CN101928520B - Grinding composite for planarization metal layer - Google Patents
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- CN101928520B CN101928520B CN200910147773.1A CN200910147773A CN101928520B CN 101928520 B CN101928520 B CN 101928520B CN 200910147773 A CN200910147773 A CN 200910147773A CN 101928520 B CN101928520 B CN 101928520B
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Abstract
The invention discloses a grinding composite for planarization metal layer. The grinding composite at least comprises 7,500ppm to less than 5,000ppm by weight of gridding granules, hydrogen peroxide, accelerator, co-corrosion inhibitor and water, wherein the co-corrosion inhibitor comprises a first corrosion inhibitor and a second corrosion inhibitor, and the co-corrosion inhibitor is applied to the planarization metal layer. The composite is capable of maintaining a high grinding removing rate for the metal layer and inhibiting metallic etching; moreover, the composite is capable of reducing gridding deficiencies including dish down, abrasion and the like.
Description
Technical field
The present invention is about a kind of grinding composite for planarization metal layer, and object is providing a kind of grinding composite for chemical machinery, can improve the planarization effect of processing object.
Background technology
Along with the critical size (Critical Dimension) of electronic package is more and more little and the rapid increase of the wire number of plies, resistance/capacitance time lag (RC Time Delay) will have a strong impact on the operating speed of integrated circuit.In order to improve along with metal inline line width is dwindled caused time lag and electronic migration integrity problem, so select the copper conductor material that resistivity is low and anti-electronic migration destructiveness is high, replace Al-alloy metal.Yet, because having, copper metal is difficult for etched characteristic, and must change and adopt another kind (Damascene) mode of inlaying and form copper plain conductor.
Inlaying (Damascene) mode processing procedure is different from tradition and first defines metal pattern and with dielectric layer, fill out the metallization process of ditch again, its method is first in a smooth dielectric, to etch after the groove of metal wire, again metal level is inserted, finally unnecessary metal is removed, and obtain one, there is the flat structures of damascene in dielectric layer.Inserted processing procedure has the following advantages compared with traditional metallization process: (1) can make substrate surface keep at any time smooth; (2) can get rid of the shortcoming that conventional process dielectric material is difficult for inserting plain conductor gap: (3) can solve the etching of metal layered material difficult problem, the particularly etching of copper metal.
In addition, for overcoming contact hole structure in the processing procedure of traditional interconnect, need make respectively with wire pattern, make the extremely complicated shortcoming of whole fabrication steps, separately develop at present a kind of dual damascene (dual damascene) processing procedure, its making processes is to carry out selective etch twice, after respectively wire dielectric substance (line dielectric) and interlayer dielectric substance (via dielectric) erosion being opened, once finish the barrier layer of metal level and connector, and once conducting metal is inserted to interlayer hole and interconnect groove, reach the effect of simplifying fabrication steps.In recent years, for the development of matable assembly size downsizing and the demand that improves assembly operation speed, the copper metal with low resistance constant and high electron mobility impedance, is used to the material as metal interconnect gradually, replaces aluminum metal processing procedure technology in the past.The inserted interconnect technology of copper metal, not only can reach the downsizing of interconnect and can reduce RC time lag, has also solved the difficult problem of metallic copper etching simultaneously, has therefore become the main development trend of multiple interconnect now.
Be no matter singly to inlay or the copper wiring of dual damascene, after the filling that completes copper metal, all need to carry out planarization processing procedure, with by metal removal unnecessary on dielectric layer.At present, conventionally by cmp processing procedure, reach this object.Yet, in the technology of metallochemistry mechanical mill, at layer on surface of metal, still usually there is metal stamper and fall into the grinding defects such as (Dishing) and abrasion (Erosion).
Metal stamper falls into and abrasion phenomenon has great relation with grinding rate and etching than (RR/DER), lower etch-rate can guarantee that pattern recess clearance is low, effectively suppress by this dish and fall into defect, but considering that under the quantum of output of unit time, grinding rate also needs to be maintained at tolerance interval; In addition, grinding uniformity coefficient also has certain influence to smooth result, and poor uniformity coefficient needs more milling time that copper is completely worn, thereby causes more serious metal stamper to fall into and abrasion phenomenon.
For the unit's of taking into account quantum of output and suppress that metal stamper falls into and abrasion phenomenon, conventionally by copper-cmp processing procedure, be divided into two steps.First stage removes most copper with grinding rate faster, to increase unit quantum of output.Subordinate phase, with the worn remaining a small amount of copper of slower grinding rate, is used the phenomenon of avoiding the copper in groove to cause excessive abrasion.Conventionally, the copper of two-stage grinds processing procedure, needs to change the different grinding composites that form, and to meet the copper of different steps, grinds demand.Yet, not only change grinding composite and be unfavorable for simplifying processing procedure, also may cause the increase of waste material.
The grinding composite that US publication discloses for No. 2008/0254629 includes: Amino acid, the about 5ppm of weighing scale be to abrasive particle, triazole compounds and water lower than 700ppm, this grinding composite copper with respect to the removal selectivity on blocking layer on over 50: 1; And No. 2004/0020135 patent document of the U.S. discloses the copper metal grinding constituent that comprises silicon-dioxide, oxygenant, Amino acid, triazole compounds and water; Moreover, United States Patent (USP) the 6th, 440, No. 186 patents also disclose a kind of grinding composite and include: abrasive particle, protective film binder and a hydrogen peroxide, this Abrasive Particle Size size is 50～120nm, and accounts for 0.5～5 % by weight (wt%) of grinding composite gross weight; In addition, United States Patent (USP) the 6th, 679, No. 929 patents also disclose a kind of grinding composite and include: abrasive particle, have at least 10 carbon aliphatic carboxylic acid, be selected from alkaline matter accelerator, corrosion inhibitor, hydrogen peroxide and the water of ammonium hydroxide etc.Yet above-mentioned each patent does not disclose uses common inhibitor, can, maintaining under the condition of high grinding clearance, slow down grinding composite for the etch-rate of metal, and be applicable to the copper metal grinding in first and second stage simultaneously.
Summary of the invention
Main purpose of the present invention is providing a kind of grinding composite for planarization metal layer, can improve the planarization effect of processing object.
Another object of the present invention is to provide a kind of grinding composite that is simultaneously applicable to two-stage metal grinding.
For on reaching, take off object, grinding composite of the present invention at least includes the about 750ppm of weighing scale to the abrasive particle lower than 5000ppm, hydrogen peroxide, accelerator, common corrosion inhibitor and water, wherein, this common corrosion inhibitor includes first, second corrosion inhibitor, this common corrosion inhibitor is applied in planarization metal layer, can when maintaining the height grinding clearance of metal level, have the characteristic of inhibition metal etch concurrently, can reduce dish and fall into and the grinding such as abrasion defect.
Accompanying drawing explanation
Fig. 1 is wear particle concentration and grinding clearance graph of a relation;
Fig. 2 is that the abrasive particle that particle diameter is larger has the linear performance figure that slope is larger;
Fig. 3 is the sunken result figure of the concentration of abrasive particle and metal stamper.
Embodiment
Feature of the present invention, can consult the detailed description of the graphic and embodiment of this case and obtain and be well understood to.
The present invention is for the grinding composite of planarization metal layer; this grinding composite at least includes: the about 750ppm of weighing scale is to the abrasive particle lower than 5000ppm, hydrogen peroxide, accelerator, common corrosion inhibitor and water; wherein; this common corrosion inhibitor includes first, second corrosion inhibitor; and this common corrosion inhibitor is for planarization metal layer; can when cmp, form layer protecting film in the surface in processing object; to avoid processing object to be subject to excessive corrosion, can improve the inhibition corrosive power of processing object.
The about 750ppm of weighing scale of this abrasive particle is extremely lower than 5000ppm, and with 1000ppm to lower than 3000ppm for better, and the particle diameter of this abrasive particle is less than 90nm (wherein to be less than 50nm for better), and the example of this abrasive particle comprises, but the non-silicon-dioxide that is limited to calcination; The silicon dioxide gel forming from the hydrolysis of water glass or potassium silicate or silane hydrolyzate and condensation; The aluminium dioxide of precipitation or calcination; The titanium dioxide of precipitation or calcination; Macromolecular material; And metal oxide and macromolecular material mixture (hybrid).Preferably is silicon dioxide gel.If abrasive particle consumption is too low, be unfavorable for mechanical mill, cannot reach desired grinding clearance; On the other hand, if the too high effect of can acceleration mechanical grinding of abrasive particle consumption increases the clearance of barrier layer and insulating oxide, also easily produce the grinding defect of surface abrasion.
This oxygenant accounts for 0.25 to 5 % by weight of constituent gross weight; And for the example of the accelerator of this grinding composite, comprise, but non-be limited to citric acid, oxalic acid, tartrate, histidine, Beta Alanine or glycine with and ammonium salt, sodium salt, sylvite or lithium salts.This accelerator is used for promoting metal to be ground, for example the dissolving of copper.Improve the accelerator addition in grinding composite, contribute to promote the grinding clearance of metal level, the metal level that is applicable to the first stage grinds.Yet, improve the accelerator addition in grinding composite, also can increase static etched speed simultaneously, be unfavorable for the fine ground of subordinate phase.In a specific examples, this accelerator accounts for 0.01 to 5 % by weight of constituent gross weight.
This common corrosion inhibitor grinds under the condition of clearance at height, effectively suppresses static etch rate, and to be applicable to the grinding light processing procedure of first stage and subordinate phase, the first corrosion inhibitor of the present invention is selected from 1-H-benzotriazole, N-anilide musculamine acid (N-acyl sarcosine), alkyl-sulphate (Alkyl sulfate) or alkylsulfonate (Alkyl sulfonate), and this second corrosion inhibitor is selected from 1,2,3-triazoles, 1,2,4-triazole, tolytriazole (totyltriazole), 5-amido tetrazolium (5-amino tertraazole), 3-amido-1, and 2,4-triazole (3-Amino-1,2,4-triazole), 4-amido-4H-1,2,4 ,-triazole (4-Amino-4H-1,2,4-triazole), 3-nitro-1, and 2,4-triazole (3-Nitro-1,2,4-triazole), 3-sulfydryl-1, and 2,4-triazole (3-Mercapto-1,2,4-triazole), 1H-1, and 2,3-triazole-1-ethanol (1H-1,2,3TRIAZOLE-1-ETHANOL), benzoglyoxaline (benzimidazole), imidazoles (imidazole), pyrroles (Pyrrole), pyrroline (Pyrroline), oxazole (Oxazole), isoxzzole (Isoxazole), indazole (INDAZOLE) or indolizine (INDOLIZINE), and this common corrosion inhibitor accounts for 0.001 to 1 % by weight of constituent gross weight.
By particular specific embodiment, further illustrate feature of the present invention and effect below, but non-for limiting category of the present invention.
embodiment 1-5
Listed according to table 1, use and comprise silicon dioxide gel abrasive particle, glycine, hydrogen peroxide, 1-H-benzotriazole (BTA), 1,2, the ground slurry constituent of 4-triazole and water is implemented sample and is tested.
Table 1
Grinding test carries out according to following condition.
Grinder station: Mirra polisher (Applied Materials)
Type of wafer: 8 ", 15KA Copper blanket wafer (Ramco Co)
Grind overdraft: 3,1.5 and 0psi
Platform rotating speed: 93rpm
Carrier rotating speed: 87rpm
Grinding pad: IC1010 (Rohm Hass Electronic Materials)
Grind slurry flow velocity: 150ml/min.
This wafer use 4 point probes measure to grind before and after the thickness of copper films with computation rate, its result is as table 2:
Table 2
Wherein, this RR refers to grind clearance (Removal Rate), and DER refers to dynamic etch rate (Dynamic etching rate), i.e. clearance under 0psi.
Known according to table 2 result, this embodiment 1,2 can illustrate the effect of common corrosion inhibitor, wherein embodiment 2 is used common corrosion inhibitor, this result shows that it has higher RR/DER value, and BTA in this common corrosion inhibitor is for grinding the function of removal mechanisms at work coarse regulation, 1,2,4-triazole is for the function of fine adjustment; And in embodiment 4,5, accelerator content is more, grind clearance higher, but dynamic etch rate also can with rising, need to adjust inhibitor as control, therefore optimal grinding composite must average out grinding between clearance and RR/DER value.
embodiment 5-6
Listed according to table 3, use and comprise silicon dioxide gel abrasive particle, glycine, hydrogen peroxide, 1-H-benzotriazole (BTA), 1,2, the ground slurry constituent of 4-triazole and water is implemented sample and is tested.
Table 3
Grinding test carries out according to following condition, and its result is embedded in table 4.
Type of wafer: MIT854patterned wafer (Ramco Co)
Grind overdraft: 3psi
Platform rotating speed: 93rpm
Carrier rotating speed: 87rpm
Grind slurry flow velocity: 150ml/min.
The sunken degree of each measured place metal stamper after utilizing HRP220profiler (KLA-Tenco) instrument measure to grind, the copper cash of 100x100 micron of take during measurement is measurement point, measures the crystal grain outcome record of the center of circle, stage casing and edge of wafer in table 4:
Table 4
It is to carry out 30% over-mastication (over-polished) after end point that these metal stampers fall into value again, known according to table 4 result, these numerical value all lower than
(Angstrom).For wafer process, this is the surface profile (Topographies) that has practicality.The effect of the constituent tool excellence that this case is developed and verified can be for use as being the CMP of wafer process.
embodiment 7-13
Listed according to table 5, use and comprise silicon dioxide gel abrasive particle, glycine, hydrogen peroxide, benzotriazole, 1,2, the grinding composite control sample of 4-triazole and water is tested.
Table 5
Each embodiment of table 5 is on the grinder station of Mirra polisher (Applied Materials), and carry out grinding test according to condition listed in embodiment 1-5, the wafer grinding has Cu, Ta and TaN Blanket wafers, and its result is as table 6, and Fig. 1:
Table 6
Known according to table 6 result, this wear particle concentration is higher, and copper grinding clearance is higher, and this phenomenon is more obvious in Abrasive Particle Size the greater; And arrive after certain content when wear particle concentration, this grinding clearance can reach the region that maintains an equal level and no longer raise, and the particle diameter abrasive particle less than particle diameter compared with conference comparatively fast reaches this fair region.This result demonstration, the lifting of reaching clearance via silica concentration will meet with limitation; No matter use the silicon-dioxide of small particle size or large particle diameter at this on the one hand equal indifference.Because the concentration of silicon-dioxide has its restriction in the lifting of clearance, so can choose suitably effectively concentration range in application.
embodiment 8-11
Listed according to table 7, use embodiment 8 and embodiment 11 to grind under overdraft and carry out in difference.
Table 7
Each embodiment of table 7 is on the grinder station of Mirra polisher (Applied Materials), and according to condition listed in embodiment 1-5, and wherein grind overdraft (Df) be respectively 1.5,2 and 3psi carry out grinding test, and use 4 point probes to measure, its result is as table 8, and Fig. 2:
Table 8
Known according to table 8 result, grinding overdraft, be under 3psi condition, the abrasive particle of particle diameter large (87nm) has higher copper and grinds clearance, grinding overdraft, be under 1.5psi condition, the abrasive particle of particle diameter little (32nm) has higher copper and grinds clearance, Fig. 2 shows that the abrasive particle that this particle diameter is larger has the linearity performance that slope is larger, and the abrasive particle that particle diameter is larger grinds under overdraft condition more effective in height; Yet, in advanced Cu CMP processing procedure, under high overdraft, there is a shortcoming, that is can cause damage and can produce defect (defects) for low k value material.So avoiding using as far as possible, most of cmp processing procedure is greater than the grinding overdraft of 2.5psi, therefore be necessary the particle diameter of abrasive particle to be limited to less scope in cmp processing procedure.
Listed according to table 7, utilize equally 11 pairs of patterned wafers of embodiment 8 and embodiment (type is MIT854) to grind under identical parameters condition.Patterned wafer is after end point, to carry out 30% over-mastication (over-polished) again, and the copper cash of 100x100 micron of take during measurement is measurement point, measures the sunken outcome record of the crystal grain place metal stamper of the center of circle, stage casing and edge of wafer in table 9:
Table 9
Although showing the abrasive particle of greater particle size, result can provide the high clearance (shorter milling time) that grinds, but with the grinding defects such as metal stamper falls into that but make of coming more worsen, so be comparatively favourable compared with the abrasive particle of small particle size in cmp processing procedure.
embodiment 14-17
Listed according to table 10, use and comprise silicon dioxide gel abrasive particle, glycine, hydrogen peroxide, benzotriazole, 1,2, the grinding composite of 4-triazole and water is implemented sample and is tested.
Table 10
Each embodiment of table 10 grinds in the grinder station of Mirra polisher (Applied Materials) and to code-pattern copper wafer (Blanket Cu wafers) and patterned wafer (type is MIT854), wherein, this grind clearance and grind after the sunken outcome record such as mean value of the center of circle, stage casing and each measured place metal stamper of edge crystal grain of wafer in table 11 and Fig. 3:
Table 11
| Silicon dioxide gel (ppm) | Cu RR@3psi (A/min) | The mean value (A) that metal stamper is sunken | |
| Embodiment 14 | 1000 | 6468 | 710 |
| Embodiment 15 | 5000 | 7312 | 1277 |
| Embodiment 16 | 10500 | 7659 | 1840 |
| Embodiment 17 | 5000 | 7307 | 1213 |
Table 11 discloses this and grinds clearance slowly lifting along with the increase of wear particle concentration, but this increasing degree is very small, for instance, comparing embodiment 14 and 16, this grinding clearance only increases by 18%, but needs the concentration that increase more than surpassing 10 times just to be reached.And in Fig. 3, can obviously learn that the concentration of abrasive particle can affect the sunken result of metal stamper really, and that is abrasive particle more (concentration is higher), metal stamper the grinding defect such as falls into and more worsens.For guaranteeing that metal stamper falls into, be controlled in acceptable degree, wear particle concentration certainly will be confined to certain limit.
Technology contents of the present invention and technical characterstic disclose as above, yet the personage who is familiar with the technology still may do various replacement and the modifications that do not deviate from this case invention spirit based on announcement of the present invention.Therefore, protection scope of the present invention should be not limited to those disclosed embodiments, and should comprise various do not deviate from replacement of the present invention and modifications, and is contained by following claim.
