CN104513627B - A kind of integrated circuit copper CMP composition and preparation method thereof - Google Patents
A kind of integrated circuit copper CMP composition and preparation method thereof Download PDFInfo
- Publication number
- CN104513627B CN104513627B CN201410808839.8A CN201410808839A CN104513627B CN 104513627 B CN104513627 B CN 104513627B CN 201410808839 A CN201410808839 A CN 201410808839A CN 104513627 B CN104513627 B CN 104513627B
- Authority
- CN
- China
- Prior art keywords
- polishing
- composition
- abrasive particle
- agent
- copper cmp
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23F—NON-MECHANICAL REMOVAL OF METALLIC MATERIAL FROM SURFACE; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL; MULTI-STEP PROCESSES FOR SURFACE TREATMENT OF METALLIC MATERIAL INVOLVING AT LEAST ONE PROCESS PROVIDED FOR IN CLASS C23 AND AT LEAST ONE PROCESS COVERED BY SUBCLASS C21D OR C22F OR CLASS C25
- C23F3/00—Brightening metals by chemical means
- C23F3/04—Heavy metals
- C23F3/06—Heavy metals with acidic solutions
Abstract
The present invention relates to a kind of integrated circuit copper CMP composition and preparation method thereof, belongs to microelectronics auxiliary material and Ultra-precision Turning technology field, more particularly to a kind of polishing composition with catalytic action.The present composition includes deionized water, abrasive particle containing catalyst combination, oxidant, complexing agent, corrosion inhibiter, interfacial reaction auxiliary agent, pH adjusting agent, surfactant, and the pH value of the polishing combination liquid is 2.0～5.5.The present invention makes polishing abrasive particle combine with catalyst, make polishing abrasive particle that there is catalysis activity while mechanical grinding effect is played, ability with catalysis oxidation, have mechanism and chemical action concurrently simultaneously, polished surface quality can be kept and a kind of copper CMP composition of quick removal can be realized.
Description
Technical field
The invention belongs to microelectronics auxiliary material and Ultra-precision Turning technology field, more particularly to a kind of to have catalysis
The polishing composition of effect.
Background technology
With the continuous development of super large-scale integration, characteristic size constantly reduces, and chip area constantly increases, mutually
Wire length causes impedance to sharply increase therewith increasing.Line capacitance is with the continuous reduction of distance between adjacent interconnection line
Persistently rise.An important means for reducing interconnection impedance is exactly to reduce the resistivity of interconnection metal, strengthen the anti-of interconnection metal
Electron transfer characteristic.Copper is employed and has replaced aluminium to become super large-scale integration system as a kind of low metal of resistivity
Main flow interconnection technique in making.
As the etching to copper is extremely difficult, thin copper film technique typically completes multilayer interconnection structure by embedded process,
Now electroplate diffusion impervious layer and copper in a groove, then by chemically-mechanicapolish polish (CMP) technology remove excess surface copper and
Diffusion impervious layer.
Thin copper film is polished as one of critical process in integrated circuit production process, and which polishes removal efficiency with polishing matter
Amount will directly influence the production efficiency and yield rate of IC devices.CMP is widely used in collection as a kind of global planarizartion technique
Into the ultra-precision surface manufacture field such as circuit.Electric dielectric material in copper interconnection structure belongs to low-K dielectric (k ＜ 2.2), and its machinery is strong
It is low that degree is mutually coupled with material than aluminium, and under the conditions of high down forces, Cu/ low K dielectric layers film layer easily occur and separate, peel off, crossing to throw etc. and lack
Fall into, therefore low pressure (≤0.5psi) is more suitable for the polishing of Cu/ low K dielectric layers.And the size of pressure is the most important ginsengs of CMP
One of number, the material removing rate of CMP is directly proportional to lower pressure, typically, reduces the polishing speed that lower pressure can directly be reduced CMP
Rate.For example, copper polishing is carried out using ripe commercial copper polishing composition, polishing speed is 333.3nm/ when pressure is 5.0Psi
Min, and when pressure be reduced to about, 0.5Psi when, polishing speed is decreased to 101.9nm/min, differs 3 times or so.
