CN101449207B - Antireflective hardmask composition - Google Patents
Antireflective hardmask composition Download PDFInfo
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- CN101449207B CN101449207B CN2006800547445A CN200680054744A CN101449207B CN 101449207 B CN101449207 B CN 101449207B CN 2006800547445 A CN2006800547445 A CN 2006800547445A CN 200680054744 A CN200680054744 A CN 200680054744A CN 101449207 B CN101449207 B CN 101449207B
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/09—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers
- G03F7/091—Photosensitive materials characterised by structural details, e.g. supports, auxiliary layers characterised by antireflection means or light filtering or absorbing means, e.g. anti-halation, contrast enhancement
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Abstract
The present invention discloses a hardmask composition having antireflective properties useful for a lithographic process. The hardmask composition provides excellent optical properties, superior mechanical properties and high etch selectivity. In addition, the hardmask composition can be easily applied by a spinE-TFCon coating technique. Advantageously, the hardmask composition is suitable for a short- wavelength lithographic process and has a minimum residual acid content.
Description
Technical field
The present invention relates to have the hard mask composition that is used for photoetching process of antireflective property, more specifically, relate to and comprise the hard mask composition that contains the aromatic rings polymkeric substance and have strong absorption in short wavelength range (for example, 157nm, 193nm and 248nm).
Background technology
People constantly require to reduce the size of the structural shape in microelectronics industry and other the related industries, comprise microstructural manufacturing (for example, micromechanics, magnetoresistive head (magnetoresist head) and analog).In microelectronics industry, exist for the needs that reduce microelectronic component (or device) size, so that on the appointment chip size, a plurality of circuit are provided.
Photoetching technique is necessary for the reduction that obtains the structural shape size efficiently.Be generally used for the angle of the mask of this imaging from direct imaging pattern and generation on particular substrate, photoetching technique affects microstructural production.
Typical photoetching process comprises making public (patternwise exposure) towards the pattern direction of radiosensitive resist, carries out radiant image, to be formed with the resist layer of one patterned.Afterwards, this image that develops contacts through resist layer and certain material (common, water miscible alkaline development solution) with exposure.Then, the material that the vacancy at the resist of one patterned is existed carries out etching, so that with pattern transfer to following material.After shift accomplishing, the remainder of resist layer is removed.
For the better solution in most of photoetching processes, used ARC (ARC) so that make imaging layer, for example radiosensitive erosion resistant layer, and the reflectivity between the following layer minimizes.Yet,, therefore in etching step subsequently, need further to form pattern owing in the ARC etching process after forming pattern, removed the mass part of imaging layer.
That is to say that in some optical patterning technologies, employed resist can not provide enough repellences to etching step subsequently, to reach the degree that is enough to effectively the layer of desired pattern transfer to resist.In the application of reality (for example, under the situation that needs the ultrathin membrane resist layer, it is thick carrying out etched following material, needs sizable etch depth, and/or needs to use specific etchant in the material below).Used so-called " hard mask layer " as the resist layer of one patterned and can shift through resist from one patterned be patterned below material between the middle layer.Hard mask layer must be able to hold and (or is applicable to, accommodate) from the pattern of the resist layer of one patterned, and resists needed etching, so that with pattern transfer to following material.
Summary of the invention
Technical matters
Although still there are lasting needs in known multiple hard mask material for improved hard mask composition.Because traditional hard mask material is difficult to be applied to substrate, therefore need to use chemistry and physical vapour deposition (PVD), specific solvent and/or high-temperature baking.A kind of preferred hard mask composition can apply through spin coating technique, and need not high-temperature baking.Another kind of preferred hard mask composition can be to carry out selective etch in a kind of easy mode photoresists below, and simultaneously, for making following layer, the particularly following necessary etching of metal level one patterned has resistibility.Another kind of preferred hard mask composition provides excellent memory property, and has avoided and the bad interaction between the resist layer of the forming images acid pollution of hard mask (for example, from).Another kind of preferred hard mask composition has short wavelength (for example, 157nm, 193nm and 248nm) more locates to resist the specific optical property of image-forming radiation.
Another object of the present invention provides a kind ofly to be used hard mask composition and makes the method for the material layer one patterned below suprabasil.
Technical scheme
According to an aspect of the present invention, a kind of antireflective hardmask composition is provided, has comprised:
(a) have and contain the aromatic rings polymkeric substance by the structural unit of formula 1 expression:
Wherein, m and n satisfy 0=m<190,0=n<190 and the integer of m+n=190 relation, it is zero that condition is that m and n all are not equal to; R
1And R
3They can be identical or different, is selected from hydrogen atom, oh group (OH), C independently of one another
1-C
10Alkyl group, C
6-C
10Aromatic yl group, allyl group and halogen atom; R
2And R
4They can be identical or different, is selected from independently of one another
(wherein, R
5Be selected from hydrogen atom, oh group (OH), C
1-C
10Alkyl group, C
6-C
10Aromatic yl group, allyl group and halogen atom), and
(b) organic solvent.
Hard mask composition of the present invention can further comprise (c) linked and (d) acidic catalyst (or acid catalyst, acid catalyst).
In this case, hard mask composition of the present invention can comprise by weight 1 to 20% contain aromatic rings polymkeric substance (a), 75 to 98.8% organic solvent (b), 0.1 to 5% linked (c) and 0.001 to 0.05% acidic catalyst (d) by weight by weight by weight.
Contain the aromatic rings polymkeric substance and can have 1,000 to 30,000 weight-average molecular weight.
If necessary, hard mask composition of the present invention can further comprise surfactant.
Linked can be selected from by the amino resins class of etherificate, N-methoxy-melamine resin class, N-butoxymethyl-melamine resin class, the Lauxite class that methylates, butylated urea formaldehyde resin class, glycoluril derivatives class, 2, the group that two (methylol) paracresol of 6-, diepoxides class and their potpourri constitute.
Acidic catalyst can be selected from by p-toluenesulfonic acid monohydrate, p-toluenesulfonic acid pyridine, 2,4,4, the group that the alkyl esters of 6-tetrabromo cyclohexadiene ketone, styrax tosylate, 2-nitrobenzyl tosylate and organic sulfonic acid constitutes.
According to another aspect of the present invention, a kind of method of using hard mask composition in substrate, to form the material layer of one patterned is provided.
Particularly; Method of the present invention comprises step: material layer (a) is provided in substrate, (b) uses hard mask composition on material layer, to form antireflective hardmask layer, (c) on antireflective hardmask layer, form radiosensitive imaging layer; (d) radiosensitive imaging layer is exposed to (patternwise exposing) radiation towards the pattern direction; So that on imaging layer, form the pattern in radiant exposure zone, (e) optionally remove a part of radiosensitive imaging layer and a part of antireflective hardmask layer, so that expose this part of material layer to the open air; And (f) this part of the material layer that exposes to the open air of etching, so that form the material layer of one patterned.
Method of the present invention also can comprise the step that forms bottom antireflective coating (BARC) before in addition in step (c).
According to another aspect of the present invention, a kind of semiconductor device that uses this method to process (or device) is provided.
Embodiment
To describe the present invention in detail below.
The invention provides a kind of antireflective hardmask composition, be included in short wavelength range, what particularly have strong absorption at the 248nm place contains the aromatic rings polymkeric substance.
Particularly, this antireflective hardmask composition of the present invention comprises:
(a) have and contain the aromatic rings polymkeric substance by the structural unit of formula 1 expression:
Wherein, m and n satisfy 0=m<190,0=n<190 and the integer of m+n=190 relation, it is zero that condition is that m and n all are not equal to; R
1And R
3They can be identical or different, is selected from hydrogen atom, oh group (OH), C independently of one another
1-C
10Alkyl group, C
6-C
10Aromatic yl group, allyl group and halogen atom; R
2And R
4They can be identical or different, is selected from independently of one another
(wherein, R
5Be selected from hydrogen atom, oh group (OH), C
1-C
10Alkyl group, C
6-C
10Aromatic yl group, allyl group and halogen atom), and
(b) organic solvent.
Preferably, the aromatic ring that contains aromatic rings polymkeric substance (a) that in hard mask composition of the present invention, uses is present on the skeletal chain of polymkeric substance.In addition, preferably, contain aromatic rings polymkeric substance (a) and comprise and a plurality ofly can carry out the reactive activity position, and distribute along the skeletal chain of polymkeric substance with linked.In addition, contain the aromatic rings polymkeric substance and must have film forming characteristics, it helps the formation through the layer of traditional spin coating technique.
What can be used for hard mask composition of the present invention and satisfy above-mentioned requirements preferably contains the aromatic rings polymkeric substance by formula 1 expression:
Wherein, m and n satisfy 0=m<190,0=n<190 and the integer of m+n=190 relation, it is zero that condition is that m and n all are not equal to; R
1And R
3They can they be identical or different, are selected from hydrogen atom, oh group (OH), C independently of one another
1-C
10Alkyl group, C
6-C
10Aromatic yl group, allyl group and halogen atom; R
2And R
4They can be identical or different, is selected from independently of one another
(wherein, R
5Be selected from hydrogen atom, oh group (OH), C
1-C
10Alkyl group, C
6-C
10Aromatic yl group, allyl group and halogen atom).
More preferably, the weight-average molecular weight that contains the aromatic rings polymkeric substance is between about 1,000 to about 30,000.
Preferably, based on the organic solvent (b) of 100 weight portions, the amount that contains aromatic rings polymkeric substance (a) of use is 1 to 30 weight portion.When the use amount that contains the aromatic rings polymkeric substance is outside this scope, can not get desirable coating thickness, therefore, make that accurately the thickness of control (regulate) coating becomes difficult.
The kind of organic solvent (b) does not receive special restriction, as long as this contains aromatic rings polymkeric substance (a) and in organic solvent (b), has enough dissolubilities.As appropriate organic solvent, that can give an example has, propylene glycol monomethyl ether acetate (PGMEA), cyclohexanone and ethyl lactate.
Hard mask composition of the present invention can further comprise (c) linked and (d) acidic catalyst.
Preferably, the linked of in hard mask composition of the present invention, using (c) is to come in the reaction of catalysis in the acid that is produced by heating, can make the crosslinked a kind of component of repetitive of polymkeric substance.Preferably, acidic catalyst (d) is a kind of catalyzer of thermal activation.
As the acidic catalyst that in hard mask composition of the present invention, uses (d), can use common organic acid, for example, the p-toluenesulfonic acid monohydrate.In order to improve storage stability, can use hot acid propellant (thermal acid generator) (TAG) compound as acidic catalyst (c).TAG is a kind of once heat-treating acidic compound.The instance of preferred TAG class comprises p-toluenesulfonic acid pyridine, 2,4,4; 6-tetrabromo cyclohexadiene ketone (2; 4,4,6-tetrabromocyclohexadienol), the alkyl esters of styrax tosylate, 2-nitrobenzyl tosylate and organic sulfonic acid.
Can also use other known radiosensitive acid catalyzer in the resist field, as long as other components in they and the antireflective composition are compatible.
On the other hand, can react with the oh group that contains the aromatic rings polymkeric substance, any crosslinking chemical that promptly carries out catalysis through the acid that produces by this way can be used as linked (c).
The instance that can be used for the crosslinking chemical of antireflective hardmask composition of the present invention comprises: the amino resins class of etherificate, alkoxyalkyl melamine resin class are (for example; N-methoxy-melamine resin class and N-butoxymethyl-melamine resin class), the Lauxite class that methylates, butylated urea formaldehyde resin class (Cymel U-65 resin and UFR80 resin), glycoluril derivatives class (for example; The Powderlink 1174 of formula 2 expression), 2, two (methylol) paracresol of 6-and diepoxides class.
In hard mask composition of the present invention; The preferred amount of using of aromatic rings polymkeric substance (a) that contains that in short wavelength range, has a strong absorption is by weight 1 to 20%; More preferably by weight 3 to 10%; The preferred amount of using of organic solvent (b) is by weight 75 to 98.8%; (c) the preferred amount of using of linked (c) is by weight 0.1 to 5% and more preferably by weight 0.1 to 3%, and the amount of the preferred use of acidic catalyst (d) is by weight 0.001 to 0.05% and more preferably by weight 0.001 to 0.03%.
When the used amount that contains the aromatic rings polymkeric substance by weight less than 1% or when surpassing 20% by weight, can not obtain needed coating thickness, therefore, make the thickness of the accurate control coating difficulty that becomes.
When the amount of employed linked for by weight less than 0.1% the time, crosslinking feature is unsafty.Simultaneously, when the amount of employed linked by weight greater than 5% the time, possibly change the optical property of coated film.
Consumption is for possibly cause crosslinking feature unsatisfactory less than the application of 0.001% acidic catalyst by weight.Simultaneously, consumption can cause the increase of acidity for the application that surpasses 0.05% acidic catalyst by weight, and this possibly cause negative effect to the storage stability of hard mask composition.
If the amount of employed organic solvent less than 75% or by weight above 98.8%, then can not get desired coating thickness for by weight, therefore, make accurate control coating thickness become difficult.
If desired, hard mask composition of the present invention may further include at least a adjuvant, like surfactant.
The present invention also provides a kind of method of using hard mask composition on the material layer that is positioned at below suprabasil, to form pattern.
Particularly, method of the present invention may further comprise the steps:
(a) a kind of material layer is provided in substrate;
(b) on material layer, use hard mask composition to form antireflective hardmask layer;
(c) on antireflective hardmask layer, form radiosensitive imaging layer;
(d) should be exposed to radiation towards the pattern direction by radiosensitive imaging layer, in imaging layer, to form the pattern in radiant exposure zone;
(e) optionally remove a part of radiosensitive imaging layer and a part of antireflective hardmask layer, to expose this part of material layer to the open air; And
(f) this part of the material layer that etching exposed to the open air is to form the material layer of one patterned.
Method of the present invention can comprise the step that forms bottom antireflective coating (BARC) before in addition in step (c), to guarantee anti-reflection function.
Method of the present invention can be implemented according to following process.At first, with a kind of material that will form pattern, be applied to silicon base through conventional art such as aluminium or silicon nitride (SiN).As the material that will form pattern, can use material electric conductivity, semiconduction, magnetic or insulation.Afterwards; With hard mask composition spin coating of the present invention become thickness be 500 to
then 100-300 ℃ of down baking 10 seconds to 10 minutes, to form hard mask layer.On hard mask layer, formed radiosensitive image layer.The part of the pattern that will form via the exposure of imaging layer through making public is implemented to develop.Subsequently, with imaging layer and anti-reflecting layer selective removal, with the part of exposing material layer, then, using gases is such as CHF
3/ CF
4Mixed gas implement dry ecthing.After the material layer of one patterned forms, use common photoresists stripper that the remainder of resist is removed.The method of the application of the invention can provide semiconductor device (or device).
Therefore, according to general semiconductor fabrication process, the material layer of composition of the present invention and the one patterned that in substrate, forms can be used for the manufacturing and the design of IC-components (or device).For example; Composition of the present invention can be used in the formation of material layer structures of one patterned; Such as metal line, the hole that is used for contact and tilt (biases), isolated part (insulating section) (for example, embedded groove (DT) and shallow trench isolation leave (STI)), be used for the groove of capacitor arrangement.Should be appreciated that the present invention is not limited to any specific photoetching technique and device (or device) structure.
To describe the present invention with reference to following examples below.Yet these embodiment that given are merely illustrative purposes, are not to be intended to limit protection scope of the present invention.
Embodiment
[synthetic embodiment 1]
(1,5-dihydroxy naphthlene and 1, the multipolymer of 4-bi-methoxy methylbenzene synthetic)
With being equipped with 2 of thermometer, condenser, mechanical stirrer and tap funnel, the 000ml there-necked flask is immersed in 140 ℃ the oil bath (oil bath).Flask and magnetic agitation are carried out on the heat dish.The temperature of the chilled water in the condenser is adjusted into 40 ℃.Add 1 of 160.17g (1 mole), 5-dihydroxy naphthlene 1 and is dissolved in the propylene glycol monomethyl ether acetate (PGMEA) of 656.02g to reactor.In solution, add the dithyl sulfate (DS) of 4.63g (0.03 mole).
With 1 of 116.35g (0.7 mole), 4-bi-methoxy methylbenzene (MMB) is introduced in the tap funnel.When the temperature of reactor reaches 130 ℃, slowly dropwise in 1.5 hours, MMB is added in the reactor, so that carry out the polyreaction of reactant.
In course of reaction, with the time of viscosity number to confirm that reaction is accomplished of the time interval measurement reaction mixture of rule.For the measurement of viscosity number, sampling 1g reaction mixture is cooled to room temperature rapidly from reactor, uses PGMEA to dilute as solvent, becomes by weight 20% until solids content.When reaction is accomplished, the triethanolamine of 4.48g (0.03 mole) is added in the reactor as neutralizing agent, stir and stop this reaction.Reaction mixture is slowly cooled to room temperature.
Use this reaction mixture of PGMEA dilution of 500g, and be transferred to 2, in the separating funnel of 000ml.Under vigorous stirring, polymer solution dropwise is added in the alcohol mixture of methyl alcohol and monoethylene glycol (90:10 (g/g)) of 4kg.The collected polymer product in the bottom of flask, and with supernatant (supernatant) separation storage.Use rotary evaporator methyl alcohol to be removed in following 10 minutes, obtain multipolymer at 60 ℃.
The weight-average molecular weight of this multipolymer and polydispersity are measured through gel permeation chromatography (GPC).The result finds that this multipolymer has 14,000 weight-average molecular weight and 2.5 polydispersity.
[synthetic embodiment 2]
(2,7-dihydroxy naphthlene and 1, the multipolymer of 4-bi-methoxy methylbenzene synthetic)
According to synthetic embodiment 1 in identical mode come synthetic copolymer, only be to use 2 of 160.17g (1 mole), the 7-dihydroxy naphthlene replaces 1 of 160.17g, 5-dihydroxy naphthlene.
In tetrahydrofuran, measure the weight-average molecular weight and the polydispersity of multipolymer through gel permeation chromatography (GPC).The result finds that this multipolymer has 13,000 weight-average molecular weight and 2.8 polydispersity.
[synthetic embodiment 3]
(1-naphthols and 1, the multipolymer of 4-bi-methoxy methylbenzene synthetic)
According to synthetic embodiment 1 in identical mode come synthetic copolymer, only be to use the 1-naphthols of 144.17g (1 mole) to replace 1 of 160.17g (1 mole), 5-dihydroxy naphthlene.
In tetrahydrofuran, measure the weight-average molecular weight and the polydispersity of multipolymer through gel permeation chromatography (GPC).The result finds that this multipolymer has 14,000 weight-average molecular weight and 2.5 polydispersity.
[synthetic embodiment 4]
(synthesizing of the multipolymer of 1-naphthols and formaldehyde)
According to synthetic embodiment 3 in identical mode come synthetic copolymer, only be to use the paraformaldehyde of 21.02g (0.7 mole) to replace 1 of 116.35g (0.7 mole), 4-bi-methoxy methylbenzene (MMB).
In tetrahydrofuran, measure the weight-average molecular weight and the polydispersity of multipolymer through gel permeation chromatography (GPC).The result finds that this multipolymer has 11,000 weight-average molecular weight and 2.2 polydispersity.
[synthetic embodiment 5]
(1-naphthols, formaldehyde and 1, the terpolymer of 4-bi-methoxy methylbenzene synthetic)
According to synthetic embodiment 1 in identical mode synthesize this terpolymer; Only be to use 15.02g (0.5 mole) paraformaldehyde and 83.11g (0.5 mole) 1; 4-bi-methoxy methylbenzene (MMB) replaces 1 of 116.35g (0.7 mole), 4-bi-methoxy methylbenzene (MMB).
In tetrahydrofuran, measure the weight-average molecular weight and the polydispersity of terpolymer through gel permeation chromatography (GPC).The result finds that this multipolymer has 12,000 weight-average molecular weight and 2.4 polydispersity.
[embodiment 1 to 5]
Each polymkeric substance, the 0.2g of preparation among the synthetic embodiment 1 to 5 of 0.8g are dissolved in the 9g propylene glycol monomethyl ether acetate (PGMEA) as the Powderlink1174 (formula 2) of linked and the p-toluenesulfonic acid pyridine of 2mg, filter with the preparation sample solution.
Each sample solution that will in embodiment 1 and 2, prepare is spin-coated on the silicon wafer; And 200 ℃ down 60 seconds of baking with form 1,500
thick film.On the other hand; Each sample solution that will in embodiment 3 to 5, prepare is spin-coated on the silicon wafer; And 200 ℃ down 60 seconds of baking with form 2,500
thick film.
Use ellipsometric measurement appearance (J.A.Woollam) to measure the refraction index (n) and the extinction coefficient (k) of film.The result lists in the table 1.
This result shows that this film has at 193nm (ArF) and 248nm (KrF) locates suitable refraction index and absorptance as anti-reflective film.
[synthetic embodiment 6]
(9, the two hydroxy phenyl fluorenes and 1 of 9-, the multipolymer of 4-bi-methoxy methylbenzene synthetic)
With 9 of 350.41g (1.0 moles); The two hydroxy phenyl fluorenes of 9-, the dithyl sulfate of 3.08g (0.02 mole) and the propylene glycol monomethyl ether acetate of 350g; Be dissolved in fully in 3 liters the four-hole boiling flask that is equipped with mechanical stirrer and condenser under stirring, keeping the temperature of reactor is 115 ℃.Dissolve after 10 minutes, with 1 of 116.35g (0.7 mole), 4-bi-methoxy methylbenzene dropwise is added in the solution, then, resulting potpourri is reacted 15 hours under uniform temp.The triethanolamine that in reaction mixture, adds 2.98g (0.02 mole) as neutralizing agent to stop this reaction.After reaction is accomplished, make water and methanol mixture from reaction mixture, remove acid, use the low molecular weight compound that methyl alcohol will contain oligomer and monomer to remove, produced polymkeric substance (M by formula 3 expressions
w=12,000, polydispersity=2.0, n=23).
[comparative example 1]
With being dissolved in the 9g propylene glycol monomethyl ether acetate (PGMEA) of the polymkeric substance of 0.8g, 0.2g, filter with the preparation sample solution as the Cymel303 of linked and the p-toluenesulfonic acid pyridine of 2mg by synthetic embodiment 6 preparations.
Then; The sample solution of preparation is spin-coated on the silicon wafer; And 200 ℃ down 60 seconds of baking with form 2,500
thick film.
Use ellipsometric measurement appearance (J.A.Woollam) to measure the refraction index (n) and the extinction coefficient (k) of film.The result lists in the table 1.
This result shows that this film has at 193nm (ArF) locates suitable refraction index and absorptance (extinction coefficient) as anti-reflective film, but has located to demonstrate relatively low absorptance at 248nm (KrF).
Table 1
[embodiment 6 to 10]
Each sample solution of preparation in embodiment 1 and 2 is spin-coated on the silicon wafer of aluminium coating; And 200 ℃ down 60 seconds of baking with form 1,500
thick film.On the other hand; Each sample solution that will in embodiment 3 to 5, prepare is spin-coated on the silicon wafer of aluminium coating; And 200 ℃ down 60 seconds of baking with form 2,500
thick film.
On each film, apply the KrF photoresists; 110 ℃ of following 60 seconds of baking, use by ASML (XT:1400, the exposure system of NA0.93) making is made public; Utilize TMAH (WS of 2.38wt%) to develop, to form line and the space pattern of 90-nm.Use FE-SEM to observe this pattern, the result of gained is shown in the following table 2.Measured exposure latitude (EL) nargin according to the variation of exposure energy (or the limit, margin) and according to apart from depth of focus (DoF) nargin of the variation of the distance of measurement light source (or the limit, margin), and record (table 2).
As a result, this pattern is demonstrating good result aspect profile (profile) and the nargin (margin).
[comparative example 2]
To be spin-coated on by the sample solution of preparation in the comparative example 1 on the silicon wafer of aluminium coating; And 200 ℃ down 60 seconds of baking with form 2,500
thick film.
On film, apply the KrF photoresists, toasted for 60 seconds down, use the exposure system of making by ASML (XT:1400, NA 0.93) to make public, utilize TMAH (WS of 2.38wt%) to develop, to form line and the space pattern of 90-nm at 110 ℃.Use FE-SEM to observe this pattern, the result of gained is shown in the following table 2.Measured according to exposure latitude (EL) nargin of the variation of exposure energy with according to depth of focus (DoF) nargin apart from the variation of the distance of measurement light source, and record (table 2).
As a result, this pattern is demonstrating relatively poor relatively result aspect profile and the nargin, it is believed that this is the difference owing to the absorption characteristic of locating at 248nm wavelength (KrF).
Table 2
[embodiment 11 to 15]
Use CHF
3/ CF
4Mixed gas carries out dry ecthing to the sample (embodiment 6 to 10) of one patterned, utilizes BCl
3/ Cl
2Mixed gas carries out further dry ecthing.At last, use O
2All residue organic materials are removed, use FE-SEM to observe the cross section of sample.The result lists in the table 3.
Like what from this result, can find out, etched pattern has demonstrated good etching outline and high etching selectivity.
[comparative example 3]
Use CHF
3/ CF
4Mixed gas carries out dry ecthing to the sample (comparative example 2) of one patterned, utilizes BCl
3/ Cl
2Mixed gas carries out further dry ecthing.At last, use O
2All residue organic materials are removed, use FE-SEM to observe the cross section of sample.The result lists in the table 3.
Like what from this result, can find out, in the profile of etching pattern centrum has appearred.The appearance that it is believed that this centrum is because the low etching selectivity under etching condition.
Table 3
| The sample that in the formation of film, uses | The shape of etched pattern |
| Comparative example 3 | Taper, rough surface |
| Embodiment 11 | Vertical |
| Embodiment 12 | Vertical |
| Embodiment 13 | Vertical |
| Embodiment 14 | Vertical |
| Embodiment 15 | Vertical |
Commercial Application
Anti-reflective hard mask composition of the present invention can be used for forming such film: it is located (for example, ArF (193nm), KrF (248nm) etc.) and has suitable refraction index and absorptance as anti-reflective film at deep ultraviolet (DUV).That is, when antireflective hardmask composition of the present invention was used for photoetching process, it demonstrated high etching selectivity, had enough resistibilitys for multiple etching, and can make the reflectivity between resist and the following layer reduce to minimum.Therefore, antireflective hardmask composition of the present invention can be used for being provided at the profile of pattern and the photolithographic structures that the nargin aspect has better result.
Claims (10)
1. an antireflective hardmask composition comprises
(a) have and contain the aromatic rings polymkeric substance by the structural unit of formula 1 expression:
Wherein, m and n are the integers that satisfies 0＜m＜190,0＜n＜190 and m+n=190 relation; R
1And R
3Can be identical or different, they are selected from hydrogen atom and oh group (OH) independently of one another; And R
2Be-CH
2-and R
4Be
Wherein, R
5Be hydrogen atom, and
(b) organic solvent.
2. antireflective hardmask composition according to claim 1 further comprises (c) linked and (d) acidic catalyst.
3. antireflective hardmask composition according to claim 2, wherein said hard mask composition comprises
(a) 1% to 20% the said aromatic rings polymkeric substance that contains by weight,
(b) 75% to 98.8% said organic solvent by weight,
(c) 0.1% to 5% said linked by weight, and
(d) 0.001% to 0.05% said acidic catalyst by weight.
4. antireflective hardmask composition according to claim 1, the wherein said aromatic rings polymkeric substance that contains has 1,000 to 30,000 weight-average molecular weight.
5. antireflective hardmask composition according to claim 1 further comprises surfactant.
6. antireflective hardmask composition according to claim 2; Wherein said linked is selected from by the amino resins of etherificate, N-methoxy-melamine resin, N-butoxymethyl-melamine resin, the Lauxite that methylates, butylated urea formaldehyde resin, glycoluril derivant, 2, the group that two (methylol) paracresol of 6-, diepoxides and their potpourri constitute.
7. antireflective hardmask composition according to claim 2; Wherein said acidic catalyst is selected from by p-toluenesulfonic acid monohydrate, p-toluenesulfonic acid pyridine, 2; 4; 4, the group that the Arrcostab of 6-tetrabromo cyclohexadiene ketone, styrax tosylate, 2-nitrobenzyl tosylate and organic sulfonic acid constitutes.
8. method that is used in substrate forming the material layer of one patterned said method comprising the steps of:
(a) material layer is provided in substrate;
(b) use forms antireflective hardmask layer according to each described hard mask composition in the claim 1 to 7 on said material layer;
(c) on said antireflective hardmask layer, form radiosensitive imaging layer;
(d) said radiosensitive imaging layer is exposed to radiation towards the pattern direction, so that on said imaging layer, form the pattern in radiant exposure zone;
(e) optionally remove the said radiosensitive imaging layer of a part and a part of said antireflective hardmask layer, so that expose the said part of said material layer to the open air; And
(f) the said part of the said material layer that exposes to the open air of etching is so that form the material layer of one patterned.
9. method according to claim 8 in step (c) before, further comprises the step that forms bottom antireflective coating (BARC).
10. semiconductor device that utilizes method according to claim 8 and process.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020060048430 | 2006-05-30 | ||
| KR1020060048430A KR100826103B1 (en) | 2006-05-30 | 2006-05-30 | Hardmask composition having antireflective property |
| KR1020060120724 | 2006-12-01 | ||
| PCT/KR2006/005906 WO2007139268A1 (en) | 2006-05-30 | 2006-12-29 | Antireflective hardmask composition |
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| Publication Number | Publication Date |
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| CN101449207A CN101449207A (en) | 2009-06-03 |
| CN101449207B true CN101449207B (en) | 2012-12-12 |
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| KR (1) | KR100826103B1 (en) |
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| KR101344794B1 (en) | 2009-12-31 | 2014-01-16 | 제일모직주식회사 | Aromatic ring-containing polymer for resist underlayer and resist underlayer composition including same |
| KR101423171B1 (en) | 2010-12-30 | 2014-07-25 | 제일모직 주식회사 | Hardmask composition and method of forming patterns and semiconductor integrated circuit device including the patterns |
| KR101713251B1 (en) * | 2015-01-14 | 2017-03-07 | 최상준 | A Composition of Anti-Reflective Mask |
| US9907166B2 (en) * | 2015-03-31 | 2018-02-27 | Mitsubishi Gas Chemical Company, Inc. | Resin composition for printed circuit board, prepreg, resin composite sheet and metal foil clad laminate |
| KR102510788B1 (en) * | 2018-06-01 | 2023-03-15 | 최상준 | A composition of anti-reflective hardmask |
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| JP3587393B2 (en) * | 1994-09-22 | 2004-11-10 | 積水化学工業株式会社 | Sulfur-containing polymer |
| DE60105523T2 (en) * | 2000-11-14 | 2005-09-29 | Jsr Corp. | Anti-reflective coating composition |
| KR100512171B1 (en) * | 2003-01-24 | 2005-09-02 | 삼성전자주식회사 | Compositon for a bottom layer resist |
| JP2005196067A (en) * | 2004-01-09 | 2005-07-21 | Toyo Ink Mfg Co Ltd | Antireflection film |
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| CN101449207A (en) | 2009-06-03 |
| KR20070114866A (en) | 2007-12-05 |
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