
Micro-Electro-Mechanical Systems (MEMS) are Micro Systems that integrate functional units, such as Micro sensors, Micro actuators, Micro energy sources, etc., with characteristic dimensions of less than 1mm but greater than 1 μm on a Micro-nano scale. The micro-electro-mechanical system is widely applied to the fields of information communication, aerospace, biomedical treatment, automatic control, automotive electronics, national defense safety and the like. According to the prediction, only one microsensor, 2016-. The special plan of scientific and technological innovation in the technical field of advanced manufacturing in thirteen five advanced manufacturing published in 4 months in 2017 clearly indicates that: aiming at the special process requirements of the equipment in the fields of MEMS devices and the like, the research and development of key equipment and process are carried out, and the key technology and the development characteristic process are mastered.
At present, a micro-electromechanical system has developed from a large-scale integration to a functional integration direction, and a complex micro-electromechanical system with a multifunctional high-integration design has become a necessary trend for future development, and at the moment, a micro sensor, a micro actuator, a micro-mechanical structure, a micro power supply and the like all require a complex three-dimensional microstructure, and materials are extended to non-silicon materials such as metals and the like, such as copper and nickel. Meanwhile, in order to further improve the reliability of the micro-electro-mechanical system, the micro-assembly process is required to be avoided, and the complex three-dimensional microstructure is directly manufactured without assembly. The micro-scale 3D printing technology based on electrochemical deposition represented by electrochemical mechanical failure (EFAB) has great potential and advantages in the manufacturing of complex three-dimensional microstructures, high aspect ratio microstructures and three-dimensional microstructures of metal materials. Based on the principle of additive manufacturing, EFAB can manufacture a metal three-dimensional microstructure with any shape by selectively electrochemically depositing a plurality of metal layers (including a structural layer and a sacrificial layer) by using a real-time mask technology. The technical route of EFAB is described below: 1) selectively depositing a metal layer on the cathode substrate by using a real-time mask according to the section data of the microstructure, wherein the metal layer can be a sacrificial layer or a structural layer; 2) covering the material of the front layer with a new material by using a conventional electrochemical deposition method, and if the deposited layer of the previous step is a sacrificial layer, the step is a structural layer, and vice versa; 3) flattening: flattening the sacrificial layer and the structural layer by using methods such as micro-milling, precision grinding and the like, and ensuring high surface flatness and surface integrity; 4) according to different microstructure pattern designs of each layer, the first step to the third step are circulated until the processing requirements such as the number of structural layers are met; 5) and selectively etching and removing the sacrificial layer by using an electrochemical or chemical corrosion method, and releasing to obtain the complex three-dimensional microstructure consisting of the structural layer metal. In the EFAB microscale 3D printing technology, nickel has good mechanical property, temperature property and corrosion resistance property, so that the requirements of most micro-electromechanical systems are met, and the magnetism of the nickel is widely applied to electromagnetic devices, so that the nickel is used as a structural layer; while copper is easily selectively etched away relative to nickel and thus acts as a sacrificial layer. In conclusion, copper and nickel form a proper material system and are respectively used for a sacrificial layer and a structural layer in EFAB microscale 3D printing to form a copper/nickel heterogeneous microstructure.
As described above, planarization is one of the key processes of EFAB micro-scale 3D printing technology, and is used to realize high surface flatness and high surface integrity processing of a complex three-dimensional heterogeneous microstructure surface, which directly determines the manufacturing accuracy and service life of a micro-electromechanical system. With the introduction of high-precision lithography and the increasingly stringent requirements of the application field on the reliability of the micro-electro-mechanical system, the traditional pure mechanical planarization method (such as milling and grinding) can not meet the manufacturing requirements of the ultra-precise micro-scale 3D printing of the micro-electro-mechanical system, and becomes a technical bottleneck restricting the further development of the micro-electro-mechanical system, specifically as follows:
1. from the viewpoint of surface flatness, a great difference in mechanical properties usually exists between a plurality of heterogeneous materials such as a sacrificial layer and a structural layer, and for pure mechanical processing methods such as milling and grinding, the removal amount is directly related to the mechanical properties of the materials, so that improvement of the surface flatness is limited. Meanwhile, different layers have different microstructure patterns, which further increases the planarization difficulty. If the surface flatness does not meet the requirement, pattern transfer cannot be smoothly realized, and micro-scale 3D printing of the micro-electro-mechanical system cannot be finished.
2. From the perspective of surface integrity, mechanical processing methods such as milling and grinding are limited by a pure mechanical removal principle, contact pressure needs to reach the yield limit of a material during removal, the minimum removal thickness is limited, various surface/subsurface damages (such as dislocation pile, vacancy, microcrack and the like) and residual stress can not be generated under the action of thermal coupling, high surface integrity processing is difficult to realize, and then fatigue fracture failure of a device is easily caused under extreme service working conditions such as alternating load and the like, so that the service life is influenced.
