JP5360062B2 - Electron beam resist sensitized film forming material and method for manufacturing semiconductor device - Google Patents

Description

  The present invention relates to a resist sensitizing film forming material suitable for forming a fine pattern in a semiconductor device, a mask, a magnetic head, and the like, and a method of manufacturing a semiconductor device using the resist sensitizing film forming material.

Currently, with the improvement of the degree of integration in a semiconductor device such as an LSI (semiconductor integrated circuit) and the recording density of a hard disk, the formation of a fine pattern is required. It is essential to establish a microfabrication technique corresponding to the formation of this fine pattern, and in the field of lithography technology, a pattern formation technique by electron beam exposure has been studied.
Pattern formation technology by electron beam exposure is promising as a next-generation pattern formation technology because it can relatively easily form fine patterns of 0.1 μm or less, which is impossible with pattern formation technology by ultraviolet exposure. . However, the pattern formation technique by electron beam exposure has a low throughput because the exposure time is long due to the characteristic drawing method of the electron beam.
In order to solve this problem, it is necessary to improve the sensitivity of the electron beam resist, shorten the exposure time, and improve the throughput.
As a method for improving the sensitivity of the electron beam resist, a method of forming an electron scattering layer made of a material having a large electron scattering coefficient (single metal such as Pt or Mo) on the base of the electron beam resist is known (for example, , See Patent Document 1).
In this method, due to an increase in electron scattering in the electron scattering layer, a large number of scattered electrons are distributed in the vicinity of the electron beam incident position, and the electron scattering distributed in the vicinity of the electron beam incident position is used for the exposure of the electron beam resist. Therefore, the sensitivity of the electron beam resist is improved. However, in this method, the steps of forming the electron scattering layer on the base of the electron beam resist and selectively removing the electron scattering layer after forming the pattern on the substrate are respectively performed. Becomes complicated.
Further, in the electron beam resist, there is a trade-off relationship between higher sensitivity and higher resolution. For example, when the content of the acid generator in the electron beam resist composition is increased, the sensitivity of the electron beam resist is improved, but the resolution of the electron beam resist is lowered.
Further, as a problem specific to electron beam exposure, there are influences of forward scattering of electrons (scattering in a resist at the time of incidence) and back scattering (bounce from the inside of the substrate). Since the degree of scattering of the electron beam depends on the atomic weight of the colliding element, if there is a heavy element (for example, a semiconductor wiring) below the pattern formation location, backscattering increases and apparent sensitivity is improved. That is, when a pattern containing a heavy element exists below the pattern formation location, it is difficult to form a resist pattern with a certain size.
Therefore, development of materials and process technologies that improve the sensitivity of the electron beam resist without compromising the resolution of the electron beam resist is eagerly desired.

JP 58-105140 A

An object of the present invention is to solve the above-described problems and achieve the following objects.
That is, the present invention provides a resist sensitizing film forming material capable of forming a resist sensitizing film that improves the sensitivity of the electron beam resist without degrading the resolution of the electron beam resist, and the resist sensitizing film forming material. It is an object of the present invention to provide a method for manufacturing a used semiconductor device.

  Means for solving the problems are as follows. That is, the disclosed resist sensitizing film forming material includes a metal salt, a resin, and a solvent.

  The disclosed semiconductor device manufacturing method includes a resist sensitizing film forming step of applying a disclosed resist sensitizing film forming material on a surface to be processed to form a resist sensitizing film, and the resist sensitizing film on the resist sensitizing film. A resist film forming step of forming a resist film by applying a resist composition; a resist pattern forming step of exposing and developing the resist film to form a resist pattern; and the surface to be processed using the resist pattern as a mask A patterning step of patterning by etching.

  The disclosed method of manufacturing a semiconductor device includes a resist film forming step of forming a resist film by applying a resist composition on a surface to be processed, and applying the disclosed resist sensitizing film forming material on the resist film. A resist sensitizing film forming step for forming a resist sensitizing film, a resist pattern forming step for exposing and developing the resist film and the resist sensitizing film to form a resist pattern, and using the resist pattern as a mask, A patterning step of patterning the surface to be processed by etching.

  According to the disclosed resist sensitizing film forming material, it is possible to solve a conventional problem and to form a resist sensitizing film that improves the sensitivity of the electron beam resist without degrading the resolution of the electron beam resist. is there.

