CN1930664A - Polishing agent and polishing method - Google Patents
Polishing agent and polishing method Download PDFInfo
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- CN1930664A CN1930664A CN 200580006988 CN200580006988A CN1930664A CN 1930664 A CN1930664 A CN 1930664A CN 200580006988 CN200580006988 CN 200580006988 CN 200580006988 A CN200580006988 A CN 200580006988A CN 1930664 A CN1930664 A CN 1930664A
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Abstract
To provide a polishing composition which has a high removal rate and enables to suppress occurrence of dishing and erosion, in polishing of a surface to be polished in the production of a semiconductor integrated circuit device. A chemical mechanical polishing composition for polishing a surface to be polished of semiconductor integrated circuit devices comprises (A) fine oxide particles, (B) pullulan, and (C) water. The polishing composition further contains (D) an oxidizing agent, and (E) a compound represented by the formula 1: wherein R is a hydrogen atom, a C 1-4 alkyl group, a C 1-4 alkoxy group or a carboxylic acid group.
Description
Technical field
The present invention relates to the grinding agent that in the manufacturing process of semiconductor device, uses.Relate in particular to use Cu be metal as wiring material, use tantalum be the grinding agent that is suitable for when forming the flush type metal line of metal and the conductor integrated circuit device that uses it as barrier material by the Ginding process of abradant surface.
Background technology
In recent years, be accompanied by the highly integrated multifunction of semiconductor integrated circuit, exploring the exploitation of the Micrometer-Nanometer Processing Technology that can realize the miniaturization densification always.In semiconductor device manufacturing process, particularly in forming the operation of multilayer wiring, the planarization of interlayer dielectric or the wiring imbedded is very important.Promptly, by the miniaturization densification of semiconductor fabrication, wiring forms multiple stratification, follows the concavo-convex of surface at each layer just to increase easily with it, in order to prevent that this height difference from surpassing the problems such as depth of focus of photoetching, more and more important in the high planarization that multilayer wiring forms in the operation.
As wiring material, with the Al alloy phase ratio that used in the past, Cu is owing to than good the receiving publicity of low, the anti-electromigration of resistance.Because the steam of the chloride gas of Cu forces down, be difficult to be processed into wiring shape by the reactive ion-etching (RIE:Reactive Ion Etching) that uses in the past, therefore in the formation of wiring, use embedded method.This method is: recesses such as the groove pattern of formation wiring usefulness or hole in insulating barrier, then after forming the barrier layer, by film forming such as sputtering method or plating methods Cu is embedded to slot part, then unnecessary Cu and barrier layer are passed through chemistry, mechanical milling method (CMP:ChemicalMechanical Polishing, hereinafter referred to as CMP) remove, up to the surface of insulating layer that exposes beyond the recess, thereby, form the flush type metal line with flattening surface.In recent years, be formed on so simultaneously that recess is imbedded the Cu wiring of Cu and the dual embedded method of via portion becomes main flow.
Form in this Cu buried wiring, in insulating barrier, spread, form tantalum compound layers such as tantalum, tantalum alloy or stopping up tantalum as the barrier layer in order to prevent Cu.Therefore imbedding outside the wiring portion of Cu, need remove the barrier layer of exposing by CMP.But therefore,, usually can not obtain sufficient grinding rate because that the barrier layer is compared with Cu is very hard.At this as shown in Figure 1, proposed by the 1st grinding step of removing the unnecessary wiring metal level and removed 2 sections polishings that the 2nd grinding step on unnecessary barrier layer forms.
Fig. 1 shows the sectional view that forms the method for buried wiring by CMP.(a) shown grind before, (b) shown the 1st grinding step of removing unnecessary wiring metal level 4 finish after, after (c) shown in the process of the 2nd grinding step of removing unnecessary barrier layer 3, (d) shown that the 2nd grinding step finishes.At first, as forming groove in Fig. 1 (a) institute insulating barrier that is shown in 2.This is the groove that is used for forming at Si substrate 1 buried wiring 6.Form barrier layer 3 in the above, form wiring metal layer 4 (Cu film) more in the above, in the 1st grinding step, remove unnecessary wiring metal level 4.Then, in the 2nd grinding step, remove unnecessary barrier layer 3.After common the 1st grinding step finishes, produce the loss of the wiring metal layer that is called depression 7.Therefore in the 2nd grinding step, need following way, that is, as (c), remove barrier layer unnecessary on the insulating barrier fully, the while insulating barrier, making it becomes same plane with the wiring metal layer shown in (d), subdue the planarization that residual depression 7 reaches height.In addition, when in insulating barrier 2, using the material of low-k, sometimes and the barrier layer between form (gap) layer 5 at interval.During this situation, residual sometimes wall carries out planarization, removes wall sometimes fully, grinds up to exposing advanced low-k materials.(d) shown in that residual wall carries out the situation of planarization.
Carry out planarization by grinding like this, but to be to use among the CMP of grinding agent in the past, to have the depression of buried wiring 6 of Cu and the problem that abrasion increases.At this, depression is meant that overmastication wiring metal layer 4 makes its central portion be the state of depression shown in the symbol 7 of Fig. 1 (c) or Fig. 2, and the wiring portion big at width easily takes place.Abrasion is an incident phenomenon in thin wires portion or intensive wiring portion, just following phenomenon, promptly, as shown in Figure 2, compare the insulating barrier 2 of overmastication wiring portion, the phenomenon of insulating barrier 2 part attenuation with the insulating barrier part (Global portion) of no wiring pattern.That is, produce the abrasion part 8 of comparing over-lapping with the means of abrasion 10 of Global portion.In Fig. 2, omitted barrier layer 3 in addition.
When using grinding agent in the past, owing to the grinding rate with respect to wiring metal layer 4, the grinding rate on barrier layer 3 is little, and therefore in the process of removing barrier layer 3, the Cu overmastication with wiring portion has produced big depression.In addition, compare with the part that wiring density is low, put on high-density wiring portion barrier layer 3 and under the grinding pressure of insulating barrier 2 increase relatively.Therefore, because the wiring density difference, the degree of carrying out of grinding in the 2nd grinding step also has a great difference, the result, and insulating barrier 2 overmastications with high-density wiring portion produce big abrasion.If depression or abrasion take place, easily cause the increase or the electromigration of cloth line resistance, there is the problem of the reliability decrease that makes device.
The tantalum or the tantalum compound that use as the barrier layer are difficult to chemical etching, in addition, owing to compare the hardness height with Cu, therefore are not easy to remove by mechanical lapping.As increasing hardness of grain in order to improve grinding rate, then in the Cu of softness wiring, form scratch, be prone to electric problem such as bad.In addition,, then be difficult to keep the dispersity of abrasive particle in the grinding agent as improving the concentration of abrasive particle in the grinding agent, be prone to generation through the time sedimentation or gelation etc. disperse problem on the stability.
In addition, need among the CMP to prevent to grind in the abrasion of Cu.In the abrasion inhibitor to Cu and copper alloy, as the most effective and be widely used known have BTA (below, be called BTA) and derivative is (for example, with reference to " BTA be the abrasion of inhibitor suppress mechanism with and use " (can step on Gu Wuji, Japanese antirust technology association, 1986, P.1)).This BTA forms compact protective film at Cu and copper alloy surface, suppresses redox reaction, prevents abrasion.Therefore, the additive as the depression that prevents Cu wiring portion is effective.Make and contain BTA or its derivative in the grinding agent, form diaphragm, thereby prevent depression on the surface of Cu.(for example, with reference to USP5,770, No. 095 communiques).But if only the BTA addition is increased, then the Cu grinding rate descends, and milling time increases, the problem that the defective of therefore existence depression or abrasion increases.
In the past, also studied the water soluble polymer that forms one of agent as the Cu diaphragm that suppresses depression.That they all are metals is bigger than (metal/barrier layer) with the grinding rate on barrier layer, the grinding rate of metal and insulating barrier is than (insulator/metal layer) also big grinding agent.That is can suppress to grind the barrier layer when, it removes Cu to grind at a high speed, insulating barrier is a purpose.(for example, opening 2001-144047 communique, Japan Patent spy with reference to the Japan Patent spy opens 2001-144048 communique, Japan Patent spy and opens that 2001-144049 communique, Japan Patent spy are opened the 2001-1440451 communique, the Japan Patent spy opens the 2003-188120 communique)
In addition, exploitation in recent years with the multilayer wiring manufacturing process that suppresses use low dielectric constant that signal delay is purpose and copper wiring in the grinding agent that uses, also studied water soluble polymer (for example, opening the 2003-68683 communique) with reference to the Japan Patent spy.
But all to remove the 1st grinding step of Cu relevant with grinding in these researchs.That is, grind at a high speed the barrier layer, grind Cu, realize when subduing insulating barrier also not occurring effective grinding agent so far in the 2nd grinding step of high planarization with the grinding rate of appropriateness.
This is because following reason, promptly, grinding agent to the 1st grinding step, major requirement is ground wiring metal with high grinding rate, relative therewith, to the grinding agent of the 2nd grinding step, require to grind the barrier layer, grind insulating barrier with the grinding rate higher than the grinding wiring metal with high grinding rate, there is very big difference in both characteristics that requires.
As mentioned above, the effect of the 2nd grinding step is to remove unnecessary barrier layer portions fully among the CMP, reduces the depression that produces in the 1st grinding step simultaneously.In Fig. 1, when the size of the depression that generates in the 1st grinding step is thinner than the thickness on barrier layer, can only need in the 2nd grinding step except that removing depression in the barrier layer, also can not need the grinding of wiring metal or insulating barrier.But the thickness on barrier layer is little, generally at 20～40nm, and removes Cu to grind at a high speed in the 1st grinding step, and therefore extremely difficulty is suppressed at depression than in the thinner scope of the thickness on barrier layer.In addition, in the 1st grinding step, when there was different situations in the Cu grinding rate, owing to the super grinding that need be used for removing fully the unnecessary Cu residue in the face, it was just difficult more therefore to reduce depression.
Therefore, in the 2nd grinding step, require to repair the depression greater than the thickness on barrier layer, the planarization of realization height, this depression generates in the 1st grinding step.In addition, generally as shown in Figure 2, in spy thin wiring or high-density wiring, compare with the insulating barrier part (Global portion) of no wiring pattern, with insulating barrier 2 overmastications of wiring portion, insulating barrier 2 easy attenuation.In recent years, weed out the old and bring forth the new and the miniaturization more of wiring portion, reduce this abrasion and become bigger problem along with semi-conductive.
The announcement of invention
At this, the purpose of this invention is to provide a kind of grinding agent, this grinding agent in the manufacturing of conductor integrated circuit device by in the grinding of abradant surface, by having high grinding rate, inhibition differential grinding recess differential grinding simultaneously protuberance, can form the flush type wiring portion of reliability height, good electric performance.More particularly, the purpose of this invention is to provide a kind of grinding agent, on insulating barrier, be formed with wiring metal layer and barrier layer by in the grinding of abradant surface, this grinding agent has high barrier layer grinding rate, can suppress the generation of caving in or denuding, and can form that scratch is few, reliability is high, the flush type wiring portion of good electric performance, it is formed by the slurry that is dispersed with abrasive particle, this grinding agent be difficult to take place through the time precipitation or gelation etc., be very stable grinding agent.Other purpose of the present invention and advantage illustrate by following description.
The 1st aspect of the present invention provides a kind of grinding agent, and this grinding agent is in the manufacturing of conductor integrated circuit device, is used to grind the cmp grinding agent by abradant surface, wherein contains (A) oxide fine particle, (B) pulullan polysaccharide and (C) water.
The 2nd aspect provides as the described grinding agent in the 1st aspect, and (wherein, R is that hydrogen atom, carbon number are that 1～4 alkyl, carbon number are wherein, also to contain the compound shown in (D) oxidant, (E) formula (1)
1～4 alkoxyl or carboxyl).
The 3rd aspect provides the grinding agent described in the 1st or 2 aspects, and wherein, the weight average molecular weight of composition (B) is in 10,000～1,000,000 scope.
The 4th aspect provides the grinding agent described in the 1st, 2 or 3 aspects, and wherein, composition (A) is formed by the material more than a kind that is selected from silicon dioxide, aluminium oxide, cerium oxide, zirconia, titanium oxide, tin oxide, zinc oxide and manganese oxide.
The 5th aspect provides as each described grinding agent in the 1st～4 aspect, and wherein, composition (A) is a silicon dioxide microparticle.
The 6th aspect provides as each described grinding agent in the 1st～5 aspect, wherein, gross mass with respect to grinding agent, the amount of composition (A) is in the scope of 0.1～20 quality %, the amount of composition (B) is at 0.005～20 quality %, and the amount of composition (C) is in the scope of 40～98 quality %.
The 7th aspect provides as each described grinding agent in the 2nd～6 aspect, and wherein, with respect to the gross mass of grinding agent, the amount of composition (D) is in the scope of 0.01～50 quality %, and the amount of composition (E) is in the scope of 0.001～5 quality %.
The 8th aspect provides as each described grinding agent in the 1st～7 aspect, wherein, this grinding agent be used to grind be formed with wiring metal layer, barrier layer and insulating barrier by the grinding agent of abradant surface.
The 9th aspect provides as the described grinding agent in the 8th aspect, and wherein, the wiring metal layer is formed by copper, and the barrier layer is formed by the material more than a kind that is selected from tantalum, tantalum alloy and tantalum compound.
The 10th aspect provide conductor integrated circuit device by a kind of Ginding process of abradant surface, this method is to supply with grinding agent in grinding pad, make by abradant surface and contact with grinding pad, by relative motion between the two grind by the Ginding process of abradant surface, wherein, grind the wiring metal level, in the grinding stage after the barrier layer occurring, each described grinding agent in the occupation mode 1～9.
By the present invention, in the manufacturing of conductor integrated circuit device by in the grinding of abradant surface, by having differential grinding, the differential grinding protuberance of high grinding rate, inhibition recess, can suppress the generation of caving in or denuding, and form that scratch is few, reliability is high, the flush type wiring portion of good electric performance.The dispersion stabilization of the abrasive particle of this grinding agent is also good.
The simple declaration of accompanying drawing
[Fig. 1] is the schematic cross-section of conductor integrated circuit device in the operation that shows the formation method that forms the flush type wiring by CMP.
[Fig. 2] is the schematic cross-section of conductor integrated circuit device that is used to illustrate the definition of depression and abrasion.
The explanation of symbol
1 Si substrate
2 insulating barriers
3 barrier layers
4 wiring metal layers
5 walls
The wiring of 6 flush types
7 sunk parts
8 abrasion parts
9 maximum differences of height
The means of abrasion of 10 globular parts
The best mode that carries out an invention
Below, wait by use figure, table, formula, embodiment embodiments of the present invention are described.In addition, these figure, table, formula, embodiment etc. and explanation only are examples of the present invention, are not limitation of the scope of the invention.As long as other execution mode of inventive concept according to the invention also belongs to scope of the present invention.
The grinding agent of using among the present invention is the cmp grinding agent that is used to grind in the manufacturing of conductor integrated circuit device by abradant surface, wherein, contains (A) oxide fine particle, (B) pulullan polysaccharide and (C) water.In addition, be preferably also and contain (D) oxidant and (E) compound shown in the formula (1) (wherein, R is that hydrogen atom, carbon number are that 1～4 alkyl, carbon number are 1～4 alkoxyl or carboxyl).
As use these grinding agents, then in the manufacturing process of conductor integrated circuit device, grind its surface,
Form easily have the flat surfaces that forms by insulating barrier etc. layer.More particularly, can realize high grinding rate, can suppress the generation of caving in or denuding by suppressing differential grinding recess, the protuberance of differential grinding simultaneously.In addition, can form that scratch is few, reliability is high, the flush type wiring portion of good electric performance.The dispersion stabilization of the abrasive particle of this grinding agent is also good.
The present invention is especially to by abradant surface being conductor integrated circuit device useful by abradant surface that is formed with wiring metal layer, barrier layer and insulating barrier.In addition, in the present invention, " by abradant surface " is meant the surface in the interstage that occurs in the process of making conductor integrated circuit device.Therefore, also can be the surface that wiring metal layer, barrier layer and insulating barrier do not have coexistence.
In the grinding agent, composition (A) oxide fine particle is to grind abrasive particle.Specifically, be preferably and be selected from more than a kind of silicon dioxide, aluminium oxide, cerium oxide, zirconia, titanium oxide, tin oxide, zinc oxide, germanium oxide and manganese oxide.As silicon dioxide, can use the silicon dioxide of making by various known methods.Can exemplify the colloidal silica that forms through ion-exchange as the silicon tetrachloride aerosil that gas phase is synthesized in the flame of oxygen and hydrogen, sodium metasilicate, perhaps the silicon dioxide microparticles such as colloidal silica that form at the liquid-phase hydrolysis alkoxyl silicone.
Equally, also better use colloidal alumina.Perhaps better use cerium oxide, zirconia, titanium oxide, tin oxide or the zinc oxide of making by liquid phase method or vapor phase method.Wherein, better use can obtain the colloidal silica of high-purity product of uniform particle diameter.
Consider that from the angle of abrasive characteristic and dispersion stabilization the average grain diameter of composition (A) is preferably 5～500nm, more preferably 10～300nm.In addition, be preferably and consider that grinding rate, homogeneity, material selectivity and dispersion stabilization wait the suitable concentration of selecting the composition (A) in this grinding agent in the scope of 0.1～20 quality % of grinding agent gross mass.Above-mentioned concentration is better in the scope of 1～15 quality % of grinding agent gross mass.
Composition (B) uses for the grinding rate that promotes insulating barrier.In general, when insulating barrier uses the situation of silicon dioxide, compare with the grinding rate of the coating wafer that does not form pattern (blanket wafer), the grinding rate of the part that does not form pattern (globular part) in the patterned wafers has slack-off trend.Relative therewith, because it is big to form the contact area of figuratum partial insulating layer and grinding agent, so grinding rate has the trend of quickening.Therefore, even in same wafer, the grinding rate of the insulating barrier of globular part and wiring portion has a great difference, causes abrasion to enlarge in the 2nd grinding step.Along with the progressive width that connects up in epoch is more and more narrow, this tendency is also more and more significant, therefore is difficult in thin thread part and suppresses abrasion.
During this situation,, then, promote the grinding of globular part, can realize that therefore planarization reduces abrasion by suppressing differential grinding recess, the protuberance of differential grinding simultaneously as adding ingredient (B).Its reason and indeterminate, but think because the hydroxyl on abrasive particle surface interacts with the hydroxyl of composition (B) and the hydroxyl of surface of insulating layer, so improved grinding rate in zone widely.Therefore, think if abrasive particle is oxide, partly is oxide-film by abradant surface that then its interaction is worked.When abrasive particle is silicon dioxide, when being the situation of principal component by abradant surface part with silicon dioxide, plays further effect with composition (B) as the interaction partners planarization characteristics of medium.
Pulullan polysaccharide is the maltotriose of 3 molecule glucose α-1,4 combinations, the polysaccharide that carries out α-1,6 combination again.Its effect height when situation in 10,000～1,000,000 scopes of the weight average molecular weight of composition (B).Think that the existence of hydroxyl is important factor.Not to 10,000, the effect that then improves grinding rate reduces as weight average molecular weight, also can not enlarge markedly even surpass 1,000,000 effects.Particularly preferably in 50,000～300,000 scope.In addition, weight average molecular weight can be measured by gel permeation chromatography (GPC).
From the angle of the effect that promoted fully to grind, the concentration of composition (B) in grinding agent is preferably the homogeneity of considering grinding rate, abrasive slurry and waits suitably and sets in 0.005～20 quality % scope.
Composition (C) is to make oxide fine particle disperse, make the solvent of agent dissolves.Be preferably pure water or deionized water.Because glassware for drinking water has the function of the flowability of this grinding agent of control, so its content can suitably be set as the abrasive characteristic of target according to grinding rate, planarization characteristics etc.More fortunately contain 40～98 quality % in this grinding agent.In the scope of special 60～90 quality % fortunately.
Composition (D) is used to make barrier layer surface to form oxide-film, thereby promotes to grind the barrier layer by mechanical force from removed oxide-film by abradant surface.
As composition (D), be preferably and be selected from more than a kind of hydrogen peroxide, iodate, periodates, hypochlorite, perchlorate, persulfate, percarbonate, perborate and perphosphate.As iodate, periodates, hypochlorite, perchlorate, persulfate, percarbonate, perborate and perphosphate, can use alkali metal salts such as ammonium salt, sylvite.Wherein, better use the alkali-free metal ingredient, do not generate the hydrogen peroxide of harmful accessory substance.
Consider that from the effect of being ground promotion fully the concentration of composition in this grinding agent (D) is the scope of 0.01～50 quality % in the grinding agent more fortunately, and the homogeneity of considering grinding rate, abrasive slurry waits suitably and sets.More preferably in the scope of 0.5～5 quality %.
Composition (E) has the function that forms diaphragm for the depression that prevents wiring metal portion on the wiring metal surface.When situation that wiring metal is formed by Cu, as long as just can by the stripping that forms diaphragm inhibition Cu in the absorption of Cu surface physics or chemisorbed.In the formula (1), R is that hydrogen atom, carbon number are that 1～4 alkyl, carbon number are 1～4 alkoxyl or carboxyl.
Specifically, can exemplify as a H atom of 4 or 5 in the phenyl ring of BTA, BTA by methyl substituted azimido-toluene (TTA), by the BTA of carboxyl substituted-4-carboxylic acid etc.These compounds can use separately also and can use mixing more than 2 kinds.From the aspect of abrasive characteristic, better contain composition (E) 0.001～5 quality % in the grinding agent, better in the scope of 0.01～0.5 quality %.
In this grinding agent, better except composition (A)～(C) or composition (A)～(E), also contain acid.As acid, be preferably and be selected from more than a kind of nitric acid, sulfuric acid and carboxylic acid.Wherein, be preferably oxyacid, perhaps not halogen-containing nitric acid with oxidability.In addition, the concentration of the acid in this grinding agent is more fortunately in the scope of 0.01～20 quality %.By adding acid, can improve the grinding rate of barrier layer or dielectric film.In addition, the dispersion stabilization of this grinding agent is improved.
In addition, for this grinding agent being adjusted to the pH of regulation, can when adding acid, in this grinding agent, add alkali compounds.As alkali compounds, can use ammonia, potassium hydroxide, perhaps such quaternary ammonium base of tetramethylammonium hydroxide or tetraethylamine hydroxide (below, be called TEAH) etc.When better not containing alkali-metal situation, be preferably ammonia.In addition, during situation about using as the composition of grinding agent after composition under in composition (A)～(C) or the composition (A)～(E) handled with acid or alkali compounds, also suitably add the acid or the alkali compounds of above-mentioned explanation.
The pH of this grinding agent can use in 2～10 broad range.As consider the abrasive characteristic and the dispersion stabilization of grinding agent, when oxide fine particle uses silicon dioxide, pH is better smaller or equal to 5 or more than or equal to 7, the desirable grinding rate of corresponding wiring metal (for example Cu) can use at acid range (pH2～5) and neutral range alkaline range (pH7～10) respectively.
When oxide fine particle is the situation of aluminium oxide or ceria, consider their isoelectric point, gelation scope, adjust to the suitableeest pH value.Therefore also can use the pH buffer.As the pH buffer,, but be preferably more than a kind of butanedioic acid, citric acid, oxalic acid, phthalic acid, tartaric acid and adipic acid that is selected from as polybasic carboxylic acid so long as the common material with pH buffer capacity can use material arbitrarily.Perhaps also can use glycylglycine or carbonic acid alkali metal salt.In addition, the concentration of the pH buffer in this grinding agent is preferably 0.01～10 quality % of grinding agent gross mass.
The grinding agent that the present invention relates to not necessarily will all be mixed for the grinding-material that constitutes grinding in advance.Also can supply when grinding, grinding-material to be mixed the composition that forms grinding agent.
This grinding agent is suitable grind the conductor integrated circuit device that is formed with insulating barrier by abradant surface, carry out planarization.This grinding agent is because the also grinding rate of may command wiring metal (for example Cu), therefore also be more suitable for grinding be formed with wiring metal layer, barrier layer and insulating barrier by abradant surface.During this situation, particularly the barrier layer can obtain high effect when being selected from the layer that forms more than a kind of tantalum, tantalum alloy and tantalum compound.But, also be suitable for for the film that forms by other metal etc., use by metal or metallic compound beyond the tantalum as the barrier layer, for example Ti, TiN, TiSiN, WN etc. form film the time, also can obtain effect of sufficient.
That is, this grinding agent has the high speed grinding on barrier layer and the function of insulating barrier planarization two aspects simultaneously.When only using the latter's function, in the planarization operation of so-called interlayer insulating film, the formation operation that shallow ridges (shallowtrench) is isolated (STI) etc., also can effectively use.
In addition, this grinding agent can obtain high effect when the wiring metal layer is selected from the situation more than a kind of Cu, copper alloy and copper compound, but for the metal beyond the Cu, for example metal films such as Al, W, Ag, Pt, Au are also applicable.
In addition, as above-mentioned insulating barrier is known silicon oxide film arranged.As such silicon oxide film, be generally the film that tetraethoxysilane (TEOS) accumulation is formed through the CVD method.
In addition, in recent years,, use low dielectric constant to replace this SiO in order to suppress signal delay
2The situation of film is more and more.As this material, except advanced low-k materials such as the film that forms by the silica (SiOF) that adds fluorine, organic SOG (by the film that contains organic principle of Spin on glass gained), porous silica, the also known SiOC film that has through CVD method (chemical gas-phase method) formation.
The SiOC film that forms by the CVD method is developing conventional art as technology, can reach the mass-produced technology of wide accommodation by suitable technology adjustment.Therefore, need the technology of the film planarization of this insulating barrier will be used.
Organosilicon material as advanced low-k materials, can exemplify as trade name: Black Diamond (dielectric constant is 2.7, ア プ ラ イ De マ テ リ ア Le ズ society technology), trade name Coral (dielectric constant be 2.7, Novellus Systems society technology), Aurora2.7 (dielectric constant is 2.7, Japanese ASM society technology) etc.Special good the use has Si-CH
3The compound of key.
The grinding agent that the present invention relates to can suit to use the situation adopting these various insulating barriers.
In addition, in recent years, when using the film having low dielectric constant of organosilicon material, being formed with wall thereon becomes main flow.Wall is the erosion property in order to improve the adaptation between barrier layer and the organosilicon material and to improve organosilicon material.As the silicon oxide film that wall uses, generally the cross-linked structure by Si and O forms, and Si is 1: 2 with the ratio of the atomicity of O.But, also can be to contain the equiatomic film of N, C, also contain Si
3N
4, SiC etc. is as the situation of accessory ingredient.Grinding agent of the present invention also can well use in the situation that has adopted this wall.
Grinding agent of the present invention is applicable to following Ginding process,, supplies with grinding agent to grinding pad that is, makes it and is contacted by abradant surface, and make by abradant surface and grinding pad relative motion and carry out abrasive method.As required, pad conditioner is contacted with the surface of grinding pad, grind while carry out the adjusting on grinding pad surface.
This grinding agent is applicable to following method, promptly, in the insulating barrier on substrate, form recesses such as the groove pattern of wiring usefulness or hole, then form after the barrier layer, by sputtering method or plating method etc. general for example the Cu film forming be embedded to slot part, when forming like this by the situation of abradant surface, remove Cu and barrier layer by CMP,, thereby form the method for flush type metal line up to the surface of insulating layer that exposes beyond the recess.
In the grinding step in 2 stages shown in Figure 1, the grinding agent that the present invention relates to can use any stage of grinding.If the grinding stage manifesting the barrier layer after of particularly using promptly is ground to the 2nd grinding step of state of Fig. 1 (d) from the state of Fig. 1 (b), then depression or abrasion will be difficult to form, so comparatively suitable.
Embodiment
Below, be described more specifically the present invention by embodiment (example 1～3,8～12) and comparative example (example 4～7).
(1) preparation of grinding agent
Each grinding agent of preparation example 1～7 as described below.In water, add bronsted lowry acids and bases bronsted lowry compound and pH buffer, stir and obtained a liquid in 10 minutes.Then composition (E) being dissolved in the ethylene glycol, is 40 quality % up to the solid concentration that forms branch, it is added in a liquid again, and adding ingredient (B) stirred 10 minutes more afterwards, obtained b liquid.
Then, slowly join the aqueous dispersions of composition (A) in the b liquid after, slowly add alkali compounds, adjust pH to 3.The aqueous solution of adding ingredient (D) stirred 30 minutes again, obtained grinding agent.The kind of the composition that uses in each example (B), composition (E) and composition (A) and they are shown in table 1 respectively with respect to the concentration (quality %) of grinding agent gross mass, and the kind of the composition of use (D), acid, alkali compounds and pH buffer and they are shown in table 2 respectively with respect to the concentration of grinding agent gross mass.Use pure water as water.In addition, in the comparative example, the material in the use table 1 replaces composition (B).
(2) grinding condition
Grinding is carried out by following device and under following condition.
Grinder: full-automatic CMP device MIRRA (APPLIED MATERIALS society system)
Grind and press: 14kPa
Rotation number: platen (platform) 123rpm, grinding head (substrate maintaining part) 117rpm
Grinding agent feed speed: 200mL/ minute
Grinding pad: IC1000 (ロ デ one Le society system).
(3) grinding charge
Wafer below using.
(3-1) coating wafer
(a) Cu (wiring metal layer) grinding rate wafer for evaluation sheet
Use by being plated on and be formed with the 8 inch wafers of thickness on the substrate as the Cu layer of 1500nm.
(b) tantalum (barrier layer) grinding rate wafer for evaluation sheet
Use by sputtering at and be formed with the 8 inch wafers of thickness on the substrate as the tantalum layer of 200nm.
(c) SiO
2(insulating barrier) grinding rate wafer for evaluation sheet
Use by plasma CVD and on substrate, be formed with the SiO of thickness as 800nm
28 inches wafers of layer.
(d) SiOC (low dielectric constant) grinding rate wafer for evaluation sheet
Use by plasma CVD and on substrate, be formed with the 8 inch wafers of thickness as the SiOC layer of 800nm.
(3-2) patterned wafers
Use 8 inches following wafers (trade name: 831BDM000, SEMATECH system), promptly, the relative insulating barrier that forms onboard, wiring density with 50%, form the wiring pattern of wiring width 5 μ m to 100 μ m, to form thickness by sputter be the tantalum layer of 25nm being formed with on the insulating barrier of this wiring pattern, and forming thickness by plating thereon again is the Cu layer of 1500nm.
(4) evaluation method of grinding agent characteristic
Grinding rate calculates from the thickness before and after grinding.In the mensuration of thickness, use the sheet resistance determinator RS75 (KLA テ Application コ one Le society system) that calculates from by the sheet resistance of four probe method gained for Cu and tantalum, use light interference type full-automatic determining film thickness device UV 1280SE (KLA テ Application コ one Le society system) for insulating barrier.For the evaluation of depression, use high-resolution sea-floor relief precision measuring instrument (the プ ロ Off ア イ ラ) HRP100 (KLA テ Application コ one Le society system) that measures difference of height by contact pin type with the planarization characteristics of abrasion.
(5) evaluation of coating wafer grinding characteristic
Estimate wiring metal layer, barrier layer, insulating barrier grinding rate separately respectively, use each above-mentioned coating wafer.During this is estimated, use the grinding agent of the composition of above-mentioned each example.
The Cu, tantalum, the SiO that use coating wafer gained have been displayed in Table 3
2, each film of SiOC grinding rate (unit is nm/ minute).By this result as can be known, the grinding agent that the present invention relates to, the grinding rate of tantalum is big, and the grinding rate of Cu is less relatively.As the character utilizing, promptly obtained being fit to the grinding agent of the grinding of the 2nd grinding step as can be known, in the 2nd grinding step, require to grind the barrier layer, and grind insulating barrier with the speed that is higher than wiring metal with high grinding rate.
(6) evaluation of pattern abrasive characteristic
In the evaluation of depression, abrasion, use patterned wafers.What the grinding of patterned wafers was carried out is the 2 stage polishings that are made of the 1st grinding step of removing the wiring metal layer and the 2nd grinding step of removing the barrier layer.The 1st grinding step grinding agent, use the grinding agent of following formation, that is, with respect to the gross mass of grinding agent, aluminium oxide, hydrogen peroxide, citric acid, ammonium polyacrylate and water are respectively 3 quality %, 4 quality %, 0.1 quality %, 0.05 quality % and 92.85 quality %.In the 2nd grinding step, use the grinding agent of the composition of above-mentioned each example.
For each example, eliminate the performance of the difference of height of insulating barrier in order to estimate grinding agent, prepared to remove fully the patterned wafers of the tantalum of redundance by the 1st grinding step.In this difference of height, because the locational depression of wiring width 5 μ m is 10nm, denudes and be 50nm, therefore maximum difference of height (part that is equivalent to the symbol 9 among Fig. 2) is 60nm.
By carrying out the 2nd grinding step, subdue the insulating barrier 60 seconds of this wafer, the maximum difference of height of measuring in the wiring has been eliminated much degree.The degree (unit is nm) that the value of the maximum difference of height gained after initial maximum difference of height-grinding is eliminated as difference of height.By the result of table 4, the grinding agent of embodiment is effective for the elimination of difference of height as can be known.
For the dispersion stabilization of grinding agent, estimate by observing the firm variation for preparing afterwards and prepare 1 week average grain diameter afterwards.Average grain diameter is measured by microtrack UPA (day machine dress society system).Average grain diameter be increased in 50% with interior zero (well), bigger or being designated as * (bad) of gelation take place that be designated as.
In addition, with the grinding agent of example 1 as benchmark, be transformed to TTA for the example (example 10) of the pulullan polysaccharide molecular weight of the example (example 8,9) of the kind of the abrasive particle of conversion composition (A), conversion composition (B) and with BTA, and maintain that it is the example (example 11,12) of low amount, also can be according to table 1, composition shown in 2 is with example 1～7 same preparation lapping liquid.For the lapping liquid (example 8～12) of gained, estimate equally with example 1～7 and to obtain the result shown in the table 3,4.
In the example 11,12, as shown in table 3, tantalum, SiO
2, SiOC grinding rate big, and the grinding rate of Cu is little, and is as shown in table 4, the degree that difference of height is eliminated is big.
In addition, fractographic result shows, does not generate scratch in the Cu wiring of embodiment.
Table 1 Mw: weight average molecular weight
| Example | Composition (A) | Composition (B) or sub | Composition (E) | |||
| The material title | Concentration (quality %) | The material title | Concentration (quality %) | The material title | Concentration (quality %) | |
| 1 | | 6 | Pulullan polysaccharide (Mw:200000) | 0.05 | | 1 |
| 2 | | 6 | Pulullan polysaccharide (Mw:200000) | 0.1 | | 1 |
| 3 | | 6 | Pulullan polysaccharide (Mw:200000) | 1 | | 1 |
| 4 | | 6 | Polyvinyl alcohol (Mw:24000) | 0.1 | | 1 |
| 5 | | 6 | Trehalose | 0.1 | | 1 |
| 6 | | 6 | Polyvinylpyrrolidone (Mw:9000) | 0.1 | | 1 |
| 7 | | 6 | Do not have | Do not have | | 1 |
| 8 | | 1 | Pulullan polysaccharide (Mw:200000) | 0.05 | | 1 |
| 9 | | 1 | Pulullan polysaccharide (Mw:200000) | 0.05 | | 1 |
| 10 | | 6 | Pulullan polysaccharide (Mw:100000) | 0.1 | | 1 |
| 11 | | 6 | Pulullan polysaccharide (Mw:200000) | 0.05 | TTA | 0.5 |
| 12 | | 6 | Pulullan polysaccharide (Mw:200000) | 0.05 | TTA | 0.2 |
Table 2
| Example | Composition (D) | Acid | Alkali compounds | The pH buffer | ||||
| The material title | Concentration (quality %) | The material title | Concentration (quality %) | The material title | Concentration (quality %) | The material title | Concentration (quality %) | |
| 1 | | 1 | Nitric acid | 0.6 | KOH | 0.6 | Citric acid | 0.2 |
| 2 | | 1 | Nitric acid | 0.6 | KOH | 0.6 | Citric acid | 0.2 |
| 3 | | 1 | Nitric acid | 0.6 | KOH | 0.6 | Citric acid | 0.2 |
| 4 | | 1 | Nitric acid | 0.6 | KOH | 0.6 | Citric acid | 0.2 |
| 5 | | 1 | Nitric acid | 0.6 | KOH | 0.6 | Citric acid | 0.2 |
| 6 | | 1 | Nitric acid | 0.6 | KOH | 0.6 | Citric acid | 0.2 |
| 7 | | 1 | Nitric acid | 0.6 | KOH | 0.6 | Citric acid | 0.2 |
| 8 | | 3 | Nitric acid | 0.1 | Ammonia | 0.1 | Tartaric acid | 0.1 |
| 9 | Hydrogen peroxide | 0 | Nitric acid | 0.1 | Ammonia | 0.1 | Butanedioic acid | 0.1 |
| 10 | | 1 | Nitric acid | 0.6 | KOH | 0.6 | Citric acid | 0.2 |
| 11 | Hydrogen peroxide | 0.5 | Nitric acid | 0.6 | KOH | 0.6 | Citric acid | 0.2 |
| 12 | Hydrogen peroxide | 0.2 | Nitric acid | 0.6 | KOH | 0.6 | Citric acid | 0.2 |
Table 3
| Example | Cu grinding rate (nm/ minute) | Ta grinding rate (nm/ minute) | SiO 2Grinding rate (nm/ minute) | SiO 2Grinding rate (nm/ minute) |
| 1 | 50 | 90 | 120 | 60 |
| 2 | 50 | 90 | 120 | 60 |
| 3 | 50 | 90 | 120 | 60 |
| 4 | 70 | 70 | 80 | 40 |
| 5 | 60 | 80 | 50 | 20 |
| 6 | - | - | - | - |
| 7 | 40 | 100 | 100 | 60 |
| 8 | 40 | 100 | 100 | 60 |
| 9 | 40 | 100 | 100 | 60 |
| 10 | 50 | 90 | 120 | 60 |
| 11 | 40 | 120 | 80 | 80 |
| 12 | 40 | 100 | 80 | 80 |
Table 4
| Example | The degree (nm) that difference of height is eliminated | |
| 1 | 40 | ○ |
| 2 | 40 | ○ |
| 3 | 40 | ○ |
| 4 | 10 | ○ |
| 5 | 10 | ○ |
| 6 | - | × |
| 7 | 5 | ○ |
| 8 | 35 | ○ |
| 9 | 35 | ○ |
| 10 | 35 | ○ |
| 11 | 40 | ○ |
| 12 | 40 | ○ |
In addition, be incorporated herein by Japanese Patent Laid that the application requires basis for priority and be willing to that 2004-063366 number (on March 8th, 2004 filed an application to the Japan special permission Room) and Japanese Patent Laid be willing to the content of whole specifications of 2004-305238 number (on October 20th, 2004 speciallyyed permit the Room to Japan and files an application), as the disclosure of specification of the present invention.
Claims (10)
1. grinding agent, it is the cmp grinding agent that is used to grind in the manufacturing of conductor integrated circuit device by abradant surface, it is characterized in that, contains (A) oxide fine particle, (B) pulullan polysaccharide and (C) water.
2. grinding agent as claimed in claim 1 is characterized in that, also contains (D) oxidant and (E) compound shown in the formula (1),
Wherein, R is the alkyl of hydrogen atom, carbon number 1～4, the alkoxyl or the carboxyl of carbon number 1～4.
3. grinding agent as claimed in claim 1 or 2 is characterized in that, the weight average molecular weight of composition (B) is in 10,000～1,000,000 scope.
4. as each described grinding agent in the claim 1～3, it is characterized in that composition (A) is formed by the material more than a kind that is selected from silicon dioxide, aluminium oxide, cerium oxide, zirconia, titanium oxide, tin oxide, zinc oxide and manganese oxide.
5. as each described grinding agent in the claim 1～4, it is characterized in that composition (A) is a silicon dioxide microparticle.
6. as each described grinding agent in the claim 1～5, it is characterized in that, gross mass with respect to grinding agent, the amount of composition (A) is in the scope of 0.1～20 quality %, the amount of composition (B) is at 0.005～20 quality %, and the amount of composition (C) is in the scope of 40～98 quality %.
7. as each described grinding agent in the claim 2～6, it is characterized in that with respect to the gross mass of grinding agent, the amount of composition (D) is in the scope of 0.01～50 quality %, the amount of composition (E) is in the scope of 0.001～5 quality %.
8. as each described grinding agent in the claim 1～7, it is characterized in that, it be used to grind be formed with wiring metal layer, barrier layer and insulating barrier by the grinding agent of abradant surface.
9. grinding agent as claimed in claim 8 is characterized in that the wiring metal layer is formed by copper, and the barrier layer is formed by the material more than a kind that is selected from tantalum, tantalum alloy and tantalum compound.
10. by the Ginding process of abradant surface, it is to supply with grinding agent to grinding pad, make by abradant surface and contact with grinding pad, by relative motion between the two grind by the Ginding process of abradant surface, it is characterized in that, grind the wiring metal level, in the grinding stage after manifesting the barrier layer, use each described grinding agent in the claim 1～9.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP063366/2004 | 2004-03-08 | ||
| JP2004063366 | 2004-03-08 | ||
| JP305238/2004 | 2004-10-20 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1930664A true CN1930664A (en) | 2007-03-14 |
| CN100468647C CN100468647C (en) | 2009-03-11 |
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ID=37859592
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200580006988 Expired - Fee Related CN100468647C (en) | 2004-03-08 | 2005-03-07 | Polishing agent and polishing method |
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| Country | Link |
|---|---|
| JP (1) | JP2010010717A (en) |
| CN (1) | CN100468647C (en) |
| TW (1) | TW200535215A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011072490A1 (en) * | 2009-12-18 | 2011-06-23 | 安集微电子（上海）有限公司 | Chemical-mechanical polishing liquid |
| CN105378011A (en) * | 2013-07-11 | 2016-03-02 | 巴斯夫欧洲公司 | Chemical-mechanical polishing composition comprising benzotriazole derivatives as corrosion inhibitors |
| CN108473851A (en) * | 2016-03-31 | 2018-08-31 | 福吉米株式会社 | Composition for polishing |
| CN111500197A (en) * | 2019-01-30 | 2020-08-07 | 弗萨姆材料美国有限责任公司 | Shallow trench isolation chemical mechanical planarization polishing with adjustable silicon oxide and silicon nitride removal rates |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2017122134A (en) * | 2014-05-22 | 2017-07-13 | 日立化成株式会社 | Polishing liquid for metal film and polishing method using the same |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPWO2003038883A1 (en) * | 2001-10-31 | 2005-02-24 | 日立化成工業株式会社 | Polishing liquid and polishing method |
-
2005
- 2005-03-07 CN CN 200580006988 patent/CN100468647C/en not_active Expired - Fee Related
- 2005-03-08 TW TW94107023A patent/TW200535215A/en unknown
-
2009
- 2009-10-13 JP JP2009236024A patent/JP2010010717A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011072490A1 (en) * | 2009-12-18 | 2011-06-23 | 安集微电子（上海）有限公司 | Chemical-mechanical polishing liquid |
| CN105378011A (en) * | 2013-07-11 | 2016-03-02 | 巴斯夫欧洲公司 | Chemical-mechanical polishing composition comprising benzotriazole derivatives as corrosion inhibitors |
| TWI656201B (en) * | 2013-07-11 | 2019-04-11 | 德商巴斯夫歐洲公司 | Chemical mechanical polishing composition comprising a benzotriazole derivative as an anticorrosive agent |
| CN108473851A (en) * | 2016-03-31 | 2018-08-31 | 福吉米株式会社 | Composition for polishing |
| CN111500197A (en) * | 2019-01-30 | 2020-08-07 | 弗萨姆材料美国有限责任公司 | Shallow trench isolation chemical mechanical planarization polishing with adjustable silicon oxide and silicon nitride removal rates |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100468647C (en) | 2009-03-11 |
| TW200535215A (en) | 2005-11-01 |
| JP2010010717A (en) | 2010-01-14 |
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