KR20170014948A - Method of producimg hardmask layer, and method of forming patterns - Google Patents
Method of producimg hardmask layer, and method of forming patterns Download PDFInfo
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- KR20170014948A KR20170014948A KR1020150109030A KR20150109030A KR20170014948A KR 20170014948 A KR20170014948 A KR 20170014948A KR 1020150109030 A KR1020150109030 A KR 1020150109030A KR 20150109030 A KR20150109030 A KR 20150109030A KR 20170014948 A KR20170014948 A KR 20170014948A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/033—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers
- H01L21/0334—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane
- H01L21/0337—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising inorganic layers characterised by their size, orientation, disposition, behaviour, shape, in horizontal or vertical plane characterised by the process involved to create the mask, e.g. lift-off masks, sidewalls, or to modify the mask, e.g. pre-treatment, post-treatment
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31144—Etching the insulating layers by chemical or physical means using masks
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/312—Organic layers, e.g. photoresist
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
- H01L21/56—Encapsulations, e.g. encapsulation layers, coatings
Abstract
And a method of manufacturing the hard mask layer.
According to one embodiment, there is provided a method of manufacturing a semiconductor device, comprising: coating a first composition comprising an organic compound on a patterned substrate and then curing to form a first hardmask layer; and forming a second hardmask layer on the first hardmask layer, Coating the composition and then curing to form a second hard mask layer.
Description
And more particularly, to a method of fabricating a hard mask layer for forming a multi-pattern structure such as a dual damascene wiring structure, and a method of forming a pattern according to the method.
BACKGROUND ART [0002] In recent years, the semiconductor industry has developed into an ultrafine technology having a pattern of a few to a few nanometers in a pattern of a size of several hundred nanometers. Effective lithographic techniques are essential to realize this ultrafine technology.
A typical lithographic technique involves forming a material layer on a semiconductor substrate, coating a photoresist layer thereon, exposing and developing the photoresist layer to form a photoresist pattern, and etching the material layer using the photoresist pattern as a mask do.
In recent years, as the size of a pattern to be formed decreases, it is difficult to form a fine pattern having a good profile only by the typical lithographic technique described above. Accordingly, a fine pattern can be formed by forming an organic film called a hardmask layer between the material layer to be etched and the photoresist layer.
The hard mask layer acts as an interlayer to transfer the fine pattern of the photoresist to the material layer through the selective etching process. Therefore, the hard mask layer needs to have heat resistance and resistance to erosion resistance so as to withstand the multiple etching process.
Further, in the case where there is a step on the substrate to be processed in the multiple patterning process, or in the case where the pattern density portion and the patternless region are present together on the wafer, the hard mask layer filled in the pattern has a planarization characteristic This is especially important.
Therefore, a hard mask layer capable of satisfying the above-mentioned characteristics is required.
One embodiment provides a method of manufacturing a hard mask layer capable of minimizing a step between a hard mask layer formed on a pattern portion of a substrate and a hard mask layer formed on the non-pattern portion.
Another embodiment provides a method of forming a pattern using a hard mask layer formed according to the above method.
According to one embodiment, there is provided a method of manufacturing a semiconductor device, comprising: coating a first composition comprising an organic compound on a patterned substrate and then curing to form a first hard mask layer; And then curing the first hard mask layer to form a second hard mask layer.
The second hardmask layer may be formed directly on the first hardmask layer.
The organic compound content in the first composition may be 1 wt% to 30 wt%, and the organic compound content in the second composition may be 1 wt% to 20 wt%.
The curing of the first composition and the second composition may each independently be carried out at 100 ° C to 500 ° C for 10 seconds to 1 hour.
The carbon content of the organic compound contained in the first composition and the carbon content of the organic compound contained in the second composition may independently be 60 atom% to 96 atom%.
The organic compound contained in the first composition and the organic compound contained in the second composition are each independently at least one substituted or unsubstituted aromatic ring group, a substituted or unsubstituted aliphatic ring group, a substituted or unsubstituted hetero ring An aromatic ring group, a substituted or unsubstituted heteroaliphatic ring group, or a combination thereof.
The first composition and the second composition may each independently comprise an organic polymer, an organic monolayer, or a combination thereof.
The organic polymer may have a weight average molecular weight of 500 to 200,000.
The organic monomolecular molecule may have a molecular weight of 250 to 5,000.
The first composition or the second composition may further comprise an additive including a surfactant, a plasticizer, a crosslinking agent, a thermal acid generator (TAG), a photoacid generator (PAG), or a combination thereof.
The amount of the additive contained in the first composition is about 0.001 to 40 parts by weight based on 100 parts by weight of the first composition and the amount of the additive included in the second composition is about 0.001 to 40 parts by weight based on 100 parts by weight of the second composition. Weight portion.
Wherein the first composition further comprises a first solvent and the second composition further comprises a second solvent, wherein the first solvent and the second solvent are each independently selected from the group consisting of propylene glycol, propylene glycol diacetate, methoxypropane Diethylene glycol, diethylene glycol butyl ether, tri (ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolactone, N-dimethylformamide, N, N-dimethylacetamide, methylpyrrolidone, methylpyrrolidinone, acetylacetone, ethyl 3-ethoxypropionate, or combinations thereof.
The first composition and the second composition may each independently be coated to a thickness of 50 A to 10 mu m.
The first composition and the second composition may be coated by spin-on coating, screen printing, slit coating, dipping, inkjet printing, casting or spray coating.
According to another embodiment, there is provided a method of manufacturing a hard mask comprising: providing a hard mask layer made according to the above-described fabrication method; Forming a silicon-containing thin film layer on the hard mask layer; Forming a photoresist layer on the silicon-containing thin film layer; Exposing and developing the photoresist layer to form a photoresist pattern; And selectively removing the silicon-containing thin film layer and the hard mask layer using the photoresist pattern.
And forming a material layer on the substrate prior to forming the first hardmask layer.
And forming a bottom anti-reflective layer (BARC) before the step of forming the photoresist.
The silicon-containing thin film layer may comprise SiCN, SiOC, SiON, SiOCN, SiC, SiN, or a combination thereof.
A hard mask layer having good step characteristics can be formed even on a wafer having a relatively deep pattern depth.
1 is a cross-sectional view of a hard mask layer formed according to a method of manufacturing a hard mask layer according to an embodiment,
Fig. 2 is a reference diagram for explaining the calculation formula 1 for evaluating the planarization characteristic,
3 is a reference diagram for explaining calculation formula 2 for evaluating the step property.
Hereinafter, exemplary embodiments of the present invention will be described in detail so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
In the drawings, the thickness is enlarged to clearly represent the layers and regions. Like parts are designated with like reference numerals throughout the specification. Whenever a portion of a layer, film, region, plate, or the like is referred to as being "on" another portion, it includes not only the case where it is "directly on" another portion, but also the case where there is another portion in between. Conversely, when a part is "directly over" another part, it means that there is no other part in the middle.
The singular forms used in this specification include plural forms unless the context clearly dictates otherwise. The word " comprises "and / or" comprising ", as used herein, refers to features, integers, steps, operations, Elements, components, and / or components, but does not preclude the addition of one or more other aspects, numbers, steps, operations, component elements, and / or sets thereof.
Unless otherwise defined herein, "substituted" means that the hydrogen atom in the compound is a halogen atom (F, Br, Cl, or I), a hydroxy group, an alkoxy group, a nitro group, a cyano group, an amino group, A thio group, an ester group, a carboxyl group or a salt thereof, a sulfonic acid group or a salt thereof, a phosphoric acid or a salt thereof, a C1 to C20 alkyl group, a C2 to C20 alkenyl group, a C2 to C20 alkenyl group, a C2 to C20 alkenyl group, A C3 to C30 heteroaryl group, a C3 to C30 heteroaryl group, a C3 to C30 cycloalkyl group, a C3 to C30 aryl group, a C7 to C30 arylalkyl group, a C1 to C30 alkoxy group, a C1 to C20 heteroalkyl group, a C2 to C20 hetero aryl group, Substituted with a substituent selected from the group consisting of a cycloalkenyl group, a C 6 to C 15 cycloalkynyl group, a C 2 to C 30 heterocycloalkyl group, and combinations thereof.
In addition, unless otherwise defined herein, "hetero" means containing 1 to 3 heteroatoms selected from N, O, S and P.
Hereinafter, a method of manufacturing a hard mask layer according to one embodiment will be described with reference to FIG.
A method of fabricating a hard mask layer according to an embodiment includes forming a first hard mask layer (S1) by coating a patterned substrate with a first composition containing an organic compound and curing the patterned substrate, (S2) coating a second composition containing an organic compound on the layer and curing the second composition to form a second hard mask layer.
The substrate may be, for example, a silicon wafer, a glass substrate, or a polymer substrate. Alternatively, the substrate may be a silicon substrate, a silicon nitride, a TiSi, a silicide, a polysilicon tungsten, copper, aluminum, TiN, TaN or a combination thereof on a glass substrate or a polymer substrate.
The substrate has a plurality of patterns on one surface, and the shape of the pattern is not limited to a triangle, a square, a circle, and the like. The average size (length, width) of the patterns may be, for example, several nanometers to several hundred nanometers, and the average size (length, depth) of the patterns may be several tens of micro Meter.
According to one embodiment, the hardmask layer is formed through a two-step coating and curing process. That is, a first hard mask layer is first formed (S1) through a primary coating and curing process, and a second hard mask layer is formed thereon through a secondary coating and curing process (S2). In one example, the second hardmask layer may be formed directly on the first hardmask layer.
The hard mask layer thus formed by the multiple coating and curing process can have a relatively small step value as compared with the hard mask layer formed by the single coating and curing process. That is, the difference in thickness between the hard mask layer formed in the pattern portion of the substrate and the hard mask layer formed in the non-pattern portion can be minimized.
For example, the organic compound content in the first composition may be 1 to 30 wt%, and the organic compound content in the second composition may be 1 to 20 wt%. The method of manufacturing the hard mask layer can easily adjust the level difference of the layer by coating and hardening the composition having a relatively low solid content in two divided portions.
The first composition and the second composition may be coated on the substrate by, for example, spin-on coating, screen printing, slit coating, dipping, inkjet printing, casting or spray coating. The thickness of the first hard mask layer and the thickness of the second hard mask layer may be determined in consideration of the total thickness of the desired hard mask layer. For example, the first composition and the second composition may each independently have a thickness 10 탆 thick.
For example, curing of the first composition and the second composition may include applying energy to the first composition and the second composition, wherein the energy is selected from the group consisting of thermal energy, ultraviolet light, microwave, And all possible means for curing the first and second compositions. Also, the curing of the first composition and the second composition may each independently be carried out at 100 ° C to 500 ° C for 10 seconds to 1 hour.
For example, the hard mask layer may have a total thickness, that is, a sum of a thickness of the first hard mask layer and a thickness of the second hard mask layer of 50 to 100,000 angstroms.
For example, the carbon content of the organic compound contained in the first composition and the carbon content of the organic compound contained in the second composition may independently be 60 atom% to 96 atom%.
The kind of the organic compound contained in the first composition and the kind of the organic compound contained in the second composition may be the same or different.
The organic compound may include an organic polymer or an organic monomolecular molecule, and the organic polymer and the organic monomolecular molecule may include a blended form. The organic polymer may have a weight average molecular weight of, for example, about 500 to 200,000, or about 1,000 to 100,000, and the organic monomers may have a molecular weight of, for example, about 250 to 5,000, or about 500 to about 3,000, It is not.
For example, the organic compound may include at least one substituted or unsubstituted aromatic ring group, a substituted or unsubstituted aliphatic ring group, a substituted or unsubstituted heteroaromatic ring group, a substituted or unsubstituted heteroaliphatic ring group, As shown in FIG. In this case, the corrosion resistance of the first hard mask layer and the solubility in solvents can be further improved.
For example, the organic compound may include a monovalent or divalent organic group derived from a substituted or unsubstituted cyclic group selected from the following Group 1.
[Group 1]
In the group 1,
Z 1 represents a single bond, a substituted or unsubstituted C1 to C20 alkylene group, a substituted or unsubstituted C3 to C20 cycloalkylene group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroaryl (O), sulfur (S), or a combination thereof, wherein R is a substituted or unsubstituted C2 to C20 alkenylene group, a substituted or unsubstituted C2 to C20 alkynylene group, a is a hydrogen atom, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group, a halogen atom,
Z 3 to Z 18 each independently represent C = O, NR a , oxygen (O), sulfur (S), CR b R c Or a combination thereof, wherein each of R a to R c is independently hydrogen, a substituted or unsubstituted C1 to C10 alkyl group, a substituted or unsubstituted C6 to C20 arylene group, a substituted or unsubstituted C2 to C20 heteroarylene group , A halogen atom, a halogen-containing group, or a combination thereof.
Here, the "monovalent group derived from the A compound" means a monovalent group formed by substituting one hydrogen in the A compound. For example, a monovalent group derived from a benzene group is a phenyl group. Further, the term "bivalent group derived from A compound" means a bivalent group in which two hydrogen atoms in A compound are substituted to form two connecting points. For example, a divalent group derived from a benzene group becomes a phenylene group.
The physical properties of the first composition can be controlled by selecting the kind and the number of the functional groups contained in the organic compound. The functional group may be a hydroxyl group, a halogen atom, a halogen-containing group, a thionyl group, a thiol group, a cyano group, A substituted or unsubstituted C1 to C30 alkyl group, a substituted or unsubstituted C3 to C30 cycloalkyl group, a substituted or unsubstituted C6 to C30 aryl group, a substituted or unsubstituted C3 to C30 cycloalkenyl group, A substituted or unsubstituted C7 to C20 arylalkyl group, a substituted or unsubstituted C1 to C20 heteroalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, a substituted or unsubstituted C2 to C30 heterocycloalkyl group, C30 heteroaryl group, a substituted or unsubstituted C1 to C30 alkoxy group, a substituted or unsubstituted C2 to C30 alkenyl group, a substituted or unsubstituted C2 to C30 alkoxy A substituted or unsubstituted C1 to C20 aldehyde group, a substituted or unsubstituted C1 to C4 alkyl ether, a substituted or unsubstituted C7 to C20 arylalkylene ether, a substituted or unsubstituted C1 to C30 haloalkyl group, A substituted C1 to C20 alkyl group, a substituted C1 to C20 alkyl group, a substituted C1 to C20 alkyl group, and a substituted or unsubstituted C6 to C30 aryl group.
The first composition further comprises a first solvent, and the second composition further comprises a second solvent, and if the first solvent and the second solvent have sufficient solubility or dispersibility for the organic compound, But are not limited to, propylene glycol, propylene glycol diacetate, methoxypropanediol, diethylene glycol, diethylene glycol butyl ether, tri (ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, N-dimethylformamide, N, N-dimethylacetamide, methylpyrrolidone, methylpyrrolidinone, acetylacetone, and ethyl 3-ethoxypropionate, such as cyclohexanone, ethyl lactate, gamma-butyrolactone, And at least one selected from Nate.
The first composition or the second composition may further include additives such as a surfactant, a plasticizer, a crosslinking agent, a thermal acid generator (TAG), and a photoacid generator (PAG).
The surfactant may be, for example, an alkylbenzenesulfonate, an alkylpyridinium salt, a polyethylene glycol, or a quaternary ammonium salt, but is not limited thereto.
The plasticizer may be selected from, for example, DOP (dioctyl phthalate), DOA (dioctyl adipate), TCP (tricresylphostate), diisocctyl phthalate (DIOP), diheptyl, nonyl phthalate (DINP), diunecyl phthalate Di-2-ethylhexyl sebacate (DIDA), diisooctyl azelate (DIOZ), di-2-ethylhexyl sebacate Triethyl 2-ethylhexyl trimellitate (TOTM), polyethylene gpycol ester, ASE (triethyl phosphate), TTP (triphenyl phosphate), CDP (cresyldephenyl phosphate), tricresyl phosphate alkylsulphonic acid phenyl ester), 3G6 (triethylene glycol dihexanoate), 4g7 (tetraethyleneglycol diheptanoate), ATEC (acetyl triethyl citrate), Tributyl citrate (TBC), trioctyl citrate (ATC), acetyl trioctyl citrate ), TMC (trimethyl citrate), DMAD (dimethyl adipate_, MMAD (monomethyl adipate), DBM (dibutyl maleate), DIBM (2, 2-dinitropropyl) formal, BDNPF (2,2,2-trinitroethyl 2-nitroxyethyl ether) polyethylene glycol, polypropylene, or a combination thereof. It is not.
Examples of the cross-linking agent include melamine-based, substitution-based, or polymer-based ones. Preferably, the crosslinking agent having at least two crosslinking substituents is, for example, a methoxymethylated glycerol, a butoxymethylated glyceryl, a methoxymethylated melamine, a butoxymethylated melamine, a methoxymethylated benzoguanamine, a butoxy Methoxymethylated thiourea, methoxymethylated thiourea, methoxymethylated benzene, butoxymethylated benzene, methoxymethylated phenol, butoxymethylated phenol, or a combination thereof, or a combination thereof. But is not limited thereto.
As the crosslinking agent, a crosslinking agent having high heat resistance can be used. As the crosslinking agent having high heat resistance, a compound containing a crosslinking forming substituent group having an aromatic ring (for example, a benzene ring or a naphthalene ring) in the molecule can be used.
Examples of the thermal acid generators include organic sulfonic acid alkyl ester compounds such as benzoin tosylate and 2-nitrobenzyl tosylate, diphenyl iodonium trifluoromethanesulfonate, diphenyl iodonium dodecylbenzenesulfonate , Bis (4-tert-butylphenyl) iodonium camphor sulfonate, bis (4-tert-butylphenyl) iodonium nonafluoro n-butanesulfonate, bis And onium salt compounds such as trifluoromethane sulfonate and triphenylsulfonium trifluoromethane sulfonate. Further, it is also possible to use 2,4,4,6-tetrabromocyclohexadienone, phenyl-bis (trichloromethyl) -s-triazine and N-hydroxysuccinimide trifluoromethanesulfonate, pyridinium p- Pyridinium p-toluenesulfonate, or a combination thereof may be used, but the present invention is not limited thereto.
Examples of the photoacid generators include triphenylsulfonium triflate, triphenylsulfonium antimonate, diphenyliodonium triflate, diphenyliodonium antimonate diphenyliodonium antimonate, methoxydiphenyliodonium triflate, di-t-butyldiphenyliodonium triflate, 2,6-dinitrobenzylsulfonate (2 , 6-dinitrobenzyl sulfonates, pyrogallol tris (alkylsulfonates), N-hydroxysuccinimide triflate, norbornene-dicarboximide-triflate norbornene-dicarboximide-triflate, triphenylsulfonium nonaflate, diphenyliodonium nonaflate, methoxydiphenyl, But are not limited to, methoxydiphenyliodonium nonaflate, di-t-butyldiphenyliodonium nonaflate, N-hydroxysuccinimide nonaflate, norbornene- Norbornene-dicarboximide-nonaflate, triphenylsulfonium perfluorobutanesulfonate, triphenylsulfonium perfluorooctanesulfonate (PFOS), diphenylsulfonium perfluorobutanesulfonate, Diphenyliodonium PFOS, methoxydiphenyliodonium PFOS, di-t-butyldiphenyliodonium triflate, N-hydroxysuccinimide PFOS, (N-hydroxysuccinimide PFOS), norbornene-dicarboximide PFOS (PFOS), or a combination thereof. The.
The additive may be selected from a range that can improve not only the solubility but also the gap fill and the etch performance without changing the optical properties of the first composition or the second composition. For example, 100 parts by weight of the first composition or the second composition Based on the total weight of the composition.
As described above, the method of manufacturing the hard mask layer can minimize the occurrence of step differences in the layer formed by coating and hardening the composition in two portions in a relatively low solid content.
According to another embodiment, there is provided a hard mask layer formed according to the above-described manufacturing method.
1 is a cross-sectional view showing a hard mask layer formed according to the above-described manufacturing method. Referring to FIG. 1, the
The planarization degree is calculated by the following method.
Planarization degree (%) = (1-h 1 / h 2 ) * 100
Wherein h 1 is a thickness of the hard mask layer in a cell portion where a pattern is formed, h 2 is a thickness of the hard mask layer in a peri portion where no pattern is formed, A width of 500 nm, and a depth of 50 nm.
Hereinafter, a pattern forming method according to another embodiment will be described.
The pattern forming method includes: providing the hard mask layer; Forming a silicon-containing thin film layer on the hard mask layer; Forming a photoresist layer on the silicon-containing thin film layer; Exposing and developing the photoresist layer to form a photoresist pattern; And selectively removing the silicon-containing thin film layer and the hard mask layer using the photoresist pattern.
For example, the method may further include forming a material layer on the substrate prior to the step of forming the hard mask layer, wherein the step of forming a bottom anti-reflective layer (BARC) .
For example, the silicon-containing thin film layer may include, but is not limited to, SiCN, SiOC, SiON, SiOCN, SiC, SiN, or combinations thereof.
The step of exposing the photoresist layer may be performed using, for example, ArF, KrF or EUV. Further, after the exposure, the heat treatment process may be performed at about 100 to 500 ° C.
The step of etching the exposed portion of the material layer may be performed by dry etching using an etching gas, and the etching gas may be, for example, CHF 3 , CF 4 , Cl 2 , BCl 3 and a mixed gas thereof.
The etched material layer may be formed in a plurality of patterns, and the plurality of patterns may be a metal pattern, a semiconductor pattern, an insulation pattern, or the like, and may be applied to various patterns in a semiconductor integrated circuit device, for example.
Hereinafter, embodiments of the present invention will be described in detail with reference to examples. The following examples are for illustrative purposes only and are not intended to limit the scope of the invention.
Synthetic example
Synthetic example One
The flask was charged with 70 g (0.2 mol) of 4,4 '- (9H-fluorene-9,9-diyl) diphenol (4,4' 70 g of propyleneglycol monomethyl ether acetate (PGMEA) and 1.23 g (8 mmol) of diethylsulfate were charged into a flask equipped with a stirrer, a reflux condenser and a reflux condenser, and charged with 33.2 g (0.2 mol) of bis (methoxymethyl) benzene Thereafter, the polymerization was carried out while maintaining the temperature at 110 ° C. A sample was taken from the polymerization reaction product at intervals of 1 hour, and the weight average molecular weight of the sample was measured. When the weight average molecular weight was 2,500 to 3,000, the reaction was completed. After completion of the polymerization reaction, the reaction product was slowly cooled to room temperature, and then the reaction product was added to 30 g of distilled water and 300 g of methanol, stirred vigorously, and allowed to stand. The supernatant was removed and the precipitate was dissolved in 60 g of propylene glycol monomethyl ether acetate (PGMEA), followed by vigorous stirring with 250 g of methanol and allowed to stand (primary). The resulting supernatant was again removed and the precipitate was dissolved in 60 g of propylene glycol monomethyl ether acetate (PGMEA) (second order). The primary and secondary processes were referred to as a one-time purification process, and this purification process was performed three times in total. The purified polymer was dissolved in 60 g of propylene glycol monomethyl ether acetate (PGMEA), and the methanol and distilled water remaining in the solution were removed under reduced pressure to obtain a polymer (Mw: 3000) represented by the following formula (1a).
[Formula 1a]
Synthetic example 2
Diene sulphate (0.6 g, 4 mmol) and propylene glycol (20.2 g, 0.1 mol) were added to a solution of 1,4-bis (methoxymethyl) benzene (33.2 g, 0.2 mol) 70 g of monomethyl ether acetate (PGMEA) was used to obtain a polymer (Mw: 3000) represented by the following formula (2a) using the same method as Synthesis Example 1 at 120 占 폚.
(2a)
Synthetic example 3
Carbazole (16.7 g, 0.1 mol), 4,4'-oxybis (25.8 g, 0.1 mol), diethylsulfite (0.77 g, 0.05 mol), and propylene glycol monomethyl ether acetate PGMEA) (43 g) was used to obtain a polymer (Mw: 3000) represented by the following formula (3a) using the same method as Synthesis Example 1 at 120 ° C.
[Chemical Formula 3]
Synthetic example 4
Carbazole (16.7 g, 0.1 mol), 9-Fluorenone (18 g, 0.1 mol), p-Toluenesulfonic acid monohydrate (19 g, 0.1 mol), and propylene glycol mono Using methyl ether acetate (PGMEA) (46 g), a polymer (Mw: 3000) represented by the following general formula (4a) was obtained at 120 ° C in the same manner as in Synthesis Example 1.
[Chemical Formula 4a]
Manufacture of thin films
Example One
The hard mask composition solution was prepared by dissolving the compound represented by Formula 1a in a solvent (PGMEA / EL = 1: 1) such that the amount of the compound represented by Formula 1a was 6 wt% in the entire composition (100 wt%). The formed solution was spin-on coated on a silicon wafer and then baked at 400 ° C for 2 minutes to form a thin film. Next, a secondary coating was performed on the hard mask composition, followed by hard baking at 400 DEG C for 2 minutes to adjust the thickness of the composition on the bare wafer to 2500 ANGSTROM (thickness measurement: manufactured by KMAC (ST5000) The same is true for the comparative example).
Example 2 to 4
A hard mask composition was prepared in the same manner as in Example 1, except that the compounds of the formulas (2a) to (4a) obtained in Synthesis Examples 2 to 4 were respectively used instead of the compound (1a) obtained in Synthesis Example 1.
Comparative Example One
The hard mask composition solution was prepared by dissolving the compound represented by Formula 1a in a solvent (PGMEA / EL = 1: 1) to 10wt% of the total composition (100 wt%). The formed solution was spin-on coated on a silicon wafer and hard-baked at 400 ° C for 2 minutes to adjust the thickness of the composition on the bare wafer to 2500 Å (thickness measurement: manufactured by KMAC (ST5000) being).
Comparative Example 2 to 4
A hard mask composition was prepared in the same manner as in Comparative Example 1, except that the compounds represented by Formulas 2a to 4a obtained in Synthesis Examples 2 to 4 were respectively used instead of Formula 1a obtained in Synthesis Example 1.
Rating 1: Step characteristic
The step characteristics and the gap - fill characteristics of the thin films were evaluated.
A hard mask composition was applied on a pattern wafer having a C / H 1: 1 60 nm hole to form the hard mask thin films according to Examples 1 to 4 and Comparative Examples 1 to 4.
The gap-fill characteristic was determined by observing the pattern section by FE-SEM and determining the void formation. The planarization characteristic was measured by FE-SEM and the film thickness was measured from the image of the pattern section. Respectively. At this time, the smaller the difference between h1 and h2, the better the planarization characteristic.
The results are shown in Table 1.
(Presence or absence of voids)
(Presence or absence of voids)
Referring to Table 1, it can be seen that the thin films formed from the hard mask compositions according to Examples 1 to 4 exhibit excellent planarization characteristics as compared with the thin films formed from the hard mask composition according to Comparative Examples 1 to 4.
Evaluation 2: Step characteristic
A hard mask composition was applied on a patterned wafer having a line width of 1: 1 and 1: 1 50 nm lines to form hard mask thin films according to Examples 1 to 4 and Comparative Examples 1 to 4, and then samples were cut out. Subsequently, the sample was coated with Pt, and the step difference was confirmed by FE-SEM (Hitachi SU-8030).
3 is a reference diagram for explaining calculation formula 2 for evaluating the step property.
Referring to FIG. 3, the planarization characteristic is improved as the difference between the film thickness h0 of the peri portion where no pattern is formed and the film thickness h1 of the cell portion where the pattern is formed is small will be. That is, the smaller the value of | h0-h1 | + | h0-h2 | + | h0-h3 |, the better the step property.
The evaluation results are shown in Table 2 below.
+ │h0-h3│
(nm)
+ │h0-h3│
(nm)
Referring to Table 2, it can be seen that the thin films formed from the hard mask compositions according to Examples 1 to 4 have superior step characteristics as compared with the thin films formed from the hard mask composition according to Comparative Examples 1 to 4.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments, And falls within the scope of the invention.
100: hard mask layer 110: patterned substrate
120: first hard mask layer 130: second hard mask layer
Claims (18)
Coating a second composition comprising an organic compound on the first hard mask layer and curing the second composition to form a second hard mask layer
≪ / RTI >
Wherein the second hardmask layer is formed directly over the first hardmask layer.
Wherein the organic compound content in the first composition is 1 wt% to 30 wt%, and the organic compound content in the second composition is 1 wt% to 20 wt%.
Wherein the curing of the first composition and the second composition each independently proceed at 100 DEG C to 500 DEG C for 10 seconds to 1 hour.
Wherein the carbon content of the organic compound contained in the first composition and the carbon content of the organic compound contained in the second composition are each independently 60 atom% to 96 atom%.
The organic compound contained in the first composition and the organic compound contained in the second composition are each independently at least one substituted or unsubstituted aromatic ring group, a substituted or unsubstituted aliphatic ring group, a substituted or unsubstituted hetero ring An aromatic ring group, a substituted or unsubstituted heteroaliphatic ring group, or a combination thereof.
Wherein the first composition and the second composition each independently comprise an organic polymer, an organic monolayer, or a combination thereof.
Wherein the organic polymer has a weight average molecular weight of 500 to 200,000.
Wherein the organic monomolecular molecule has a molecular weight of 250 to 5,000.
Wherein the first composition or the second composition further comprises an additive comprising a surfactant, a plasticizer, a crosslinker, a thermal acid generator (TAG), a photoacid generator (PAG), or a combination thereof.
The amount of the additive contained in the first composition is about 0.001 to 40 parts by weight based on 100 parts by weight of the first composition and the amount of the additive included in the second composition is about 0.001 to 40 parts by weight based on 100 parts by weight of the second composition. By weight of the hard mask layer.
Wherein the first composition further comprises a first solvent and the second composition further comprises a second solvent, wherein the first solvent and the second solvent are each independently selected from the group consisting of propylene glycol, propylene glycol diacetate, methoxypropane Diethylene glycol, diethylene glycol butyl ether, tri (ethylene glycol) monomethyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, cyclohexanone, ethyl lactate, gamma-butyrolactone, N, N-dimethylacetamide, methylpyrrolidone, methylpyrrolidinone, acetylacetone, ethyl 3-ethoxypropionate, or a combination thereof.
Wherein the first composition and the second composition are independently coated to a thickness of 50 A to 10 mu m.
Wherein the first composition and the second composition are coated by spin-on coating, screen printing, slit coating, dipping, inkjet printing, casting or spray coating.
Forming a silicon-containing thin film layer on the hard mask layer;
Forming a photoresist layer on the silicon-containing thin film layer;
Exposing and developing the photoresist layer to form a photoresist pattern; And
Selectively removing the silicon-containing thin film layer and the hard mask layer using the photoresist pattern
≪ / RTI >
Further comprising forming a material layer on the substrate prior to forming the first hardmask layer.
And forming a bottom anti-reflective layer (BARC) before the step of forming the photoresist.
Wherein the silicon-containing thin film layer comprises SiCN, SiOC, SiON, SiOCN, SiC, SiN, or a combination thereof.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190063096A (en) * | 2017-11-29 | 2019-06-07 | 삼성에스디아이 주식회사 | Method of forming patterns |
| KR20210016274A (en) * | 2019-08-02 | 2021-02-15 | 타이완 세미콘덕터 매뉴팩쳐링 컴퍼니 리미티드 | Patterning process of a semiconductor structure with enhanced adhesion |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20190063096A (en) * | 2017-11-29 | 2019-06-07 | 삼성에스디아이 주식회사 | Method of forming patterns |
| KR20210016274A (en) * | 2019-08-02 | 2021-02-15 | 타이완 세미콘덕터 매뉴팩쳐링 컴퍼니 리미티드 | Patterning process of a semiconductor structure with enhanced adhesion |
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