CN1982401B - Cmp abrasive and method for polishing substrate - Google Patents
Cmp abrasive and method for polishing substrate Download PDFInfo
- Publication number
- CN1982401B CN1982401B CN2007100015632A CN200710001563A CN1982401B CN 1982401 B CN1982401 B CN 1982401B CN 2007100015632 A CN2007100015632 A CN 2007100015632A CN 200710001563 A CN200710001563 A CN 200710001563A CN 1982401 B CN1982401 B CN 1982401B
- Authority
- CN
- China
- Prior art keywords
- grinding
- film
- represent
- independently
- ground
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Landscapes
- Mechanical Treatment Of Semiconductor (AREA)
Abstract
A CMP (chemical-mechanical polishing) technique of polishing a substrate efficiently and at high-speed so as to planarize an interlayer insulating film and an insulating film for shallow trench isolation in the manufacturing process of a semiconductor device. A CMP abrasive containing cerium oxide particles, an organic compound having an acetylene bond (a triple bond between carbon atoms), and water, and a substrate polishing method for polishing a film of a substrate by using such a CMP abrasive.
Description
Technical field
The method that the present invention relates to a kind of chemico-mechanical polishing (Chemical Mechanical Polishing) grinding agent and use this grinding agent to grind substrate, it is used for the interlayer insulating film planarization operation of manufacture process of semiconductor devices such as semiconductor element or shallow isolating trough and forms in the operation etc.
Background technology
In ultra-large type integrated circuit (ULSI) field, for improving packaging density, researched and developed out multiple Micrometer-Nanometer Processing Technology now, design specification (Design Rule) has reached deep-submicron (sub half micron) level.And one of technology that can satisfy this height miniaturization requirement promptly is chemico-mechanical polishing (CMP).The CMP technology is accepted the complete planarization of exposure layer by making, and can realize miniaturization and improve yield.Thus, CMP is a necessary technology when carrying out the planarization of interlayer dielectric for example and shallow isolating trough etc.
In the past, used LOCOS method (silicon selective oxidation method) in the element separation in integrated circuit always.But, begin to adopt the shallow isolating trough method in recent years for to make the width of element separation littler.In the shallow isolating trough method, on the wafer substrate after the film forming silicon oxide film of remainder must remove with CMP.Stop for making to grind, generally can under silicon oxide film, form silicon nitride film earlier as suspension layer.
In the manufacture process of semiconductor device, as being used to make with Plasma Enhanced Chemical Vapor Deposition (PECVD) (plasma CVD) (Plasma-Chemical Vapor Deposition, chemical vapor deposition method), Low Pressure Chemical Vapor Deposition (the CMP grinding agent of the silicon oxide insulating film planarization that low pressure-CVD) etc. forms, in the past, many uses surpassed 9 alkaline grinding agent with the silicon dioxide of firing (fumed silica) as abrasive grains and pH value.Yet, this kind remains on the grinding agent of alkalescence for the grinding rate that improves silicon dioxide film, to also quite high as the grinding rate of the silicon nitride film that grinds suspension layer, so have evenly impaired (promptly can't reach the high planarization effect) on the whole surface of wafer, or cause the problems such as grinding damage of electrical characteristic variation.
On the other hand, as the glass surface grinding agent of light shield or lens etc., year use cerium oxide (for example with reference to Japanese kokai publication hei 5-326469 communique) more.Compare with silica abrasive, the advantage of cerium oxide abrasive is its grinding rate height to silicon dioxide film, and the grinding that is caused damage is also fewer.Therefore, carried out in recent years using the discussion of cerium oxide abrasive as the feasibility of polishing compound for semiconductor, wherein some has realized practicability (for example with reference to Japanese kokai publication hei 9-270402 communique) as polishing compound for semiconductor.
But, also do not obtain making the complete planarization in whole surface of the substrate that is formed with various elements, can produce the cerium oxide abrasive of the grinding damage that causes the electrical characteristic variation simultaneously again hardly.
Summary of the invention
The object of the present invention is to provide a kind of CMP grinding agent and use its method of grinding substrate, this grinding agent can make polished surface reach high planarization under the situation that produces the grinding damage that causes the electrical characteristic variation hardly.
The present invention by with the carbon-to-carbon triple bond absorption of organic compound with acetylene bond by the surface of grinding film, and be able under the situation that can produce the grinding damage that causes the electrical characteristic variation hardly, make polished surface reach high planarization.
That is, the present invention relates to following (1)～(7):
(1) a kind of CMP grinding agent, it comprises cerium oxide particle, has the organic compound and the water of acetylene bond.
(2) according to above-mentioned (1) described CMP grinding agent, wherein, described organic compound with acetylene bond is represented with following general formula (I):
R
1-C≡C-R
2 (I)
Wherein, R
1Expression hydrogen atom or carbon number are 1～5 replacement or substituted alkyl not, R
2The expression carbon number is 4～10 replacement or substituted alkyl not.
(3) according to above-mentioned (1) described CMP grinding agent, wherein, described organic compound with acetylene bond is represented with following general formula (II):
Wherein, R
3～R
6Independent separately, expression hydrogen atom or carbon number are 1～5 replacement or substituted alkyl not, R
7With R
8Independent separately, the expression carbon number is 1～5 replacement or unsubstituting alkylidene, and m and n are independent separately, expression 0 or positive number.
(4), wherein, also comprise the water-soluble high-molecular compound that polymer constituted in this CMP grinding agent by vinyl compound according to each described CMP grinding agent in above-mentioned (1)～(3).
(5) substrate Ginding process, it comprises: the substrate pressure that will be formed with film to be ground is attached on the grinding pad of grinding table, each described CMP grinding agent in above-mentioned (1)～(4) is supplied between film to be ground and the grinding pad, simultaneously, make the film to be ground and the grinding pad of substrate do relative motion, to grind film to be ground.
(6) substrate Ginding process, it comprises: the substrate pressure that will be formed with film to be ground is attached on the grinding pad of grinding table, to contain cerium oxide particle, have the organic compound of acetylene bond and the grinding agent of water is supplied between film to be ground and the grinding pad, simultaneously, partly be adsorbed at the acetylene bond of described organic compound under the state of film to be ground and make the film to be ground and the grinding pad of substrate do relative motion, to grind film to be ground.
(7), wherein, also comprise the water-soluble high-molecular compound that polymer constituted in the described CMP grinding agent by vinyl compound according to above-mentioned (6) described substrate Ginding process.
Embodiment
General cerium oxide particle is to be got by carbonate, nitrate, sulfate or the oxalates compound oxidation of cerium.Be used to grind the cerium oxide particle of the silicon dioxide film that forms with methods such as TEOS-CVD etc., though its manufacture method does not have special restriction, its crystallization particle diameter is preferably 5～300nm.In addition, make the grinding of related substrate for being applicable to semiconductor device, the content of alkali metal such as sodium ion in the cerium oxide particle and potassium ion and halide ion etc. preferably is controlled at smaller or equal to 10ppm.
In the present invention, as the manufacture method of ceria oxide powder, can use sintering method or hydrogen peroxide oxidation process, wherein the temperature of sintering method is preferably 350～900 ℃.
Because the cerium oxide particle with the said method manufacturing often has agglutination phenomenon, so preferably pulverized with mechanical means again.The dry type comminuting method that breaking method preferably uses jet pulverizer etc. to carry out, or the case of wet attrition method of using planetary ball mill etc. to carry out, wherein jet grinding method is as described in (1980) the 527th～532 pages of No. the 5th, chemical industry collection of thesis the 6th volumes.
CMP grinding agent of the present invention, for example, by as the above-mentioned cerium oxide particle that obtains, dispersant and water constitute in the dispersion liquid, add organic compound described later and make.Herein, the concentration of cerium oxide particle is also unrestricted, but for for the purpose of the processing of dispersion liquid is convenient, preferably the content in the CMP grinding agent is 0.5～20 weight %.
Preferably contain dispersant in the grinding agent of the present invention.As dispersant, preferably contain at least a kind that is selected from water soluble anion dispersant, water-soluble nonionic dispersant, water-soluble cationic dispersant and the soluble amphoteric dispersant, more preferably use wherein more than 2 kinds or 2 kinds.In addition, the content of alkali metal in the dispersant and halide ion preferably is controlled at smaller or equal to 10ppm.
As the water soluble anion dispersant, for example can use dodecyltriethanolamine sulfate, ammonium lauryl sulfate, polyoxyethylene alkane ether sulfuric acid triethanolamine or the like, also can be the anionic species compound in the water-soluble high-molecular compound described later.
As the water-soluble nonionic dispersant, for example can use polyoxyethylene dodecane ether, polyoxyethylene hexadecane ether, polyoxyethylene octadecane ether, polyoxyethylene oil alkene ether, other polyoxyethylene higher alcohol ethers, polyoxyethylene octyl group phenylate, polyoxyethylene nonyl phenylate, polyoxy alkane allylic alkylation ether, the single dodecanoate of polyoxyethylene sorbitol, the single Palmitate of polyoxyethylene sorbitol, the polyoxyethylene sorbitol monostearate, Polyoxyethylene sorbitol tristearate, octadecanoic acid ester of polyethylene glycol, the polyoxyethylene sorbitol trioleate, Polyoxyethylene sorbitol tetraoleate, the polyethyleneglycol dodecanoate, polyethylene glycol mono stearate, polyglycol distearate, polyethylene glycol monooleate, polyoxyethylene alkyl amine, polyoxyethylene hardened castor oil, alkyl alkanolamide or the like.
As the water-soluble cationic dispersant, for example can enumerate acetate coconut palm amine and stearylamine acetate or the like.As the soluble amphoteric dispersant, for example can enumerate lauryl betaine, stearyl betaine, lauryl dimethyl amine oxide, 2-alkyl-N-carboxymethyl-N-hydroxyethyl imidazole betaine or the like.
Addition when adding these dispersants, the dispersiveness of the particle from the pulpous state grinding agent and prevent precipitation, and the relation of grinding between damage and dispersant addition considers, for the cerium oxide particle of 100 weight portions, is preferably 0.01～2.0 weight portion.
The molecular weight of dispersant is preferably 100～50, and 000, more preferably 1,000～10,000.This be because, if the molecular weight of dispersant less than 100, when abrasive silica film or silicon nitride film, can't produce enough grinding rates; Surpass at 50,000 o'clock and work as molecular weight, it is big that viscosity becomes, and the storage stability of CMP grinding agent has the tendency of reduction.
As the method that cerium oxide particle is dispersed in the water,, also can adopt homogenizer, ultrasonic disperser, wet ball mill or the like except with the general blender dispersion treatment commonly used.
Average grain diameter with the cerium oxide particle in the CMP grinding agent of said method making is preferably 0.01～1.0 μ m.This is because when the average grain diameter of cerium oxide during less than 0.01 μ m, grinding rate is often not enough; When greater than 1.0 μ m, then be easy to generate damage on the grinding film.
In addition, in the present invention, the average grain diameter of cerium oxide particle is measured with the laser diffraction granularity analyzer, gets the median of particle diameter, and wherein the visual actual needs of the slurries of cerium oxide is diluted to debita spissitudo.
Of the present inventionly have acetylene bond, be that there is no particular restriction for the organic compound of triple bond of the structure of closing with 3 valence electron bonds mutually between the carbon-to-carbon atom, as long as have carbon-to-carbon triple bond, but particularly, preferably with the compound shown in the following general formula (I), and the compound shown in the general formula (II):
R
1-C≡C-R
2(I)
Wherein, R
1For hydrogen atom or carbon number are 1～5 replacement or substituted alkyl not, R
2For carbon number is 4～10 replacement or substituted alkyl not;
Wherein, R
2～R
6Independent separately, expression hydrogen atom or carbon number are 1～5 replacement or substituted alkyl not, R
7With R
8Independent separately, the expression carbon number is 1～5 replacement or unsubstituting alkylidene, and m and n are independent separately, expression 0 or positive number.In addition, aforementioned m, n generally represent with mean value.For improving flatness, the value of m+n is preferably 2～20.These can be independent, or will be used in combination more than 2 kinds or 2 kinds.
In these compounds, more preferably 1-decine, 5-decine, 2,4,7,9-tetramethyl-5-decine-4,7-glycol, 2,4,7,9-tetramethyl-5-decine-4, ethoxylate of 7-glycol or the like.
For obtaining enough flatness, the ideal concentration of organic compound in the CMP grinding agent with acetylene bond is 0.05～5.00 weight %.
For adjusting aqueous characteristics such as viscosity, pH and surface tension, grinding agent of the present invention preferably also contains water miscible macromolecular compound, particularly contains the high molecular weight water soluble polymer that polymer constituted by vinyl compound, but because of its flatness.Should be by the water-soluble high-molecular compound that polymer constituted of vinyl compound, specifically can enumerate, polyacrylic acid, ammonium polyacrylate, polyacrylic acid amine salt, polyvinyl acetate, polyvinyl imidazole, polyvinylpyrrolidone or the like, wherein preferably polyethylene pyrroles.Above-mentioned all cpds can be used in combination separately or more than 2 kinds or 2 kinds.In addition, also can use at least a compound that is selected from acrylic acid, ammonium acrylate, acrylic acid amine salt, vinylacetate, the ethene imidazoles and the copolymer of vinylpyrrolidone.
Weight average molecular weight by the water-soluble high-molecular compound that polymer constituted (hereinafter to be referred as water-soluble high-molecular compound) of vinyl compound is preferably 1,000～100,000, and more preferably 5,000～50,000.In addition, for reaching enough flatness, the concentration of water-soluble high-molecular compound in the CMP grinding agent is preferably 0.05～3.0 weight %, and more preferably 0.06～1.0 weight % especially is preferably 0.07～0.5 weight %.
Except above-mentioned material, in the scope of the effect that does not undermine grinding agent, also can add colouring agents such as an amount of dyestuff, pigment in the grinding agent of water invention, the pH value is adjusted the general normal additives that are added in the grinding agent such as the solvent beyond agent and the water.
In addition, grinding agent of the present invention can divide two kinds of solution of work to preserve, for example, can divide and do to contain organic compound with alkynyl and the annex solution (first solution) that preferably also contains water-soluble high-molecular compound, with contain cerium oxide particle, water and preferably also contain the slurries (second solution) of dispersant, can adopt when grinding these two kinds of solution are supplied on the grinding table respectively, and the modulator approach of on grinding table, mixing; Also can adopt before grinding (before preserving or just before grinding) to be pre-mixed above-mentioned two kinds of solution, be supplied to the modulator approach on the grinding table again.No matter adopt any method modulation grinding agent, all can obtain stable abrasive characteristic.
The pH value of CMP grinding agent is preferably 3～9, and more preferably 5～8.5.When pH less than 3 the time, chemical action dies down, the danger that has grinding rate to reduce; And when pH greater than 9 the time, then chemical action can be strong excessively, and the danger that produces hollow bent (dishing) is arranged.PH value usable acid or ammonium, tetramethyl ammonium hydroxide alkaline components such as (TMAH) are adjusted.
Substrate Ginding process of the present invention is characterised in that, grinds the film to be ground of the substrate that is formed with film to be ground with above-mentioned CMP grinding agent of the present invention.As the substrate that is formed with film to be ground, for example can enumerate, the substrate relevant with semiconductor device fabrication, particularly be the semiconductor substrate in stage of forming circuit element and Wiring pattern, or form the substrate that on semiconductor substrate, has been formed with silicon dioxide film at least of semiconductor substrate etc. in the stage of circuit element.Film to be ground then can be enumerated inorganic insulating membrane, for example is aforementioned silica coating or silicon nitride film layer and silica coating or the like.
So, Ginding process of the present invention comprises that the substrate pressure that will be formed with film to be ground is attached on the grinding pad of grinding table, CMP grinding agent of the present invention is supplied between film to be ground and the grinding pad again, make the film to be ground of substrate do relative motion simultaneously, to grind film to be ground with grinding gesture.Particularly, substrate on the lapping device and grinding table in the two at least one motionless mode better, below be example promptly with the motionless situation of semiconductor substrate, Ginding process of the present invention is described.
Grind silicon dioxide film or the silicon nitride film that is formed on the semiconductor substrate with above-mentioned CMP grinding agent, can eliminate the concavo-convex of silica insulation film laminar surface, make the whole surface of semiconductor substrate become smooth surface.In addition, the method also is applicable to shallow isolating trough.
Herein,, can use to have the holder of supporting semiconductor substrate, and can attach grinding pad and be equipped with the general lapping device of the grinding table of the variable motor of rotation number etc. as lapping device.As the grinding pad on the grinding table, there is no particular restriction, can use non woven fabric, polyurathamc, porous fluoride resin or the like.In addition, grinding pad preferably forms groove through processing, to store the CMP grinding agent.Grinding condition does not have special restriction yet, but the rotating speed of grinding table is preferably smaller or equal to the slow-speed of revolution of 200rpm, in order to avoid substrate flies out.Put on pressure (grinding pressure) on the substrate preferably smaller or equal to 98kpa (1kg/cm
2), in order to avoid after grinding, produce damage.During grinding, the grinding agent of pulpous state of the present invention is to be continuously supplied between grinding pad and the film to be ground with pump etc.There is no particular restriction for the supply of grinding agent, preferably can cover the surface of grinding pad constantly.
Exist concavo-convexly by grinding film (silicon dioxide film) global planarization for making, optionally the part of worn protrusion is necessary.As use CMP grinding agent of the present invention to grind, then above-mentioned acetylene bond part with organic compound of acetylene bond will be adsorbed on by on the grinding film.When carrying out by the grinding of abradant surface, promptly optionally grind projection and reach high flatness with this adsorbed state.If contain the water-soluble high-molecular compound that polymer constituted by vinyl compound in the lapping liquid again, then flatness can more improve.After grinding is finished, in flowing water, fully clean semiconductor substrate, preferably use spinner (spindryer) etc. then, get rid of the water droplet of attached work on semiconductor substrate, make its drying.
For example, behind the shallow trench isolation structure that forms planarization in the above described manner, can on silicon dioxide insulating layer, form aluminum wiring, again between aluminum wiring and on form silica insulation film again, use above-mentioned CMP grinding agent to grind equally then, eliminating the concavo-convex of inorganic insulating membrane surface, and make the whole surface of semiconductor substrate become smooth surface.Carry out the above-mentioned operation of stipulated number at repetitiousness after, can make the required number of plies.
Be fit to get the formation method of the inorganic insulating membrane of CMP grinding agent and Ginding process grinding, for example can enumerate methods such as low pressure-CVD method and plasma CVD method with the present invention.As desire to form silicon dioxide film with low pressure-CVD method, can single silane (SiH
4) be that Si originates oxygen (O
2) be that oxygen is originated this SiH
4With O
2Oxidation reaction can take place at low temperature smaller or equal to 400 ℃, after the CVD operation, also can under smaller or equal to 1000 ℃ temperature, heat-treat as required.As desire to make therefore high temperature levelling and the planarization and when adopting the mode of phosphorus doping, preferably use SiH again of dielectric film surface
4-O
2-PH
3The class reacting gas.
The advantage of plasma CVD method is that it can carry out the chemical reaction that need carry out with high temperature under common thermal equilibrium condition at low temperatures.Isoionic production method for example can be enumerated two kinds of capacitance coupling type and inductive coupling types.As reacting gas, can enumerate, with SiH
4Be Si source, N
2O is the SiH of nitrogenous source
4-N
2O class gas and be the TEOS-O in Si source with tetraethoxysilane (TEOS)
2Class gas (TEOS-plasma CVD method).The preferable substrate temperature is 250～400 ℃, and reaction pressure is 67～400Pa.Like this, but also element such as Doping Phosphorus, boron in the silicon dioxide film that grinding agent and Ginding process of the present invention was suitable for.Similarly, when forming silicon nitride film, use with dichlorosilane (SiH with the low pressure chemical vapor deposition method
2Cl
2) be the Si source, ammonia (NH
3) be nitrogenous source.This SiH
2Cl
2-NH
3The class oxidation reaction is carried out under 900 ℃ high temperature.For this plasma CVD method,, can enumerate with SiH as reacting gas
4Be silicon source, NH
3SiH for nitrogenous source
4-NH
3Class gas.Substrate temperature is preferably 300～400 ℃.
CMP grinding agent of the present invention and Ginding process not only can be used to grind the silicon dioxide film that is formed on the semiconductor substrate, also can grind the silicon dioxide film that is formed on the wiring board with regulation distribution, glass, inorganic insulating membranes such as silicon nitride, polysilicon, mainly contain aluminium, copper, titanium, titanium nitride, tungsten, the film of tantalum or tantalum nitride etc., optical glass such as light shield/lenses/prisms, tin indium oxide inorganic conductive films such as (ITO), constitute the glass and the crystalline material of optic integrated circuit/switching element/light guide path, the end face of optical fiber, scintillator optics monocrystalline such as (scintillator), the solid-state laser monocrystalline, the sapphire substrate that blue laser LED uses, carborundum, semiconductor monocrystal such as gallium phosphide and GaAs, magnetic disc is with glass substrate and magnetic head etc.
Embodiment
Then, enumerate embodiment and Comparative Examples illustrates the present invention, but the present invention is not limited to these embodiment.
Embodiment 1
The preparation of＜cerium oxide seriflux 〉
At first hydration cerous carbonate 2kg is placed alumina container, in 850 ℃ air, burnt till 2 hours again, promptly get ceria oxide powder.Then cerium oxide particle 1kg, 40 weight % polyacrylic acid aqueous ammonium 23g and the deionized water 8977g with above-mentioned gained mixed, and ultrasonic dispersion 10 minutes when stirring, and promptly gets cerium oxide seriflux.The gained slurries filter with 1 μ m filter, add deionized water again, obtain the cerium oxide seriflux that cerium oxide content is 5.0 weight %.
The preparation of＜CMP grinding agent 〉
Get above-mentioned cerium oxide seriflux 1000g, have the organic compound 2 of acetylene bond, 4,7,9-tetramethyl-5-decine-4, the ethoxylate of 7-glycol (Aldrich corporate system reagent, be the m+n=3.5 in the aforementioned formula (II)) 15g, and water 1985g mixed, and obtains CMP grinding agent (1), and the concentration that wherein has the organic compound of acetylene bond is 0.5 weight %, the concentration of cerium oxide particle is 1.67 weight %, and the pH value is 8.4.
The grinding of＜insulating film layer and shallow isolating trough layer 〉
The width that at first forms line/space (line/space) on the Si of 8 inches (20.3cm) substrate is 0.05～5mm, highly is the aluminum wiring Line portion of 1000nm, and then, promptly get wafer with insulating film layer pattern thereon with the silicon dioxide film of TEOS-plasma CVD method formation thickness 2000nm.
This wafer (hereinafter to be referred as wafer (1)) with insulating film layer pattern is placed the lapping device (lapping device of ebara corporatlon corporate system: on supporter EPO111), again on the grinding table of the above-mentioned lapping device of the grinding pad that under silicon dioxide film (dielectric film) state down of wafer supporter is placed the porous system of being pasted with polyurethane resin system.
When being supplied in above-mentioned CMP grinding agent (1) between dielectric film and the grinding pad, to the polishing insulation film of wafer (1) 3 minutes, wherein the rotating speed of grinding table is that 80rpm, grinding head rotating speed are that 80rpm, grinding loading are 20kPa, and the grinding agent quantity delivered is 200ml/min.Consequently, protuberance and the difference in height between the recess after the grinding are 40nm, show high flatness.
In addition, on 8 inches wafers, form silicon dioxide film, thereby obtain wafer (2A) with plasma CVD method; On another wafer, form silicon nitride film with low-voltage plasma CVD method, thereby obtain wafer (2B) with diameter.
Use above-mentioned CMP grinding agent (1), this wafer (2A) and silicon dioxide film (2B) and silicon nitride film were ground respectively 1 minute, wherein, the rotating speed of grinding table is that 80rPm, grinding head rotating speed are that 80rpm, grinding loading are 20kPa, and the grinding agent quantity delivered is 200ml/min.Use the light interference type film thickness measurement device then, measure the thickness difference before and after grinding, calculate grinding rate thus, consequently, the grinding rate of the silicon dioxide film of wafer (2A) is 220nm/min, the grinding rate of the silicon nitride film of wafer (2B) is 52nm/min, and their grinding rate ratio is 4.2.In addition, silicon dioxide film after wafer (2A) grinds, the wafer appearance detection microscope AL-2000 that wafer defect checkout gear Surfscan6220 that produces with KLA Tencor company and Olympus company produce measures, and consequently the number more than or equal to the grinding damage of 0.2 μ m is 15 a/wafer.
In addition, form the square protuberance of length of side 350nm～0.1mm on 8 inches silicon substrate, and form the recess of dark 400nm, making protuberance density is respectively 2～40% the wafer with shallow isolating trough layer pattern.On these protuberances, form the silicon nitride film of thick 100nm, and form the silicon dioxide film of thick 600nm thereon with the TEOS-plasma CVD method, the wafer that obtains is called patterned wafers (3).Then use above-mentioned CMP grinding agent (1), this wafer (3) is carried out grinding in 2 minutes, wherein, the rotating speed of grinding table is that 80rpm, grinding head rotating speed are that 80rpm, grinding loading are 20kPa, and the grinding agent feed speed is 200ml/min.Consequently, the difference in height after the grinding is 40nm, shows high flatness.
Example 2
The preparation of＜CMP grinding agent 〉
Get the cerium oxide seriflux 750g, 2 that example 1 makes, 4,7,9-tetramethyl-5-decine-4, the ethoxylate of 7-glycol (Aldrich corporate system, the same) 50g, and water 4200g mixed, and promptly gets CMP grinding agent (2), and the concentration that wherein has the organic compound of acetylene bond is 1.0 weight %, the concentration of cerium oxide particle is 0.75 weight %, and the pH value is 8.4.
The grinding of＜insulating film layer and shallow isolating trough layer 〉
Then use above-mentioned CMP grinding agent (2), wafer (1) was ground 3 minutes, the lapping device that uses ebara corporatlon company to produce: EPO111, the rotating speed of grinding table are that 50rpm, grinding head rotating speed are that 50rpm, grinding loading are 30kPa, and the grinding agent quantity delivered is the 200ml/ branch.Consequently, protuberance and the difference in height between the recess after the grinding are 40nm, show high flatness.
Use above-mentioned CMP grinding agent (2), wafer (2A) and silicon dioxide film (2B) and silicon nitride film were ground respectively 1 minute, in addition, other conditions are then identical with present embodiment wafer (1).The grinding rate that found that silicon dioxide film is 290nm/min, and the grinding rate of silicon nitride film is 68nm/min, and the grinding rate ratio of the two is 4.26.In addition, silicon dioxide film after the grinding and embodiment 1 the same the detection, consequently the number more than or equal to the grinding of 0.2 μ m damage is 15 a/wafer.
In addition, use above-mentioned CMP grinding agent (2), with the same grinding condition of wafer (1) of present embodiment, above-mentioned grinding wafers (3) is carried out grinding in 3 minutes.Consequently, the difference in height after the grinding is 50nm, shows high flatness.
Example 3
The preparation of＜CMP lapping liquid 〉
Get above-mentioned example 1 described cerium oxide seriflux 750g, 2,4,7,9-tetramethyl-5-decine-4, (Aldrich company produces the ethoxylate of 7-glycol, the same) 50g, (Tokyo changes into industrial society system to polyvinylpyrrolidone, K30, weight average molecular weight 40000) 3.75g and deionized water 4196.25g mixed, promptly obtain CMP grinding agent (3), wherein the concentration of cerium oxide particle is 0.75 weight %, concentration with organic compound of acetylene bond is 1.0 weight %, and the concentration of polyvinylpyrrolidone is 0.075 weight %, and the pH value is 8.40.
The grinding of＜insulating film layer and shallow isolating trough layer 〉
Use above-mentioned CMP grinding agent (3) that wafer (1) was ground 3 minutes, its grinding condition is identical with the wafer (1) of example 2.Consequently, protuberance and the difference in height between the recess after the grinding are 20nm, show high flatness.
Use above-mentioned CMP grinding agent (3), wafer (2A) and silicon dioxide film (2B) and silicon nitride film ground respectively 1 minute, other conditions then with the wafer (2A) of example 2 and (2B) identical.The grinding rate that found that silicon dioxide film and silicon nitride film is 50nm/min, and the grinding rate of silicon nitride film is 65nm/min, and the grinding rate ratio of the two is 0.77.In addition, silicon dioxide film after the grinding and embodiment 1 the same the detection, consequently the number more than or equal to the grinding of 0.2 μ m damage is 15 a/wafer.
In addition,, patterned wafers (3) is carried out grinding in 200 seconds with above-mentioned CMP grinding agent (3), in addition the same with the grinding condition of the wafer (3) of embodiment 2, grind.Consequently, the difference in height after the grinding is 10nm, shows high flatness.
Comparative example 1
The preparation of＜CMP grinding agent 〉
At first with deionized water with 3 times of the described cerium oxide seriflux dilutions of embodiment 1, make wherein that cerium oxide particle concentration is 1.67 weight %, promptly get the CMP grinding agent, wherein do not add embodiment 1 described organic compound, and pH value is 7.0.
The grinding of＜insulating film layer and shallow isolating trough layer 〉
Except that using above-mentioned CMP grinding agent (cerium oxide particle is 1.67 weight %), all the other all with embodiment 1 under the same conditions, grinding wafers (1) 3 minute, grinding wafers (2A) and (2B) respectively 1 minute, grinding wafers (3) 2 minutes.The difference in height that found that the wafer (1) after the grinding is 150nm, its flatness extreme difference.In addition, the silicon dioxide film and embodiment 1 the same detect of wafer (2A) after grinding consequently, is 30/wafer more than or equal to the number of the grinding damage of 0.2 μ m.In addition, the difference in height of grinding back wafer (3) is 150nm, and flatness is poor.
The possibility of utilizing on the industry
As use the Ginding process of CMP grinding agent of the present invention and substrate, can make to be polished mask high flatness is arranged, so the present invention is applicable to the manufacture process of the semiconductor device of semiconductor element etc., for example shallow isolating trough. In addition, the present invention can in that silica insulation film etc. is polished under the undamaged state on surface, carry out speed lapping.
Claims (11)
1. abrasives for chemical mechanical polishing, it comprises cerium oxide particle, has the organic compound and the water of acetylene bond, is used for the grinding of inorganic insulating membrane, and wherein, described organic compound with acetylene bond is represented with following general formula (II):
Wherein, R
3～R
6Represent that independently of one another hydrogen atom or carbon number are 1～5 alkyl, R
7With R
8Represent that independently of one another carbon number is 1～5 alkylidene, m and n represent 0 or positive number independently of one another, and m+n is 2～20.
2. abrasives for chemical mechanical polishing according to claim 1, wherein, also comprise water-soluble high-molecular compound, described water-soluble high-molecular compound comprises from least a by what select the following group of forming: polyacrylic acid, ammonium polyacrylate, polyacrylic acid amine salt, polyvinyl acetate, polyvinyl imidazole, polyvinylpyrrolidone and be selected from least a compound in acrylic acid, ammonium acrylate, acrylic acid amine salt, vinylacetate, the ethene imidazoles and the copolymer of vinylpyrrolidone.
3. substrate Ginding process, it comprises: the substrate pressure that will be formed with film to be ground is attached on the grinding pad of grinding table, each described abrasives for chemical mechanical polishing in claim 1 or 2 is supplied between film to be ground and the grinding pad, simultaneously, make the film to be ground and the grinding pad of substrate do relative motion, to grind film to be ground.
4. substrate Ginding process, it comprises: the substrate pressure that will be formed with film to be ground is attached on the grinding pad of grinding table, each described abrasives for chemical mechanical polishing in claim 1 or 2 is supplied between film to be ground and the grinding pad, simultaneously, partly be adsorbed at the acetylene bond of described organic compound under the state of film to be ground and make the film to be ground and the grinding pad of substrate do relative motion, to grind film to be ground.
5. cmp agent annex solution, wherein, contain with the organic compound with acetylene bond of following general formula (II) expression and by the water-soluble high-molecular compound that polymer was constituted of vinyl compound:
Wherein, R
3～R
6Represent that independently of one another hydrogen atom or carbon number are 1～5 alkyl, R
7～R
8Represent that independently of one another carbon number is 1～5 alkylidene, m and n represent 0 or positive number independently of one another, and m+n is 2～20.
6. cmp agent annex solution according to claim 5, wherein, the described water-soluble high-molecular compound that polymer constituted by vinyl compound is from least a by what select the following group of forming: polyacrylic acid, ammonium polyacrylate, polyacrylic acid amine salt, polyvinyl acetate, polyvinyl imidazole, polyvinylpyrrolidone and be selected from least a compound in acrylic acid, ammonium acrylate, acrylic acid amine salt, vinylacetate, the ethene imidazoles and the copolymer of vinylpyrrolidone.
7. according to claim 5 or 6 described cmp agent annex solutions, wherein, when grinding or before grinding, mix with the slurries that contain cerium oxide particle and water at least and to use.
With the organic compound with acetylene bond of following general formula (II) expression as the application of cmp agent with annex solution,
Wherein, R
3～R
6Represent that independently of one another hydrogen atom or carbon number are 1～5 alkyl, R
7～R
8Represent that independently of one another carbon number is 1～5 alkylidene, m and n represent 0 or positive number independently of one another, and m+n is 2～20.
9. contain mixed liquor with the organic compound with acetylene bond of following general formula (II) expression and water-soluble high-molecular compound as the application of cmp agent with annex solution,
Wherein, R
3～R
6Represent that independently of one another hydrogen atom or carbon number are 1～5 alkyl, R
7～R
8Represent that independently of one another carbon number is 1～5 alkylidene, m and n represent 0 or positive number independently of one another, and m+n is 2～20.
10. according to claim 8 have the organic compound of acetylene bond as the application of cmp agent with annex solution, wherein, when grinding or before grinding, make describedly to have the organic compound of acetylene bond and mix with the slurries that contain cerium oxide particle and water at least and use.
11. mixed liquor according to claim 9 as the application of cmp agent with annex solution, wherein, when grinding or before grinding, makes described mixed liquor mix with the slurries that contain cerium oxide particle and water at least and uses.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2002233702 | 2002-08-09 | ||
| JP2002233702 | 2002-08-09 | ||
| JP2002-233702 | 2002-08-09 | ||
| JP2003-59280 | 2003-03-06 | ||
| JP200359280 | 2003-03-06 | ||
| JP2003059280 | 2003-03-06 |
Related Parent Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB038189461A Division CN100339954C (en) | 2002-08-09 | 2003-08-06 | CMP abrasive and substrate polishing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1982401A CN1982401A (en) | 2007-06-20 |
| CN1982401B true CN1982401B (en) | 2011-04-06 |
Family
ID=38165256
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007100964257A Expired - Lifetime CN101029214B (en) | 2002-08-09 | 2003-08-06 | CMP abrasive and method for polishing substrate |
| CN2007100015632A Expired - Lifetime CN1982401B (en) | 2002-08-09 | 2003-08-06 | Cmp abrasive and method for polishing substrate |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007100964257A Expired - Lifetime CN101029214B (en) | 2002-08-09 | 2003-08-06 | CMP abrasive and method for polishing substrate |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN101029214B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP5819076B2 (en) * | 2010-03-10 | 2015-11-18 | 株式会社フジミインコーポレーテッド | Polishing composition |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0897744A1 (en) * | 1993-11-29 | 1999-02-24 | Air Products And Chemicals, Inc. | Waterborne coating and ink comprising ethoxylated acetylenic glycols having low dynamic surface tension |
-
2003
- 2003-08-06 CN CN2007100964257A patent/CN101029214B/en not_active Expired - Lifetime
- 2003-08-06 CN CN2007100015632A patent/CN1982401B/en not_active Expired - Lifetime
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0897744A1 (en) * | 1993-11-29 | 1999-02-24 | Air Products And Chemicals, Inc. | Waterborne coating and ink comprising ethoxylated acetylenic glycols having low dynamic surface tension |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101029214B (en) | 2011-03-16 |
| CN1982401A (en) | 2007-06-20 |
| CN101029214A (en) | 2007-09-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100339954C (en) | CMP abrasive and substrate polishing method | |
| KR101419156B1 (en) | Polishing liquid for cmp and polishing method using the same | |
| CN102585765B (en) | Cmp polishing agent and method for polishing substrate | |
| WO2010067844A1 (en) | Polishing solution for cmp and polishing method using the polishing solution | |
| KR20000069823A (en) | Composition for Oxide CMP | |
| TW201632605A (en) | CMP polishing fluid, polishing method of substrate, and electronic component | |
| JP2015005762A (en) | Polishing liquid for cmp | |
| JP2012146973A (en) | Polishing solution and substrate polishing method using polishing solution | |
| JP2006318952A (en) | Cmp abrasive and method of polishing substrate | |
| JP2012186339A (en) | Polishing liquid and polishing method of substrate using the same | |
| JP5375025B2 (en) | Polishing liquid | |
| CN1982401B (en) | Cmp abrasive and method for polishing substrate | |
| WO2016021325A1 (en) | Polishing liquid for cmp and polishing method using same | |
| JP4830194B2 (en) | CMP polishing agent and substrate polishing method | |
| JP2009266882A (en) | Abrasive powder, polishing method of base using same, and manufacturing method of electronic component | |
| JP4491857B2 (en) | CMP polishing agent and substrate polishing method | |
| JP2001332516A (en) | Cmp abrasive and method for polishing substrate | |
| JP2001308043A (en) | Cmp-polishing agent and polishing method for substrate | |
| JP6938855B2 (en) | Polishing liquid for CMP and polishing method using it | |
| KR20240027830A (en) | Polishing liquid for CMP, polishing liquid set for CMP and polishing method | |
| JP4878728B2 (en) | CMP abrasive and substrate polishing method | |
| JP2003347246A (en) | Cmp polishing agent for semiconductor insulating film and method of polishing substrate |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CX01 | Expiry of patent term |
Granted publication date: 20110406 |
|
| CX01 | Expiry of patent term |