Disclosure of Invention
The invention aims to overcome the defects that the surface flatness and the surface integrity obtained by the existing pure mechanical planarization methods such as milling, grinding and the like are not high and cannot meet the requirements of ultra-precise micro-scale 3D printing and manufacturing of a micro electro mechanical system, and provides a micro-scale 3D printing copper/nickel heterogeneous microstructure surface planarization method, which can efficiently realize the surface planarization of the copper/nickel heterogeneous microstructure, obtain the nanoscale surface roughness and sub-surface damage approaching zero, and break through the key common technology of planarization, which restricts the micro-scale 3D printing precision and quality based on electrochemical deposition.
The purpose of the invention is realized by the following technical scheme: a surface planarization method for a micro-scale 3D printed copper/nickel heterogeneous microstructure comprises the following steps:
s1, carrying out rough planarization on the surface of the copper/nickel heterogeneous microstructure by adopting mechanical grinding;
s2, adopting chemical mechanical polishing to carry out fine planarization on the surface of the copper/nickel heterogeneous microstructure mechanically ground in the step S1;
the polishing solution used in the chemical mechanical polishing in step S2 includes the following components: 0-10 wt% of metal oxidant, 0-2 wt% of compound metal corrosion inhibitor, 0.01-10 wt% of metal complexing agent, 0.01-40 wt% of grinding particles, and the balance of water and a small amount of pH value regulator, wherein the pH value is 3-7, and the wt% represents mass percentage.
The step S1 mechanical grinding employs a grinding disk including: one of a sand paper grinding disc, a diamond grinding disc, an alumina grinding disc, an oilstone grinding disc, a silica grinding disc, a glass grinding disc, a ceramic grinding disc, a cast iron grinding disc, a brass grinding disc, a red copper grinding disc and a tin alloy grinding disc, preferably a sand paper grinding disc.
The polishing pad of the step S2 chemical mechanical polishing is: one of a polyurethane polishing pad, an artificial leather polishing pad, and a felt polishing pad, preferably a polyurethane polishing pad.
In the step S2 of chemical mechanical polishing, the copper and nickel material removal rate selection ratio is adjusted and controlled by adjusting the content of the metal oxidizer in the polishing solution, so as to obtain constant-speed removal of copper and nickel, and realize surface planarization of the copper/nickel heterogeneous microstructure.
The metal oxidizing agent in the chemical mechanical polishing solution is as follows: one or more of hydrogen peroxide, sodium peroxide, carbamide peroxide, peroxyformic acid, peroxyacetic acid and sodium percarbonate, preferably hydrogen peroxide.
The compound metal corrosion inhibitor in the chemical mechanical polishing solution comprises two components: one is one or more azole compounds, the other is one or more surfactants, and the two components are compounded.
In the compound metal corrosion inhibitor, the azole compound is: 1,2, 3-benzotriazole, 4-methyl-1H-benzotriazole, 5, 6-dimethyl-1, 2, 3-benzotriazole, 1-hydroxybenzotriazole, 1,2, 3-triazole, 1,2, 4-triazole, 3-methyl-1H-1, 2, 4-triazole, 3-amino-1, 2, 4-triazole, 4-amino-1, 2, 4-triazole, 3, 5-diamino-1, 2, 4-triazole, 1H-1,2,3, 4-tetrazole, 5-methyl tetrazole, 5-amino-1H-tetrazole, 5-amino-1-methyl tetrazole, One of 5-phenyl-1H-tetrazole, pyrazole, imidazole and benzimidazole, and preferably 1,2, 3-benzotriazole.
In the compound metal corrosion inhibitor, the surfactant is: sodium dodecylbenzene sulfonate, alpha-sodium alkenyl sulfonate, ammonium lauryl sulfate, sodium N-lauroyl glutamate, sodium dodecyl phosphate, sodium oleate, triethanolamine lauryl sulfate, sodium fatty alcohol isethionate, sodium cocoyl methyl taurate, disodium lauryl polyoxyethylene ether sulfosuccinate, sodium secondary alkyl sulfonate, disodium lauryl polyoxyethylene ether sulfosuccinate, sodium lauryl polyoxyethylene ether sulfate, sodium N-lauroyl sarcosinate, sodium lauryl ether sulfate, sodium lauryl polyoxyethylene ether carboxylate, dodecyl phosphate, sodium dodecyl sulfate, magnesium amido polyoxyethylene ether sulfate, potassium dodecyl phosphate triethanolamine, and sodium stearate, preferably sodium dodecyl benzene sulfonate.
The metal complexing agent is oxalic acid dihydrate.
The abrasive particles are colloidal silica.
The pH value regulator is sulfuric acid and potassium hydroxide.
Compared with the prior art, the invention has the following beneficial effects:
1. the surface planarization of the copper/nickel heterogeneous microstructure is efficiently realized. Through the planarization process flow of firstly carrying out mechanical grinding in the step S1 and then carrying out chemical mechanical polishing in the step S2, the technical indexes of each step are reasonably designed, the planarization efficiency is greatly improved, the whole planarization time is less than 40 minutes, and the practical application requirements can be met.
2. A high integrity surface is obtained. By optimizing the synergistic effect of chemical reaction and mechanical force in the chemical mechanical polishing in the step S2, particularly adding the compound metal corrosion inhibitor, the surface roughness of the copper/nickel heterogeneous microstructure after chemical mechanical planarization reaches the nanometer level, the processing damage of the sub-surface substrate approaches zero, and the method is far superior to pure mechanical processing methods such as milling, grinding and the like.
Drawings
FIG. 1 is a schematic view of a method for planarizing a surface of a Cu/Ni heterostructure according to an embodiment of the present invention;
FIG. 2 is a comparison of the surface topography of copper and nickel after polishing in example 4 of the present invention;
wherein, FIG. 2(a) is a surface topography of copper after polishing in example 4 of the present invention, and FIG. 2(b) is a surface topography of nickel after polishing in example 4 of the present invention;
FIG. 3 is a comparison of the surface topography of copper and nickel after polishing using example 12 of the present invention;
wherein, FIG. 3(a) is a surface topography of copper after polishing in accordance with example 12 of the present invention, and FIG. 3(b) is a surface topography of nickel after polishing in accordance with example 12 of the present invention;
FIG. 4 is a comparison of the surface topography of copper and nickel after polishing in example 17 of the present invention;
FIG. 4(a) is a surface topography of copper after polishing in example 17 of the present invention, and FIG. 4(b) is a surface topography of nickel after polishing in example 17 of the present invention;
FIG. 5 is a potentiodynamic polarization curve of copper and nickel in electrolyte solutions corresponding to examples 4, 12 and 17 of the present invention;
FIG. 6 is a high resolution TEM image of copper after polishing in example 17;
FIG. 7 is a high resolution TEM image of nickel after polishing in example 17;
FIG. 8 is a schematic view of a process flow for planarizing a surface of a copper/nickel heterogeneous microstructure;
FIG. 9 is a photograph and a schematic cross-sectional structure of a Cu/Ni heterostructure prior to planarization;
wherein, FIG. 9(a) is a photo of the copper/nickel heterogeneous microstructure before planarization, and FIG. 9(b) is a schematic cross-sectional structure of the copper/nickel heterogeneous microstructure before planarization;
fig. 10 is a comparative photograph of copper/nickel heterogeneous microstructure surfaces before and after planarization using example 20 of the present invention.
Detailed Description
To facilitate understanding of the technical contents of the present invention, those skilled in the art will further describe the technical solutions of the present invention with reference to the accompanying drawings and specific embodiments.
In the description of the present invention, the average surface roughness refers to an average value of surface roughness at four different positions of the surface, and wt% refers to mass%.
First, the feasibility and advantages of the present invention for performing the fine planarization on the mechanically ground copper/nickel heterogeneous microstructure surface by using the chemical mechanical polishing in step S2 are illustrated in examples 1 to 19.
Table 1 shows examples 1 to 19 of the chemical mechanical polishing solution of step S2 in the present invention, in which the components of the polishing solution listed in the table are weighed accurately, water is added first, then the metal complexing agent, the metal corrosion inhibitor, the abrasive particles, and the metal oxidant are sequentially added, and after all the components are mixed uniformly, the pH value is adjusted to a target value using sulfuric acid and potassium hydroxide.
TABLE 1 examples 1 to 19
The working principle of chemical mechanical polishing is described as follows: as shown in fig. 1, during the chemical mechanical polishing process, the polishing head is pressed by a certain downward pressure to press the clamped sample on the polishing pad and rotate in the same direction as the polishing disk. Meanwhile, polishing solution containing nano-grade grinding particles and various chemical reagents is conveyed to the surface of the polishing pad, and the material on the surface of the sample is removed through continuous chemical reaction film formation and mechanical action film removal, so that ultra-precise low-damage processing of the surface of the sample is realized. It is worth proposing that the polishing process is carried out on the basis of the traditional grinding polisher, and for a special polishing system, the chemical mechanical polishing can be finished by reasonably adjusting the execution mode according to the actual working condition. The working principle of mechanical grinding is similar.
The samples used in this example are copper and nickel, wherein copper is a pure copper metal sheet with a purity of 99.99%, nickel is a nickel thin film electroplated on a copper substrate, and the sizes of the two samples are both: the diameter is 50.8 mm; the grinding polisher is a UNIPOL-1200S bench polisher manufactured by Shenyang Kejing company, and the process parameters are as follows: the loading pressure is 5.0kg (the set value of the display panel), the rotating speed of the polishing head is 60rpm, the rotating speed of the polishing disk is 60rpm, the center distance between the polishing head and the polishing disk is 105mm, the flow of polishing solution is 100mL/min, and the polishing time is 1 min; the polishing pad used was an IC1010/Suba IV composite polishing pad manufactured by Dow Electronic Materials, USA. The material removal rate was calculated by measuring the weight change of the sample before and after polishing using a ME36S microbalance produced by sidoris germany. The surface topography and surface roughness of the samples were measured using a SuperView W1 optical 3D surface profiler manufactured by FIG. Instrument Inc., measuring an area of 97.9. mu. m.times.97.9. mu.m.
The chemical mechanical polishing solutions of examples 1 to 19 shown in Table 1 were used to perform chemical mechanical polishing on copper and nickel, respectively, and the results of the material removal rates are shown in Table 2.
TABLE 2 Material removal rates for copper and nickel after polishing using examples 1-19
| Examples | Copper material removal rate (nm/min) | Removal rate of nickel material (nm/min) |
| 1 | 5 | 31 |
| 2 | 125 | 266 |
| 3 | 236 | 366 |
| 4 | 495 | 506 |
| 5 | 958 | 642 |
| 6 | 2166 | 698 |
| 7 | 3387 | 620 |
| 8 | 39 | 74 |
| 9 | 51 | 122 |
| 10 | 109 | 165 |
| 11 | 172 | 215 |
| 12 | 205 | 214 |
| 13 | 259 | 215 |
| 14 | 316 | 219 |
| 15 | 11 | 76 |
| 16 | 46 | 93 |
| 17 | 75 | 79 |
| 18 | 94 | 74 |
| 19 | 146 | 71 |
As can be seen from Table 2, in comparative examples 1 to 7, as the content of the hydrogen peroxide in the metal oxidant increases, the material removal rate of copper increases rapidly, and the material removal rate of nickel increases first and then decreases slightly. As shown in example 4, when the hydrogen peroxide content is 0.5 wt%, the material removal rates of copper and nickel are basically equal, namely 495nm/min and 506nm/min respectively, and the constant-speed removal of copper and nickel is basically realized.
As can be seen from Table 2, in comparative examples 8 to 14, after the metal corrosion inhibitor benzotriazole is added, the material removal rate of copper is increased approximately linearly and rapidly along with the increase of the hydrogen peroxide content of the metal oxidant, and the material removal rate of nickel tends to be gentle after being increased first. As shown in example 12, when the hydrogen peroxide content is 1.2 wt%, the material removal rates of copper and nickel are basically equal, namely 205 nm/min and 214 nm/min, and the constant-speed removal of copper and nickel is basically realized.
As can be seen from table 2, in comparative examples 15 to 19, the content of oxalic acid dihydrate as a metal complexing agent is reduced, the pH value of the polishing solution is increased, and after the compounded metal corrosion inhibitor benzotriazole and sodium dodecylbenzenesulfonate are added, the removal rate of the copper material is rapidly increased along with the increase of the content of hydrogen peroxide, and the removal rate of the nickel material is first increased and then decreased. As shown in example 17, when the hydrogen peroxide content is 1.3 wt%, the material removal rates of copper and nickel are basically equal, namely 75 nm/min and 79 nm/min, and the constant-speed removal of copper and nickel is basically realized.
The chemical mechanical polishing liquids of example 4, example 12 and example 17 were used to perform chemical mechanical polishing on copper and nickel, respectively, to obtain surface roughness RaThe results are shown in Table 3.
TABLE 3 surface roughness R of copper and nickel after polishing using examples 4, 12 and 17a
| Examples | Copper surface roughness Ra(nm) | Surface roughness R of nickela(nm) |
| 4 | 95.9 | 3.0 |
| 12 | 51.0 | 2.3 |
| 17 | 6.1 | 2.2 |
As can be seen from table 3, as shown in example 4, when no metal corrosion inhibitor is added, the surface morphologies of copper and nickel after polishing are respectively shown in fig. 2(a) and fig. 2(b), and the copper surface is severely corroded; as shown in example 12, after 5mM benzotriazole was added, the surface topography of copper and nickel after polishing was slightly inhibited as shown in fig. 3(a) and 3(b), respectively, but good surface quality could not be obtained; as shown in example 17, the pH value of the polishing solution and the content of the metal complexing agent are adjusted, and the surface morphology of copper and nickel after polishing is respectively shown in fig. 4(a) and 4(b) by using the compound metal corrosion inhibitor, so that the corrosion of the copper surface is significantly inhibited, and the surface roughness is reduced.
Electrochemical experiments were performed on copper and nickel using the electrolyte solutions corresponding to examples 4, 12 and 17, i.e., removing the abrasive particles from the cmp slurry, respectively, and the results are shown in fig. 5. As can be seen, in the electrolyte solution corresponding to example 17, the corrosion potential difference Δ E between copper and nickel was observedcorrIs obviously smaller than that of the embodiment 4 and the embodiment 12, and shows that the embodiment 17 can effectively inhibit the galvanic corrosion between copper and nickel and avoid the corrosion defect.
Further, the polished copper and nickel were analyzed and characterized by high-resolution transmission electron microscopy, and the results are shown in fig. 6 and 7. As shown in fig. 6, after polishing using example 17, an oxide layer having a thickness of about 1.6nm was present on the copper surface, and the subsurface crystal structure remained intact without damage caused by polishing. In addition, floc having a thickness of about 10.6nm was present above the copper oxide layer, possibly as a mixture of copper oxide debris and sodium dodecylbenzenesulfonate remaining on the surface. As shown in fig. 7, after polishing using example 17, the nickel surface had an oxide layer with a thickness of about 1.3nm, which was substantially equal to the copper oxide layer, and the subsurface crystal structure remained intact without damage caused by polishing. In conclusion, in example 17, the copper and nickel can be removed at the same speed, the galvanic corrosion between the copper and the nickel can be effectively inhibited, and the nanoscale surface roughness and the sub-surface damage approaching zero can be obtained.
Those skilled in the art will appreciate that the specific data of the type and content of the metal oxidizing agent, the type and content of the metal corrosion inhibitor, the type and content of the metal complexing agent and the pH value of the polishing solution are not limited to those in example 17 shown in Table 1. In practical applications, for combinations of different metal oxidant types, types and contents of the compound metal corrosion inhibitor, types and contents of the metal complexing agent, and the pH value of the polishing solution, the corresponding optimum metal oxidant content is also different, and is not limited to the hydrogen peroxide content of 1.3 wt% in example 17. Namely, the type and the content of the metal oxidant, the type and the content of the compound metal corrosion inhibitor, the type and the content of the metal complexing agent, the type and the content of the grinding particles and the pH value of the polishing solution jointly influence the chemical and mechanical polishing effect of the surface of the copper/nickel heterogeneous microstructure.
Next, a method for planarizing a surface of a copper/nickel heterogeneous microstructure according to the present invention is further described in embodiment 20, and as shown in fig. 8, a schematic view of a planarization process flow is shown.
Example 20
Step S1 mechanical grinding: and (4) carrying out rough planarization on the surface of the copper/nickel heterogeneous microstructure by adopting mechanical grinding until all the nickel columns are completely exposed. Wherein, the grinding disc is a sand paper grinding disc, and the grinding fluid is water. Water constantly supplements to the abrasive paper abrasive disc with certain flow on, the sample on the rubbing head under the effect of the pressure that exerts with abrasive paper abrasive disc contact, and abrasive paper abrasive disc and sample do the equidirectional rotation, constantly supplement the contact area with water through rotary motion and centrifugal force, and the sample surface material is realized removing under the mechanical grinding effect.
Step S2 chemical mechanical polishing: and (3) carrying out fine planarization on the surface of the mechanically ground copper/nickel heterogeneous microstructure by adopting chemical mechanical polishing until the surface is completely planarized and the surface roughness reaches the nanometer level. Wherein, the polishing solution is the polishing solution of example 17, and the chemical mechanical polishing process is the same as that described above.
Specifically, the sample used in this embodiment is a copper/nickel heterogeneous microstructure obtained by micro-scale 3D printing based on electrochemical deposition, as shown in fig. 9, there are regularly arranged steps on the surface of the copper/nickel heterogeneous microstructure, each step is composed of a nickel pillar and copper covering the nickel pillar, and the sample size is: diameter 25.4 mm; the grinding polisher is a UNIPOL-1200S bench polisher manufactured by Shenyang Kejing company, and the process parameters of the step S1 mechanical grinding and the step S2 chemical mechanical polishing are as follows: the loading pressure is 1.0kg (the set value of the display panel), the rotating speed of a polishing head is 60rpm, the rotating speed of a polishing disk is 60rpm, the central distance between the polishing head and the polishing disk is 105mm, and the flow of polishing solution is 50 mL/min; the used abrasive paper is P2000 silicon carbide abrasive paper, and is attached to a cast aluminum plate with a flat surface to form an abrasive paper grinding plate, and the used polishing pad is an IC1010/Suba IV composite polishing pad produced by Dow Electronic Materials in America. The material removal rate was calculated by measuring the weight change of the sample before and after polishing using a ME36S microbalance produced by sidoris germany. The surface topography and surface roughness of the samples were measured using a SuperView W1 optical 3D surface profiler manufactured by FIG. Instrument Inc., measuring an area of 97.9. mu. m.times.97.9. mu.m. As shown in fig. 9(a), a step is selected in the center, inside and edge of the copper/nickel heterogeneous microstructure sample, and designated as point a, point B and point C, and the step height change is measured using a P-7 contact profiler produced by KLA.
By adopting the planarization method, the total planarization time of the copper/nickel heterogeneous microstructure surface is 36min, wherein the mechanical grinding time of the step S1 is 13min, and the chemical mechanical polishing time of the step S2 is 23 min. The average material removal rate of the mechanical grinding in the step S1 is 33.75mg/min, and the average material removal rate of the chemical mechanical polishing in the step S2 is 0.53mg/min, which is about 1/60 of the mechanical grinding in the step S1, so that it can be seen that the mechanical grinding process is introduced into the process flow of the copper/nickel heterogeneous microstructure surface planarization, and the planarization efficiency can be significantly improved. After planarization, the surface roughness of the copper/nickel heterogeneous microstructure is nano-scale, and the surface roughness of copper and nickel is 1.6 nm. The step heights of the points A, B and C of the copper/nickel heterogeneous microstructure sample are respectively reduced from initial 245 mu m, 243 mu m and 239 mu m to-1120 nm, -1186nm and-1260 nm, and the absolute value of the step heights is only initial 1/200. As shown in fig. 10, after planarization, the surface of the copper/nickel heterogeneous microstructure sample has high flatness and small surface roughness, and clear reflection can be observed.
In the description herein, references to the description of the term "one embodiment," "some embodiments," "an example," "a specific example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Moreover, various embodiments or examples and features of different embodiments or examples described herein can be combined and combined by one skilled in the art without contradiction.
It will be appreciated by those of ordinary skill in the art that the embodiments described herein are intended to assist the reader in understanding the principles of the invention and are to be construed as being without limitation to such specifically recited embodiments and examples. Various modifications and alterations to this invention will become apparent to those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the claims of the present invention.
Claims (10)
1. A surface planarization method for a micro-scale 3D printed copper/nickel heterogeneous microstructure is characterized by comprising the following steps:
s1, carrying out rough planarization on the surface of the copper/nickel heterogeneous microstructure by adopting mechanical grinding;
s2, carrying out fine planarization on the mechanically ground copper/nickel heterogeneous microstructure surface by adopting chemical mechanical polishing;
the polishing solution used in the chemical mechanical polishing in step S2 includes the following components: 0-10 wt% of metal oxidant, 0-2 wt% of compound metal corrosion inhibitor, 0.01-10 wt% of metal complexing agent, 0.01-40 wt% of grinding particles, and the balance of water and a small amount of pH value regulator, wherein the pH value is 3-7, and the wt% represents mass percentage.
2. The method for planarizing the surface of the micro-scale 3D printed copper/nickel heterogeneous microstructure according to claim 1, wherein the mechanical grinding in step S1 adopts a grinding disc comprising: one of a sand paper grinding disc, a diamond grinding disc, an alumina grinding disc, an oilstone grinding disc, a silicon oxide grinding disc, a glass grinding disc, a ceramic grinding disc, a cast iron grinding disc, a brass grinding disc, a red copper grinding disc and a tin alloy grinding disc.
3. The method for planarizing the surface of the micro-scale 3D printed copper/nickel heterogeneous microstructure according to claim 1, wherein the polishing pad used in the step S2 of chemical mechanical polishing is: one of a polyurethane polishing pad, an artificial leather polishing pad, and a felt polishing pad.
4. The method for planarizing the surface of the micro-scale 3D printed copper/nickel heterogeneous microstructure according to claim 1, wherein in the step S2 of chemical mechanical polishing, the copper/nickel heterogeneous microstructure surface is planarized by adjusting the content of a metal oxidizing agent in a polishing solution and adjusting and controlling the removal rate selection ratio of copper and nickel materials to achieve constant removal rate of copper and nickel.
5. The method for planarizing the surface of the micro-scale 3D printed copper/nickel heterogeneous microstructure according to claim 1, wherein the metal oxidizing agent in the polishing solution is: one or more of hydrogen peroxide, sodium peroxide, carbamide peroxide, peroxyformic acid, peroxyacetic acid and sodium percarbonate.
6. The method for planarizing the surface of the micro-scale 3D printed copper/nickel heterogeneous microstructure according to claim 1, wherein the compound metal corrosion inhibitor in the polishing solution comprises two components: one is one or more azole compounds, and the other is one or more surfactants; the two components are combined and compounded.
7. The method for flattening the surface of the micro-scale 3D printed copper/nickel heterogeneous microstructure according to claim 6, wherein the azole compound is: 1,2, 3-benzotriazole, 4-methyl-1H-benzotriazole, 5, 6-dimethyl-1, 2, 3-benzotriazole, 1-hydroxybenzotriazole, 1,2, 3-triazole, 1,2, 4-triazole, 3-methyl-1H-1, 2, 4-triazole, 3-amino-1, 2, 4-triazole, 4-amino-1, 2, 4-triazole, 3, 5-diamino-1, 2, 4-triazole, 1H-1,2,3, 4-tetrazole, 5-methyl tetrazole, 5-amino-1H-tetrazole, 5-amino-1-methyl tetrazole, 5-phenyl-1H-tetrazole, pyrazole, imidazole and benzimidazole.
8. The method for flattening the surface of the micro-scale 3D printed copper/nickel heterogeneous microstructure according to claim 6, wherein the surfactant is: one of sodium dodecyl benzene sulfonate, alpha-sodium alkenyl sulfonate, ammonium dodecyl sulfate, sodium N-lauroyl glutamate, sodium dodecyl phosphate, sodium oleate, triethanolamine lauryl sulfate, sodium fatty alcohol isethionate, sodium cocoyl methyl taurate, disodium lauryl polyoxyethylene ether sulfosuccinate, sodium secondary alkyl sulfonate, disodium lauryl polyoxyethylene ether sulfosuccinate, sodium lauryl polyoxyethylene ether sulfate, sodium N-lauroyl sarcosinate, sodium lauryl ether sulfate, sodium lauryl polyoxyethylene ether carboxylate, dodecyl phosphate, sodium dodecyl sulfate, magnesium amido polyoxyethylene ether sulfate, potassium dodecyl phosphate, triethanolamine dodecyl phosphate, and sodium stearate.
9. The method of claim 1, wherein the metal complexing agent in the polishing solution is oxalic acid dihydrate.
10. The method of claim 1, wherein the abrasive particles in the polishing solution are colloidal silica.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110809582.8A CN113526459B (en) | 2021-07-16 | 2021-07-16 | Surface planarization method for micro-scale 3D printing copper/nickel heterogeneous microstructure |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110809582.8A CN113526459B (en) | 2021-07-16 | 2021-07-16 | Surface planarization method for micro-scale 3D printing copper/nickel heterogeneous microstructure |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113526459A true CN113526459A (en) | 2021-10-22 |
| CN113526459B CN113526459B (en) | 2023-03-24 |
Family
ID=78128568
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110809582.8A Active CN113526459B (en) | 2021-07-16 | 2021-07-16 | Surface planarization method for micro-scale 3D printing copper/nickel heterogeneous microstructure |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113526459B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114888646A (en) * | 2022-06-18 | 2022-08-12 | 西南交通大学 | Grinding and polishing method for porous polyimide surface for high-speed bearing |
| CN116023907A (en) * | 2023-02-16 | 2023-04-28 | 西南交通大学 | Polishing solution for flattening copper/nickel microstructure and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20050059941A (en) * | 2003-12-15 | 2005-06-21 | 매그나칩 반도체 유한회사 | Method of forming a inductor in semiconductor devices |
| CN101891143A (en) * | 2009-05-18 | 2010-11-24 | 张刚 | Method for manufacturing multilayer three-dimensional device or structure |
| CN102373013A (en) * | 2010-08-24 | 2012-03-14 | 安集微电子（上海）有限公司 | Chemically mechanical polishing solution |
| CN106078487A (en) * | 2016-06-07 | 2016-11-09 | 大连理工常州研究院有限公司 | Nickel-base alloy solidified abrasive grinding and cmp method |
| CN107164764A (en) * | 2017-06-09 | 2017-09-15 | 大连理工大学 | A kind of environment protection chemical mechanical polishing method of copper |
| CN108153108A (en) * | 2017-12-22 | 2018-06-12 | 青岛理工大学 | A kind of large scale is without splicing micro-nano mould manufacturing method |
| CN109848821A (en) * | 2018-12-28 | 2019-06-07 | 大连理工大学 | A kind of environmentally protective cmp method of nickel alloy |
| CN110625460A (en) * | 2019-09-18 | 2019-12-31 | 北京遥测技术研究所 | Planarization process method for wafer-level heterostructure |
| CN112441555A (en) * | 2019-08-30 | 2021-03-05 | 中国科学院微电子研究所 | Preparation method of micro-nano metal three-dimensional structure |
| CN112563132A (en) * | 2020-11-13 | 2021-03-26 | 北京遥测技术研究所 | Rapid thinning and polishing method for surface heterostructure |
-
2021
- 2021-07-16 CN CN202110809582.8A patent/CN113526459B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20050059941A (en) * | 2003-12-15 | 2005-06-21 | 매그나칩 반도체 유한회사 | Method of forming a inductor in semiconductor devices |
| CN101891143A (en) * | 2009-05-18 | 2010-11-24 | 张刚 | Method for manufacturing multilayer three-dimensional device or structure |
| CN102373013A (en) * | 2010-08-24 | 2012-03-14 | 安集微电子（上海）有限公司 | Chemically mechanical polishing solution |
| CN106078487A (en) * | 2016-06-07 | 2016-11-09 | 大连理工常州研究院有限公司 | Nickel-base alloy solidified abrasive grinding and cmp method |
| CN107164764A (en) * | 2017-06-09 | 2017-09-15 | 大连理工大学 | A kind of environment protection chemical mechanical polishing method of copper |
| CN108153108A (en) * | 2017-12-22 | 2018-06-12 | 青岛理工大学 | A kind of large scale is without splicing micro-nano mould manufacturing method |
| CN109848821A (en) * | 2018-12-28 | 2019-06-07 | 大连理工大学 | A kind of environmentally protective cmp method of nickel alloy |
| CN112441555A (en) * | 2019-08-30 | 2021-03-05 | 中国科学院微电子研究所 | Preparation method of micro-nano metal three-dimensional structure |
| CN110625460A (en) * | 2019-09-18 | 2019-12-31 | 北京遥测技术研究所 | Planarization process method for wafer-level heterostructure |
| CN112563132A (en) * | 2020-11-13 | 2021-03-26 | 北京遥测技术研究所 | Rapid thinning and polishing method for surface heterostructure |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114888646A (en) * | 2022-06-18 | 2022-08-12 | 西南交通大学 | Grinding and polishing method for porous polyimide surface for high-speed bearing |
| CN116023907A (en) * | 2023-02-16 | 2023-04-28 | 西南交通大学 | Polishing solution for flattening copper/nickel microstructure and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113526459B (en) | 2023-03-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN113526459B (en) | Surface planarization method for micro-scale 3D printing copper/nickel heterogeneous microstructure | |
| JP3249233B2 (en) | Formation of microstructure by multilevel deep X-ray lithography with sacrificial metal layer | |
| US20130105331A1 (en) | Nano-precision photo/electrochemical planarization and polishing methods and apparatus therefor | |
| US7271022B2 (en) | Process for forming microstructures | |
| Yang et al. | Effects of various ion-typed surfactants on silicon anisotropic etching properties in KOH and TMAH solutions | |
| CA2431591A1 (en) | Composition for chemical mechanical planarization of copper, tantalum and tantalum nitride | |
| TW200428531A (en) | Copper chemical mechanical polishing solutions using sulfonated amphiprotic agents | |
| CN101541913A (en) | Chemical mechanical polishing composition for copper comprising zeolite | |
| Tian et al. | Effects of chemical slurries on fixed abrasive chemical-mechanical polishing of optical silicon substrates | |
| EP3523103B1 (en) | Method of machining brittle materials and machined product obtained by such a method | |
| Gao et al. | Polystyrene/CeO2 core/shell abrasives for high-quality 4H-SiC surface in ECMP: The effects of shell thickness | |
| Gao et al. | Experimental study on abrasive-free polishing for KDP crystal | |
| Kasai et al. | Physics and tribology of chemical mechanical planarization | |
| Hou et al. | Intermolecular and surface forces in atomic-scale manufacturing | |
| US20020173252A1 (en) | Chemical mechanical polishing | |
| CN104263248B (en) | A kind of faintly acid copper polishing fluid suitable in low downforce | |
| Kourouklis et al. | The application of chemical–mechanical polishing for planarizing a SU-8/permalloy combination used in MEMS devices | |
| CN101162645A (en) | Permanent magnet microstructure integrated manufacturing method of micro electro-mechanical systems | |
| TW201118037A (en) | Multi material secondary metallization scheme in MEMS fabrication | |
| Ting et al. | Review of micromachining of ceramics by etching | |
| Dong-hui et al. | A hydrodynamic suspension polishing method for ultrasmooth and low-damage surface | |
| CN101759143A (en) | Method for controlling growth of micro-nano pore structure on silicon surface | |
| CN116023907A (en) | Polishing solution for flattening copper/nickel microstructure and application thereof | |
| Gao et al. | Material removal rate of 4H-SiC polishing with polystyrene/CeO2 Core/shell abrasives | |
| JP5484538B2 (en) | Surface treatment method for conductive substrate surface |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |