CN109188866A - A kind of composition for the organic hard mask of antireflection - Google Patents
A kind of composition for the organic hard mask of antireflection Download PDFInfo
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- CN109188866A CN109188866A CN201810933107.XA CN201810933107A CN109188866A CN 109188866 A CN109188866 A CN 109188866A CN 201810933107 A CN201810933107 A CN 201810933107A CN 109188866 A CN109188866 A CN 109188866A
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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
Abstract
A kind of composition for the organic hard mask of antireflection, it is characterised in that: composition includes the polymer containing aromatic ring, and the polymer is as shown in Equation 1:
Description
Technical field
The present invention relates to a kind of hard mask compositions suitable for lithography.The present invention relates more specifically to a kind of use
In the composition of the organic hard mask of antireflection
Background technique
Recently, due to the miniaturization of Electronic equipment panel, complicate and the design of high clustering, accelerate more advanced material
It is also required to the imprint lithography of the exploitation of related process, therefore existing photoresist using new material and technology.
In order to which holding pattern has enough depth and will not collapse in pattern forming technology, thus by the essence of photoresist
Thin pattern is transferred to substrate, can form the organic film of referred to as hard mask layer (hardmask layer), which is
Middle layer.
Hard mask layer is that the fine pattern of photoresist is transferred to material layer by selective etch technique as middle layer.
Therefore, hard mask layer must have the property of heat resistance and corrosion resistance and can bear the ability of multiple etch process.
Meanwhile in recent years it has been proposed that replacing chemical vapor deposition by spin coating cladding process (spin-on coating)
(CVD) method forms hard mask nitride layer.Spin coating cladding process is not only easy to process, and can be improved fill up vacancy (gap-fill) and
Planarization characteristics.
In general, etch resistance is conflicting with spin coating coating characteristic, and it is required to meet all these performances
Organic film material.
Summary of the invention
The present invention is carried out to solve the above problem in the prior art, and the present invention provides a kind of with high etching choosing
The composition of selecting property and multiple etching and enough anti-reflectives makes the reflectivity between photoresist (resist) and back layer
It minimizes.It is in mask material with enough elching resistants outstanding novel organic hard of dissolubility simultaneously the present invention relates to content
Mask material.
A kind of composition for the organic hard mask of antireflection, composition include the polymer containing aromatic ring, and the polymer is such as
Shown in formula 1:
Wherein, Ar1For hydrogen, deuterium, halogen radical, hydroxyl, cyano, nitro, amino, amidino groups, C substituted or unsubstituted1~C30Alkyl,
C substituted or unsubstituted2~C30Alkenyl, C substituted or unsubstituted2~C30Alkynyl, C substituted or unsubstituted1~C10Alcoxyl
Base, C substituted or unsubstituted3~C10Naphthenic base, C substituted or unsubstituted2~C10Heterocyclylalkyl, C substituted or unsubstituted6~C30
Aryl, C substituted or unsubstituted2~C30Heteroaryl, C substituted or unsubstituted6~C30Aryloxy group, C substituted or unsubstituted6~
C30Arylthio；Or their any combination；
X is singly-bound, substituted or unsubstituted C1~C20Alkylidene, substituted or unsubstituted C6~C30Arlydene or they
Any combination；
Y is with the substituted C of at least one hydroxyl1~C20Alkylidene, have the substituted C of at least one hydroxyl6~C30
Arlydene, have the substituted C of at least one hydroxyl2~C30Heteroaryl or their any combination；
Z1~Z3Value range be respectively Z1/(Z1+Z2+Z3)=0.05~0.45, Z2/(Z1+Z2+Z3)=0.5, Z3/(Z1+Z2+
Z3)=0.05~0.45.
Preferably: Ar1For any one of the substituent group listed in formula 2:
Preferably: X is any one of the substituent group listed in formula 3:
Preferably: Y is any one of the substituent group listed in formula 4:
Preferably: the weight average molecular weight of polymer is 1,000 to 30,000.
Preferably: composition further includes crosslinking agent and acid catalyst.
Preferably: crosslinking agent is one of melamine resin, amino resins, glycoluril compounds and diepoxides
Or any combination thereof.
Preferably: acid catalyst is p-methyl benzenesulfonic acid monohydrate, p-methyl benzenesulfonic acid pyridine, 2,4,4,6- tetrabromo hexamethylene
Alkane, dienone, styrax, 2- nitrobenzoyl benzene sulfonate and organic sulfonic acid Arrcostab in one or any combination thereof.
Preferably: the composition contains the polymer containing aromatic ring of 1~20 weight %, the crosslinking of 0.1~5 weight %
Agent, the acid catalyst of 0.001~0.05 weight % and 74.95~98.899 weight % organic solvents.
Beneficial effects of the present invention:
According to the present invention, the organic hard mask of antireflection is to have ArF (193nm) and KrF (248nm) when forming film with composition
Anti-reflective film in equal UV short wavelength field, refractive index and absorptivity with useful range, can make photoresist and back layer it
Between reflectivity minimize.And existing organic hard mask object is compared, and etching selectivity example mentions when in imprint lithography technique
Height can be improved to the resistance repeatedly etched.It is organic to can provide the antireflection with excellent graphic (pattern) assessment result
Hard mask composition.
Specific embodiment
It is described in still more detail by the following examples the present invention.However, following embodiment is for illustration purposes only, and unlimited
Make interest field of the invention.
According to the present invention, one kind is provided for the organic hard mask composition of antireflection, and it includes indicated by chemical formula 1
Polymer and organic solvent.
[chemical formula 1]
Wherein, Ar1For hydrogen, deuterium, halogen radical, hydroxyl, cyano, nitro, amino, amidino groups, C substituted or unsubstituted1~C30Alkyl,
C substituted or unsubstituted2~C30Alkenyl, C substituted or unsubstituted2~C30Alkynyl, C substituted or unsubstituted1~C10Alcoxyl
Base, C substituted or unsubstituted3~C10Naphthenic base, C substituted or unsubstituted2~C10Heterocyclylalkyl, C substituted or unsubstituted6~C30
Aryl, C substituted or unsubstituted2~C30Heteroaryl, C substituted or unsubstituted6~C30Aryloxy group, C substituted or unsubstituted6~
C30Arylthio；Or their any combination；
X is singly-bound, substituted or unsubstituted C1~C20Alkylidene, substituted or unsubstituted C6~C30Arlydene or they
Any combination；
Y is with the substituted C of at least one hydroxyl1~C20Alkylidene, have the substituted C of at least one hydroxyl6~C30
Arlydene, have the substituted C of at least one hydroxyl2~C30Heteroaryl or their any combination；
Z1~Z3Value range be respectively Z1/(Z1+Z2+Z3)=0.05~0.45, Z2/(Z1+Z2+Z3)=0.5, Z3/(Z1+Z2+
Z3)=0.05~0.45；
Here " displacement " shown is hydrogen atom by C1~C5Alkyl, C6~C30Aryl, C2~C30Heterocycle or they
Any combination replace.
In above-mentioned chemical formula 1, Ar1It can be any one of the substituent group listed in the following group 1.
[group 1]
X in above-mentioned chemical formula 1 is mainly to carry out the one-to-one copolymerization polymerizeing with aromatic cycle compound under the conditions of acid catalyst
Monomer forms bonding, and there is raising to be formed by the deliquescent polymeric linkers group of polymer in a solvent for it
(linkage group), X has following structure.
X can be the compound with aldehyde form, such as paraformaldehyde (paraformaldehyde), benzaldehyde
(benzaldehyde) etc. or the compound with dimethoxy (dimethoxy), diethoxy (di-ethoxy), in acid
Preparation is reacted with above-mentioned carbazole derivates under catalyst.
For example, X can be any one of the substituent group listed in following 2nd group in chemical formula 1.
[group 2]
Y in chemical formula 1 is another form aryl compound with hydroxyl (OH), primarily to improving entire polymer
Thermosetting property (thermosetting) reactivity of structure and improvement etch (etching) selection percentage and introduce.
For example, Y can be any one of the substituent group illustrated in following 3rd group in chemical formula 1.
[group 3]
At this point, the structure indicated without hydroxyarylene (hydroxyarylene) mentioned in above-mentioned group 3 also implies that shape
At conventional hydroxyarylene structure.
The weight average molecular weight (Mw) of polymer can be 1,000 to 30,000.Above-mentioned weight average molecular weight can be by solidifying
Glue penetration chromatography measures the average molecular weight of polymer.
Above-mentioned polymer includes the anti-reflective of polymer by possessing weight average molecular weight in above range, adjustable and optimization
Penetrate the solubility of organic hard mask composition in organic solvent.As described above, according to the actual situation to polymer organic
Solubility in solvent, which optimizes and is conducive to organic solvent, to be stablized, the organic hard mask of the antireflection comprising above-mentioned polymer
With composition as photoresist lower membrane materials'use when, can make in photoetching agent pattern forming process due to solvent remove
Or byproduct caused by chemicals generation minimizes, and top can to thickness loss caused by photoresist solvent
To be minimized.
Organic solvent is not particularly limited, as long as it has enough dissolubilities or dispersibility, example in the polymer
Such as, propylene glycol, propylene glycol diacetate, methoxy propylene glycol, ethylene glycol, butyl, triethylene glycol monomethyl ether, propylene glycol
Monomethyl ether, propylene glycol methyl ether acetate, cyclohexanone, ethyl oleate, butyrolactone, N,N-dimethylformamide, N, N- dimethyl
At least one of acetamide, N-Methyl pyrrolidone, acetylacetone,2,4-pentanedione and 3- ethoxy ethyl ester.
Meanwhile the above-mentioned organic hard mask of antireflection can further include crosslinking agent and acid catalyst with composition.
Crosslinking agent preferably considers, is heated in the reaction being catalyzed by the acid of generation come the repetitive unit of cross-linked polymer,
And acid catalyst is preferably the acid catalyst of thermal activation.
More specifically, crosslinking agent is not particularly limited, as long as it is the mode that can be caused catalysis by generated acid
The crosslinking agent reacted with the hydroxyl with the polymer containing aromatic ring.
For example, above-mentioned crosslinking agent, which can be, selects melamine resin (melamine resin), amino resins, glycoluril
(glycoluril) at least one of compound and bifunctional epoxy resin compound.
More specifically, above-mentioned crosslinking agent, which is selected from, is etherified caused amino resins, such as methylation or butylated melamine
Amine-formaldehyde resins (especially methylated melamine and butylated melamine resins), methylation or butylated urea resins
(UreaResin) (specific example is for (specific example is 80 resin of Cymel U-65 resin or UFR), glycoluril compounds
Powderlink 1174) and diepoxides (specific example is resorcinolformaldehyde resin) or any combination thereof.
Acid catalyst for antireflection organic hard mask composition of the invention is that p-methyl benzenesulfonic acid one can be used
The organic acids such as hydrate, in addition it is possible to use promoting hot acid propellant (the Thermal Acid of storage stability
Generater, TAG) system compound as catalyst.The acid-producing agent chemical combination of release acid when hot acid propellant is heat treatment
Object, for example, p-methyl benzenesulfonic acid pyridine, 2,4,4,6- tetrabromo cyclohexadiene, styrax, 2- nitrobenzoyl benzene sulfonate and organic sulphur
At least more than one in the Arrcostab of acid.
In another example, acid catalyst is selected from p-methyl benzenesulfonic acid monohydrate, p-methyl benzenesulfonic acid monohydrate, to first
Benzene sulfonic acid pyridine, 2,4,4,6- tetrabromo hexamethylene dienone, styrax, 2- nitrobenzoyl benzene sulfonate and organic sulfonic acid alkyl
One or combinations thereof in ester.
In addition, the above-mentioned organic hard mask object of antireflection is the above-mentioned polymer comprising weight 1~20%, weight with composition
0.1~5% crosslinking agent, 74.95~98.899% organic solvent of acid catalyst and weight of weight 0.001~0.05%.
According to specific embodiment, antireflection organic hard mask object composition includes above-mentioned polymer weight 1~20%,
The polymer of weight 3~15% can be used in synthesis example；Weight can be used in synthesis example for above-mentioned crosslinking agent weight 0.1~5%
The crosslinking agent of amount 0.001~0.03%；Acid catalyst weight 0.001~0.05%, can be used in synthesis example weight 0.001 to
Organic solvent can be used in 0.03% acid catalyst and remaining ingredient and total amount reaches 100% weight；Organic solvent can account for
Weight 74.95~98.899%.
When above-mentioned polymer weight is less than 1% or is more than weight 30%, more than desired coating layer thickness or will be less than
Target coating calipers, it is difficult to reach target coating calipers.
When the amount of above-mentioned crosslinking agent is less than weight 0.1%, bridging property characteristic may not be shown, when the amount of crosslinking agent is big
When weight 5%, since excessive addition can change the optical characteristics of film.
If the amount of acid catalyst will not show bridging property characteristic when being less than weight 0.001%, if acid catalyst
Amount is excessively added when being more than weight 0.05% will increase acidity, may influence storage stability.
Have an existing mode according to work, the organic hard mask of antireflection with composition be have when forming film ArF (193nm) and
Anti-reflective film in the UV short wavelength fields such as KrF (248nm), refractive index and absorptivity with useful range, can make photoresist
Reflectivity between back layer minimizes.And existing organic hard mask object is compared, and is etched when in imprint lithography technique
Selection percentage improves, and can be improved to the resistance repeatedly etched.
Synthesis of the present invention by following polymer and the preparation of the organic hard mask composition of the antireflection comprising it
Embodiment is next, and the present invention will be described in more detail.But the present invention is not limited by the following examples.
Synthesis example
Synthesis example 1-1) 2- (8- bromine how -1- base) aniline synthesis
Three (the dibenzylidenes of the 2- aminobenzoic acid of 10.0g, the 1,8- dibromine naphthalene of 22.97g, 8.44g are added in the reaction vessel
Acetone) two palladiums, 200mL dimethylformamide after, in reaction mixture add 170mL (2mol/kg) potash water
Solution.Reaction mixture is heated to 80 DEG C and is stirred.After the reaction was completed, reaction mixture is cooled to room temperature and is added thereto
Enter 400mL ethyl acetate.Organic layer is cleaned with the distilled water of 100mL.30 are stirred in organic layer plus after 10g anhydrous magnesium sulfate
Point.Condensed organic matter is evaporated under reduced pressure after organic layer filtering.It is purified using silica gel chromatograph (hexanes/ch=3/1)
To 2- (8- bromine how -1- base) aniline (yield 56.2%, MS:[M]=298) of 12.24g.
Synthesis example 1-2) 7H- benzo [kl] acridine synthesis
2- (8- bromonaphthalene -1- base) aniline of 10.0g, the tris(dibenzylideneacetone) dipalladium of 2.83g are added in the reaction vessel,
The toluene of 200mL is added after the tetrafluoro boric acid tri-tert-butylphosphine that 0.90g is added in the sodium tert-butoxide of 11.28g.Reaction mixture
It is heated to reflux 12 hours.After reaction terminates, reaction mixture is cooled to room temperature, and the ethyl acetate of 200mL is added thereto.With
100mL distills water washing organic layer.5g anhydrous magnesium sulfate is added in organic layer, then stirs 30 minutes.Organic layer is filtered
And it is concentrated under reduced pressure.The residue of concentration is purified using silica gel chromatograph (hexane/ethyl acetate=4/1), obtains the 7H- of 4.85g
Benzo [kl] acridine (yield 66.5%, MS:[M]=217).
Synthesis example 1-3) 7- phenyl -7H- benzo [kl] acridine synthesis
The bromobenzene of 5.03g, 7H- benzo [kl] acridine of 7.66g, the three (dibenzylidenes third of 2.70g are added in reaction vessel
Ketone) two palladiums, the sodium tert-butoxide of 10.78g, be added 0.86g tetrafluoro boric acid tri-tert-butylphosphine after, the toluene of 200mL is added.It will
Reaction mixture is heated to reflux 12 hours.After reaction terminates, reaction mixture is cooled to room temperature, 400mL is added thereto
Ethyl acetate.The distillation water washing of organic layer 200mL.The anhydrous magnesium sulfate of 15g is added into organic layer, then stirs 30
Minute.Organic layer is filtered and is concentrated under reduced pressure.The residue of concentration is carried out to utilize silica gel chromatograph (hexane/ethyl acetate=4/
1) purifying obtain 5.10g 7-phenyl-7H- benzo [kl] acridine (yield 58%, MS:[M]=293).
Synthesis example 1-4) other synthesis
According into 1-3, identical mode obtains in following table 1 A-1 to A-8 compound with synthesis example 1-1.
[table 1]
Synthesis example 2-1) synthesis 7- phenyl -7H- benzo [kl] acridine, paraformaldehyde, 1- naphthols polymer.
In inner 7- phenyl -7H- benzo [kl] acridine, the 6.4g that 29.3g (100mmol) is added of reaction vessel (250mL)
The 1- naphthols of (200mmol) paraformaldehyde and 14.4g (100mmol), use the propylene glycol methyl ether acetate (PGMEA) of 107g as
The sulfuric acid of 0.8g is added in solvent.It is polymerize while under the conditions of keeping reaction temperature to be about 120 DEG C, and is made in reaction
Molecular weight is surveyed with GPC.After reaction about 12 hours, reaction mixture is added dropwise in excessive methanol/water (9:1) cosolvent,
And obtained solid is dissolved in suitable PGMEA (propylene glycol methyl ether acetate) solvent again and is added dropwise to excessive second again later
Sediment is obtained in alcohol/water (9:1) cosolvent.Obtained solid is 20 hours dry in about 50 DEG C of vacuum drying oven, it obtains
To 2,700 weight average molecular weight (Mw) polymer.
Synthesis example 2-2) synthesis 7- phenyl -7H- benzo [kl] acridine, bis- (methoxy) benzene of 1,4-, beta naphthal gather
Close object.
In inner 7- phenyl -7H- benzo [kl] acridine, the 20g that 17.6g (60mmol) is added of reaction vessel (250mL)
Bis- (methoxy) benzene of the 1,4- of (120mmol) (1,4-Bis (methoxymethyl) benzene (MBB)), 8.7g
The beta naphthal of (60mmol) is dissolved in 102g propylene glycol methyl ether acetate (PGMEA), is then added into reaction vessel
0.5g sulfuric acid.
After being polymerize in such a way that synthesis example 2-1 is identical, dry by polymer purification and in vacuum drying oven to obtain
The polymer that weight average molecular weight is 2,900.
Synthesis example 2-3) synthesis 7- phenyl -7H- benzo [kl] acridine, benzaldehyde, 1- naphthols polymer.
7- phenyl -7H- benzo [kl] acridine, the 13g of 17.6g (60mmol) are added in 250mL reaction vessel
Benzaldehyde, 8.7g (60mmol) the 1- naphthols of (120mmol) are dissolved in the propylene glycol methyl ether acetate (PGMEA) of 93g, so
The sulfuric acid of 0.5g is added in backward reaction vessel.
After being polymerize in such a way that synthesis example 2-1 is identical, dry by polymer purification and in vacuum drying oven to obtain
The polymer that weight average molecular weight is 2,800.
Synthesis example 2-4) synthesis 7- (phenanthrene -9- base) -7H- benzo [kl] acridine, benzaldehyde, 1- naphthols copolymer.
In inner 7- (phenanthrene -9- base) -7H- benzo [kl] acridine (7- that 15.7g (40mmol) is added of reaction vessel (250mL)
(phenanthren-9-yl) -7H-benzo [kl] acridine)/(A-3) and 11g (100mmol) benzaldehyde
(benzaldehyde), the 1- naphthols of 8.7g (60mmol) is dissolved in the propylene glycol methyl ether acetate (PGMEA) of 79g, so
The sulfuric acid of 0.4g is added in backward reaction vessel.
After polymerizeing in such a way that synthesis example 2-1 is identical, dry by polymer purification and in vacuum drying oven to obtain weight
The polymer that molecular weight is 3,100.
Synthesis example 2-5) synthesis 7- (pyrene -1- base) -7H- benzo [kl] acridine, benzaldehyde, 1- naphthols polymer
Inner 7- (pyrene -1- base) -7H- benzo [kl] acridine (7- (pyren- that 25.1g (60mmol) is added of reaction vessel (250mL)
1-yl) -7H-benzo [kl] acridine)/(A-5), the benzaldehyde of 13g (120mmol), 13g (60mmol) 1- hydroxyl pyrene
It is dissolved in the propylene glycol methyl ether acetate (PGMEA) of 93g, the sulfuric acid of 0.5g is then added into reaction vessel.
After polymerizeing in such a way that synthesis example 2-1 is identical, dry by polymer purification and in vacuum drying oven to obtain weight
The polymer that molecular weight is 2,800.
Synthesis example 2-6) synthesis 7- ([1,1'- biphenyl] -4- base) -7H- benzo [kl] acridine, benzaldehyde, 1- naphthols be total to
Polymers.
In inner 7- ([1,1'- biphenyl] -4- the base) -7H- benzo that 22.1g (60mmol) is added of reaction vessel (250mL)
[kl] acridine (7- ([1,1'-biphenyl] -4-yl) -7H-benzo [kl] acridine)/(A-1), 13g (120mmol)
Benzaldehyde, 13g (60mmol) 1- hydroxyl pyrene be dissolved in the propylene glycol methyl ether acetate (PGMEA) of 107g, then to anti-
Answer the sulfuric acid that 0.5g is added in container.
After polymerizeing in such a way that synthesis example 2-1 is identical, dry by polymer purification and in vacuum drying oven to obtain weight
The polymer that molecular weight is 3,000.
Synthesis example 2-7) synthesis 7- (pyrene -1- base) -7H- benzo [kl] acridine, paraformaldehyde, 1- naphthols copolymer.
In inner 7- (pyrene -1- base) -7H- benzo [kl] acridine/(A- that 25.1g (60mmol) is added of reaction vessel (250mL)
5), the paraformaldehyde of 4.3g, 13g (60mmol) 1- hydroxyl pyrene be dissolved in the propylene glycol methyl ether acetate (PGMEA) of 93g
It is put into reaction vessel, the sulfuric acid of 0.5g is then wherein added into reaction vessel.
After polymerizeing in such a way that synthesis example 2-1 is identical, dry by polymer purification and in vacuum drying oven to obtain weight
The polymer that molecular weight is 3,100.
Synthesis example 2-8) synthesis 7- (pyrene -1- base) -7H- benzo [kl] acridine, paraformaldehyde, 9,9- bis- (4- hydroxy phenyls)
The copolymer of fluorenes.
In inner 7- (pyrene -1- base) -7H- benzo [kl] acridine/(A- that 20.9g (50mmol) is added of reaction vessel (250mL)
5), bis- (4- hydroxy phenyl) fluorenes (9,9-Bis (4- of 9,9- of the paraformaldehyde of 3.6g, 17.5g (50mmol)
Hydroxyphenyl) fluorine) it is dissolved in the propylene glycol methyl ether acetate (PGMEA) of 93g and is put into reaction vessel,
Then the sulfuric acid of 0.4g is added into reaction vessel.
After polymerizeing in such a way that synthesis example 2-1 is identical, dry by polymer purification and in vacuum drying oven to obtain weight
The polymer that molecular weight is 3,000.
Synthesis example 2-9) synthesis 7- (pyrene -1- base) -7H- benzo [kl] acridine, the bis- toluene of 1,4-, 1- naphthols copolymer.
In inner 7- (pyrene -1- base) -7H- benzo [kl] acridine/(A- that 25.1g (60mmol) is added of reaction vessel (250mL)
5), the bis- toluene of 1,4- (1,4-Bis (methoxymethyl) benzene), 13g (60mmol) 1- hydroxyl of 20g (120mmol)
Pyrene is dissolved in the propylene glycol methyl ether acetate (PGMEA) of 130g and is put into reaction vessel, is then added into reaction vessel
The sulfuric acid of 0.5g.
After polymerizeing in such a way that synthesis example 2-1 is identical, dry by polymer purification and in vacuum drying oven to obtain weight
The polymer that molecular weight is 2,700.
Synthesis example 2-10) synthesis 7- (naphthalene -1- base) -7H- benzo [kl] acridine, benzaldehyde, 1- naphthols copolymer.
In inner 7- (naphthalene -1- base) -7H- benzo [kl] acridine (7- that 20.6g (60mmol) is added of reaction vessel (250mL)
(naphthalen-1-yl) -7H-benzo [kl] acridine)/(A-2) and 20g (120mmol) benzaldehyde, by 13g
The 1- hydroxyl pyrene of (60mmol) is dissolved in the propylene glycol methyl ether acetate (PGMEA) of 119g and is put into reaction vessel, then
The sulfuric acid of 0.5g is added into reaction vessel.
After polymerizeing in such a way that synthesis example 1 is identical, dry by polymer purification and in vacuum drying oven to be divided equally again
The polymer that son amount is 2,700.
Compare synthesis example: (copolymer of synthesis 4,4'- (9H- fluorenes -9,9- diyl) diphenol and benzaldehyde)
In inner addition 35g (100mmol's) 4,4'- of reaction vessel (250mL) (9H- fluorenes -9,9- diyl) diphenol (4,4'- (9H-
Fluorene-9,9-diyl) diphenol) and 11g (100mmol) dissolution of benzaldehyde 110g propylene glycol monomethyl ether acetic acid
In ester (PGMEA), 1g sulfuric acid is then wherein added.
It is polymerize under conditions of keeping reaction temperature at about 120 DEG C, and uses gpc measurement molecular weight in reaction.
After reaction about 12 hours, reaction mixture is added drop-wise in excessive methanol/water (9:1) cosolvent, and again by obtained solid
It is dissolved in suitable PGMEA solvent, then excessive ethanol/water (9:1) is added dropwise is put into cosolvent and precipitate.Obtained solid is true
It is about 20 hours dry at about 50 DEG C in empty baking oven, obtain the polymer that weight average molecular weight (Mw) is 3100.
Embodiment example 1 to 10 and comparative example
The preparation of the organic hard mask compositions of antireflection
Weigh synthesis exampleWith compare each 0.9g of polymer prepared in synthesis example, it is sweet that 0.1g is added thereto respectively
Carbamide compound crosslinking agent (Powderlink1174) and 1mg carbamate curing catalysts (p-methyl benzenesulfonic acid pyridine) dissolution
In the propylene glycol methyl ether acetate (PGMEA) of 9g, and filter to prepare synthetic example 2-1 to 2-10 and compare synthesis in fact
Apply the sample solution in example.
By synthesis example 2-1 to 2-10 and compare each sample solution spin coating under conditions of 240 DEG C, 60 seconds prepared in synthesis example
On silicon, and obtain 3000nm film forms embodiment 1 to 10 and a comparative example organic hard mask compositions.
Evaluate the optical property (refractive index, extinction coefficient) of embodiment 1 to 10 and comparative example
The refractive index n and extinction coefficient k of the film formed in measurement embodiment 1 to 10 and comparative example.The instrument used is the U.S.
The ellipsometer of JAWoollam company.Measurement result is as shown in table 2.
[table 2]
As shown in table 2, by using respectively according to the film of the sample solution of embodiment 1-10 preparation in 193nm (ArF) and
The refractive index and absorption coefficient of anti-reflection coating are used as at 248nm (KrF) wavelength.Although on the contrary, by making respectively
Have with the film prepared according to comparative example 1 and shows that they are used as anti-reflection coating at 193nm (ArF) wavelength
Refractive index and absorbance (absorptivity), but relatively low absorbance is shown at 248nm (KrF) wavelength.
The evaluation of pattern performance
By synthesis example 2-3,2-6,2-8, the sample solution of 2-10 and comparative example 1 is spin-coated on respectively on the silicon wafer for being coated with aluminium, and
It is toasted 60 seconds at 240 DEG C, forms the embodiment 3 with the film of 3000nm thickness, embodiment 6, embodiment 8,10 He of embodiment
Comparative example 1.
KrF photoresist is coated on the film and is toasted 60 seconds at 110 DEG C, after baking process, is set using exposure
Standby (ASML (XT:1400, NA 0.93)) exposes obtained product, and (concentration is using tetramethylammonium hydroxide
The aqueous solution of 2.38wt%) development.Then the 90nm line and space diagram of film are checked using field-emission scanning Electronic Speculum (FE-SEM)
Case (line and space pattern).Show in table 3 and has located result.Measure the variation for depending on exposure metering of pattern
Exposure latitude (EL) nargin and depending on the depth of focus (DOF) nargin with a distance from light source.It has been shown in table 3 result.
[table 3]
As shown in table 3, for pattern distribution and nargin, by using the sample solution system according to embodiment 3,6,8,10 respectively
Standby film has good result.On the contrary, for pattern distribution or nargin, by using the sample according to comparative example 1 respectively
The film of solution preparation has relatively poor as a result, this is because the difference in 248nm (KrF) absorbing at wavelengths characteristic causes
's.
The evaluation of etching characteristic
In the Patterned Sample of embodiment 3,6,8,10 and comparative example 1, silicon nitride (SiN) film is arranged under anti-reflective film
Layer.Use CHF3/CF4The mixed gas of (fluoroform/carbon tetrafluoride) carries out dry method erosion to SiON bottom anti-reflective film (BARC)
It carves, and then uses O again2/N2Mixed gas carries out dry etching to SiON bottom anti-reflective film, uses CHF3/CF4Mixed gas
Dry etching is carried out as organic hard mask object silicon nitride (SiN) film, then remaining organic hard mask and remaining organic matter
Carry out O2Cineration technics and wet stripping techniques.
After organic hard mask object etching and silicon nitride etch, the transversal of each sample is checked with FE-SEM respectively immediately
As a result face is shown in Table 4.
[table 4]
As shown in table 4, by using the patterned sample prepared according to the sample solution of embodiment 3,6,8,10 organic hard
There is good etch profile (distribution) after the etching of mask object and after silicon nitride (SiN) etching, show that they have pole
Good etching selectivity.Erosion by using the patterned sample of 1 sample solution of comparative example preparation in etching assessment on the contrary
Carving shape has the phenomenon that bending, shows that they lack selectivity under etching condition.
Although having been described above and describing specific embodiments of the present invention, it should be appreciated that, the present invention is not limited to
The disclosed embodiments, and can make various changes and modifications without departing from the spirit and scope of the present invention and be
For possessing for these technical side's dough figurines easily thing.
It should therefore be understood that these modifications or change should not be detached from from technical spirit and viewpoint of the invention and understand,
And the embodiment modified should be included in the scope of the claims of the invention.
Claims (9)
1. a kind of composition for the organic hard mask of antireflection, it is characterised in that: composition includes the polymer containing aromatic ring, should
Polymer is as shown in Equation 1:
Wherein, Ar1For hydrogen, deuterium, halogen radical, hydroxyl, cyano, nitro, amino, amidino groups, C substituted or unsubstituted1~C30Alkyl,
C substituted or unsubstituted2~C30Alkenyl, C substituted or unsubstituted2~C30Alkynyl, C substituted or unsubstituted1~C10Alcoxyl
Base, C substituted or unsubstituted3~C10Naphthenic base, C substituted or unsubstituted2~C10Heterocyclylalkyl, C substituted or unsubstituted6~C30
Aryl, C substituted or unsubstituted2~C30Heteroaryl, C substituted or unsubstituted6~C30Aryloxy group, C substituted or unsubstituted6~
C30Arylthio；Or their any combination；
X is singly-bound, substituted or unsubstituted C1~C20Alkylidene, substituted or unsubstituted C6~C30Arlydene or they
Any combination；
Y is with the substituted C of at least one hydroxyl1~C20Alkylidene, have the substituted C of at least one hydroxyl6~C30
Arlydene, have the substituted C of at least one hydroxyl2~C30Heteroaryl or their any combination；
Z1~Z3Value range be respectively Z1/(Z1+Z2+Z3)=0.05~0.45, Z2/(Z1+Z2+Z3)=0.5, Z3/(Z1+Z2+
Z3)=0.05~0.45.
2. composition according to claim 1, it is characterised in that: Ar1For any one of the substituent group listed in formula 2:
3. composition according to claim 1, it is characterised in that: X is any one of the substituent group listed in formula 3:
4. composition according to claim 1, it is characterised in that: Y is any one of the substituent group listed in formula 4:
5. composition described in -4 according to claim 1, it is characterised in that: the weight average molecular weight of polymer is 1,000 to 30,
000。
6. composition described in -4 according to claim 1, it is characterised in that: composition further includes crosslinking agent and acid catalyst.
7. composition according to claim 6, it is characterised in that: crosslinking agent is melamine resin, amino resins, glycoluril
One of compound and diepoxides or any combination thereof.
8. composition according to claim 6, it is characterised in that: acid catalyst is p-methyl benzenesulfonic acid monohydrate, to first
Benzene sulfonic acid pyridine, 2,4,4,6- tetrabromo hexamethylene, dienone, styrax, 2- nitrobenzoyl benzene sulfonate, organic sulfonic acid alkyl
One or any combination thereof in ester.
9. composition according to claim 6, it is characterised in that: the composition contains containing for 1~20 weight %
The polymer of aromatic ring, the crosslinking agent of 0.1~5 weight %, the acid catalyst and 74.95~98.899 of 0.001~0.05 weight %
Weight % organic solvent.
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| JP2022525533A (en) * | 2019-04-09 | 2022-05-17 | ヨンチャン ケミカル カンパニー リミテッド | High-thickness spin-on carbon hard mask composition and patterning method using it |
| TWI824696B (en) * | 2021-09-07 | 2023-12-01 | 南韓商三星Ｓｄｉ股份有限公司 | Hardmask composition, hardmask layer, and method of forming patterns |
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Application publication date: 20190111 |