CN104745083B - A kind of chemical mechanical polishing liquid and polishing method - Google Patents
A kind of chemical mechanical polishing liquid and polishing method Download PDFInfo
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- CN104745083B CN104745083B CN201310726698.0A CN201310726698A CN104745083B CN 104745083 B CN104745083 B CN 104745083B CN 201310726698 A CN201310726698 A CN 201310726698A CN 104745083 B CN104745083 B CN 104745083B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09G—POLISHING COMPOSITIONS; SKI WAXES
- C09G1/00—Polishing compositions
- C09G1/02—Polishing compositions containing abrasives or grinding agents
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Abstract
The present invention relates to a kind of application of chemical mechanical polishing liquid in improving silica polishing speed, the chemical mechanical polishing liquid includes abrasive grains, siliceous organic compound, the electrolyte ion of ionic strength more than or equal to 0.1mol/Kg, and acid, and the siliceous organic compound is following general formula
Description
Technical field
The present invention relates to a kind of chemical mechanical polishing liquid and polishing methods.
Background technology
With the continuous development of semiconductor technology and being continuously increased for large scale integrated circuit interconnection layer, conductive layer and
The planarization of insulating medium layer becomes particularly critical.Twentieth century eighties, the chemically mechanical polishing initiated by IBM Corporation
（CMP）Technology is considered as the most efficient method of current global planarizartion.
Chemically mechanical polishing（CMP）It is combined by chemical action, mechanism and both effects.It is usually by one
A grinding table and a grinding head composition for carrying chip with polishing pad.Wherein grinding head fixes chip, then
The front of chip is pressed on polishing pad.When being chemically-mechanicapolish polished, grinding head linear movement or edge on polishing pad
The direction of motion rotation as grinding table.At the same time, the slurries containing abrasive grains are dripped on polishing pad, and because from
Heart effect is laid on polishing pad.Chip surface realizes global planarizartion under double action mechanically and chemically.
Currently, chemical mechanical polishing liquid（CMP）Abrasive grains generally use silica used, including Ludox
（colloidal silica）And aerosil（fumed silica）.Themselves it is solid, but in aqueous solution
Can be evenly dispersed, it does not settle, it might even be possible to keep 1 to 3 year long-time stability.
Stability of the abrasive grains in water phase（It does not settle）Can be explained with double electrode layer theory-due to each particle
Surface carries identical charge, they are mutually exclusive, not will produce cohesion.According to Stern models, colloidal ion during exercise,
It will produce Zeta electric potential in tangent plane.Zeta electric potential is an important indicator of colloidal stability, because the stabilization of colloid is
It is closely related with interparticle electrostatic repulsion forces.The reduction of Zeta electric potential can be such that electrostatic repulsion forces reduce, and cause interparticle
Van der Waals attractions are dominant, so as to cause the aggregation and sedimentation of colloid.The height of ionic strength is to influence Zeta electric potential
An important factor for.
The stability of colloid is also influenced by other many factors in addition to being influenced by zeta potentials.For example, by temperature
It influences, at relatively high temperatures, particle irregular heat movement aggravation, the probability mutually collided increases, can accelerate to agglomerate；For example, by
PH value influences, and more stable than neutral under strong alkaline and strong acid condition, neutral and alkali is most stable, and the sections pH value 4-7 are most unstable；
For example, being influenced by kinds of surfactants, some surface-actives can play the role of dispersant, improve stability, and have
A little surfactants can reduce nanoparticle surface charge, reduce electrostatic repulsion, accelerated sedimentation.In surfactant, usually
Anionic surfactant is conducive to the stability of nano particle, and cationic surface active agent is easily reduced stability；
For another example the molecular weight with additive is related, too long of polymer long-chain winds nano particle sometimes, increases the viscous of dispersion liquid
Degree accelerates particle aggregation.Therefore, the stability of Ludox is influenced by many factors.
United States Patent (USP) 60142706 and United States Patent (USP) 09609882 disclose the polishing fluid containing silane coupling agent and polishing
Method.Wherein silane coupling agent plays the role of changing the polishing velocity of multiple material and improves surface roughness.This two
Patent is not found：In high ionic strength（>0.1mol/Kg）When, silane coupling agent can play confrontation high ionic strength
Effect, stable nanoparticles.Because usually when containing very high ionic strength（Such as containing more than>0.2mol/Kg potassium from
Son）, the electric double layer of silica sol granule can substantially be compressed, and electrostatic repulsion forces reduce, and quickly form gel, precipitation.And the U.S.
Patent 60142706 and United States Patent (USP) 09609882, which are not found silane coupling agent, can improve the polishing velocity of silica,
More do not find：There is significant synergistic effect between silane coupling agent and other additives, the polishing velocity of silica is deposited
In 1+1>2 effect.
Invention content
The present invention discloses a kind of method, can be stablized in polyelectrolyte ionic strength using siliceous organic compound
Abrasive grains, meanwhile, there is significant synergistic effect between the silicon-containing compound and other additives, greatly improves silica
Polishing velocity.
The present invention relates to a kind of application of chemical mechanical polishing liquid in improving silica polishing speed, chemical machinery is thrown
Light liquid includes abrasive grains, and siliceous organic compound is greater than or equal to the electrolyte ion of the ionic strength of 0.1mol/Kg,
And acid.
The siliceous organic compound can be indicated with the following general formula：
General formula：
In above formula, R is nonhydrolyzable substituent group, and D is the organo-functional group being connected on R, these reactive groups can be with
Organic substance is reacted and is combined.A, B are same or different hydrolyzable substituent group or hydroxyl, and C can be hydrolyzable groups
Or hydroxyl, can also be the alkyl substituent of non-hydrolysable.Further saying, R is typically alkyl, such as 1-50 carbon atom
Alkyl is more preferably the alkyl of 1-20 carbon atom, is the alkyl of 2-10 carbon atom most preferably.And those skilled in the art
Continue to take it is understood that the carbon atom in R substituent can also continue to other atoms by oxygen, nitrogen, sulphur, phosphine, halogen, silicon etc.
Generation.D can be amino, urea groups, sulfydryl, epoxy group, acrylic, vinyl, acryloxy etc..A, B and C are typically chlorine
Base, methoxyl group, ethyoxyl, methoxy ethoxy, acetoxyl group, hydroxyl etc. generate silanol when these groups hydrolyze（Si
(OH)3）, and combined with inorganic substances, form siloxanes.
Representative siliceous organic compound is silane coupling agent, such as with lower structure：
3-aminopropyltriethoxysilane（Trade name KH-550）
γ-(2,3- glycidoxies) propyl trimethoxy silicane（Trade name KH-560）
γ-(methacryloxypropyl) propyl trimethoxy silicane（Trade name KH-570）
Gamma-mercaptopropyltriethoxysilane（Trade name KH-580）
γ-mercaptopropyl trimethoxysilane（Trade name KH-590）
N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxysilanes（Trade name KH-602）
γ-aminoethyl amino propyl trimethoxy silane（Trade name KH-792）
γ-aminopropyltriethoxy diethoxy silane（Trade name KH-902）
The siliceous organic compound can be added to by number of ways in polishing fluid, and 1：Abrasive grains are preparing polishing fluid
It is first bonded before with silicon-containing compound（The modification of the surfaces particle, the surface treatment being commonly called as）, then grind surface is modified
Abrasive particle is added in polishing fluid.2：The siliceous organic compound is when producing polishing fluid and abrasive grains and other components
It mixes simultaneously.3：The siliceous organic compound can first complete hydrolysis or partial hydrolysis, generate Si-OH groups, then again plus
Enter in polishing fluid, Si-OH groups and the surfaces particle Si-OH bondings completely or part bonding in polishing fluid.Therefore this hair
There may be a variety of shapes such as free, bonding, partial hydrolysis, complete hydrolysis in polishing for the siliceous organic compound of bright use
State.
Acid used in the present invention can be organic and or inorganic acids.Organic acid is preferably polybasic carboxylic acid and/or hydroxyl carboxylic
In acid, preferably benzoic acid, glycine, acetic acid, citric acid, maleic acid, malonic acid, propionic acid, tartaric acid, oxalic acid and aspartic acid
It is one or more；The content of the organic acid is preferably mass percent 0.01~1.5%, more preferably 0.05~
0.5%.Inorganic acid used in the present invention is preferably one or more in boric acid and phosphoric acid；The content of the inorganic acid is preferable
It is mass percent 0.01~1.5%, more preferably 0.05~0.5%.
The polishing composition can work under acid ph value or alkaline ph values.Preferably, the pH value of polishing composition
In 1-7.Within this range, pH value is preferably greater than or equal to 2, and is less than or equal to 6, and most preferably pH value is 3-5.
Affiliated polishing composition also may include inorganic or organic pH adjusting agent, and the pH value of polishing composition is down to
Acid ph value, or pH value is increased into alkaline ph values.It includes such as nitric acid, sulfuric acid, hydrochloric acid, phosphorus that suitable inorganic pH value, which reduces agent,
Acid or the combination for reducing agent comprising at least one above-mentioned inorganic pH value.Suitable pH value height increasing agent includes one kind below：Metal
Hydroxide, ammonium hydroxide or nitrogenous organic base or above-mentioned pH value increase the combination of agent.
In the polishing fluid, a concentration of mass percent 0.001%~1% of siliceous organic compound, preferably 0.01%~
0.5%。
In the polishing fluid, a concentration of mass percent 1%~50% of Silica abrasive particle, preferably 2%~10%.Grain
Diameter is 20~200nm, preferably 20~120nm.
In the polishing fluid, the electrolyte ion of the ionic strength more than or equal to 0.1mol/Kg is metal ion and Fei Jin
Belong to ion.For example, can be potassium ion, sodium ion, calcium ion is one or more in ammonium ion and potassium ion.
Preferably, electrolyte ion is potassium ion.
The positive effect of the present invention is that：
1：The present invention is steady by the dispersion for realizing the chemical mechanical polishing liquid under high ionic strength in silane coupling agent
Qualitative question.
2：By the synergistic effect of silane coupling agent and organic/inorganic acid, the throwing of silica further greatly improved
Ray velocity；
3：Highly concentrated chemical mechanical polishing liquid can be prepared by this method.
4：The costs such as product raw material, packaging, transport, storage, management, manpower can be greatly reduced by highly concentrated.
Specific implementation mode
The advantages of the present invention is further explained below by specific embodiment, but protection scope of the present invention is not only limited to
In following embodiments.
Polishing fluid is prepared according to the ingredient and its ratio of each embodiment in table 1 and comparative example, is uniformly mixed, uses water
Mass percent is supplied to 100%.With KOH, HNO3Or pH adjusting agent is adjusted to required pH value.Wherein polishing condition is：It throws
Ray machine platform is Mirra boards, Fujibo polishing pads, 200mm Wafer, lower pressure 3psi, 150ml/ points of polishing fluid rate of addition
Clock.
Comparative example 1 shows：Under very high ionic strength, the removal rate of silica only has 350A/min, and throws
Light liquid is unstable, rapid delaminating deposition.Comparative example 3 and comparative example 1 contrast and show：Under very high ionic strength, silicon is added
The removal rate of alkane coupling agent, silica increases 120A/min, also, polishing fluid is very stable, abrasive grains average grain diameter
（particle mean size）Do not increase.Comparative example 2 shows：Asparatate is added, the polishing speed of silica can be made
Degree increases 517A/min, but polishing fluid is unstable, rapid delaminating deposition.Embodiment 1 and comparative example 2 contrast and show：In day
In the presence of L-aminobutanedioic acid, silane coupling agent is added, the removal rate ratio of silica is not added with asparatate and is not added with silane
Coupling agent increases 1082A/min, this increments is more than silane coupling agent（120A/min）With asparatate (517A/
Min) the sum of the two contribution, shows：There is collaboration between silane coupling agent and asparatate and other organic/inorganic acids to make
With the polishing velocity of silica can be greatly improved.Comparative example 1~2 does not all add silane coupling agent, polishing fluid unstable.It is real
Example 1~14 is applied, there is silane coupling agent, polishing fluid is more stable, and the removal speed of silica is obviously improved.
Embodiment 1~14 all shows that silane coupling agent has the function of " anti-high ionic strength ", and polishing fluid is highly stable.
Specific embodiments of the present invention are described in detail above, but it is intended only as example, the present invention is simultaneously unlimited
It is formed on particular embodiments described above.To those skilled in the art, it is any to the equivalent modifications that carry out of the present invention and
It substitutes also all among scope of the invention.Therefore, without departing from the spirit and scope of the invention made by impartial conversion and
Modification, all should be contained within the scope of the invention.
Claims (10)
1. a kind of application of chemical mechanical polishing liquid in improving silica polishing speed, which is characterized in that the chemistry machine
Tool polishing fluid is by abrasive grains, siliceous organic compound, the electrolyte of the ionic strength more than or equal to 0.1mol/Kg from
Son, pH adjusting agent and acid composition, wherein the siliceous organic compound is following general formula,
Wherein, R is nonhydrolyzable substituent group, and D is the organo-functional group being connected on R, can react and tie with organic substance
It closes, A, B are same or different hydrolyzable substituent group or hydroxyl, and C is the alkane of hydrolyzable groups or hydroxyl or non-hydrolysable
Base substituent group, wherein the electrolyte ion of the ionic strength more than or equal to 0.1mol/Kg is potassium ion, sodium ion, calcium
It is one or more in ion, ammonium ion and potassium ion, the electricity of the ionic strength more than or equal to 0.1mol/Kg
A concentration of 0.1mol/Kg-1mol/Kg of matter ion is solved, the abrasive grains are Silica abrasive particle, the abrasive grains
A concentration of mass percent 2%~10%, the acid is organic and or inorganic acids, and the content of the organic acid is quality
The content of percentage 0.01~1.5%, inorganic acid is mass percent 0.01~1.5%, the siliceous organic compound
The pH of a concentration of mass percent 0.001%~1%, the chemical mechanical polishing liquid is 1-7.
2. application as described in claim 1, which is characterized in that the grain size of the abrasive grains is 20~200nm.
3. application as claimed in claim 2, which is characterized in that the grain size of the abrasive grains is 20~120nm.
4. application as described in claim 1, which is characterized in that wherein R is alkyl, and the carbon atom quilt on the alkyl carbon chain
Oxygen, nitrogen, sulphur, phosphine, silicon atom continue to replace；A, B and C are respectively chloro, methoxyl group, ethyoxyl, methoxy ethoxy, acetyl oxygen
Base or hydroxyl；D is amino, urea groups, sulfydryl, epoxy group, acrylic, vinyl or acryloxy.
5. application as described in claim 1, which is characterized in that the siliceous organic compound is silane coupling agent.
6. application as claimed in claim 5, which is characterized in that the siliceous organic compound is three ethoxy of 3- aminopropyls
Base silane, γ-(2,3- glycidoxy) propyl trimethoxy silicane, γ-(methacryloxypropyl) propyl trimethoxy silicane,
Gamma-mercaptopropyltriethoxysilane, γ-mercaptopropyl trimethoxysilane, N- (β-aminoethyl)-γ-aminopropyltriethoxy dimethoxies
Base silane, it is one or more in γ-aminoethyl amino propyl trimethoxy silane, γ-aminopropyltriethoxy diethoxy silane.
7. application as described in claim 1, which is characterized in that organic acid is benzoic acid, glycine, acetic acid, citric acid, Malaysia
It is one or more in acid, malonic acid, propionic acid, tartaric acid, oxalic acid and aspartic acid；The inorganic acid is in boric acid and phosphoric acid
It is one or more.
8. application as described in claim 1, which is characterized in that the content of the organic acid be mass percent 0.05~
0.5%, the content of inorganic acid is mass percent 0.05~0.5%.
9. application as described in claim 1, which is characterized in that a concentration of mass percent of the siliceous organic compound
0.01%~0.5%.
10. application as described in claim 1, which is characterized in that the pH of the chemical mechanical polishing liquid is 3-5.
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| CN1255854C (en) * | 2001-01-16 | 2006-05-10 | 卡伯特微电子公司 | Ammonium oxalate-containing polishing system and method |
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