CN101358125B - Slurry products of concentrating chemical-mechanical planarization and method of use thereof - Google Patents
Slurry products of concentrating chemical-mechanical planarization and method of use thereof Download PDFInfo
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- CN101358125B CN101358125B CN 200710044585 CN200710044585A CN101358125B CN 101358125 B CN101358125 B CN 101358125B CN 200710044585 CN200710044585 CN 200710044585 CN 200710044585 A CN200710044585 A CN 200710044585A CN 101358125 B CN101358125 B CN 101358125B
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Abstract
The present invention discloses a concentrated slurry product for chemical-mechanical planarization and a use method thereof. In the product, the concentrated ingredients affecting other ingredients are independently packaged. The use method is as follows: given that the concentrated slurry product for chemical-mechanical planarization has n independently packaged parts, the concentration multiples of the parts are A1, A2...An in order; when the product needs to be used, the parts are diluted and mixed according to the following proportion: concentrated part 1 : concentrated part 2 :-: concentrated part n : deionized water equal to (1/A1) : (1/A2) :-: (1/An) : (1-1/A1-1A2-1/A2). The concentrated slurry product for chemical-mechanical planarization can increase the concentration ratio, the service life of the concentrated slurry product for chemical-mechanical planarization is greatly prolonged, the bottle neck problem of the prior art preparing concentrated slurry for chemical-mechanical planarization is resolved, and cost in product manufacturing, transportation, storage, etc. is greatly reduced, so the concentrated slurry product for chemical-mechanical planarization has high economic value.
Description
Technical field
The present invention relates to a kind of chemical-mechanical planarization slurry products and using method thereof, be specifically related to a kind of slurry products of concentrating chemical-mechanical planarization and using method thereof.
Background technology
Development along with microelectronics, the very large scale integration chip integration has reached tens components and parts, characteristic dimension has entered nano level, this just requires hundreds of procedure, especially multilayer wiring, substrate, medium in the microelectronic technique must pass through chemical-mechanical planarization (CMP).The chemical-mechanical planarization slurry can optionally promote the removal of particular semiconductor surfacing, conventional chemical-mechanical planarization slurry comprises abrasive grains and various chemical additive, grinding rate elevator for example, corrosion inhibitor, oxygenant, acidity-basicity regulator etc. and carrier.Usually, can account for the 70-80% of gross weight in the chemical-mechanical planarization slurry as the water of carrier, in addition higher, and almost each user side has all had deionized water with low cost.Therefore, this is obviously unreasonable on cost.Thereby the preparation of concentrating chemical-mechanical planarization slurry receives the concern of industry day by day.At present, in the preparation of concentrating chemical-mechanical planarization slurry and the use thereof, have a bottleneck problem of bringing a lot of puzzlements: some compositions in the slurry may influence concentrating of other compositions, especially abrasive grains may have compound action with some chemical additives, makes that the concentrated ratio that concentrates slurry receives greatly to limit and reduce greatly work-ing life.And, for which composition influence concentrates in the slurry be concentrating of other compositions actually, need the analysis and research of great deal of experiment data.The report that this respect is not arranged at present, as yet.Therefore, in the long run, this problem needs to be resolved hurrily.
Summary of the invention
Technical problem to be solved by this invention is: in the prior art, because between each composition interaction being arranged in the concentrating chemical-mechanical planarization slurry, influence concentrating each other each other makes the concentrated ratio that concentrates slurry receive restriction greatly and reduces greatly work-ing life; And actually be that concentrating of which other composition of composition influence do not have report at present as yet for concentrating in the slurry, and also non-this area result that can run away with.For overcoming the problems referred to above, the invention provides a kind of slurry products of concentrating chemical-mechanical planarization and using method thereof.
In the slurry products of concentrating chemical-mechanical planarization of the present invention, influence other compositions and concentrate, perhaps be subject to other concentration components influences, perhaps unsettled composition is independent packing under enrichment stage.