The content of the invention
The invention aims to provide under the conditions of ultra low pressure (≤0.5psi), polished surface quality can be kept
A kind of copper CMP composition of quick removal can be realized again.The present invention utilizes catalytic oxidation principle, makes polishing abrasive particle
Combine with catalyst, make polishing abrasive particle that there is catalysis activity while mechanical grinding effect is played, with catalysis oxidation
Ability, while having mechanism and chemical action concurrently, can be catalyzed the oxidants such as hydrogen peroxide, produce more polyradical, improve CMP's
Chemical action, it is same under the conditions of ultralow lower pressure (≤0.5psi) to realize efficiently removing.
A kind of integrated circuit copper CMP composition, it is characterised in that said composition includes deionized water, containing catalyst combination
Abrasive particle, oxidant, complexing agent, corrosion inhibiter, interfacial reaction auxiliary agent, pH adjusting agent, surfactant, the polishing combine the pH value of liquid
For 2.0～5.5, the content of each component is as follows：
The composition of the present invention is applied to polish pressure for≤0.5psi..
The oxidant is hydrogen peroxide, carbamide peroxide, Peracetic acid, benzoyl peroxide, potassium peroxydisulfate, permonosulphuric acid
At least one in potassium, ammonium persulfate, potassium permanganate, the potassium ferricyanide, ammonium nitrate, ferric nitrate, in hydrogen peroxide.
The complexing agent is amion acetic acid, alanine, glutamic acid, proline, aspartic acid, serine, hydroxyglutamic acid, hydroxyl
Base ethylidene diphosphonic acid, ATMP, 2- hydroxyl phosphinylidyne guanidine-acetic acids, acetic acid, oxalic acid, oxamides, sodium gluconate, second two
In amine tetraacethyl, disodium ethylene diamine tetraacetate, tetrasodium ethylenediamine tetraacetate, the big sodium acetate of ethylenediamine diphosphonic acid phenyl at least one
Kind.
The corrosion inhibiter be BTA, methylbenzotrazole, 5- methylbenzotrazoles, imidazoles, urea, ascorbic acid,
At least one in thiocarbamide, ethylene thiourea.
The interfacial reaction auxiliary agent be maleic acid, diethyl maleate, maleic anhydride, in di-2-ethylhexyl maleate at least one
Kind.
The surfactant be Surfactant-Polymer MAG-AA, carboxylic anion surfactant,
At least one in sulfonate type anion surfactant, phosphoric acid ester anion surfactant.
The particle diameter of the abrasive particle is 10～35nm.
The complexing agent of the composition is the aspartic acid of 1wt%, oxidant is the hydrogen peroxide of 2wt%, corrosion inhibiter is
The methylbenzotrazole of 0.01wt%, interfacial reaction auxiliary agent are the diethyl maleate of 0.05wt%, 0.05wt% poly alkyl alcohols
The average grain diameter of oxygen ethene ether sodium sulfate surfactant and 5wt% is 10～30nm, and pH value is 4 catalyst combination abrasive particle.
A kind of preparation method of integrated circuit copper CMP composition, it is characterised in that comprise the following steps：
With noble metal chlorate, transition-metal oxide as presoma, sodium borohydride is reducing agent, cetyl trimethyl
Ammonium bromide is that protective agent synthesizes nano-noble metal or excessive metalcatalyzing agent particle；
Prepare 10wt%-40wt% concentration noble metal chlorate aqueous solution, wherein noble metal chlorate include gold chloride,
Chloroplatinic acid or palladium bichloride；Transition-metal oxide includes the oxide of the elements such as titanium, manganese, iron, cobalt, nickel, copper, zinc；
1) under the conditions of 40 DEG C -80 DEG C, the 0.1wt%-2wt% cetyl trimethylammonium bromide aqueous solution is prepared, is continued
Stir to being completely dissolved；Noble metal or the transition metal oxide precursor body aqueous solution are rapidly added into cetyl trimethyl bromination
In aqueous ammonium, wherein the cetyl trimethylammonium bromide aqueous solution and precursor water solution volume ratio are 1～30, and stirring is equal
It is even；
2) prepare 0.05M～2M sodium silicate solution, using cationic ion-exchange resin exchange sodium silicate solution in sodium from
Son, and pH value is adjusted to 8-10 scopes, obtain active silicic acid solution；
3) by step 2) in gained silicate solution, with step 1) in resulting solution mixing and stirring；
4) by step 2) middle gained silicate solution, pH value is adjusted to 9～10 scopes with NaOH or ammoniacal liquor, be heated to 90
～100 degree, after fully reacting, then it is added dropwise over step 3) middle gained mixed solution, appropriate boron is added dropwise over after fully reacting
Change hydrogen sodium solution, fully reaction is continued stirring until in water bath with thermostatic control, the colloidal sol of metal target catalyst can be contained；
The present invention's has the advantage that：
The combination abrasive particle containing catalyst in polishing composition of the present invention, compared with tradition polishing abrasive particle, in polishing
During, except playing a part of mechanical grinding, the chemical reactions such as catalysis oxidation are simultaneously participated in, promote polishing fluid generation more certainly
By base, strengthen the chemical action during copper CMP, even if under the conditions of ultralow lower pressure, still can obtain higher
Removal rate, its removal rate>0.6 μm/min, under the conditions of solving ultralow lower pressure, copper CMP removes low asking
Topic.
Preparing for polishing composition of the present invention can adopt preparation method commonly used in the art, for example, each composition be pressed
Proportioning is stirred in adding deionized water and ultrasonic disperse is uniform.
Specific embodiment
Polishing experiments will be used for the polishing fluid for postponing, polishing experiments parameter is as follows：
Polishing machine：12 inches of chemical-mechanical polishing mathings (Strasbaugh 6EG types), are furnished with 1 rubbing head, can throw 1 12
Inch electroless copper plating film (is customized from magnificent power semiconductor, thickness of coated copper layer is 2 microns)；
Polishing rotary speed：100 turns/min；
Rubbing head rotating speed：95 turns/min；
Polishing electroless copper plating film specification：3 00mm of diameter；
Polishing time：1min；
Polishing pad：IC 1000-XY/SUBA IV20 type composite polishing pads；
Polishing flow quantity：80ml/min；
Polish pressure：0.2-0.5psi；
Polish temperature：25℃
Polishing speed：Polish removal rate is obtained by the change calculations of wafer weight before and after polishing, its available electron day
Flat to measure, polishing speed is that polishing removes weight and is converted into the ratio removed after thickness with polishing time.
Copper sheet surface quality detection after polishing：
The surface roughness of copper sheet after polishing is detected using AFM (AFM).The adopted AFM of experiment is the U.S.
The production of Brooker company, model DIMENSION ICON.Probe radius is 10nm, and its vertical resolution is 0.01nm, is swept
Frequency is retouched for 1.5Hz, 5 × 5 μm 2 of sweep limits.To avoid the attachment impact of the impurity to experimental result of copper sheet surface presence,
Chip is cleaned by ultrasonic in acetone, absolute ethyl alcohol, deionized water respectively before experiment.
Based on the present invention, 7 embodiments and 2 comparative examples, polishing composition situation and its correspondence polishing effect are listed
As shown in table 1.Wherein 7 embodiments combine abrasive particle using catalyst made from platonic of the same race, and the combination abrasive particle adopts above-mentioned preparation side
It is prepared by method.
As shown in embodiment in table, the embodiment of the present invention 1 to 7 is compared with 9 with comparative example 8, and removal rate is greatly improved
, and surface roughness Ra is greatly reduced, and absolutely proves that the polishing fluid of the present invention is that a kind of CMP of function admirable is polished
Material, is suitable for copper polishing.
Wherein, in the optimal polishing combination liquid under polishing technological conditions of the present invention, each component content is (embodiment
4)：Aspartic acid containing 1wt%, 2wt% hydrogen peroxide, 0.01wt% methylbenzotrazoles, 0.05wt% diethyl maleates,
0.05wt% sodium sulfate of polyethenoxy ether of fatty alcohol, average grain diameter containing 5wt% are 4 containing catalyst less than the pH value of 30nm
Combination abrasive particle, the electroless copper plating film surface roughness as little as 0.26nm after polishing combination liquid polishing, removal rate reach 534.8nm/min.
The above is only the preferred embodiment of the present invention, it should be pointed out that be general technology for the art
For personnel, on the premise of without departing from the technology of the present invention principle, corresponding adjustment can also be made and improved, these adjustment and
Improvement also should be regarded as protection scope of the present invention.
Embodiment list：
Claims (1)
1. a kind of integrated circuit copper CMP composition, it is characterised in that said composition by deionized water, abrasive particle containing catalyst combination,
Oxidant, complexing agent, corrosion inhibiter, interfacial reaction auxiliary agent, pH adjusting agent, surfactant composition, the composition is applied to be thrown
Light pressure is≤0.5psi；The complexing agent of the composition is the aspartic acid of 1wt%, oxidant for 2wt% hydrogen peroxide,
Corrosion inhibiter is the methylbenzotrazole of 0.01wt%, interfacial reaction auxiliary agent for 0.05wt% diethyl maleate, 0.05wt%
The average grain diameter of sodium sulfate of polyethenoxy ether of fatty alcohol surfactant and 5wt% is the catalyst combination abrasive particle of 10～30nm,
The pH value of polishing combination liquid is 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410808839.8A CN104513627B (en) | 2014-12-22 | 2014-12-22 | A kind of integrated circuit copper CMP composition and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410808839.8A CN104513627B (en) | 2014-12-22 | 2014-12-22 | A kind of integrated circuit copper CMP composition and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104513627A CN104513627A (en) | 2015-04-15 |
| CN104513627B true CN104513627B (en) | 2017-04-05 |
Family
ID=52789506
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410808839.8A Expired - Fee Related CN104513627B (en) | 2014-12-22 | 2014-12-22 | A kind of integrated circuit copper CMP composition and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104513627B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10217645B2 (en) * | 2014-07-25 | 2019-02-26 | Versum Materials Us, Llc | Chemical mechanical polishing (CMP) of cobalt-containing substrate |
| CN108085687A (en) * | 2017-12-01 | 2018-05-29 | 东方电气集团东方汽轮机有限公司 | Cupric piece surface processing polishing agent |
| CN109811343B (en) * | 2019-03-19 | 2020-11-17 | 惠州市瑞翔丰科技有限公司 | Ammonia nitrogen-free environment-friendly etching solution and etching method |
| CN110093606A (en) * | 2019-06-14 | 2019-08-06 | 大连亚太电子有限公司 | A kind of etching solution and preparation method thereof for pcb board |
| CN110434680A (en) * | 2019-07-19 | 2019-11-12 | 大连理工大学 | A kind of chemical mechanical polishing liquid and polishing method of propeller |
| KR20230139386A (en) * | 2020-12-14 | 2023-10-05 | 버슘머트리얼즈 유에스, 엘엘씨 | Chemical mechanical planarization (CMP) for copper and through-silicon vias (TSVs) |
| CN115477899B (en) * | 2022-07-29 | 2023-09-08 | 深圳市永霖科技有限公司 | Gallium nitride chemical mechanical polishing solution based on oxidation-reduction potential mechanism |
| CN116023907A (en) * | 2023-02-16 | 2023-04-28 | 西南交通大学 | Polishing solution for flattening copper/nickel microstructure and application thereof |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6068787A (en) * | 1996-11-26 | 2000-05-30 | Cabot Corporation | Composition and slurry useful for metal CMP |
