CN116948531A - Integrated circuit copper chemical mechanical polishing composition and preparation method and application thereof - Google Patents
Integrated circuit copper chemical mechanical polishing composition and preparation method and application thereof Download PDFInfo
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- 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
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Abstract
本发明涉及半导体集成电路制造技术领域，尤其涉及一种集成电路铜化学机械抛光组合物及其制备方法、用途。该抛光组合物按重量份数计由以下原料组成：纳米研磨粒子3～5份、高铈氧化剂0.1～5.0份、金属络合剂或金属螯合剂0.01～2.0份、表面活性剂0.01～5.0份。本发明以高铈为氧化剂取代现用的双氧水，以氧化硅及氧化铈复合物为研磨粒子，控制硅铈比使金属层和介质层的研磨速率达到平衡，解决现有铜互连化学机械抛光过程中铜与介质层去除率不平衡所造成的碟陷。
The present invention relates to the technical field of semiconductor integrated circuit manufacturing, and in particular to an integrated circuit copper chemical mechanical polishing composition and its preparation method and use. The polishing composition consists of the following raw materials in parts by weight: 3 to 5 parts of nano-abrasive particles, 0.1 to 5.0 parts of high cerium oxidant, 0.01 to 2.0 parts of metal complexing agent or metal chelating agent, and 0.01 to 5.0 parts of surfactant. . The present invention uses high cerium as the oxidant to replace the currently used hydrogen peroxide, uses silicon oxide and cerium oxide composites as abrasive particles, controls the ratio of silicon to cerium to balance the polishing rates of the metal layer and the dielectric layer, and solves the problem of existing chemical mechanical polishing of copper interconnects. Dishes caused by unbalanced copper and dielectric layer removal rates during the process.
Description
Technical Field
The invention relates to the technical field of semiconductor integrated circuit manufacturing, in particular to an integrated circuit copper chemical mechanical polishing composition, a preparation method and application thereof.
Background
The 60-year history of integrated circuits (Integrated Circuit, IC) is a history of continuous development toward high integration, high density, high speed and high performance, and low energy consumption, so as to meet the application requirements of various fields such as computers, automotive electronics, satellite communications, electronic consumption, intelligent control, and the internet of things. According to moore's law, the number of transistors per unit area is doubled every 18 months, and the integration level of chips is over 100 hundred million at present, and the chip enters the ultra-large-scale integrated circuit (GLSI) era. In the process of shrinking transistor dimensions, various new processes, techniques, materials are continually introduced into integrated circuit fabrication in order to achieve smaller line widths. Today, the IC technology node has been stepped into the 3nm age, multilayer copper interconnection is an important technology in the process, the number of interconnection layers is up to more than 60 layers, and the total length of the interconnection line can reach 10 km.
As integrated circuit feature sizes continue to shrink, the gate delay requirements of the circuits become smaller. However, the RC delay of the conventional aluminum interconnect is relatively large, and the atomic stack formed in the interconnect line accompanying the atomic migration of the electron flow obstructs the electron flow, degrading the device reliability. To solve the above problems, IBM corporation in 1997 realized copper interconnect technology using a dual damascene process with copper metal material instead of conventional aluminum. Copper has a resistivity of 1.7 mu omega cm compared to aluminum, which is doubled lower than aluminum, which is advantageous for reducing RC delay. Meanwhile, in order to reduce the thickness of the interconnection layer, the low-K dielectric or the ultra-low-K dielectric is adopted to replace the traditional silicon dioxide for the intermetal insulating dielectric. The process reduces the distributed capacitance between the interconnection layers and the parasitic capacitance between the interconnection lines, thereby improving the working efficiency. In addition, copper has a higher melting point (1083 ℃) than aluminum (660 ℃) and can reduce the reliability problem caused by the electromigration phenomenon. So far, copper interconnection technology is developed rapidly and is a necessary process in the preparation process of integrated circuits. Although copper has a lower resistance than aluminum or tungsten, copper has a higher diffusion coefficient in silicon and tends to diffuse into the dielectric layer, so that it is common to deposit, for example, tantalum (Ta), tantalum nitride (TaN), titanium (Ti) or titanium nitride (TiN), cobalt (Co), ruthenium (Ru), etc., as diffusion barriers prior to depositing metallic copper on the sidewalls and bottom of the via.
The copper interconnect structure is completed by a dual damascene process (dual damascene) which can fill the trench and the wiring via simultaneouslyThe process is simple and the production efficiency is high. Etching a groove and a through hole in one or more dielectric layers on a substrate, then depositing metal in the groove and the through hole, and flattening the metal layer, the interlayer dielectric layer and the diffusion barrier layer by a CMP (chemical mechanical polishing) process, so that the surfaces of the metal layer and the dielectric layer are on the same plane. Fig. 1 is a schematic diagram of a typical copper interconnect damascene process. The chemical mechanical polishing (Chemical Mechanical Polishing, CMP) process is the only effective global planarization technique for integrated circuit fabrication and its principle is the interaction of mechanical polishing action and chemical etching action of the polishing liquid (slurry). The mechanism of action is generally believed that metallic copper is first oxidized to monovalent or divalent copper ions and then removed by mechanical action of abrasive particles, which cycle back and forth to planarize. The polishing liquid for CMP contains abrasive particles such as silicon oxide SiO 2 CeO of cerium oxide 2 Zirconium oxide ZrO 2 Alumina Al 2 O 3 Titanium oxide TiO 2 And an oxidizing agent such as hydrogen peroxide H 2 O 2 Potassium permanganate KMnO 4 Potassium periodate KIO 3 And a complexing agent. At present, the oxidant used for preparing the polishing solution is hydrogen peroxide (namely peroxide), but the hydrogen peroxide is unstable and is easy to decompose, so that the CMP rate is unstable, and only the existing preparation is realized. Copper is a corrosion-resistant element and a dielectric layer such as TEOS, siO 2 The hardness of the two materials is different, and the polishing rate of copper is slower than that of the dielectric layer. Over-polishing is often required in the process to completely remove copper, whereby dishing occurs on the surface of the dielectric layer. As the number of layers increases, the superposition of recessed regions becomes more and more severe, so that copper metal residues are generated on the surface of the dielectric layer, resulting in a decrease in circuit reliability. Therefore, in the copper CMP process, not only is the high removal rate required for the polishing slurry required, but also the polishing rate ratio of copper to the dielectric layer is controlled within a reasonable range to achieve balanced polishing and finally achieve global high planarization.
The dishing (dishing) is solved by using a high valence metal compound similar to the wiring metal instead of the conventional use of an oxidizing agent in CMP without adding an oxidizing agent (CN 111826089A) under CMP conditions, such as an inorganic copper salt, an organic copper salt, a cobalt high valence salt or a ruthenium high valence salt. However, the oxidation of the high-valence metal compound of the same metal is insufficient, resulting in a decrease in polishing rate and an increase in polishing time. Therefore, there is a need for improvements in CMP polishing agents, developing a highly efficient polishing liquid for copper interconnect lines and a process for producing the same.
Disclosure of Invention
The invention provides an integrated circuit copper chemical mechanical polishing composition and a preparation process thereof, which are used for solving the problems of dishing caused by unbalanced copper and dielectric layer removal rate in the conventional copper interconnection chemical mechanical polishing process, and low polishing rate caused by insufficient oxidizing property of high-valence metal compounds using the same metal.
The invention provides an integrated circuit copper chemical mechanical polishing composition which comprises the following raw materials in parts by weight: 3 to 5 parts of nano abrasive particles, 0.1 to 5.0 parts of high cerium oxidant, 0.01 to 2.0 parts of metal complexing agent or metal chelating agent and 0.01 to 5.0 parts of surfactant;
the nano grinding particles are composed of silicon oxide and cerium oxide; the mol ratio of the silicon oxide to the cerium oxide is 1:1-5.
Preferably, the granularity of the silicon oxide is 10-160 nm, and the granularity of the cerium oxide is 20-100 nm.
Preferably, the cerium oxide is obtained by calcining basic cerium carbonate at 500-800 ℃ for 6-24 hours, and 2 theta angles of XRD diffraction characteristic peaks of the cerium oxide are 15.9 degrees, 20.2 degrees, 30.2 degrees, 38.1 degrees and 42.8 degrees.
Preferably, the high cerium oxidant is one or a mixture of a plurality of cerous sulfate, cerous nitrate, cerous acetate, ammonium ceric nitrate and ceric hydroxide.
Preferably, the metal complexing agent or metal chelating agent is selected from one or more of glycine, glutamic acid, lysine, tartaric acid, maleic acid, citric acid, oxalic acid, ethylenediamine tetraacetic acid, disodium ethylenediamine tetraacetic acid, polyacrylic acid, hydrolyzed polymaleic anhydride, citric acid chelating agent or diethylenetriamine pentaacetic acid.
Preferably, the surfactant is selected from one or a mixture of more of ammonium polyacrylate, polyacrylamide, sodium tripolyphosphate, sodium polyphosphate, polyethylene glycol, polyvinyl alcohol, sodium dodecyl benzene sulfonate, sodium hydrogen phosphate and sodium pyrophosphate.
Preferably, the polishing composition further comprises a pH adjustor selected from one or more of sulfuric acid, nitric acid, hydrochloric acid, acetic acid, ammonium hydroxide, potassium hydroxide, sodium hydroxide, monoethanolamine, diethanolamine, and triethanolamine.
The invention also provides a preparation method of the polishing composition, which comprises the following steps:
weighing nano grinding particles, a high cerium oxidant, a metal complexing agent or a metal chelating agent and a surfactant according to parts by weight;
and (3) sanding and mixing the nano grinding ions and the high cerium oxide, adding the metal complexing agent or the metal chelating agent and the surfactant, adjusting the pH to 1.0-6.0, centrifuging, taking supernatant and grinding.
The invention also provides the use of the polishing composition in planarization of integrated circuit fabrication.
Compared with the prior art, the invention has the beneficial effects that:
1. the invention uses high cerium as oxidant to replace the existing hydrogen peroxide, the high cerium oxidant has higher oxidation performance and better stability, and simultaneously uses silicon oxide and cerium oxide compound as grinding particles, controls the silicon-cerium ratio to balance the grinding rate of the metal layer and the dielectric layer, and solves the problem of dishing caused by unbalanced removal rate of copper and the dielectric layer in the existing copper interconnection chemical mechanical polishing process and the problem of reduction of the grinding rate caused by insufficient oxidizing property of high-valence metal compounds using the same metal.
2. The invention selects the ceric as the oxidant, which not only has higher oxidation effect, but also generates Ce 4+ The ions can enhance the chemical action during polishing (the same as the cerium oxide in the abrasive component) and thus achieve a higher selectivity.
3. The total amount of silica and ceria in the polishing composition is not more than 5%, and particularly between 3% and 5%, is effective in improving polishing efficiency.
4. The complexing agent used in the invention can react with metal ions in the solution to form a stable water-soluble complex. The complex can prevent metal ions from gathering on the surface of the material, promote the decomposition and regeneration of oxide on the surface of the metal, and is beneficial to forward progress of reaction and removal of the material and post-cleaning process.
Drawings
FIG. 1 is a schematic cross-sectional view of an IC circuit;
FIG. 2 shows cerium oxide (CeO) 2 ) XRD pattern;
FIG. 3 shows cerium oxide (CeO) 2 ) A TEM image;
fig. 4 shows a basic cerium carbonate (Ce (CO) 3 ) 2 OH 2 O) XRD pattern.
Detailed Description
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
The purpose of the present invention is to convert the higher hardness metal into a metal oxide that is easier to remove. The oxidizing agent commonly used in the prior art is potassium periodate (KIO) 4 ) Hydrogen peroxide (H) 2 O 2 ) Potassium permanganate (KMnO) 4 ) Etc. H 2 O 2 Is weak in oxidizing property and has a deviation in stability. KMnO in alkaline solution 4 The high-oxidation-resistance polishing agent has high stability and strong oxidizing property, but is dissolved in water to form mauve, and the high oxidizing property of the high-oxidation-resistance polishing agent is extremely easy to damage polishing equipment and polishing pads, so that the later cleaning work is seriously influenced, and the high-oxidation-resistance polishing agent is unfavorable for large-scale industrial application. The invention selects the ceric compound as the oxidant, such as ceric nitrate [ Ce (NO) 3 ) 4 ]Ceric sulfate [ Ce (SO) 4 ) 2 ]Ceric ammonium nitrate [ Ce (NH) 4 ) 2 (NO 3 ) 6 ]Cerium perchlorate [ Ce (ClO) 4 ) 4 ]Cerium hydroxide [ Ce (OH) 4 ]Ceric acetate [ Ce (CH) 3 COO) 4 ]。
Complexing agents useful in the present invention may beWith metal ions in solution (e.g. Ce 3+ 、Cu 2+ 、Co 3+ ) The reaction forms a stable water-soluble complex. The complex can prevent metal ions from gathering on the surface of the material, promote the decomposition and regeneration of oxide on the surface of the metal, and is beneficial to forward progress of reaction and removal of the material and post-cleaning process. Complexing agents which can be used in the invention are disodium ethylenediamine tetraacetate (C 10 H 16 N 2 O 8 Na 2 ) Sodium citrate (C) 6 H 8 O 7 Na), oxalic acid (H 2 O 4 C 2 ) Glycine (C) 2 H 5 NO 2 ) Tartaric acid (C) 4 H 6 O 6 ) Glutamic acid, lysine, citric acid, ethylenediamine tetraacetic acid, polyacrylic acid, hydrolyzed polymaleic anhydride, diethylenetriamine pentaacetic acid.
The pH regulator used in the present invention is selected from acetic acid [ CH ] 3 COOH]Nitric acid (HNO) 3 ) Sulfuric acid (H) 2 SO 4 ) Hydrochloric acid (HCl), monoethanolamine (C) 2 H 7 NO), diethanolamine (C) 4 H 11 NO 2 ) Triethanolamine (C) 6 H 15 NO 3 ) One or more of ammonium hydroxide, potassium hydroxide and sodium hydroxide.
The surfactant is favorable for maintaining the Zeta potential of the system at a higher absolute value, so that the grinding slurry system is stable. The surfactant used in the present invention is an anionic surfactant, a nonionic surfactant, such as sodium or potassium alkylbenzenesulfonate, sodium polyacrylate, polyethylene glycol, polyvinyl alcohol, sodium polyphosphate, sodium tripolyphosphate, polyacrylamide, sodium dodecylbenzenesulfonate, sodium hydrogen phosphate, sodium pyrophosphate, or a mixture of two or more of the above.
The silica sol used in the examples of the present invention is a dispersion of nanoscale silica particles in water or in a solvent.
Example 1
An integrated circuit copper chemical mechanical polishing composition, which consists of the following raw materials in mass fraction: 1% of silicon oxide, 2% of cerium oxide, 0.1% of ceric sulfate, 0.1% of glycine, 0.1% of ammonium polyacrylate and the balance of water.
Wherein, the cerium oxide is prepared by the following steps: cerium carbonate hydroxide (Ce (OH) CO) 3 ) Mixing with water (S: L=1:2), ball milling, filtering, drying (120 deg.C), calcining at 550deg.C for 24 hr, mixing with water to obtain slurry with 5%, and grinding with sand mill to obtain nanometer cerium oxide with particle size of 20nm. The use of cerium hydroxycarbonate can achieve a more consistent crystal structure.
Fig. 2 and 3 are XRD and TEM images of cerium oxide, respectively.
The basic cerium carbonate is prepared by adjusting the concentration of soluble cerium salt to 80g/L with deionized water, and mixing with precipitant NH at 80deg.C 4 HCO 3 The solution (concentration 40%, W/W) is reacted to obtain a precipitated product, and the precipitated product is thermally converted to obtain the basic cerium carbonate, wherein the specific reaction process is as follows:
2Ce 3+ +3CO 3 2- ＝Ce(CO 3 ) 3
Ce 2 (CO 3 ) 3 +H 2 O＝2Ce(OH)CO 3 +CO 2 。
fig. 4 shows a basic cerium carbonate (Ce (CO) 3 ) 2 OH 2 O) XRD pattern.
Cerium sulfate used Ce (SO) 2 The preparation method comprises the following steps:
Ammonium hydroxide (NH) 4 OH) is added into cerium salt solution under stirring, and hydrogen peroxide (H) is added after precipitation is completed 2 O 2 ) Stirring and reacting for 30 minutes, heating and boiling the suspension, standing and cooling at room temperature, washing and filtering to obtain the product ceric hydroxide Ce (OH) 4 Dissolving in dilute sulfuric acid to prepare ceric sulfate. The reaction involved is as follows:
Ce 3+ +3(OH) - ＝Ce(OH) 3
2Ce(OH) 3 +H 2 O 2 ＝2Ce(OH) 4
Ce(OH) 4 +2H 2 SO 4 ＝Ce(SO) 2 +4H 2 O
the mass concentration of each substance is as follows: soluble cerium80g/L of salt (CeO) 2 ) Ammonium hydroxide (NH) 4 OH) 20%, hydrogen peroxide 33% and sulfuric acid 50%.
The polishing composition is prepared according to the following method:
mixing silica sol solution (80 nm, 40%) with nano cerium oxide solution (10%), ceric sulfate [ Ce (SO) 2 ]The ultrapure water is fully mixed in a premixing cylinder of a grinder. Grinding for 40 min with a sand mill, adding ammonium polyacrylate (C 3 H 3 NH 4 O 2 ) And glycine, namely regulating the pH value to 1 by using 10% of nitric acid and 30% of triethanolamine, centrifuging the polishing slurry by using a centrifuge, and grinding the supernatant. Grinding machine Universal-200, grinding conditions: the feeding flow rate of the polishing solution is 60ml/min, the temperature is 23 ℃, the pressing force is 4psi, the rotating speed of the polishing head is 120prm, the rotating speed of the lower fixed disk is 80rpm, the polishing time is 60 seconds, 40mm x 3mm of copper test pieces are used for CVD deposition of copper thickness of 2000nm, and the silicon oxide test pieces are used for CVD deposition of copper: PVD deposition of SiO on silicon substrate 2 800nm。
Example 2
An integrated circuit copper chemical mechanical polishing composition, which consists of the following raw materials in mass fraction: 1% of silicon oxide, 2% of cerium oxide, 0.1% of ceric sulfate, 0.1% of glycine, 0.1% of ammonium polyacrylate and the balance of water.
Wherein, the cerium oxide is prepared by the following steps: cerium carbonate hydroxide (Ce (OH) CO) 3 ) Mixing with water (S: L=1:2), ball milling, filtering, drying (120 deg.C), calcining at 500 deg.C for 24 hr, mixing with water to obtain slurry with 5% concentration, and grinding with sand mill to obtain nano cerium oxide with particle size of 20nm.
The basic cerium carbonate is prepared by regulating soluble cerium salt with deionized water to 30g/L, mixing with precipitant NH at 40deg.C 4 HCO 3 The solution (concentration 10%, W/W) is reacted to obtain a precipitated product, and the precipitated product is thermally converted to obtain the basic cerium carbonate, wherein the specific reaction process is as follows:
2Ce 3+ +3CO 3 2- ＝Ce(CO 3 ) 3
Ce 2 (CO 3 ) 3 +H 2 O＝2Ce(OH)CO 3 +CO 2
cerium sulfate used Ce (SO) 2 The preparation method comprises the following steps:
ammonium hydroxide (NH) 4 OH) is added into cerium salt solution under stirring, and hydrogen peroxide (H) is added after precipitation is completed 2 O 2 ) Stirring and reacting for 30 minutes, heating and boiling the suspension, standing and cooling at room temperature, washing and filtering to obtain the product ceric hydroxide Ce (OH) 4 Dissolving in dilute sulfuric acid to prepare ceric sulfate. The reaction involved is as follows:
Ce 3+ +3(OH) - ＝Ce(OH) 3
2Ce(OH) 3 +H 2 O 2 ＝2Ce(OH) 4
Ce(OH) 4 +2H 2 SO 4 ＝Ce(SO) 2 +4H 2 O
The mass concentration of each substance is as follows: 80g/L soluble cerium salt (CeO) 2 ) Ammonium hydroxide (NH) 4 OH) 20%, hydrogen peroxide 33% and sulfuric acid 50%.
The polishing composition is prepared according to the following method:
mixing silica sol solution (80 nm, 40%) with nano cerium oxide solution (10%), ceric sulfate [ Ce (SO) 2 ]The ultrapure water is fully mixed in a premixing cylinder of a grinder. Grinding for 40 min with a sand mill, adding ammonium polyacrylate (C 3 H 3 NH 4 O 2 ) And glycine, namely regulating the pH value to 1 by using 10% of nitric acid and 30% of triethanolamine, centrifuging the polishing slurry by using a centrifuge, and grinding the supernatant. Grinding machine Universal-200, grinding conditions: the feeding flow rate of the polishing solution is 60ml/min, the temperature is 23 ℃, the pressing force is 4psi, the rotating speed of the polishing head is 120prm, the rotating speed of the lower fixed disk is 80rpm, the polishing time is 60 seconds, 40mm x 3mm of copper test pieces are used for CVD deposition of copper thickness of 2000nm, and the silicon oxide test pieces are used for CVD deposition of copper: PVD deposition of SiO on silicon substrate 2 800nm。
Example 3
An integrated circuit copper chemical mechanical polishing composition, which consists of the following raw materials in mass fraction: 1% of silicon oxide, 2% of cerium oxide, 0.1% of ceric sulfate, 0.1% of glycine, 0.1% of ammonium polyacrylate and the balance of water.
Wherein, the cerium oxide is prepared by the following steps: cerium carbonate hydroxide (Ce (OH) CO) 3 ) Mixing with water (S: L=1:2), ball milling, filtering, drying (120 ℃), calcining at 800 deg.C for 6 hr, mixing the calcined product with water to obtain 15% slurry, and grinding with sand mill to obtain nano cerium oxide with particle size of 80nm.
The basic cerium carbonate is prepared by regulating soluble cerium salt with deionized water to 30g/L, mixing with precipitant NH at 40deg.C 4 HCO 3 The solution (concentration 10%, W/W) is reacted to obtain a precipitated product, and the precipitated product is thermally converted to obtain the basic cerium carbonate, wherein the specific reaction process is as follows:
2Ce 3+ +3CO 3 2- ＝Ce(CO 3 ) 3
Ce 2 (CO 3 ) 3 +H 2 O＝2Ce(OH)CO 3 +CO 2
cerium sulfate used Ce (SO) 2 The preparation method comprises the following steps:
ammonium hydroxide (NH) 4 OH) is added into cerium salt solution under stirring, and hydrogen peroxide (H) is added after precipitation is completed 2 O 2 ) Stirring and reacting for 30 minutes, heating and boiling the suspension, standing and cooling at room temperature, washing and filtering to obtain the product ceric hydroxide Ce (OH) 4 Dissolving in dilute sulfuric acid to prepare ceric sulfate. The reaction involved is as follows:
Ce 3+ +3(OH) - ＝Ce(OH) 3
2Ce(OH) 3 +H 2 O 2 ＝2Ce(OH) 4
Ce(OH) 4 +2H 2 SO 4 ＝Ce(SO) 2 +4H 2 O
the mass concentration of each substance is as follows: 80g/L soluble cerium salt (CeO) 2 ) Ammonium hydroxide (NH) 4 OH) 20%, hydrogen peroxide 33% and sulfuric acid 50%.
The polishing composition is prepared according to the following method:
taking silica sol (80 nm, 40%) and nano cerium oxide CeO 2 (10%), ceric sulfate [ Ce (SO) 2 ]The ultrapure water is fully mixed in a premixing cylinder of a grinder. Grinding for 40 min with a sand mill, adding ammonium polyacrylate (C 3 H 3 NH 4 O 2 ) And glycine, namely regulating the pH value to 1 by using 10% of nitric acid and 30% of triethanolamine, centrifuging the polishing slurry by using a centrifuge, and grinding the supernatant. Grinding machine Universal-200, grinding conditions: the feeding flow rate of the polishing solution is 60ml/min, the temperature is 23 ℃, the pressing force is 4psi, the rotating speed of the polishing head is 120prm, the rotating speed of the lower fixed disk is 80rpm, the polishing time is 60 seconds, 40mm x 3mm of copper test pieces are used for CVD deposition of copper thickness of 2000nm, and the silicon oxide test pieces are used for CVD deposition of copper: PVD deposition of SiO on silicon substrate 2 800nm。
Example 4
An integrated circuit copper chemical mechanical polishing composition, which consists of the following raw materials in mass fraction: 1% of silicon oxide, 2% of cerium oxide, 0.1% of ceric sulfate, 0.1% of glycine, 0.1% of ammonium polyacrylate and the balance of water.
Wherein, the cerium oxide is prepared by the following steps: cerium carbonate hydroxide (Ce (OH) CO) 3 ) Mixing with water (S: L=1:2), ball milling, filtering, drying (120 ℃), calcining at 600deg.C for 6 hr, mixing with water to obtain 10% slurry, and grinding with sand mill to obtain nanometer cerium oxide with particle size of 60nm.
The basic cerium carbonate is prepared by regulating soluble cerium salt with deionized water to 30g/L, mixing with precipitant NH at 40deg.C 4 HCO 3 The solution (concentration 10%, W/W) is reacted to obtain a precipitated product, and the precipitated product is thermally converted to obtain the basic cerium carbonate, wherein the specific reaction process is as follows:
2Ce 3+ +3CO 3 2- ＝Ce(CO 3 ) 3
Ce 2 (CO 3 ) 3 +H 2 O＝2Ce(OH)CO 3 +CO 2
Cerium sulfate used Ce (SO) 2 The preparation method comprises the following steps:
ammonium hydroxide (NH) 4 OH) is added into cerium salt solution under stirring, and hydrogen peroxide (H) is added after precipitation is completed 2 O 2 ) The reaction was stirred for 30 minutes to suspendBoiling the solution, standing at room temperature for cooling, washing, and filtering to obtain ceric hydroxide Ce (OH) 4 Dissolving in dilute sulfuric acid to prepare ceric sulfate. The reaction involved is as follows:
Ce 3+ +3(OH) - ＝Ce(OH) 3
2Ce(OH) 3 +H 2 O 2 ＝2Ce(OH) 4
Ce(OH) 4 +2H 2 SO 4 ＝Ce(SO) 2 +4H 2 O
the mass concentration of each substance is as follows: 80g/L soluble cerium salt (CeO) 2 ) Ammonium hydroxide (NH) 4 OH) 20%, hydrogen peroxide 33% and sulfuric acid 50%.
The polishing composition is prepared according to the following method:
mixing silica sol solution (80 nm, 40%) with nano cerium oxide solution (10%), ceric sulfate [ Ce (SO) 2 ]The ultrapure water is fully mixed in a premixing cylinder of a grinder. Grinding for 40 min with a sand mill, adding ammonium polyacrylate (C 3 H 3 NH 4 O 2 ) And glycine, namely regulating the pH value to 1 by using 10% of nitric acid and 30% of triethanolamine, centrifuging the polishing slurry by using a centrifuge, and grinding the supernatant. Grinding machine Universal-200, grinding conditions: the feeding flow rate of the polishing solution is 60ml/min, the temperature is 23 ℃, the pressing force is 4psi, the rotating speed of the polishing head is 120prm, the rotating speed of the lower fixed disk is 80rpm, the polishing time is 60 seconds, 40mm x 3mm of copper test pieces are used for CVD deposition of copper thickness of 2000nm, and the silicon oxide test pieces are used for CVD deposition of copper: PVD deposition of SiO on silicon substrate 2 800nm。
Example 5
An integrated circuit copper chemical mechanical polishing composition, which consists of the following raw materials in mass fraction: 1% of silicon oxide, 2% of cerium oxide, 0.1% of ceric sulfate, 0.1% of glycine, 0.1% of ammonium polyacrylate and the balance of water.
Wherein, the cerium oxide is prepared by the following steps: cerium carbonate hydroxide (Ce (OH) CO) 3 ) Mixing with water (S: L=1:2), ball milling, filtering, drying (120deg.C), calcining at 800deg.C for 6 hr, mixing the obtained mixture with water to obtain 15% slurry, and grinding with sand mill to obtain nanometer powderCerium oxide, particle size 80nm.
The basic cerium carbonate is prepared by regulating soluble cerium salt with deionized water to 30g/L, mixing with precipitant NH at 40deg.C 4 HCO 3 The solution (concentration 10%, W/W) is reacted to obtain a precipitated product, and the precipitated product is thermally converted to obtain the basic cerium carbonate, wherein the specific reaction process is as follows:
2Ce 3+ +3CO 3 2- ＝Ce(CO 3 ) 3
Ce 2 (CO 3 ) 3 +H 2 O＝2Ce(OH)CO 3 +CO 2
cerium sulfate used Ce (SO) 2 The preparation method comprises the following steps:
ammonium hydroxide (NH) 4 OH) is added into cerium salt solution under stirring, 30% hydrogen peroxide (H) is added after precipitation is completed 2 O 2 ) Stirring and reacting for 30 minutes, heating and boiling the suspension, standing and cooling at room temperature, washing and filtering to obtain the product ceric hydroxide Ce (OH) 4 Dissolving in dilute sulfuric acid to prepare ceric sulfate. The reaction involved is as follows:
Ce 3+ +3(OH) - ＝Ce(OH) 3
2Ce(OH) 3 +H 2 O 2 ＝2Ce(OH) 4
Ce(OH) 4 +2H 2 SO 4 ＝Ce(SO) 2 +4H 2 O
The mass concentration of each substance is as follows: 45g/L of soluble cerium salt (CeO) 2 ) Ammonium hydroxide (NH) 4 OH) 12%, hydrogen peroxide 30% and sulfuric acid 35%.
The polishing composition is prepared according to the following method:
mixing silica sol solution (80 nm, 40%) with nano cerium oxide solution (10%), ceric sulfate [ Ce (SO) 2 ]The ultrapure water is fully mixed in a premixing cylinder of a grinder. Grinding for 40 min with a sand mill, adding ammonium polyacrylate (C 3 H 3 NH 4 O 2 ) Glycine, adjusting pH to 5 with 10% nitric acid and 30% triethanolamine, centrifuging the slurry with a centrifuge, collecting supernatantGrinding to obtain the final product. Grinding machine Universal-200, grinding conditions: the feeding flow rate of the polishing solution is 60ml/min, the temperature is 23 ℃, the pressing force is 4psi, the rotating speed of the polishing head is 120prm, the rotating speed of the lower fixed disk is 80rpm, the polishing time is 60 seconds, 40mm x 3mm of copper test pieces are used for CVD deposition of copper thickness of 2000nm, and the silicon oxide test pieces are used for CVD deposition of copper: PVD deposition of SiO on silicon substrate 2 800nm。
Example 6
An integrated circuit copper chemical mechanical polishing composition, which consists of the following raw materials in mass fraction: 1% of silicon oxide, 2% of cerium oxide, 0.1% of ceric hydroxide, 0.1% of glycine, 0.1% of ammonium polyacrylate and the balance of water.
Wherein, the cerium oxide is prepared by the following steps: cerium carbonate hydroxide (Ce (OH) CO) 3 ) Mixing with water (S: L=1:2), ball milling, filtering, drying (120 deg.C), calcining at 550deg.C for 24 hr, mixing with water to obtain slurry with 5%, and grinding with sand mill to obtain nanometer cerium oxide with particle size of 20nm.
The basic cerium carbonate is prepared by adjusting the concentration of soluble cerium salt to 80g/L with deionized water, and mixing with precipitant NH at 80deg.C 4 HCO 3 The solution (concentration is 30%, W/W) is reacted to obtain a precipitation product, and the precipitation product is thermally converted to obtain the basic cerium carbonate, wherein the specific reaction process is as follows:
2Ce 3+ +3CO 3 2- ＝Ce(CO 3 ) 3
Ce 2 (CO 3 ) 3 +H 2 O＝2Ce(OH)CO 3 +CO 2
the polishing composition is prepared according to the following method:
the silica sol solution (80 nm, 40%) was mixed with the nano cerium oxide solution (10%), ceric hydroxide and ultrapure water in a mill premix tank. Grinding for 40 min with a sand mill, adding ammonium polyacrylate (C 3 H 3 NH 4 O 2 ) Regulating pH to 5 with 10% nitric acid and 30% triethanolamine, centrifuging the slurry with a centrifuge, and grinding the supernatant. Grinding machine Universal-200, grinding conditions: the flow rate of the polishing solution is 60ml/min, the temperature is 23 ℃, and the pressure is 4psiThe polishing head rotation speed is 120prm, the lower fixed disk rotation speed is 80rpm, the polishing time is 60 seconds, the copper test piece is 40mm x 3mm, the thickness of copper deposited by silicon substrate CVD is 2000nm, and the silicon oxide test piece: PVD deposition of SiO on silicon substrate 2 800nm。
Example 7
An integrated circuit copper chemical mechanical polishing composition, which consists of the following raw materials in mass fraction: 1% of silicon oxide, 2% of cerium oxide, 0.1% of ceric sulfate, 0.1% of polyacrylic acid, 0.1% of sodium dodecyl benzene sulfonate and the balance of water.
Wherein, the cerium oxide is prepared by the following steps: cerium carbonate hydroxide (Ce (OH) CO) 3 ) Mixing with water (S: L=1:2), ball milling, filtering, drying (120 deg.C), calcining at 500 deg.C for 24 hr, mixing with water to obtain slurry with 5% concentration, and grinding with sand mill to obtain nano cerium oxide with particle size of 20nm.
The basic cerium carbonate is prepared by adjusting the concentration of soluble cerium salt to 80g/L with deionized water, and mixing with precipitant NH at 80deg.C 4 HCO 3 The solution (concentration 40%, W/W) is reacted to obtain a precipitated product, and the precipitated product is thermally converted to obtain the basic cerium carbonate, wherein the specific reaction process is as follows:
2Ce 3+ +3CO 3 2- ＝Ce(CO 3 ) 3
Ce 2 (CO 3 ) 3 +H 2 O＝2Ce(OH)CO 3 +CO 2
cerium sulfate used Ce (SO) 2 The preparation method comprises the following steps:
ammonium hydroxide (NH) 4 OH) is added into cerium salt solution under stirring, and hydrogen peroxide (H) is added after precipitation is completed 2 O 2 ) Stirring and reacting for 30 minutes, heating and boiling the suspension, standing and cooling at room temperature, washing and filtering to obtain the product ceric hydroxide Ce (OH) 4 Dissolving in dilute sulfuric acid to prepare ceric sulfate. The reaction involved is as follows:
Ce 3+ +3(OH) - ＝Ce(OH) 3
2Ce(OH) 3 +H 2 O 2 ＝2Ce(OH) 4
Ce(OH) 4 +2H 2 SO 4 ＝Ce(SO) 2 +4H 2 O
The mass concentration of each substance is as follows: 80g/L soluble cerium salt (CeO) 2 ) Ammonium hydroxide (NH) 4 OH) 20%, hydrogen peroxide 33% and sulfuric acid 50%.
The polishing composition is prepared according to the following method:
mixing silica sol solution (80 nm, 40%) with nano cerium oxide solution (10%), ceric sulfate [ Ce (SO) 2 ]The ultrapure water is fully mixed in a premixing cylinder of a grinder. Grinding for 40 min with a sand mill, adding ammonium polyacrylate (C 3 H 3 NH 4 O 2 ) And adjusting the pH of the slurry to 1 by using 10% of nitric acid and 30% of triethanolamine, centrifuging the slurry by using a centrifuge, and grinding the supernatant. Grinding machine Universal-200, grinding conditions: the feeding flow rate of the polishing solution is 60ml/min, the temperature is 23 ℃, the pressing force is 4psi, the rotating speed of the polishing head is 120prm, the rotating speed of the lower fixed disk is 80rpm, the polishing time is 60 seconds, 40mm x 3mm of copper test pieces are used for CVD deposition of copper thickness of 2000nm, and the silicon oxide test pieces are used for CVD deposition of copper: PVD deposition of SiO on silicon substrate 2 800nm。
Example 8
An integrated circuit copper chemical mechanical polishing composition, which consists of the following raw materials in mass fraction: 1% of silicon oxide, 2% of cerium oxide, 0.1% of cerous sulfate, 0.1% of citric acid chelating agent, 0.1% of polyethylene glycol and the balance of water.
Wherein, the cerium oxide is prepared by the following steps: cerium carbonate hydroxide (Ce (OH) CO) 3 ) Mixing with water (S: L=1:2), ball milling, filtering, drying (120 deg.C), calcining at 500 deg.C for 24 hr, mixing with water to obtain slurry with 5% concentration, and grinding with sand mill to obtain nano cerium oxide with particle size of 20nm.
The basic cerium carbonate is prepared by adjusting the concentration of soluble cerium salt to 80g/L with deionized water, and mixing with precipitant NH at 80deg.C 4 HCO 3 The solution (concentration 40%, W/W) is reacted to obtain a precipitated product, and the precipitated product is thermally converted to obtain the basic cerium carbonate, wherein the specific reaction process is as follows:
2Ce 3+ +3CO 3 2- ＝Ce(CO 3 ) 3
Ce 2 (CO 3 ) 3 +H 2 O＝2Ce(OH)CO 3 +CO 2
cerium sulfate used Ce (SO) 2 The preparation method comprises the following steps:
ammonium hydroxide (NH) 4 OH) is added into cerium salt solution under stirring, and hydrogen peroxide (H) is added after precipitation is completed 2 O 2 ) Stirring and reacting for 30 minutes, heating and boiling the suspension, standing and cooling at room temperature, washing and filtering to obtain the product ceric hydroxide Ce (OH) 4 Dissolving in dilute sulfuric acid to prepare ceric sulfate. The reaction involved is as follows:
Ce 3+ +3(OH) - ＝Ce(OH) 3
2Ce(OH) 3 +H 2 O 2 ＝2Ce(OH) 4
Ce(OH) 4 +2H 2 SO 4 ＝Ce(SO) 2 +4H 2 O
the mass concentration of each substance is as follows: 80g/L soluble cerium salt (CeO) 2 ) Ammonium hydroxide (NH) 4 OH) 20%, hydrogen peroxide 33% and sulfuric acid 50%.
The polishing composition is prepared according to the following method:
mixing silica sol solution (80 nm, 40%) with nano cerium oxide solution (10%), ceric sulfate [ Ce (SO) 2 ]The ultrapure water is fully mixed in a premixing cylinder of a grinder. Grinding for 40 min by starting a sand mill, adding a citric acid chelating agent and polyethylene glycol into the suspension mixture, adjusting the pH to 1 by using 10% nitric acid and 30% triethanolamine, centrifuging the polishing slurry by using a centrifuge, and grinding the supernatant. Grinding machine Universal-200, grinding conditions: the feeding flow rate of the polishing solution is 60ml/min, the temperature is 23 ℃, the pressing force is 4psi, the rotating speed of the polishing head is 120prm, the rotating speed of the lower fixed disk is 80rpm, the polishing time is 60 seconds, 40mm x 3mm of copper test pieces are used for CVD deposition of copper thickness of 2000nm, and the silicon oxide test pieces are used for CVD deposition of copper: PVD deposition of SiO on silicon substrate 2 800nm。
Example 9
An integrated circuit copper chemical mechanical polishing composition, which consists of the following raw materials in mass fraction: 3% of silicon oxide, 2% of cerium oxide, 0.2% of ceric sulfate, 0.1% of glycine, 0.2% of ammonium polyacrylate and the balance of water.
Wherein, the cerium oxide is prepared by the following steps: cerium carbonate hydroxide (Ce (OH) CO) 3 ) Mixing with water (S: L=1:2), ball milling, filtering, drying (120 deg.C), calcining at 500 deg.C for 24 hr, mixing with water to obtain slurry with 5% concentration, and grinding with sand mill to obtain nano cerium oxide with particle size of 20nm.
The basic cerium carbonate is prepared by adjusting the concentration of soluble cerium salt to 80g/L with deionized water, and mixing with precipitant NH at 80deg.C 4 HCO 3 The solution (concentration 40%, W/W) is reacted to obtain a precipitated product, and the precipitated product is thermally converted to obtain the basic cerium carbonate, wherein the specific reaction process is as follows:
2Ce 3+ +3CO 3 2- ＝Ce(CO 3 ) 3
Ce 2 (CO 3 ) 3 +H 2 O＝2Ce(OH)CO 3 +CO 2
cerium sulfate used Ce (SO) 2 The preparation method comprises the following steps:
ammonium hydroxide (NH) 4 OH) is added into cerium salt solution under stirring, and hydrogen peroxide (H) is added after precipitation is completed 2 O 2 ) Stirring and reacting for 30 minutes, heating and boiling the suspension, standing and cooling at room temperature, washing and filtering to obtain the product ceric hydroxide Ce (OH) 4 Dissolving in dilute sulfuric acid to prepare ceric sulfate. The reaction involved is as follows:
Ce 3+ +3(OH) - ＝Ce(OH) 3
2Ce(OH) 3 +H 2 O 2 ＝2Ce(OH) 4
Ce(OH) 4 +2H 2 SO 4 ＝Ce(SO) 2 +4H 2 O
the mass concentration of each substance is as follows: 80g/L soluble cerium salt (CeO) 2 ) Ammonium hydroxide (NH) 4 OH) 20%, hydrogen peroxide 33% and sulfuric acid 50%.
The polishing composition is prepared according to the following method:
mixing silica sol solution (80 nm, 40%) with nano cerium oxide solution (10%), ceric sulfate [ Ce (SO) 2 ]The ultrapure water is fully mixed in a premixing cylinder of a grinder. Grinding for 40 min with a sand mill, adding ammonium polyacrylate (C 3 H 3 NH 4 O 2 ) And glycine, namely regulating the pH value to 2.5 by using 10% of nitric acid and 30% of triethanolamine, centrifuging the polishing slurry by using a centrifuge, and grinding the supernatant. Grinding machine Universal-200, grinding conditions: the feeding flow rate of the polishing solution is 60ml/min, the temperature is 23 ℃, the pressing force is 4psi, the rotating speed of the polishing head is 120prm, the rotating speed of the lower fixed disk is 80rpm, the polishing time is 60 seconds, 40mm x 3mm of copper test pieces are used for CVD deposition of copper thickness of 2000nm, and the silicon oxide test pieces are used for CVD deposition of copper: PVD deposition of SiO on silicon substrate 2 800nm。
Example 10
An integrated circuit copper chemical mechanical polishing composition, which consists of the following raw materials in mass fraction: 3% of silicon oxide, 2% of cerium oxide, 0.5% of ceric sulfate, 0.2% of glycine, 0.2% of ammonium polyacrylate and the balance of water.
Wherein, the cerium oxide is prepared by the following steps: cerium carbonate hydroxide (Ce (OH) CO) 3 ) Mixing with water (S: L=1:2), ball milling, filtering, drying (120 deg.C), calcining at 500 deg.C for 24 hr, mixing with water to obtain slurry with 5% concentration, and grinding with sand mill to obtain nano cerium oxide with particle size of 20nm.
The basic cerium carbonate is prepared by adjusting the concentration of soluble cerium salt to 80g/L with deionized water, and mixing with precipitant NH at 80deg.C 4 HCO 3 The solution (concentration 40%, W/W) is reacted to obtain a precipitated product, and the precipitated product is thermally converted to obtain the basic cerium carbonate, wherein the specific reaction process is as follows:
2Ce 3+ +3CO 3 2- ＝Ce(CO 3 ) 3
Ce 2 (CO 3 ) 3 +H 2 O＝2Ce(OH)CO 3 +CO 2
cerium sulfate used Ce (SO) 2 The preparation method comprises the following steps:
ammonium hydroxide (NH) 4 OH) stirringAdding into cerium salt solution under stirring, precipitating completely, and adding hydrogen peroxide (H) 2 O 2 ) Stirring and reacting for 30 minutes, heating and boiling the suspension, standing and cooling at room temperature, washing and filtering to obtain the product ceric hydroxide Ce (OH) 4 Dissolving in dilute sulfuric acid to prepare ceric sulfate. The reaction involved is as follows:
Ce 3+ +3(OH) - ＝Ce(OH) 3
2Ce(OH) 3 +H 2 O 2 ＝2Ce(OH) 4
Ce(OH) 4 +2H 2 SO 4 ＝Ce(SO) 2 +4H 2 O
The mass concentration of each substance is as follows: 80g/L soluble cerium salt (CeO) 2 ) Ammonium hydroxide (NH) 4 OH) 20%, hydrogen peroxide 33% and sulfuric acid 50%.
The polishing composition is prepared according to the following method:
mixing silica sol solution (80 nm, 40%) with nano cerium oxide solution (10%), ceric sulfate [ Ce (SO) 2 ]The ultrapure water is fully mixed in a premixing cylinder of a grinder. Grinding for 40 min with a sand mill, adding ammonium polyacrylate (C 3 H 3 NH 4 O 2 ) And glycine, namely regulating the pH value to 3 by using 10% of nitric acid and 30% of triethanolamine, centrifuging the polishing slurry by using a centrifuge, and grinding the supernatant. Grinding machine Universal-200, grinding conditions: the feeding flow rate of the polishing solution is 60ml/min, the temperature is 23 ℃, the pressing force is 4psi, the rotating speed of the polishing head is 120prm, the rotating speed of the lower fixed disk is 80rpm, the polishing time is 60 seconds, 40mm x 3mm of copper test pieces are used for CVD deposition of copper thickness of 2000nm, and the silicon oxide test pieces are used for CVD deposition of copper: PVD deposition of SiO on silicon substrate 2 800nm。
Example 11
An integrated circuit copper chemical mechanical polishing composition, which consists of the following raw materials in mass fraction: 3% of silicon oxide, 1% of cerium oxide, 1% of ceric sulfate, 0.3% of glycine, 0.2% of ammonium polyacrylate and the balance of water.
Wherein, the cerium oxide is prepared by the following steps: cerium carbonate hydroxide (Ce (OH) CO) 3 ) After slurrying with water (S: L=1:2)Ball milling, filtering, drying (120 deg.C), calcining at 500 deg.C for 24 hr, mixing with water to obtain slurry with 5% concentration, and grinding with sand mill to obtain nano cerium oxide with particle size of 20nm.
The basic cerium carbonate is prepared by adjusting the concentration of soluble cerium salt to 80g/L with deionized water, and mixing with precipitant NH at 80deg.C 4 HCO 3 The solution (concentration 40%, W/W) is reacted to obtain a precipitated product, and the precipitated product is thermally converted to obtain the basic cerium carbonate, wherein the specific reaction process is as follows:
2Ce 3+ +3CO 3 2- ＝Ce(CO 3 ) 3
Ce 2 (CO 3 ) 3 +H 2 O＝2Ce(OH)CO 3 +CO 2
cerium sulfate used Ce (SO) 2 The preparation method comprises the following steps:
ammonium hydroxide (NH) 4 OH) is added into cerium salt solution under stirring, and hydrogen peroxide (H) is added after precipitation is completed 2 O 2 ) Stirring and reacting for 30 minutes, heating and boiling the suspension, standing and cooling at room temperature, washing and filtering to obtain the product ceric hydroxide Ce (OH) 4 Dissolving in dilute sulfuric acid to prepare ceric sulfate. The reaction involved is as follows:
Ce 3+ +3(OH) - ＝Ce(OH) 3
2Ce(OH) 3 +H 2 O 2 ＝2Ce(OH) 4
Ce(OH) 4 +2H 2 SO 4 ＝Ce(SO) 2 +4H 2 O
the mass concentration of each substance is as follows: 80g/L soluble cerium salt (CeO) 2 ) Ammonium hydroxide (NH) 4 OH) 20%, hydrogen peroxide 33% and sulfuric acid 50%.
The polishing composition is prepared according to the following method:
mixing silica sol solution (80 nm, 40%) with nano cerium oxide solution (10%), ceric sulfate [ Ce (SO) 2 ]The ultrapure water is fully mixed in a premixing cylinder of a grinder. Grinding for 40 min with a sand mill, adding ammonium polyacrylate (C 3 H 3 NH 4 O 2 )、And (3) adjusting the pH of glycine to 3 by using 10% of nitric acid and 30% of triethanolamine, centrifuging the polishing slurry by using a centrifuge, and grinding the supernatant. Grinding machine Universal-200, grinding conditions: the feeding flow rate of the polishing solution is 60ml/min, the temperature is 23 ℃, the pressing force is 4psi, the rotating speed of the polishing head is 120prm, the rotating speed of the lower fixed disk is 80rpm, the polishing time is 60 seconds, 40mm x 3mm of copper test pieces are used for CVD deposition of copper thickness of 2000nm, and the silicon oxide test pieces are used for CVD deposition of copper: PVD deposition of SiO on silicon substrate 2 800nm。
Example 12
An integrated circuit copper chemical mechanical polishing composition, which consists of the following raw materials in mass fraction: 1% of silicon oxide, 2% of cerium oxide, 0.5% of ceric sulfate, 0.2% of glycine, 0.2% of ammonium polyacrylate and the balance of water.
Wherein, the cerium oxide is prepared by the following steps: cerium carbonate hydroxide (Ce (OH) CO) 3 ) Mixing with water (S: L=1:2), ball milling, filtering, drying (120 deg.C), calcining at 500 deg.C for 24 hr, mixing with water to obtain slurry with 5% concentration, and grinding with sand mill to obtain nano cerium oxide with particle size of 20nm.
The basic cerium carbonate is prepared by adjusting the concentration of soluble cerium salt to 80g/L with deionized water, and mixing with precipitant NH at 80deg.C 4 HCO 3 The solution (concentration 40%, W/W) is reacted to obtain a precipitated product, and the precipitated product is thermally converted to obtain the basic cerium carbonate, wherein the specific reaction process is as follows:
2Ce 3+ +3CO 3 2- ＝Ce(CO 3 ) 3
Ce 2 (CO 3 ) 3 +H 2 O＝2Ce(OH)CO 3 +CO 2
Cerium sulfate used Ce (SO) 2 The preparation method comprises the following steps:
ammonium hydroxide (NH) 4 OH) is added into cerium salt solution under stirring, and hydrogen peroxide (H) is added after precipitation is completed 2 O 2 ) Stirring and reacting for 30 minutes, heating and boiling the suspension, standing and cooling at room temperature, washing and filtering to obtain the product ceric hydroxide Ce (OH) 4 Dissolving in dilute sulfuric acid to prepare ceric sulfate. The reaction involved is as follows:
Ce 3+ +3(OH) - ＝Ce(OH) 3
2Ce(OH) 3 +H 2 O 2 ＝2Ce(OH) 4
Ce(OH) 4 +2H 2 SO 4 ＝Ce(SO) 2 +4H 2 O
the mass concentration of each substance is as follows: 80g/L soluble cerium salt (CeO) 2 ) Ammonium hydroxide (NH) 4 OH) 20%, hydrogen peroxide 33% and sulfuric acid 50%.
The polishing composition is prepared according to the following method:
mixing silica sol solution (80 nm, 40%) with nano cerium oxide solution (10%), ceric sulfate [ Ce (SO) 2 ]The ultrapure water is fully mixed in a premixing cylinder of a grinder. Grinding for 40 min with a sand mill, adding ammonium polyacrylate (C 3 H 3 NH 4 O 2 ) And glycine, namely regulating the pH value to 4 by using 10% of nitric acid and 30% of triethanolamine, centrifuging the polishing slurry by using a centrifuge, and grinding the supernatant. Grinding machine Universal-200, grinding conditions: the feeding flow rate of the polishing solution is 60ml/min, the temperature is 23 ℃, the pressing force is 4psi, the rotating speed of the polishing head is 120prm, the rotating speed of the lower fixed disk is 80rpm, the polishing time is 60 seconds, 40mm x 3mm of copper test pieces are used for CVD deposition of copper thickness of 2000nm, and the silicon oxide test pieces are used for CVD deposition of copper: PVD deposition of SiO on silicon substrate 2 800nm。
Example 13
An integrated circuit copper chemical mechanical polishing composition, which consists of the following raw materials in mass fraction: 2% of silicon oxide, 2% of cerium oxide, 0.3% of ceric sulfate, 0.5% of glycine, 0.2% of ammonium polyacrylate and the balance of water.
Wherein, the cerium oxide is prepared by the following steps: cerium carbonate hydroxide (Ce (OH) CO) 3 ) Mixing with water (S: L=1:2), ball milling, filtering, drying (120 deg.C), calcining at 500 deg.C for 24 hr, mixing with water to obtain slurry with 5% concentration, and grinding with sand mill to obtain nano cerium oxide with particle size of 20nm.
The basic cerium carbonate is prepared by adjusting the concentration of soluble cerium salt to 80g/L with deionized water, and mixing with precipitant NH at 80deg.C 4 HCO 3 The solution (concentration 40%, W/W) is reacted to obtain a precipitated product, and the precipitated product is thermally converted to obtain the basic cerium carbonate, wherein the specific reaction process is as follows:
2Ce 3+ +3CO 3 2- ＝Ce(CO 3 ) 3
Ce 2 (CO 3 ) 3 +H 2 O＝2Ce(OH)CO 3 +CO 2
cerium sulfate used Ce (SO) 2 The preparation method comprises the following steps:
ammonium hydroxide (NH) 4 OH) is added into cerium salt solution under stirring, and hydrogen peroxide (H) is added after precipitation is completed 2 O 2 ) Stirring and reacting for 30 minutes, heating and boiling the suspension, standing and cooling at room temperature, washing and filtering to obtain the product ceric hydroxide Ce (OH) 4 Dissolving in dilute sulfuric acid to prepare ceric sulfate. The reaction involved is as follows:
Ce 3+ +3(OH) - ＝Ce(OH) 3
2Ce(OH) 3 +H 2 O 2 ＝2Ce(OH) 4
Ce(OH) 4 +2H 2 SO 4 ＝Ce(SO) 2 +4H 2 O
The mass concentration of each substance is as follows: 80g/L soluble cerium salt (CeO) 2 ) Ammonium hydroxide (NH) 4 OH) 20%, hydrogen peroxide 33% and sulfuric acid 50%.
The polishing composition is prepared according to the following method:
mixing silica sol solution (80 nm, 40%) with nano cerium oxide solution (10%), ceric sulfate [ Ce (SO) 2 ]The ultrapure water is fully mixed in a premixing cylinder of a grinder. Grinding for 40 min with a sand mill, adding ammonium polyacrylate (C 3 H 3 NH 4 O 2 ) And glycine, namely regulating the pH value to 4.5 by using 10% of nitric acid and 30% of triethanolamine, centrifuging the polishing slurry by using a centrifuge, and grinding the supernatant. Grinding machine Universal-200, grinding conditions: the feeding flow rate of the polishing solution is 60ml/min, the temperature is 23 ℃, the pressure is 4psi, the rotating speed of the polishing head is 120prm, the rotating speed of the lower fixed disk is 80rpm, the polishing time is 60 seconds,40mm for copper coupon 3mm, 2000nm for CVD deposited copper thickness for silicon substrate, silicon oxide coupon: PVD deposition of SiO on silicon substrate 2 800nm。
Example 14
An integrated circuit copper chemical mechanical polishing composition, which consists of the following raw materials in mass fraction: 2% of silicon oxide, 2% of cerium oxide, 0.3% of ceric sulfate, 0.2% of glycine, 0.2% of ammonium polyacrylate and the balance of water.
Wherein, the cerium oxide is prepared by the following steps: cerium carbonate hydroxide (Ce (OH) CO) 3 ) Mixing with water (S: L=1:2), ball milling, filtering, drying (120 deg.C), calcining at 500 deg.C for 24 hr, mixing with water to obtain slurry with 5% concentration, and grinding with sand mill to obtain nano cerium oxide with particle size of 20nm.
The basic cerium carbonate is prepared by adjusting the concentration of soluble cerium salt to 80g/L with deionized water, and mixing with precipitant NH at 80deg.C 4 HCO 3 The solution (concentration 40%, W/W) is reacted to obtain a precipitated product, and the precipitated product is thermally converted to obtain the basic cerium carbonate, wherein the specific reaction process is as follows:
2Ce 3+ +3CO 3 2- ＝Ce(CO 3 ) 3
Ce 2 (CO 3 ) 3 +H 2 O＝2Ce(OH)CO 3 +CO 2
cerium sulfate used Ce (SO) 2 The preparation method comprises the following steps:
ammonium hydroxide (NH) 4 OH) is added into cerium salt solution under stirring, and hydrogen peroxide (H) is added after precipitation is completed 2 O 2 ) Stirring and reacting for 30 minutes, heating and boiling the suspension, standing and cooling at room temperature, washing and filtering to obtain the product ceric hydroxide Ce (OH) 4 Dissolving in dilute sulfuric acid to prepare ceric sulfate. The reaction involved is as follows:
Ce 3+ +3(OH) - ＝Ce(OH) 3
2Ce(OH) 3 +H 2 O 2 ＝2Ce(OH) 4
Ce(OH) 4 +2H 2 SO 4 ＝Ce(SO) 2 +4H 2 O
the mass concentration of each substance is as follows: 80g/L soluble cerium salt (CeO) 2 ) Ammonium hydroxide (NH) 4 OH) 20%, hydrogen peroxide 33% and sulfuric acid 50%.
The polishing composition is prepared according to the following method:
taking silica sol (80 nm, 40%) and nano cerium oxide CeO 2 (10%), ceric sulfate [ Ce (SO) 2 ]The ultrapure water is fully mixed in a premixing cylinder of a grinder. Grinding for 40 min with a sand mill, adding ammonium polyacrylate (C 3 H 3 NH 4 O 2 ) Regulating pH to 6 with 10% nitric acid and 30% triethanolamine, centrifuging the slurry with a centrifuge, and grinding the supernatant. Grinding machine Universal-200, grinding conditions: the feeding flow rate of the polishing solution is 60ml/min, the temperature is 23 ℃, the pressing force is 4psi, the rotating speed of the polishing head is 120prm, the rotating speed of the lower fixed disk is 80rpm, the polishing time is 60 seconds, 40mm x 3mm of copper test pieces are used for CVD deposition of copper thickness of 2000nm, and the silicon oxide test pieces are used for CVD deposition of copper: PVD deposition of SiO on silicon substrate 2 800nm。
Example 15
An integrated circuit copper chemical mechanical polishing composition, which consists of the following raw materials in mass fraction: 1% of silicon oxide, 4% of cerium oxide, 1% of ceric sulfate, 0.1% of glycine, 0.2% of ammonium polyacrylate and the balance of water.
Wherein, the cerium oxide is prepared by the following steps: cerium carbonate hydroxide (Ce (OH) CO) 3 ) Mixing with water (S: L=1:2), ball milling, filtering, drying (120 deg.C), calcining at 500 deg.C for 24 hr, mixing with water to obtain slurry with 5% concentration, and grinding with sand mill to obtain nano cerium oxide with particle size of 20nm.
The basic cerium carbonate is prepared by adjusting the concentration of soluble cerium salt to 80g/L with deionized water, and mixing with precipitant NH at 80deg.C 4 HCO 3 The solution (concentration 40%, W/W) is reacted to obtain a precipitated product, and the precipitated product is thermally converted to obtain the basic cerium carbonate, wherein the specific reaction process is as follows:
2Ce 3+ +3CO 3 2- ＝Ce(CO 3 ) 3
Ce 2 (CO 3 ) 3 +H 2 O＝2Ce(OH)CO 3 +CO 2
Cerium sulfate used Ce (SO) 2 The preparation method comprises the following steps:
ammonium hydroxide (NH) 4 OH) is added into cerium salt solution under stirring, and hydrogen peroxide (H) is added after precipitation is completed 2 O 2 ) Stirring and reacting for 30 minutes, heating and boiling the suspension, standing and cooling at room temperature, washing and filtering to obtain the product ceric hydroxide Ce (OH) 4 Dissolving in dilute sulfuric acid to prepare ceric sulfate. The reaction involved is as follows:
Ce 3+ +3(OH) - ＝Ce(OH) 3
2Ce(OH) 3 +H 2 O 2 ＝2Ce(OH) 4
Ce(OH) 4 +2H 2 SO 4 ＝Ce(SO) 2 +4H 2 O
the mass concentration of each substance is as follows: 80g/L soluble cerium salt (CeO) 2 ) Ammonium hydroxide (NH) 4 OH) 20%, hydrogen peroxide 33% and sulfuric acid 50%.
The polishing composition is prepared according to the following method:
mixing silica sol solution (80 nm, 40%) with nano cerium oxide solution (10%), ceric sulfate [ Ce (SO) 2 ]The ultrapure water is fully mixed in a premixing cylinder of a grinder. Grinding for 40 min with a sand mill, adding ammonium polyacrylate (C 3 H 3 NH 4 O 2 ) And glycine, namely regulating the pH value to 5 by using 10% of nitric acid and 30% of triethanolamine, centrifuging the polishing slurry by using a centrifuge, and grinding the supernatant. Grinding machine Universal-200, grinding conditions: the feeding flow rate of the polishing solution is 60ml/min, the temperature is 23 ℃, the pressing force is 4psi, the rotating speed of the polishing head is 120prm, the rotating speed of the lower fixed disk is 80rpm, the polishing time is 60 seconds, 40mm x 3mm of copper test pieces are used for CVD deposition of copper thickness of 2000nm, and the silicon oxide test pieces are used for CVD deposition of copper: PVD deposition of SiO on silicon substrate 2 800nm。
Comparative example 1
An integrated circuit copper chemical mechanical polishing composition differs from example 13 only in that the ceric sulfate is replaced with hydrogen peroxide and the pH is adjusted to 4.0 during the preparation process.
Comparative example 2
An integrated circuit copper chemical mechanical polishing composition differing from example 13 in the composition of the raw materials, specifically: 3% of silicon oxide, 2% of cerium oxide, 0.5% of ceric sulfate, 0.2% of hydrogen peroxide, 0.1% of glycine, 0.2% of ammonium polyacrylate and the balance of water. And simultaneously, the pH value is adjusted to 8.5 in the preparation process.
Comparative example 3
An integrated circuit copper chemical mechanical polishing composition differing from example 13 in the composition of the raw materials, specifically: 1% of silicon oxide, 1% of cerium oxide, 1% of ceric sulfate, 0.3% of glycine, 0.2% of ammonium polyacrylate and the balance of water.
Comparative example 4
An integrated circuit copper chemical mechanical polishing composition differing from example 13 in the composition of the raw materials, specifically: 3% of silicon oxide, 3% of cerium oxide, 1% of ceric sulfate, 0.3% of glycine, 0.2% of ammonium polyacrylate and the balance of water.
Since the effects of the polishing compositions improved in examples 1 to 14 are substantially the same, the effects will be described below by taking only the polishing compositions provided in examples 11 to 16 as examples.
The removal rates of copper and silicon oxide in each of examples 1 to 14 and comparative examples 1 to 3 were measured, and the results are shown in Table 1.
Table 1 removal rates of copper and silicon oxide from each group
As is clear from Table 1, the copper removal rate increased with the increase in the content of cerium oxide, pH and silica sol (examples 11, 12 and 13). The ceric sulfate may replace hydrogen peroxide as an oxidizing agent (comparative example 1). The pH was increased and the oxidation was reduced by partial hydrolysis of the ceric oxide, resulting in a reduced removal rate (comparative example 3). SiO (SiO) 2 ∶CeO 2 The removal rate of copper and silicon oxide is balanced strongly=3:2. The improvement in cerium oxide facilitates the removal of silicon oxide (example 15).
The above description is only of the preferred embodiments of the present application and is not intended to limit the present application, but various modifications and variations can be made to the present application by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the protection scope of the present application.
Claims (9)
1. The integrated circuit copper chemical mechanical polishing composition is characterized by comprising the following raw materials in parts by weight: 3 to 5 parts of nano abrasive particles, 0.1 to 5.0 parts of high cerium oxidant, 0.01 to 2.0 parts of metal complexing agent or metal chelating agent and 0.01 to 5.0 parts of surfactant;
The nano grinding particles consist of silicon oxide and cerium oxide;
the mol ratio of the silicon oxide to the cerium oxide is 1:1-5.
2. The polishing composition of claim 1, wherein the silica has a particle size of 10 to 160nm and the ceria has a particle size of 20 to 100nm.
3. The polishing composition of claim 1, wherein the cerium oxide is a basic cerium carbonate calcined at 500 ℃ to 800 ℃ for 6 to 24 hours, and the 2 theta angles of XRD diffraction characteristic peaks of the cerium oxide are 15.9 °, 20.2 °, 30.2 °, 38.1 °, 42.8 °.
4. The polishing composition of claim 1, wherein the high cerium oxide is one or a mixture of ceric sulfate, ceric nitrate, ceric acetate, ammonium ceric nitrate, or ceric hydroxide.
5. The polishing composition of claim 1, wherein the metal complexing or metal chelating agent is selected from the group consisting of glycine, glutamic acid, lysine, tartaric acid, maleic acid, citric acid, ethylenediamine tetraacetic acid, polyacrylic acid, hydrolyzed polymaleic anhydride, citric acid chelating agent, and mixtures of one or more of diethylenetriamine pentaacetic acid.
6. The polishing composition of claim 1, wherein the surfactant is selected from one or more of ammonium polyacrylate, polyacrylamide, sodium tripolyphosphate, sodium polyphosphate, polyethylene glycol, polyvinyl alcohol, sodium dodecylbenzenesulfonate, sodium hydrogen phosphate, sodium pyrophosphate, and mixtures thereof.
7. The polishing composition of claim 1, further comprising a PH adjustor selected from one or more of sulfuric acid, nitric acid, hydrochloric acid, acetic acid, ammonium hydroxide, potassium hydroxide, sodium hydroxide, monoethanolamine, diethanolamine, and triethanolamine.
8. A method of preparing the polishing composition of claim 7, comprising the steps of:
weighing nano grinding particles, a high cerium oxidant, a metal complexing agent or a metal chelating agent and a surfactant according to parts by weight;
and (3) sanding and mixing the nano grinding ions and the high cerium oxide, adding the metal complexing agent or the metal chelating agent and the surfactant, adjusting the pH to 1.0-6.0, centrifuging, taking supernatant and grinding.
9. Use of the polishing composition of any one of claims 1-7 in planarization of integrated circuit fabrication.
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| CN119799168A (en) * | 2025-03-11 | 2025-04-11 | 大连理工大学 | A chemical mechanical polishing liquid for 440C stainless steel and a preparation method thereof |
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