Wherein, described influence composition that other compositions concentrate preferable be: under the condition of concentrating, the absolute value of the Z current potential that concentrates abrasive grains is reduced to is less than or equal to 5 millivolts chemical additive; Perhaps can make concentrate abrasive grains median size within 40-45 ℃ of next week increasing amount more than or equal to 100% chemical additive.Because the Z current potential is the charged parameter of expression particle surface, the absolute value of Z current potential is less than or equal to 5 millivolts and shows the basic neutral of particle surface, and particle just may be assembled; The remarkable increase of the median size of particle then is the significant signal that particle has been assembled.Describedly be subject to the influence of other concentration components and be oxygenant, as hydrogen peroxide etc.
Preferable example of the present invention is: this slurry products of concentrating chemical-mechanical planarization comprises the part of two independent packing: the abrasive grains that concentrating part 1. concentrates; The chemical additive that concentrating part 2. concentrates.Concrete preferred embodiments is: concentrating part 1 contains colloidal state aluminium sesquioxide particle; Concentrating part 2 contains glycine, the amino tetrazole of 5-and pH regulator agent.Wherein concentrating part 2 also can contain one or more in this area conventional surfactant, stablizer and the disinfectant.
Another preferable example of the present invention is: this slurry products of concentrating chemical-mechanical planarization comprises the part of two independent packing: concentrating part 1. abrasive grains and the enriched mixture that is beneficial to or does not influence the concentrated chemical additive of abrasive grains; Concentrating part 2. influences the chemical additive that abrasive grains concentrated or be subject to other concentration components influences.Concrete preferred embodiments is: concentrating part 1. colloidal silica particles, benzo nitrogen azoles and pH regulator agent; Concentrating part 2. polyamino polyether base tetramethylene phosphonic acids.Another concrete preferred embodiments is: concentrating part 1. colloidal silica particles, 2-phosphonic acids butane group-1,2,4-tricarboxylic acid, benzo nitrogen azoles and pH regulator agent; Described concentrating part 2. hydrogen peroxide.Wherein concentrating part 1 also can contain one or more in this area conventional surfactant, stablizer and the disinfectant.
One of the present invention comprises that the preferred embodiments of independent portioning section more than two is: concentrating part 1 contains colloidal silica particle; Concentrating part 2 contains 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, the amino tetrazole of 5-and pH regulator agent; Concentrating part 3 contains hydrogen peroxide.Wherein concentrating part 2 also can contain one or more in this area conventional surfactant, stablizer and the disinfectant.
The present invention further also relates to the using method of slurry products of concentrating chemical-mechanical planarization of the present invention, and its concrete steps are: establish total n the independent portioning section of described slurry products of concentrating chemical-mechanical planarization, the cycles of concentration of each part is followed successively by A
1, A
2A
nCarry out diluted mixture in following ratio during use: concentrating part 1: concentrating part 2: ... concentrating part n: deionized water=(1/A
1): (1/A
2): ...: (1/A
n): (1-1/A
1-1/A
2-...-1/A
2), can make the concentrating chemical-mechanical planarization slurry.
The using method of two preferable examples of the present invention is: the cycles of concentration of establishing described concentrating part 1 is A, and the cycles of concentration of described concentrating part 2 is B; Carry out diluted mixture in following ratio during use: concentrating part 1: concentrating part 2: deionized water=(1/A): (1/B): (1-1/A-1/B), can make the concentrating chemical-mechanical planarization slurry.
Agents useful for same of the present invention and raw material be commercially available getting all.
Positive progressive effect of the present invention is: compared with prior art, slurry products of concentrating chemical-mechanical planarization of the present invention can improve concentration ratio, and prolonged work-ing life of concentrating chemical-mechanical planarization slurry greatly, overcome the bottleneck problem of prior art in preparation concentrating chemical-mechanical planarization slurry, greatly reduce manufacturing, transportation such as stocks at the aspect cost.Especially through a large amount of experimental analysis research, the present invention drawn several classes concrete influence the composition that other composition concentrates, and provide several classes preferable slurry products of concentrating chemical-mechanical planarization example.
Embodiment
Mode below by embodiment further specifies the present invention, but does not therefore limit the present invention among the described scope of embodiments.Each percentage composition is mass percent among the embodiment.
Embodiment 1
Slurry products of concentrating chemical-mechanical planarization, it comprises the part of two independent packing: the abrasive grains that concentrating part 1. concentrates, cycles of concentration is 5; The chemical additive that concentrating part 2. concentrates, cycles of concentration is 8.
Specifically, the abrasive grains that concentrates is colloidal state aluminium sesquioxide particle, and concentration is 25%, and cycles of concentration is 5 times; The chemical additive that concentrates comprises 6% glycine, the amino tetrazole of 0.8%5-, and 0.02% potassium hydroxide (pH regulator agent), 1600ppm polyacrylic acid (tensio-active agent), 400ppm isothiazolinone (disinfectant), cycles of concentration is 8 times.Carry out diluted mixture in following ratio during use: concentrating part 1: concentrating part 2: deionized water=(1/5): (1/8): (1-1/5-1/8), can make spendable chemical-mechanical planarization slurry.Final slurry after dilution prescription is 5% colloidal state aluminium sesquioxide particle, 0.75% glycine, the amino tetrazole of 0.1%5-, 0.0025% potassium hydroxide, 200ppm polyacrylic acid and 50ppm isothiazolinone, pH=5.0.
In this concentrated sample, the amino tetrazole of the glycine of high density and 5-makes the median size that concentrates colloidal state aluminium sesquioxide particle increase by 100% within (40-45 ℃) week in baking oven.This shows that abrasive grains obviously assembles, and the stability that concentrates colloidal state aluminium sesquioxide particle is subjected to very big influence.So, these two kinds of chemical additives are separated with abrasive grains, thereby improve spendable concentration ratio, prolong the work-ing life of concentrating sample, and saved manufacturing, transportation such as stocks at the cost of aspect, has improved economic benefit.
Embodiment 2
Slurry products of concentrating chemical-mechanical planarization comprises the part of two independent packing: concentrating part 1. abrasive grains and the enriched mixture that is beneficial to or does not influence the concentrated chemical additive of abrasive grains, and cycles of concentration is 6; Concentrating part 2. influences the enriched material of the concentrated chemical additive of abrasive grains, and cycles of concentration is 25.
Specifically, concentrating part 1 comprises that concentration is 30% colloidal silica particle, 0.6% benzo nitrogen azoles, 0.05% potassium hydroxide (pH regulator agent), 1200ppm polyacrylic acid (tensio-active agent), 1200ppm quadrol tetramethyl subunit phosphonic acids (stablizer) and 300ppm isothiazolinone (disinfectant), cycles of concentration is 6 times; The chemical additive that concentrates comprises 50% polyamino polyether base tetramethylene phosphonic acid, and cycles of concentration is 25 times.Carry out diluted mixture in following ratio during use: concentrating part 1: concentrating part 2: deionized water=(1/6): (1/25): (1-1/6-1/25), can make spendable chemical-mechanical planarization slurry.Final slurry after dilution prescription is 5% colloidal silica particle, 2% polyamino polyether base tetramethylene phosphonic acid, 0.1% benzo nitrogen azoles, 0.0083% potassium hydroxide, 200ppm polyacrylic acid, 200ppm quadrol tetramethyl subunit phosphonic acids and 50ppm isothiazolinone, pH=2.5.
In this concentrated sample, because the polyamino polyether base tetramethylene phosphonic acid of high density makes the absolute value of the Z current potential that concentrates colloidal silica particle reduce to 5 millivolts.The basic neutral of this surface grinding particle surface, the stability that concentrates colloidal silica particle is subjected to very big influence.Benzo nitrogen azoles then has no significant effect the stability that concentrates colloidal silica particle.So polyamino polyether base tetramethylene phosphonic acid is separated with other compositions, improved spendable concentration ratio greatly, improve the work-ing life of concentrating sample, saved manufacturing, transportation such as stocks at the cost of aspect, has improved economic benefit.
Embodiment 3
Slurry products of concentrating chemical-mechanical planarization comprises the part of two independent packing: concentrating part 1. abrasive grains and the enriched mixture that is beneficial to or does not influence the concentrated chemical additive of abrasive grains, and cycles of concentration is 6; Concentrating part 2. is subject to the enriched material that other concentration components influence chemical additive, and cycles of concentration is 10.
Specifically, concentrating part 1 comprises that concentration is 30% colloidal silica particle, 1.2%2-phosphonic acids butane group-1,2,4-tricarboxylic acid, 0.6% benzo nitrogen azoles, 0.05% potassium hydroxide (pH regulator agent), 1200ppm polyacrylic acid (tensio-active agent), 1200ppm quadrol tetramethyl subunit phosphonic acids (stablizer), 300ppm isothiazolinone (disinfectant), cycles of concentration are 6 times; The enriched material that is subject to the chemical additive of other concentration components influences is concentration 30% hydrogen peroxide, and cycles of concentration is 10 times.Carry out diluted mixture in following ratio during use: concentrating part 1: concentrating part 2: deionized water=(1/6): (1/10): (1-1/6-1/10), can make spendable chemical-mechanical planarization slurry.Final slurry after dilution prescription is 5% colloidal silica particle, 0.2%2-phosphonic acids butane group-1,2,4-tricarboxylic acid, 0.1% benzo nitrogen azoles, 0.0083% potassium hydroxide, 200ppm polyacrylic acid, 200ppm quadrol tetramethyl subunit phosphonic acids, 50ppm isothiazolinone and 3% hydrogen peroxide, pH=3.0.
In this concentrated sample, because other material has no significant effect the stability that concentrates colloidal silica particle, and the hydrogen peroxide that concentrates is subject to other chemical additive influence, so with its independent packing, improved spendable concentration ratio, improved the work-ing life of concentrating sample, saved manufacturing, transportation such as stocks at the cost of aspect, has improved economic benefit.
Embodiment 4
Slurry products of concentrating chemical-mechanical planarization, it comprises the part of three independent packing: the abrasive grains that concentrating part 1. concentrates, cycles of concentration is 10; The chemical additive that concentrating part 2. concentrates, cycles of concentration is 10, the hydrogen peroxide 30% that concentrating part 3. concentrates, cycles of concentration is 6.
Specifically, the abrasive grains that concentrates is colloidal silica particle, and concentration is 20%, and cycles of concentration is 10 times; The chemical additive that concentrates comprises 5% 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, 3%1-hydrogen-tetrazole, 0.05% potassium hydroxide (pH regulator agent), 2000ppm polyacrylic acid (tensio-active agent), 2000ppm quadrol tetramethyl subunit phosphonic acids (stablizer) and 500ppm isothiazolinone (disinfectant), and cycles of concentration is 10 times; The hydrogen peroxide 30% that concentrating part 3. concentrates, cycles of concentration is 6.Carry out diluted mixture in following ratio during use: concentrating part 1: concentrating part 2: concentrating part 3: deionized water=(1/10): (1/10): (1/6): (1-1/10-1/10-1/6), can make spendable chemical-mechanical planarization slurry.Final slurry after dilution prescription is 2% colloidal silica particle, 0.5% 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, 0.3%1-hydrogen-tetrazole, 0.005% potassium hydroxide, 200ppm polyacrylic acid, 200ppm quadrol tetramethyl subunit phosphonic acids, 50ppm isothiazolinone and 5% hydrogen peroxide, pH=3.0.
In this concentrated sample, because it is bad to concentrate colloidal silica particle stability at pH=3.0, other chemical additive makes concentrated hydrogen peroxide decomposition easily simultaneously, we are separately independent respectively with abrasive grains, oxygenant and other chemical additives, have improved spendable concentration ratio greatly, improve the work-ing life of concentrating sample, saved manufacturing, transportation such as stocks at the cost of each side, has improved economic benefit.
Claims (4)
1. slurry products of concentrating chemical-mechanical planarization, it is characterized in that: this product is made up of the part of two independent packing:
Concentrating part 1: abrasive grains and the enriched mixture that is beneficial to or does not influence the concentrated chemical additive of abrasive grains;
Concentrating part 2: influence abrasive grains and concentrate, perhaps be subject to the chemical additive of other concentration components influences,
Wherein said concentrating part 1 contains colloidal silica particle, benzo nitrogen azoles and pH regulator agent; Described concentrating part 2 contains polyamino polyether base tetramethylene phosphonic acid; Perhaps
Described concentrating part 1 contains colloidal silica particle, 2-phosphonic acids butane group-1,2,4-tricarboxylic acid, benzo nitrogen azoles and pH regulator agent; Described concentrating part 2 contains hydrogen peroxide.
2. slurry products of concentrating chemical-mechanical planarization, it is characterized in that: this product comprises the part of three independent packing:
Concentrating part 1 contains: colloidal silica particle;
Concentrating part 2 contains: 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, the amino tetrazole of 5-, pH regulator agent;
Concentrating part 3 contains: hydrogen peroxide.
3. as each the described slurry products of concentrating chemical-mechanical planarization in claim 1 and 2, it is characterized in that: the described concentrating part 2 of claim 2, or concentrating part described in the claim 11 also contains in tensio-active agent, stablizer and the disinfectant one or more.
4. the using method of the slurry products of concentrating chemical-mechanical planarization described in claim 1, it is characterized in that: the cycles of concentration of establishing described concentrating part 1 is A, the cycles of concentration of described concentrating part 2 is B; Carry out diluted mixture in following ratio during use: concentrating part 1: concentrating part 2: deionized water=(1/A): (1/B): (1-1/A-1/B).
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| CN 200710044585 CN101358125B (en) | 2007-08-03 | 2007-08-03 | Slurry products of concentrating chemical-mechanical planarization and method of use thereof |
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| CN 200710044585 CN101358125B (en) | 2007-08-03 | 2007-08-03 | Slurry products of concentrating chemical-mechanical planarization and method of use thereof |
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| CN101358125B true CN101358125B (en) | 2013-07-10 |
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| US20180244955A1 (en) | 2017-02-28 | 2018-08-30 | Versum Materials Us, Llc | Chemical Mechanical Planarization of Films Comprising Elemental Silicon |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1639288A (en) * | 2002-02-22 | 2005-07-13 | 圣戈本陶瓷及塑料股份有限公司 | CMP formulations for the use on nickel-phosphorus alloys |
| CN1680508A (en) * | 2004-04-09 | 2005-10-12 | 上海月旭半导体科技有限公司 | Chemical mechanical grinder of semiconductor chips and formulation thereof |
| CN1854236A (en) * | 2005-04-21 | 2006-11-01 | 安集微电子（上海）有限公司 | Polished sizing material and its use |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1639288A (en) * | 2002-02-22 | 2005-07-13 | 圣戈本陶瓷及塑料股份有限公司 | CMP formulations for the use on nickel-phosphorus alloys |
| CN1680508A (en) * | 2004-04-09 | 2005-10-12 | 上海月旭半导体科技有限公司 | Chemical mechanical grinder of semiconductor chips and formulation thereof |
| CN1854236A (en) * | 2005-04-21 | 2006-11-01 | 安集微电子（上海）有限公司 | Polished sizing material and its use |
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