CN115678437B - Molybdenum barrier layer chemical mechanical polishing solution based on weak acidity of hydrogen peroxide system and preparation method thereof - Google Patents
Molybdenum barrier layer chemical mechanical polishing solution based on weak acidity of hydrogen peroxide system and preparation method thereof Download PDFInfo
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 65
- 239000011733 molybdenum Substances 0.000 title claims abstract description 65
- 238000005498 polishing Methods 0.000 title claims abstract description 54
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 230000004888 barrier function Effects 0.000 title claims abstract description 34
- 239000000126 substance Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 230000007797 corrosion Effects 0.000 claims abstract description 80
- 238000005260 corrosion Methods 0.000 claims abstract description 80
- 239000003112 inhibitor Substances 0.000 claims abstract description 41
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims abstract description 14
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 8
- 229910052802 copper Inorganic materials 0.000 claims abstract description 8
- 239000010949 copper Substances 0.000 claims abstract description 8
- ZUHDIDYOAZNPBV-UHFFFAOYSA-N 2-[2-hydroxyethyl-[(4-methylbenzotriazol-1-yl)methyl]amino]ethanol Chemical group CC1=CC=CC2=C1N=NN2CN(CCO)CCO ZUHDIDYOAZNPBV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000008367 deionised water Substances 0.000 claims description 16
- 229910021641 deionized water Inorganic materials 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 238000007517 polishing process Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000003513 alkali Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 2
- 230000003068 static effect Effects 0.000 abstract description 41
- 238000005516 engineering process Methods 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 9
- 239000007787 solid Substances 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 30
- 239000007788 liquid Substances 0.000 description 29
- 239000010410 layer Substances 0.000 description 28
- 230000000694 effects Effects 0.000 description 19
- 230000005764 inhibitory process Effects 0.000 description 14
- 238000005530 etching Methods 0.000 description 13
- 230000002378 acidificating effect Effects 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000001179 sorption measurement Methods 0.000 description 5
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 239000004471 Glycine Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 208000001491 myopia Diseases 0.000 description 1
- 230000004379 myopia Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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- Mechanical Treatment Of Semiconductor (AREA)
Abstract
The invention discloses a molybdenum barrier layer chemical mechanical polishing solution based on weak acidity of a hydrogen peroxide system and a preparation method thereof. The polishing solution comprises the following components: the solid concentration of the nano-scale silica sol is 1.0-10.0 wt%; the concentration of hydrogen peroxide is 0.3 to 5.0 weight percent; the concentration of the azole corrosion inhibitor is 50-500 ppm, the balance is water, and the pH value is 2.0-10.0; the azole corrosion inhibitor is 2,2' - { [ (methyl-1H-benzotriazole-1-yl) methyl]Imino } bisethanol (TT-LYK). The low-technology node copper interconnection molybdenum barrier layer acid polishing solution has the advantages that the removal rate of the molybdenum barrier layer material is low) And slow static corrosion rate Below is lower than) And has the characteristics of low cost and safe use.
Description
Technical Field
The invention belongs to the field of polishing solutions, and particularly relates to a molybdenum barrier layer chemical mechanical polishing solution based on weak acidity of a hydrogen peroxide system and a preparation method thereof.
Background
Molybdenum is widely used in the medical, chemical, metallurgical and electronic industries. Molybdenum has good development prospect in the integrated circuit manufacturing industry due to its low expansion coefficient, high conductivity and excellent thermal conductivity. Molybdenum, as the most promising barrier material, is capable of meeting many of the needs of low technology node integrated circuits. Metallic molybdenum has a relatively high melting point (2620 ℃) and a relatively low resistivity (5.34 mu. Omega. Cm). In addition, molybdenum has better adhesion to copper than tantalum and can maintain a stable barrier effect at 750 ℃. To meet the requirements of low technology nodes, the thickness of the molybdenum barrier layer should be reduced to 2nm and below. This requires the use of chemical mechanical polishing (Chemical Mechanical Polish, CMP) techniques to meet the specifications for its industrial production.
For barrier polishing, the removal rate should be controlled toWithin the range. In addition, during polishing, it is desirable to reduce the corrosion of the polishing liquid to metallic molybdenum to achieve the effect of reducing the occurrence of pitting. One of the solutions is to select a suitable inhibitor to be added to the polishing liquid. Inhibitors, also known as metal corrosion inhibitors, function to effectively reduce the removal rate of metal during CMP while protecting the metal from excessive corrosion and defects. Yang et al (DOI: http:// dx.doi.org/10.1016/j.apsusc.2017.08.140) found that glycine had a good corrosion inhibition effect on molybdenum in an alkaline environment. They found that the static etch rate of molybdenum was 20nm/min by adding 100mM glycine at pH 9.0. However, this value is still too high for the removal rate of molybdenum, and still causes severe corrosion to metallic molybdenum, thereby failing to meet the polishing requirements of low technology nodes. He et al (DOI:: 10.1149/2.0061806 jss) in an acidic System using KIO 3 As an oxidizing agent, a high removal rate (90 nm/min) and a low static etch rate (2.2 nm/min) were obtained. But due to not beingThe corrosion inhibitor of molybdenum is added into the acidic polishing solution, and the defect of higher polishing rate of molybdenum still exists.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a weak acid molybdenum barrier layer chemical mechanical polishing solution based on a hydrogen peroxide system and a preparation method thereof. The TT-LYK is added into the acidic polishing solution, so that the dissolution rate of the novel barrier material molybdenum under dynamic and static conditions can be effectively relieved. The invention is based on reducing the static corrosion rate of Mo, and determines the concentration and pH value of TT-LYK in the static corrosion liquid. And then adding silica sol on the basis of the static corrosive liquid component, determining the optimal polishing liquid component, and carrying out polishing experiment verification to obtain the polishing liquid component with lower Mo static corrosion rate and polishing rate. The low-technology node copper interconnection molybdenum barrier layer acid polishing solution has the advantages of low removal rate of molybdenum barrier layer materialAnd slow static etch rate (/ -)>Below->) And has the characteristics of low cost and safe use.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
the molybdenum barrier layer chemical mechanical polishing solution based on the weak acidity of the hydrogen peroxide system comprises the following components: the solid concentration of the nano-scale silica sol is 1.0-10.0 wt%; the concentration of hydrogen peroxide is 0.3 to 5.0 weight percent; the concentration of the azole corrosion inhibitor is 50-500 ppm, the balance is water, and the pH value is 2.0-10.0. Preferably 2.0 to 6.0.
The particle size of the silica sol is 70-90 nm.
The azole corrosion inhibitor is 2,2' - { [ (methyl-1H-benzotriazole-1-yl) methyl ] imino } diethanol (TT-LYK) with the concentration of 100 percent.
The preparation method of the polishing solution comprises the following steps: comprising the following steps: adding deionized water into the azole corrosion inhibitor according to the material concentration for dilution, then adding hydrogen peroxide solution, stirring and mixing, then adding nano-scale silica sol, continuing stirring, adding acid or alkali, adjusting the pH value of the solution to be 2.0-6.0, and finally stirring and adding deionized water for constant volume to obtain the polishing solution.
The concentration of the silica sol is 30-50wt% and the concentration of the hydrogen peroxide solution is 25-50wt%.
The acid is hydrochloric acid or sulfuric acid; the alkali is sodium hydroxide solution.
The application of the molybdenum barrier layer chemical mechanical polishing solution based on the weak acidity of the hydrogen peroxide is applied to the barrier layer polishing process of the copper interconnection molybdenum barrier layer structure integrated circuit.
Compared with the prior art, the invention has the beneficial effects that:
TT-LYK is added into the molybdenum barrier layer chemical mechanical polishing solution based on the weak acidity of the hydrogen peroxide system, so that TT-LYK has an adsorption effect on the surface of metallic molybdenum, a corrosion inhibition layer is formed on the surface layer of the molybdenum, and the corrosion inhibition layer blocks contact between metal and an oxidant, so that the effect of slowing down corrosion is achieved. In addition, under the acidic condition, the surface of the metallic molybdenum can generate insoluble molybdenum dioxide with hydrogen peroxide, and the insoluble matters also play a role in blocking corrosion to a certain extent. In conclusion, the acid polishing solution for the low-technology node copper interconnection molybdenum barrier layer has lower removal rate of molybdenumAnd static corrosion rate (/ -)>Below->) In the barrier polishing process of integrated circuit manufacture, the probability of galvanic corrosion of the molybdenum barrier material is greatly reduced, and the material is reducedMeanwhile, the polishing rate of the barrier layer material can be effectively controlled, the manufacturing requirement of the low-technology node integrated circuit is further met, and the low-technology node integrated circuit has the characteristics of low cost and safe use.
Drawings
The invention will be further described with reference to the drawings and examples.
FIG. 1 is a graph showing the effect of the different azole corrosion inhibitors of examples 1-16 on the static corrosion rate of molybdenum in an alkaline environment;
FIG. 2 is a graph showing the effect of the different azole corrosion inhibitors of examples 17-32 on the static corrosion rate of molybdenum in an acidic environment;
FIG. 3 is a graph showing the effect of TT-LYK on the static corrosion rate of molybdenum at various acidic pH values in examples 33-37;
FIG. 4 is a graph showing the effect of TT-LYK at various concentrations on the polishing rate of molybdenum in examples 38-42 at pH 4.0
Detailed Description
The present invention will be described in further detail below with reference to the drawings and preferred embodiments, so that those skilled in the art can better understand the technical solutions of the present invention.
The chemical mechanical polishing machine adopted in the application is of the model of Alpsitec-E460E in France, and the process conditions are as follows: the flow rate of the polishing solution is 300ml/min, the rotating speed of the polishing head is 87r/min, and the rotating speed of the polishing disc is as follows: 93r/min, the pressure is: 1.5psi. (the concentration percentages in this application are mass percentages unless otherwise indicated)
Example 1:
preparing 200g of static corrosive liquid
Adding corrosion inhibitor ATA and H into deionized water 100g 2 O 2 (concentration is 30 w%), and 200g of static corrosive liquid is supplemented by deionized water; the concentration of ATA in the obtained corrosive liquid is 100ppm, H 2 O 2 The concentration of (2) is 0.6wt%; and the pH value is 10.0; the preparation method comprises the following steps: ATA, H 2 O 2 Sequentially adding the components into deionized water, uniformly stirring by a pinhole negative pressure stirring mode, and then regulating the pH value of the static corrosive liquid to be the same by using 30% potassium hydroxide solutionAnd 10.0, finally, filling the balance with deionized water, and continuously and uniformly stirring.
Examples 2 to 4
Other steps are the same as in example 1 except that ATA is replaced with BTA, TT-LYK, TAZ;
examples 5 to 8
The other steps are respectively and sequentially identical to examples 1-4, except that the concentration of the added corrosion inhibitor is replaced by 200ppm from 100 ppm;
examples 9 to 12
The other steps are respectively and sequentially identical to examples 1-4, except that the concentration of the added corrosion inhibitor is replaced by 300ppm from 100 ppm;
examples 13 to 16
The other steps are respectively and sequentially identical to examples 1-4, except that the concentration of the added corrosion inhibitor is replaced by 400ppm from 100 ppm;
blank comparative example 1:
the other steps are respectively and sequentially identical to example 1, except that no corrosion inhibitor is added.
A molybdenum sheet (purity: 99.99%) having a diameter of 3inch and a thickness of 2mm was immersed, and the corrosion rates of the static etching liquid to molybdenum after the addition of ATA/BTA/TT-LYK/TAZ prepared in examples 1 to 4 were measured to be respectively
A molybdenum sheet (purity: 99.99%) having a diameter of 3inch and a thickness of 2mm was immersed, and the corrosion rates of the static etching liquid to molybdenum after the addition of ATA/BTA/TT-LYK/TAZ prepared in examples 5 to 8 were measured to be respectively
For a molybdenum plate (pure) of diameter 3inch and thickness 2mm99.99%) and the corrosion rates of the static corrosive liquid to molybdenum after the ATA/BTA/TT-LYK/TAZ of examples 9-12 were respectively measured
A molybdenum sheet (purity: 99.99%) having a diameter of 3inch and a thickness of 2mm was immersed, and the corrosion rates of the static etching liquid to molybdenum after the addition of ATA/BTA/TT-LYK/TAZ prepared in examples 13 to 16 were measured to be respectively
The molybdenum sheets (purity: 99.99%) having a diameter of 3inch and a thickness of 2mm were immersed, and the corrosion rates of the static etching liquid prepared in comparative example 1, to which a blank was added, were measured to be respectively
From this, it is concluded that the static corrosion rates of Mo obtained in the examples except for example 16 are lower than those in the blank comparative example, and it is inferred that the static corrosion solutions prepared in the examples except for example 16 have corrosion inhibition effects on Mo. This is because when the concentration of TAZ added is too high, adsorption on the Mo surface is unstable, and excessive TAZ molecules react with Mo oxide, thereby accelerating the dissolution rate of Mo. Among them, the preferred corrosion inhibitor TT-LYK has more remarkable corrosion inhibition effect in alkaline environment than other corrosion inhibitors.
As shown in FIG. 1, according to the influence of different corrosion inhibitor concentrations on the static corrosion rate and the change rule of Mo in examples 1-16, the corrosion inhibition effect of four inhibitors on Mo in alkaline environment is TT-LYK > ATA > TAZ > BTA. Wherein ATA and TAZ increase with concentration, and corrosion inhibition efficiency decreases. The reason for this is all that the slow release layer formed on the Mo surface by the inhibitor is unstable. While TT-LYK increases with increasing concentration, so that the corrosion inhibition efficiency increases with increasing concentration to 300 ppm. It is thus known that TT-LYK is the Mo corrosion inhibitor with the best performance in alkaline environments.
Example 17
The other steps are the same as in example 1 except that the pH is adjusted to 6.5;
examples 18 to 20
Other steps are the same as in example 17 except that ATA is replaced with BTA, TT-LYK, TAZ;
examples 21 to 24
The other steps are sequentially identical to examples 18-20, respectively, except that the concentration of the added corrosion inhibitor is replaced by 200ppm from 100 ppm;
examples 25 to 28
The other steps are sequentially identical to examples 18-20, respectively, except that the concentration of the added corrosion inhibitor is replaced by 300ppm from 100 ppm;
examples 29 to 32
The other steps are sequentially identical to examples 18-20, respectively, except that the concentration of the added corrosion inhibitor is replaced by 400ppm from 100 ppm;
blank comparative example 2:
the other steps are respectively and sequentially identical to example 17, except that no corrosion inhibitor is added.
A molybdenum sheet (purity: 99.99%) having a diameter of 3inch and a thickness of 2mm was immersed, and the corrosion rates of the static etching liquid to molybdenum after the addition of ATA/BTA/TT-LYK/TAZ prepared in examples 17 to 20 were measured to be respectively
Molybdenum sheets (purity: 99.99%) having a diameter of 3inch and a thickness of 2mm were immersed, and the corrosion of molybdenum by the static etching solution after the addition of ATA/BTA/TT-LYK/TAZ prepared in examples 21 to 24 was measuredThe etching rates are respectively
The molybdenum sheets (purity: 99.99%) having a diameter of 3inch and a thickness of 2mm were immersed, and the corrosion rates of the static etching liquid to molybdenum after the addition of ATA/BTA/TT-LYK/TAZ prepared in examples 25 to 28 were measured to be respectively
The molybdenum sheets (purity: 99.99%) having a diameter of 3inch and a thickness of 2mm were immersed, and the corrosion rates of the static etching liquid to molybdenum after the addition of ATA/BTA/TT-LYK/TAZ prepared in examples 29 to 32 were measured to be respectively
The molybdenum sheets (purity: 99.99%) having a diameter of 3inch and a thickness of 2mm were immersed, and the corrosion rates of the static etching liquid prepared by the blank comparative example on molybdenum were measured to be respectivelyIt follows that the corrosion rate of molybdenum is significantly reduced in an acidic environment compared to an alkaline environment. Among them, preferred example 31 has a more remarkable corrosion inhibition effect, and its rate is close to 0.
As shown in FIG. 2, it is clear from examples 17 to 32 that the corrosion inhibition efficiencies of the four inhibitors under acidic conditions were TT-LYK > BTA > ATA > TAZ, respectively. The reason for this is that the number of N contained in the four inhibitors is different, resulting in a difference in stability of the slow-release layer adsorbed on the Mo surface. In addition, in comparative examples 1 to 16, it can be seen that the corrosion inhibition effect of the four corrosion inhibitors on Mo under acidic conditions is better than that of the four corrosion inhibitors under alkaline conditions. This is because Mo generates soluble molybdate in an alkaline environment, resulting in a certain degree of Mo dissolution. Wherein, TT-LYK contains the most N, and the formed slow release layer is most stable. With the increase of TT-LYK concentration, the slow release layer adsorbed on the Mo surface becomes more and more dense, so that a better corrosion inhibition effect is presented. It is thus known that TT-LYK is also the Mo corrosion inhibitor with the best performance under acidic conditions.
Example 33: preparing 200g of static corrosive liquid
Taking 100g of deionized water, and respectively adding corrosion inhibitors TT-LYK; h 2 O 2 (concentration is 30 w%), and then the static corrosive liquid is supplemented to 200g by deionized water, so that the concentration of TT-LYK in the obtained corrosive liquid is 300ppm; h 2 O 2 The concentration of (2) is 0.6wt% and the pH of the static etching solution is 2.0; the preparation method comprises the following steps: TT-LYK, H 2 O 2 Sequentially adding the components into deionized water according to the weight, uniformly stirring by a pinhole negative pressure stirring mode, then adjusting the pH of the static corrosive liquid to 2.0 by using 30% concentration dilute nitric acid, and finally supplementing the balance with deionized water, and continuously and uniformly stirring.
Examples 34 to 37
The other steps are respectively and sequentially identical to example 33, except that the pH of the static etching solution is adjusted to 3.0 to 6.0.
The minimum corrosion rates of the static etching solutions of examples 33 to 37 on molybdenum were respectively determined to be that by immersing a molybdenum sheet (purity: 99.99%) having a diameter of 3inch and a thickness of 2mmMolybdenum has extremely low corrosion rate in strong acidic static corrosive liquid containing TT-LYK.
As shown in FIG. 3, it is understood from examples 33 to 37 that the static etch rate of Mo was close to 0 when the pH of the static etch solution containing TT-LYK was 2 to 5. This is due to the insoluble oxide MoO formed by Mo as the pH value decreases 2 The content gradually increases. The relatively stable molybdenum oxide layer can enable TT-LYK to have a better adsorption effect.
Example 38: 1000g of polishing solution is prepared
Abrasive silica sol (with concentration of 40wt%, particle size of 62.5nm and dispersity + -5%), TT-LYK and H 2 O 2 Adding deionized water, adding deionized water to 1000g of polishing solution to obtain polishing solution with silica sol concentration of 3wt%, TT-LYK concentration of 100ppm, and H 2 O 2 The concentration of (2) is 0.6wt% and the pH of the polishing solution is 4.0; the preparation method comprises the following steps: TT-LYK, H 2 O 2 And sequentially adding the silica sol into deionized water according to the component amount, uniformly stirring by a pinhole negative pressure stirring mode, regulating the pH value of the static corrosive liquid to 4.0, and finally supplementing the balance with the deionized water, and continuously and uniformly stirring.
Examples 39 to 42
The other steps were respectively identical to example 38, except that TT-LYK was contained in the prepared polishing solutions at a concentration of 200/300/400ppm, respectively.
Blank comparative example 3
The other steps are respectively and sequentially identical to example 38, except that no corrosion inhibitor is added.
Molybdenum plates (purity: 99.99%) having a diameter of 3inch and a thickness of 2mm were polished, and the polishing rates of the molybdenum were measured by adding 0/100/200/300/400ppm TT-LYK polishing liquid to the respective polishing liquids Preferably, the molybdenum barrier layer chemical mechanical polishing solution based on the weak acidity of the hydrogen peroxide system comprises 3wt% of abrasive silica sol, 300ppm TT-LYK and 0.6wt% of H 2 O 2 The pH was 4.0.
As shown in FIG. 4, it is understood from examples 38 to 42 that the addition of the corrosion inhibitor TT-LYK to the polishing liquid can effectively reduce the removal rate of Mo. Due to the mechanical grinding effect in the polishing process, the slow release layer formed on the surface of the Mo by the TT-LYK can be removed, so that the removal rate under the polishing condition is higher than the corrosion rate under the static condition. When the concentration of TT-LYK reaches 300ppm, the slow release layer formed on the surface of Mo reaches the maximum saturation value, so that polishing is performed at the concentration of TT-LYK, and the inhibition effect is the best.
TT-LYK is an organic azole corrosion inhibitor, can form stable complex with various metal ions such as copper, cobalt and the like, and can dissolve oxides on the metal surface. In addition, TT-LYK is a light yellow liquid inhibitor, which is easy to dissolve in water compared with other azole corrosion inhibitors, so that the polishing agent can be replaced. In addition, TT-LYK shows good inhibition effect on Mo, and can be well adsorbed on the surface of metal Mo to form an adsorption layer. The adsorption layer can serve as a protective film to reduce the corrosion of the oxidant to metal, so that Mo has lower corrosion in both static and dynamic environmentsOr removal rate->The method can control the removal rate of the barrier layer material and inhibit excessive corrosion of metal in the barrier layer polishing process of the copper interconnection molybdenum barrier layer structure integrated circuit.
While the preferred embodiments of the present invention have been described above with respect to the myopia, it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention and are intended to be within the scope of the present invention.
The invention is not a matter of the known technology.
Claims (4)
1. The molybdenum barrier layer chemical mechanical polishing solution based on the weak acidity of the hydrogen peroxide system is characterized by comprising the following components: nano-scale silica sol 3 wt%; hydrogen peroxide 0.6. 0.6wt%; 50-300 ppm of azole corrosion inhibitor, the balance of water, and the pH value of the azole corrosion inhibitor is 2.0-6.0;
the azole corrosion inhibitor is 2,2' - { [ (methyl-1H-benzotriazole-1-yl) methyl ] imino } diethanol (TT-LYK);
the particle size of the silica sol is 70-90 nm;
the preparation method of the molybdenum barrier layer chemical mechanical polishing solution based on the weak acidity of the hydrogen peroxide system comprises the following steps:
adding an azole corrosion inhibitor into deionized water, then adding hydrogen peroxide solution, stirring and mixing, then adding nanoscale silica sol, continuously stirring, adding acid or alkali, adjusting the pH value, and finally stirring and adding deionized water to fix the volume to obtain the polishing solution.
2. The molybdenum barrier chemical mechanical polishing solution based on the weak acidity of the hydrogen peroxide system as defined in claim 1, wherein the acid is hydrochloric acid or sulfuric acid; the alkali is sodium hydroxide solution.
3. The molybdenum barrier chemical mechanical polishing solution based on the weak acidity of the hydrogen peroxide system, as claimed in claim 1, is characterized in that the concentration of the silica sol is 30-50wt% and the concentration of the hydrogen peroxide solution is 25-50wt%.
4. The application of the molybdenum barrier chemical mechanical polishing solution based on the weak acidity of the hydrogen peroxide system as claimed in claim 1 is characterized in that the polishing solution is applied to a barrier polishing process of an integrated circuit with a copper interconnection molybdenum barrier structure.
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| CN115678437A (en) | 2023-02-03 |
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