Claims (9)
1. at two-stage copper metallization, learn a grinding composite that is simultaneously applicable to the copper metal planarization in first and second stage in grinding processing procedure, this grinding composite is comprised of following composition:
Abrasive particle, the weighing scale 750ppm of this abrasive particle is extremely lower than 5000ppm;
Hydrogen peroxide;
Accelerator, be selected from citric acid, oxalic acid, tartrate, histidine, Beta Alanine, glycine with and cohort that ammonium salt, sodium salt, sylvite or lithium salts were formed;
Common corrosion inhibitor, this common corrosion inhibitor is by first, the second corrosion inhibitor forms, wherein this first corrosion inhibitor is selected from 1-H-benzotriazole, the acid of N-anilide musculamine, the cohort that alkyl-sulphate or alkylsulfonate form, and this second corrosion inhibitor is selected from 1, 2, 3-triazole, 1, 2, 4-triazole, tolytriazole, 5-amido tetrazolium, 3-amido-1, 2, 4-triazole, 4-amido-4H-1, 2, 4,-triazole, 3-nitro-1, 2, 4-triazole, 3-sulfydryl-1, 2, 4-triazole, 1H-1, 2, 3-triazole-1-ethanol, benzoglyoxaline, imidazoles, pyrroles, pyrroline, oxazole, isoxzzole, indazole or indolizine, and
Water.
2. a kind of grinding composite that is simultaneously applicable to the copper metal planarization in first and second stage in two-stage copper metallization learn to grind processing procedure as claimed in claim 1, wherein the weight of this abrasive particle is 1000ppm to lower than 3000ppm.
3. a kind of grinding composite that is simultaneously applicable to the copper metal planarization in first and second stage in two-stage copper metallization learn to grind processing procedure as claimed in claim 1, wherein the particle diameter of this abrasive particle is less than 90nm.
4. a kind of grinding composite that is simultaneously applicable to the copper metal planarization in first and second stage in two-stage copper metallization learn to grind processing procedure as claimed in claim 1, wherein the particle diameter of this abrasive particle is less than 50nm.
5. a kind of grinding composite that is simultaneously applicable to the copper metal planarization in first and second stage in two-stage copper metallization learn to grind processing procedure as claimed in claim 1, wherein this abrasive particle is selected from the silicon-dioxide of calcination; The silicon dioxide gel forming from the hydrolysis of water glass or potassium silicate or silane hydrolyzate and condensation; The aluminium dioxide of precipitation or calcination; The titanium dioxide of precipitation or calcination; Macromolecular material; The cohort that metal oxide and macromolecular material mixture form.
6. a kind of grinding composite that is simultaneously applicable to the copper metal planarization in first and second stage in two-stage copper metallization learn to grind processing procedure as claimed in claim 1, wherein this abrasive particle is silicon dioxide gel.
7. a kind of grinding composite that is simultaneously applicable to the copper metal planarization in first and second stage in two-stage copper metallization learn to grind processing procedure as claimed in claim 1, wherein this hydrogen peroxide accounts for 0.25 to 5 % by weight of constituent gross weight.
8. a kind of grinding composite that is simultaneously applicable to the copper metal planarization in first and second stage in two-stage copper metallization learn to grind processing procedure as claimed in claim 1, wherein this accelerator accounts for 0.01 to 5 % by weight of constituent gross weight.
9. a kind of grinding composite that is simultaneously applicable to the copper metal planarization in first and second stage in two-stage copper metallization learn to grind processing procedure as claimed in claim 1, wherein this common corrosion inhibitor accounts for 0.001 to 1 % by weight of constituent gross weight.
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| WO2012096931A2 (en) * | 2011-01-11 | 2012-07-19 | Cabot Microelectronics Corporation | Metal-passivating cmp compositions and methods |
| CA2932347C (en) * | 2013-12-02 | 2023-02-14 | Ecolab Usa Inc. | Tetrazole based corrosion inhibitors |
| CN104745086A (en) * | 2013-12-25 | 2015-07-01 | 安集微电子（上海）有限公司 | Chemical mechanical polishing solution for barrier layer planarization, and use method thereof |
| US9735030B2 (en) | 2014-09-05 | 2017-08-15 | Fujifilm Planar Solutions, LLC | Polishing compositions and methods for polishing cobalt films |
| CN109971353B (en) * | 2017-12-27 | 2021-12-07 | 安集微电子（上海）有限公司 | Chemical mechanical polishing solution |
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