| US6083419A (en) * | 1997-07-28 | 2000-07-04 | Cabot Corporation | Polishing composition including an inhibitor of tungsten etching |
| US6177026B1 (en) * | 1998-05-26 | 2001-01-23 | Cabot Microelectronics Corporation | CMP slurry containing a solid catalyst |
| US6435947B2 (en) * | 1998-05-26 | 2002-08-20 | Cabot Microelectronics Corporation | CMP polishing pad including a solid catalyst |
| SG73683A1 (en) * | 1998-11-24 | 2000-06-20 | Texas Instruments Inc | Stabilized slurry compositions |
| US20030162398A1 (en) * | 2002-02-11 | 2003-08-28 | Small Robert J. | Catalytic composition for chemical-mechanical polishing, method of using same, and substrate treated with same |
| US7294576B1 (en) * | 2006-06-29 | 2007-11-13 | Cabot Microelectronics Corporation | Tunable selectivity slurries in CMP applications |
| US20140273458A1 (en) * | 2013-03-12 | 2014-09-18 | Air Products And Chemicals, Inc. | Chemical Mechanical Planarization for Tungsten-Containing Substrates |
| US20140315386A1 (en) * | 2013-04-19 | 2014-10-23 | Air Products And Chemicals, Inc. | Metal Compound Coated Colloidal Particles Process for Making and Use Therefor |
-
2014
- 2014-12-22 CN CN201410808839.8A patent/CN104513627B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN104513627A (en) | 2015-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104513627B (en) | A kind of integrated circuit copper CMP composition and preparation method thereof | |
| CN101490192B (en) | Polishing slurry for low dielectric material | |
| US11104825B2 (en) | Metal compound chemically anchored colloidal particles and methods of production and use thereof | |
| US7842193B2 (en) | Polishing liquid | |
| TWI343944B (en) | Cmp slurry, preparation method thereof and method of polishing substrate using the same | |
| CN100569882C (en) | The slurry and the method that are used for the chemical-mechanical planarization of copper | |
| CN101076575B (en) | Polishing solution | |
| JP5516734B2 (en) | Polishing liquid for polishing copper and polishing method using the same | |
| KR100928456B1 (en) | Chemical mechanical polishing slurry composition including non-ionized, heat activated nano catalyst and polishing method using the same | |
| CN102585706A (en) | Acidic chemical and mechanical polishing composition | |
| CN102372273B (en) | Silica sol with double grain diameters and preparation method thereof | |
| KR20130066561A (en) | Chemical planarization of copper wafer polishing | |
| JP2008501240A (en) | Electrochemical-mechanical polishing composition and method of using the same | |
| TW200804575A (en) | Metal polishing composition and chemical mechanical polishing method using the same | |
| KR20080042748A (en) | Polishing liquid | |
| TW200927901A (en) | A method for chemically-mechanically polishing patterned surfaces composed of metallic and nonmetallic patterned regions | |
| JP2005045229A (en) | Water dispersion for chemical mechanical polishing and chemical mechanical polishing method | |
| TWI399428B (en) | Cmp polishing agent and method of polishing substrate using the same | |
| CN108250234A (en) | A kind of synthesis technology of phosphate ester surfactants and its application | |
| TWI250202B (en) | Process and slurry for chemical mechanical polishing | |
| CN102051126B (en) | Polishing solution for tungsten chemical mechanical polishing | |
| CN108250976A (en) | A kind of chemical mechanical polishing liquid | |
| TW558751B (en) | Selective electroless deposition and interconnects made therefrom | |
| CN1170909C (en) | Chemical mechanical plane of metal wiring | |
| KR20100077814A (en) | Cmp slurry composition for polishing metal wiring and polishing method using the same |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20170405 Termination date: 20191222 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |