CN114106704A - Green environment-friendly titanium metal polishing solution - Google Patents
Green environment-friendly titanium metal polishing solution Download PDFInfo
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- CN114106704A CN114106704A CN202111540483.0A CN202111540483A CN114106704A CN 114106704 A CN114106704 A CN 114106704A CN 202111540483 A CN202111540483 A CN 202111540483A CN 114106704 A CN114106704 A CN 114106704A
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- surfactant
- corrosion inhibitor
- polishing solution
- complexing agent
- nicotinic acid
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- 238000005498 polishing Methods 0.000 title claims abstract description 46
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000010936 titanium Substances 0.000 title claims abstract description 39
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 39
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 17
- 239000002184 metal Substances 0.000 title claims abstract description 17
- PVNIIMVLHYAWGP-UHFFFAOYSA-N nicotinic acid Natural products OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims abstract description 58
- 230000007797 corrosion Effects 0.000 claims abstract description 42
- 238000005260 corrosion Methods 0.000 claims abstract description 42
- 239000003112 inhibitor Substances 0.000 claims abstract description 33
- 229960003512 nicotinic acid Drugs 0.000 claims abstract description 32
- 235000001968 nicotinic acid Nutrition 0.000 claims abstract description 32
- 239000011664 nicotinic acid Substances 0.000 claims abstract description 32
- 239000004094 surface-active agent Substances 0.000 claims abstract description 27
- 239000008139 complexing agent Substances 0.000 claims abstract description 23
- 239000007800 oxidant agent Substances 0.000 claims abstract description 11
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 229910001415 sodium ion Inorganic materials 0.000 claims abstract description 7
- 125000000627 niacin group Chemical group 0.000 claims abstract description 4
- 238000001914 filtration Methods 0.000 claims description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical group OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 11
- 238000000034 method Methods 0.000 claims description 10
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 10
- 239000003085 diluting agent Substances 0.000 claims description 7
- 239000001508 potassium citrate Substances 0.000 claims description 7
- 229960002635 potassium citrate Drugs 0.000 claims description 7
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 claims description 7
- 235000011082 potassium citrates Nutrition 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 6
- 230000000694 effects Effects 0.000 claims description 6
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 229940051841 polyoxyethylene ether Drugs 0.000 claims description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 239000002994 raw material Substances 0.000 claims description 4
- 150000007514 bases Chemical class 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- WBIQQQGBSDOWNP-UHFFFAOYSA-N 2-dodecylbenzenesulfonic acid Chemical compound CCCCCCCCCCCCC1=CC=CC=C1S(O)(=O)=O WBIQQQGBSDOWNP-UHFFFAOYSA-N 0.000 claims description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 2
- 239000004471 Glycine Substances 0.000 claims description 2
- 229920000805 Polyaspartic acid Polymers 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229940060296 dodecylbenzenesulfonic acid Drugs 0.000 claims description 2
- 230000006870 function Effects 0.000 claims description 2
- 230000005764 inhibitory process Effects 0.000 claims description 2
- 108010064470 polyaspartate Proteins 0.000 claims description 2
- AVTYONGGKAJVTE-OLXYHTOASA-L potassium L-tartrate Chemical compound [K+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O AVTYONGGKAJVTE-OLXYHTOASA-L 0.000 claims description 2
- 239000001472 potassium tartrate Substances 0.000 claims description 2
- 229940111695 potassium tartrate Drugs 0.000 claims description 2
- 235000011005 potassium tartrates Nutrition 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 abstract description 3
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 239000000126 substance Substances 0.000 description 15
- 239000002245 particle Substances 0.000 description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 235000015165 citric acid Nutrition 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000007517 polishing process Methods 0.000 description 4
- 230000009471 action Effects 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 description 2
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 2
- 229910001069 Ti alloy Inorganic materials 0.000 description 2
- 239000003082 abrasive agent Substances 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- -1 hydrogen ions Chemical class 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000007521 mechanical polishing technique Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229940068041 phytic acid Drugs 0.000 description 2
- 239000000467 phytic acid Substances 0.000 description 2
- 235000002949 phytic acid Nutrition 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F11/00—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent
- C23F11/08—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids
- C23F11/10—Inhibiting corrosion of metallic material by applying inhibitors to the surface in danger of corrosion or adding them to the corrosive agent in other liquids using organic inhibitors
- C23F11/14—Nitrogen-containing compounds
- C23F11/149—Heterocyclic compounds containing nitrogen as hetero atom
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F3/00—Brightening metals by chemical means
- C23F3/04—Heavy metals
Abstract
The invention relates to a green environment-friendly titanium metal polishing solution, which comprises an abrasive, an oxidant, an alkaline oxide, a surfactant, a complexing agent and a corrosion inhibitor, wherein the corrosion inhibitor is nicotinic acid, and the surfactant is an organic surfactant without sodium ions. The formula of the invention does not introduce new external sodium ions, and can be applied to the polishing in the field of semiconductors, thereby reducing the number of metal ions. A good titanium surface can be obtained by introducing a small amount of nicotinic acid, and the excellent surface quality can be obtained when the concentration of the nicotinic acid is 0.05 wt%, and meanwhile, the removal rate is good.
Description
Technical Field
The invention relates to a titanium polishing solution capable of inhibiting corrosion and scratch of a titanium metal surface and a preparation method thereof.
Background
At present, titanium is widely applied in the fields of aerospace, biomedicine, integrated circuits and the like due to relatively rich content, higher strength, better stability and better biocompatibility. In the IC field and the biomedical field, extremely high requirements are made on the surface quality of titanium and titanium alloy. Relevant researches show that the reduction of the surface roughness can effectively reduce the occurrence of cracks and prolong the service life of the material. Good surfaces can only be obtained by chemical mechanical polishing techniques.
A Chemical Mechanical Polishing (CMP) technique, which is a technique that can finally realize local and global planarization of a wafer by the interaction of mechanical action and chemical action. CMP technology was first introduced by Walsh et al in 1965 and was first used to manufacture high quality glass surfaces such as military telescopes. In the chemical mechanical polishing process, grinding is mainly performed through the combined action among the polishing head, the polishing pad and the polishing liquid, the polishing head and the polishing pad mainly provide the mechanical grinding function, and the polishing liquid mainly plays a chemical role. The polished wafer and the polishing pad move relatively, and the purposes of quickly removing materials and obtaining a high-quality surface are achieved by utilizing the grinding of nano-grade abrasive materials in the polishing solution and the oxidation corrosion of chemical additives such as oxidizing agents, complexing agents and the like.
From the introduction of chemical mechanical polishing techniques to the present, CMP has been developed from the original application mainly to Integrated Circuits (ICs) to the processing fields of memory disks, precision ceramics, metal alloys (titanium alloys, etc.) having special uses in the aerospace field, etc., which have special requirements for surfaces. Particularly, as the IC manufacturing technology node is continuously reduced, the research and development of the polishing solution in the direction of low pressure and low abrasive material becomes important. And the polishing solution is used as an recyclable consumable in the field of high-precision manufacturing, so that the market demand is very huge, and the treatment work after the waste liquid is discharged is very difficult, so that the environment-friendly titanium metal chemical mechanical polishing solution is especially important.
The chemical corrosion in the metal polishing solution is a main factor causing metal surface defects, the presence of chemical additives such as hydrogen ions or hydroxyl ions and complexing agents in the polishing solution causes the surface defects of titanium in the polishing process, and partial researchers research that a metal corrosion inhibitor BTA, TTA and the like is added to inhibit the surface defects after the chemical mechanical polishing of the titanium, so that the environmental pollution is large.
Disclosure of Invention
Aiming at the problems, the invention aims to provide the green and environment-friendly titanium polishing solution capable of inhibiting corrosion and scratch of the surface of the titanium wafer and the preparation method thereof, so that the quality of the titanium surface after chemical mechanical polishing is improved, and the influence on the environment is minimized.
The technical scheme adopted by the invention for solving the technical problems is as follows:
the green environment-friendly titanium metal polishing solution can inhibit corrosion and metal pollution on the surface of a titanium wafer, and comprises an abrasive, an oxidant, an alkaline oxide, a surfactant, a complexing agent and a corrosion inhibitor, and is characterized in that the corrosion inhibitor is nicotinic acid, and the surfactant is an organic surfactant without sodium ions.
The polishing solution comprises the following components in percentage by mass: silica sol: 1 wt% -10 wt%; oxidizing agent: 0.1 wt% -2 wt%; basic compound (b): 0.01 wt% -0.1 wt%; complexing agent: 0.1 wt% -5 wt%; corrosion inhibitor: 0.01 wt% -0.2 wt%; surfactant (b): 0.01 wt% -0.1 wt%; the balance of deionized water.
The complexing agent comprises potassium citrate, and the complexing agent also can comprise any one of potassium tartrate and glycine;
the oxidant is hydrogen peroxide; the alkaline compound is any one of tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, polyaspartic acid and ammonia water; the surfactant is polyvinylpyrrolidone, fatty alcohol-polyoxyethylene ether and dodecylbenzene sulfonic acid, preferably fatty alcohol-polyoxyethylene ether.
The preparation process of the green environment-friendly titanium metal polishing solution comprises the following steps: the preparation process needs to be matched with a stirrer for use, and the specific process is as follows:
1) respectively dissolving a complexing agent, a corrosion inhibitor and a surfactant into a 1 wt% diluent state;
2) filtering 1 wt% of the diluent in the step 1), wherein the aperture of a filter element is 500 nm;
3) carrying out two-stage filtration on the silica sol, wherein the filter element aperture of a filter element used in the two-stage filtration is 500nm and 300 nm;
4) mixing by a stirrer, controlling the rotating speed to be 80-120r/min, stirring for 30-60min, controlling the temperature to be 30-50 ℃, and adding deionized water, a complexing agent (1 wt% solution), a corrosion inhibitor (1 wt% solution), a surfactant (1 wt% solution), silica sol, an alkaline compound and hydrogen peroxide into the raw materials in sequence. The addition of the substances is carried out according to the required proportion, and the 1 wt% solution means that the corresponding components are dissolved in water in advance, the mass of large particles is ignored after filtration, solid chemicals cannot be directly added into silica sol, the problems of gelation and the like occur, and the total mass input of the 1 wt% solution is required when the target mass of the components to be added is calculated according to the mass of solutes in the 1 wt% solution during later addition.
Compared with the prior art, the invention has the beneficial effects that:
nicotinic acid, also known as niacin, is one of the 13 vitamins that are essential to the human body. The application adopts nicotinic acid as a corrosion inhibitor, the molecular structure of the nicotinic acid is composed of a carboxyl (-COOH) and a pyridine group, titanium is an oxygen-philic element, after the nicotinic acid is added, the carboxyl and the titanium surface can form a coordinate bond, the corrosion process is retarded in an adsorption film forming mode, the corrosion inhibition effect is achieved, the harm to a human body is small in the using process, the toxicity of the nicotinic acid is small compared with BTA and the like, the influence on the environment is small, and the titanium metal polishing solution is green and environment-friendly.
The formula of the invention does not introduce new external sodium ions, can be applied to the polishing in the semiconductor field (in the polishing process in the semiconductor field, strict requirements are provided for the content of metal ions, especially sodium ions), and the number of the metal ions is reduced.
According to the method, a good titanium surface can be obtained by introducing a small amount of nicotinic acid (0.05 wt%), the surface quality can be excellent when the concentration of the nicotinic acid is 0.05 wt%, the surface can not be optimized when the content of the nicotinic acid is continuously increased, and the removal rate can be reduced due to excessive introduction of the corrosion inhibitor.
The preparation method provided by the invention adopts a filtering technology, so that the number of large particles in the polishing solution can be obviously reduced, and the occurrence of scratches on the surface of the titanium wafer can be effectively avoided.
Drawings
FIG. 1 is a flow chart of the preparation of polishing solution.
FIG. 2 is a graph comparing the number of large particles (. gtoreq.0.5 μm) in the slurry under different process conditions.
FIG. 3 is a graph comparing surface quality (Sq) after titanium polishing under different process conditions.
FIG. 4 is a graph of the titanium surface quality Sq results for different niacin contents in example 1.
FIG. 5 is a graph showing the effect of different organic acids on the surface quality Sq of titanium.
FIG. 6 is an AFM test of titanium after 0.05 wt% citric acid and phytic acid, nicotinic acid as corrosion inhibitors in accordance with the present invention.
Detailed Description
The present invention is further explained with reference to the following examples and drawings, but the scope of the present invention is not limited thereto.
Example 1
The green environment-friendly titanium metal polishing solution comprises an abrasive, an oxidant, an alkaline oxide, a surfactant, a complexing agent and a corrosion inhibitor, wherein the corrosion inhibitor is nicotinic acid, and the surfactant is an organic surfactant without sodium ions.
The polishing solution comprises the following components in percentage by mass: silica sol: 5 wt%; oxidizing agent: 1 wt%; basic compound (b): 0.08 wt%; complexing agent: 1 wt%; corrosion inhibitor: 0.01 wt% -0.1 wt%; surfactant (b): 0.05 wt%. The complexing agent comprises potassium citrate; the oxidant is hydrogen peroxide; the alkaline compound is tetramethyl ammonium hydroxide; the surfactant is fatty alcohol-polyoxyethylene ether.
The preparation process of the polishing solution comprises the following steps:
1) respectively dissolving a complexing agent, a corrosion inhibitor and a surfactant into a 1 wt% diluent state;
2) filtering 1 wt% of the diluent in the step 1), wherein the aperture of a filter element is 500 nm; the mass concentration of the solution after filtration is 1 wt%, the purpose of filtration is to prevent the polishing result from being influenced by incompatible trace impurities in the dissolving process or large particles introduced in the preparation process, the content of the large particles is less, and the quality is ignored. The "1 wt% complexing agent" in the above formula refers to the content of potassium citrate in the polishing solution, and the "1 wt% diluent" is to dissolve each component in advance (for example, if 1g potassium citrate is required in the polishing solution, 100g potassium citrate solution (1 wt%) needs to be added).
3) Carrying out two-stage filtration on the silica sol, wherein the filter element aperture of a filter element used in the two-stage filtration is 500nm and 300 nm;
4) mixing by a stirrer, controlling the rotating speed at 100r/min, stirring for 50min, controlling the temperature at 40 ℃, and adding deionized water, a complexing agent (1 wt% solution), a corrosion inhibitor (1 wt% solution), a surfactant (1 wt% solution), silica sol, an alkaline compound and hydrogen peroxide into the raw materials in sequence. The polishing solution obtained through the four steps has 9625 large particles (not less than 0.5 μm) per milliliter.
In the embodiment, different nicotinic acid addition concentrations are set, and the test data on the influence of the nicotinic acid addition concentration on the titanium surface performance are shown in a table 4, wherein the data in the table show that the surface quality Sq is 1.5nm when the nicotinic acid is not added, and the surface quality Sq is controlled within 0.29nm when the nicotinic acid addition concentration is 0.04-0.2%. The concentration of nicotinic acid is 0.05 wt% to obtain the optimal surface, and the cost is low.
The removal rate of the polishing solution in the embodiment is lower than 100nm/min, is between 30 and 70nm/min, and is about 60nm/min when the mass concentration is 5 wt%.
Example 2
The steps of this example are the same as example 1, except that step 2 is not performed in this example, and the amount of the added corrosion inhibitor, nicotinic acid, is 0.05 wt%. The test results are as follows: large particle test equipment: ACCUSIZer780APS type Large particle tester (PSS780) manufactured by PSS particle sizer corporation, USA; surface quality test equipment: agilent model 5600LS Atomic Force Microscope (AFM) manufactured by Agilent technologies, Inc.
The experimental results are as follows: the number of large particles (not less than 0.5 mu m) per milliliter is 12685;
titanium surface quality (Sq): 0.94, under the same condition, the corrosion inhibitor is citric acid and the like, the titanium surface quality is worse, and the Sq is 1.73.
Comparing example 1 with example 2, it can be seen that, under the same conditions, if the large particles in the polishing solution are not removed, the wafer surface is scratched, and the surface quality is seriously affected.
Example 3
The steps of this example are the same as example 1, except that the amount of the added corrosion inhibitor, nicotinic acid, is 0.05 wt%, the complexing agent is a mixture of potassium citrate and glycine, and the two are added according to a ratio of 1: 1.
Example 4
The steps of this example are the same as example 1, except that the amount of the added nicotinic acid as the corrosion inhibitor is 0.05 wt%, and the surfactant is polyvinylpyrrolidone.
Comparative example 1
The steps of this example are the same as example 1, except that 0.05 wt% of citric acid and phytic acid are used as corrosion inhibitors instead of nicotinic acid, and the obtained polishing solution is tested for titanium surface quality under the same conditions, and the experimental results are shown in fig. 5. As is obvious from figure 5, the nicotinic acid can obviously reduce the surface quality of titanium metal by being used as a corrosion inhibitor, and has obvious effect.
Comparative example 2
The composition and content of each substance in the comparative example are the same as those in example 1, except that no corrosion inhibitor is added in the comparative example, and step 2) and step 3) are not performed in the preparation process. The test results are as follows:
the experimental results are as follows: the number of large particles (not less than 0.5 mu m) per milliliter is 34319;
titanium surface quality (Sq): 3.44 nm.
Because the raw materials are not filtered and the corrosion inhibitor is not added, the number of large particles is too large, scratches are generated on the surface of the wafer in the polishing process, and the surface quality is seriously influenced. Comparing comparative example 2 and example 2, it can be seen that the surface quality is greatly improved when the nicotinic acid corrosion inhibitor is added, and the citric acid added on the basis of comparative example 2 as the corrosion inhibitor has a certain protection effect on the titanium surface, but the effect is far less than that of the nicotinic acid. And because of the property of the activator, the removal rate of titanium is reduced, and nicotinic acid is selected as the corrosion inhibitor.
Nothing in this specification is said to apply to the prior art.
Claims (6)
1. The green environment-friendly titanium metal polishing solution comprises an abrasive, an oxidant, an alkaline oxide, a surfactant, a complexing agent and a corrosion inhibitor, and is characterized in that the corrosion inhibitor is nicotinic acid, and the surfactant is an organic surfactant without sodium ions.
2. The green environment-friendly titanium metal polishing solution is characterized by comprising the following components in percentage by mass: silica sol: 1 wt% -10 wt%; oxidizing agent: 0.1 wt% -2 wt%; basic compound (b): 0.01 wt% -0.1 wt%; complexing agent: 0.1 wt% -5 wt%; corrosion inhibitor: 0.01 wt% -0.2 wt%; surfactant (b): 0.01 wt% -0.1 wt%; the balance of deionized water;
the complexing agent comprises potassium citrate;
the oxidant is hydrogen peroxide; the alkaline compound is any one of tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, polyaspartic acid and ammonia water; the surfactant is at least one of polyvinylpyrrolidone, fatty alcohol-polyoxyethylene ether and dodecylbenzene sulfonic acid.
3. The polishing solution according to claim 1 or 2, wherein the surfactant is fatty alcohol-polyoxyethylene ether, and the complexing agent further comprises potassium tartrate or glycine.
4. The polishing solution according to claim 1 or 2, wherein the nicotinic acid is present in an amount of 0.04 to 0.1% by mass.
5. The polishing solution according to claim 1 or 2, wherein after the nicotinic acid is added, the carboxyl group forms a coordination bond with the titanium surface to retard the corrosion process in an adsorption film-forming manner, thereby achieving a corrosion inhibition effect.
6. The preparation method of the green environment-friendly titanium metal polishing solution as recited in any one of claims 1 to 5, characterized in that the preparation method comprises the following steps:
1) respectively dissolving a complexing agent, a corrosion inhibitor and a surfactant into a 1 wt% diluent state;
2) filtering the 1 wt% of the diluent in the step 1), wherein the aperture of a filter element is 500nm, and recording the filtered liquid as 1 wt% of solution with corresponding functions respectively;
3) carrying out two-stage filtration on the silica sol, wherein the filter element aperture of a filter element used in the two-stage filtration is 500nm and 300 nm;
4) mixing by a stirrer, controlling the rotating speed to be 80-120r/min, stirring for 30-60min, controlling the temperature to be 30-50 ℃, and adding deionized water, a complexing agent, a corrosion inhibitor, a surfactant, silica sol, an alkaline compound and hydrogen peroxide into the raw materials in sequence; and 4) when the complexing agent, the corrosion inhibitor and the surfactant are added in the step 4), calculating the total mass input of the 1 wt% solution required by the target mass of the component to be added according to the mass of the solute in the 1 wt% solution.
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| CN202111540483.0A CN114106704A (en) | 2021-12-16 | 2021-12-16 | Green environment-friendly titanium metal polishing solution |
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| CN202111540483.0A CN114106704A (en) | 2021-12-16 | 2021-12-16 | Green environment-friendly titanium metal polishing solution |
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| CN115522200A (en) * | 2022-09-27 | 2022-12-27 | 成都光明南方光学科技有限责任公司 | Rare metal deplating liquid and preparation method thereof |
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Application publication date: 20220301 |