FIG. 1 is a plan view showing a first example of a FLASH EPROM manufactured by the disclosed method for manufacturing a semiconductor device. FIG. 2 is a plan view showing a first example of a FLASH EPROM manufactured by the disclosed method for manufacturing a semiconductor device. FIG. 3A is a schematic explanatory diagram of a first example of manufacturing a FLASH EPROM by the disclosed method for manufacturing a semiconductor device. FIG. 3B is a schematic explanatory diagram of a first example of manufacturing a FLASH EPROM by the disclosed method for manufacturing a semiconductor device, and represents the next step of FIG. 3A. FIG. 3C is a schematic explanatory diagram of a first example of manufacturing a FLASH EPROM by the disclosed method for manufacturing a semiconductor device, and represents the next step of FIG. 3B. FIG. 3D is a schematic explanatory diagram of a first example of manufacturing a FLASH EPROM by the disclosed method for manufacturing a semiconductor device, and represents the next step of FIG. 3C. FIG. 3E is a schematic explanatory diagram of a first example of manufacturing a FLASH EPROM by the disclosed method for manufacturing a semiconductor device, and represents the next step of FIG. 3D. FIG. 3F is a schematic explanatory diagram of a first example of manufacturing a FLASH EPROM by the disclosed method for manufacturing a semiconductor device, and represents the next step of FIG. 3E. FIG. 3G is a schematic explanatory diagram of a first example of manufacturing a FLASH EPROM by the disclosed method for manufacturing a semiconductor device, and represents the next step of FIG. 3F. FIG. 3H is a schematic explanatory diagram of a first example of manufacturing a FLASH EPROM by the disclosed method for manufacturing a semiconductor device, and represents the next step of FIG. 3G. FIG. 3I is a schematic explanatory diagram of a first example of manufacturing a FLASH EPROM by the disclosed method for manufacturing a semiconductor device, and represents the next step of FIG. 3H. FIG. 3J is a schematic explanatory diagram of a second example of manufacturing a FLASH EPROM by the disclosed method for manufacturing a semiconductor device. FIG. 3K is a schematic explanatory diagram of a second example of manufacturing a FLASH EPROM by the disclosed method for manufacturing a semiconductor device, and represents the next step of FIG. 3J. FIG. 3L is a schematic explanatory diagram of a second example of manufacturing a FLASH EPROM by the disclosed method for manufacturing a semiconductor device, and represents the next step of FIG. 3K. FIG. 3M is a schematic explanatory diagram of a third example of manufacturing a FLASH EPROM by the disclosed semiconductor device manufacturing method. FIG. 3N is a schematic explanatory diagram of a third example of manufacturing a FLASH EPROM by the disclosed method for manufacturing a semiconductor device, and represents the next step of FIG. 3M. FIG. 3O is a schematic explanatory diagram of a third example of manufacturing a FLASH EPROM by the disclosed method for manufacturing a semiconductor device, and represents the next step of FIG. 3N. FIG. 4A is a schematic cross-sectional explanatory diagram of an example in which a resist pattern of a resist film formed on a resist sensitized film formed using the disclosed resist sensitized film forming material is applied to the manufacture of a magnetic head. 4B is a schematic cross-sectional explanatory diagram of an example in which a resist pattern of a resist film formed on a resist sensitizing film formed using the disclosed resist sensitizing film forming material is applied to the manufacture of a magnetic head. Represents the next step. FIG. 4C is a schematic cross-sectional explanatory diagram of an example in which a resist pattern of a resist film formed on a resist sensitized film formed using the disclosed resist sensitized film forming material is applied to the manufacture of a magnetic head. Represents the next step. 4D is a schematic cross-sectional explanatory diagram of an example in which a resist pattern of a resist film formed on a resist sensitized film formed using the disclosed resist sensitized film forming material is applied to the manufacture of a magnetic head. Represents the next step. FIG. 4E is a schematic cross-sectional explanatory diagram of an example in which a resist pattern of a resist film formed on a resist sensitized film formed using the disclosed resist sensitized film forming material is applied to the manufacture of a magnetic head. Represents the next step. 4F is a schematic cross-sectional explanatory diagram of an example in which a resist pattern of a resist film formed on a resist sensitized film formed using the disclosed resist sensitized film forming material is applied to the manufacture of a magnetic head. Represents the next step. FIG. 4G is a schematic cross-sectional explanatory diagram of an example in which a resist pattern of a resist film formed on a resist sensitized film formed using the disclosed resist sensitized film forming material is applied to the manufacture of a magnetic head. Represents the next step. FIG. 5 is a perspective view showing an example of a magnetic head manufactured through the steps of FIGS. 4A to 4G.

(Resist sensitized film forming material)
The disclosed resist sensitizing film forming material includes at least a metal salt, a resin, and a solvent, and further includes other components that are appropriately selected as necessary.
Further, the resist sensitized film formed from the disclosed resist sensitized film forming material may be simultaneously dissolved in a developing solution at the time of developing a resist film, which will be described later, and an opening may be formed up to the resist sensitized film base. The opening may be formed up to the resist sensitized film base by other methods such as etching as insoluble in the developer. Control of the solubility of the resist sensitizing film-forming material in the resist film developer can also be realized by adjusting the crosslinking density of the resin using a crosslinking agent or an acid generator.

-Metal salt-
The metal salt is not particularly limited as long as it promotes scattering of electron beams, and can be appropriately selected according to the purpose, but in terms of ease of formation of the metal salt, an alkali metal salt, Alkaline earth metal salts are preferred, and potassium, calcium, rubidium, strontium, cesium, and barium salts are more preferred.

  The type of the metal salt anion is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include chloride ion, nitrate ion / perchlorate ion, sulfate ion, phosphate ion, water Examples thereof include inorganic ions such as oxide ions and ammonium ions, and organic acid ions such as acetate ions, formate ions and carbonate ions. Among these, chloride ion, carbonate ion and acetate ion are preferable in terms of interaction with the resist and affinity for the solvent.

  There is no restriction | limiting in particular as content of the said metal salt, Although it can select suitably according to the objective, 1 mass%-50 mass% are preferable with respect to the said resin, and 1 mass%-40 mass% are more. preferable. When the content of the metal salt is less than 1% by mass, the effects of sensitization and suppression of backscattering may be insufficient, and when the content exceeds 50% by mass, a uniform film may not be formed.

-Resin-
The resin is not particularly limited and may be appropriately selected depending on the purpose. For example, an acrylic resin, a styrene resin, a phenol resin, an epoxy resin, a melamine resin, a urea resin, an imide resin, And polyethylene resins.
Further, as the resin, various water-soluble resins can be used. The water-soluble resin is not particularly limited and can be appropriately selected according to the purpose. For example, polyvinyl alcohol, polyvinyl acetal, polyvinyl acetate, Acrylic acid, polyvinylpyrrolidone, polyethyleneimine, polyethylene oxide, styrene-maleic acid copolymer, polyvinylamine, polyallylamine, water-soluble resin containing oxazoline group, water-soluble melamine resin, water-soluble urea resin, alkyd resin, sulfonamide resin, etc. Among these, those exhibiting water solubility capable of dissolving 0.1 g or more with respect to 100 g of water at 25 ° C. are preferable.
The polyvinyl alcohol may be partially acetalized.
There is no restriction | limiting in particular as an acetalization rate of the said polyvinyl alcohol, Although it can select suitably according to the objective, 0.1%-90% are preferable, 1%-60% are more preferable, 5%-40 % Is more preferable.
If the acetalization rate is less than 0.1%, the compatibility with nonpolar materials may be significantly reduced, and if it exceeds 90%, the compatibility with polar materials may be significantly reduced. On the other hand, when the acetalization rate is in a particularly preferable range, it is advantageous for compatibility with other constituent materials.

Moreover, as said resin, what is incompatible with the resist resin and resist solvent in the resist composition mentioned later is preferable.

  Further, a conductive resin having conductivity can be used as the resin, and as an additional function, charging of electrons during exposure can be suppressed.

The conductive resin is not particularly limited and may be appropriately selected depending on the intended purpose.For example, polyaniline, polyparaphenylvinylene, polythiophene, polypyrrole, poly-p-phenylene oxide, polyfuran, polyphenylene, polyazine, polyazine Examples include selenophene, polyphenylene sulfide, polyacetylene and the like. Among these, a substance represented by the following general formula is more preferable.

In the general formula (1) ~ (6), A represents NH, S, and O one of, R represents represents one of _{R 1} and OR _{1, R 1} is C 1 -C Represents a linear hydrocarbon of ˜8, a branched hydrocarbon, and a hydrocarbon containing an ether bond, X ₁ and X ₂ represent any of SO ₃ and COO, and Z ₁ and Z 2 ₂ represents any one of H, OR ₁ X ₁ H, OR ₁ H, and an electron donating group, and M ₁ and M ₂ are a hydrogen ion, an ammonium ion, an alkylammonium ion having 1 to 8 carbon atoms, and an aromatic group. It represents either an ammonium ion or an aromatic heterocyclic quaternary ion.
The electron donating group is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include a halogen group, an alkoxy group having 1 to 8 carbon atoms, an alkenyl group, and an alkyl group.
The aromatic ammonium ion is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aniline, 2-methoxyaniline, 3-methoxyaniline, 4-methoxyaniline, and derivatives having these skeletons. An ammonium ion etc. are mentioned.
The quaternary ion of the aromatic heterocyclic ring is not particularly limited and may be appropriately selected depending on the intended purpose. For example, piperidine, pyrrolidine, morpholine, piperazine, pyridine, α-picoline, β-picoline, γ- Examples include picoline, quinoline, isoquinoline, pyrroline, and ammonium ions of derivatives having these skeletons.

  Examples of the compounds represented by the general formulas (1) to (6) include 3-amino-4-methoxybenzenesulfonic acid polymer, furan-3- (2-ethanesulfonic acid), furan-3- (3). -Propanesulfonic acid), furan-3- (4-butanesulfonic acid), furan-3- (5-pentanesulfonic acid), furan-3- (6-hexanesulfonic acid), pyrrole-3- (2-ethane) Sulfonic acid), pyrrole-3- (3-propanesulfonic acid), pyrrole-3- (4-butanesulfonic acid), pyrrole-3- (5-pentanesulfonic acid), pyrrole-3- (6-hexanesulfonic acid) ), 2-methoxy-5- (propyloxy-3-sulfonic acid) -1,4-phenylene vinylene, 2-ethoxy-5- (propyloxy-3-sulfonic acid) -1,4-phenylene Nylene, 2-propyloxy-5- (propyloxy-3-sulfonic acid) -1,4-phenylene vinylene, 2-butyloxy-5- (propyloxy-3-sulfonic acid) -1,4-phenylene vinylene, 2, , 5-bis (propyloxy-3-sulfonic acid) -1,4-phenylene vinylene, 2,5-bis (ethyloxy-2-sulfonic acid) -1,4-phenylene vinylene, 2,5-bis (butyloxy- 4-sulfonic acid) -1,4-phenylene vinylene, 5- (propyloxy-3-sulfonic acid) -1,4-phenylene vinylene, 5- (ethyloxy-2-sulfonic acid) -1,4-phenylene vinylene, 5- (Butyloxy-4-sulfonic acid) -1,4-phenylene vinylene, 5- (pentyloxy-4-sulfonic acid) -1,4-phenylene Nylene, aniline-3- (2-ethanesulfonic acid), aniline-3- (3-propanesulfonic acid), aniline-3- (4-butanesulfonic acid), aniline-3- (5-pentanesulfonic acid), Aniline-3- (6-hexanesulfonic acid), aniline-3- (7-heptanesulfonic acid), aniline-3- (2-methyl-3-propanesulfonic acid), aniline-3- (2-methyl-4) -Butanesulfonic acid), aniline-3-sulfonic acid, aniline-N- (2-ethanesulfonic acid), aniline-N- (3-propanesulfonic acid), aniline-N- (4-butanesulfonic acid), aniline -N- (5-pentanesulfonic acid), aniline-N- (6-hexanesulfonic acid), aniline-N- (7-heptanesulfonic acid), aniline-N- (2-methyl-3) -Propanesulfonic acid), aniline-N- (2-methyl-4-butanesulfonic acid), 2-aminoanisole-3-sulfonic acid, 2-aminoanisole-4-sulfonic acid, 2-aminoanisole-5-sulfone Acid, 2-aminoanisole-6-sulfonic acid, 3-aminoanisole-2-sulfonic acid, 3-aminoanisole-4-sulfonic acid, 3-aminoanisole-5-sulfonic acid, 3-aminoanisole-6-sulfone Acid, 4-aminoanisole-2-sulfonic acid, 4-aminoanisole-3-sulfonic acid, 2-amino-4-ethoxybenzenesulfonic acid, 3-amino-4-ethoxybenzenesulfonic acid, 2-amino-4- Butoxybenzenesulfonic acid, 3-amino-5-butoxybenzenesulfonic acid, 2-amino-4-propoxybenzene Sulfonic acid, 3-amino-6-propoxybenzenesulfonic acid, 2-amino-4-isobutoxybenzenesulfonic acid, 3-amino-4-isobutoxybenzenesulfonic acid, 3-amino-4-t-butoxybenzenesulfonic acid 2-amino-4-t-butoxybenzenesulfonic acid, 2-amino-4-heptoxybenzenesulfonic acid, 3-amino-5-heptoxybenzenesulfonic acid, 2-amino-4-hexoxybenzenesulfonic acid 3-amino-5-octoxybenzenesulfonic acid, 2-amino-4-nanoxybenzenesulfonic acid, 3-amino-5-decanoxybenzenesulfonic acid, 2-amino-4-undecanoxybenzenesulfonic acid , 3-amino-5-dodecanoxybenzenesulfonic acid, and the like.

-Solvent-
The solvent includes at least one of an organic solvent and water, and further includes other solvents appropriately selected as necessary.
The organic solvent is not particularly limited and may be appropriately selected depending on the intended purpose.However, each component of the resist sensitizing film forming material can be dissolved and has an appropriate drying rate, It is required that a uniform and smooth coating film can be formed after the organic solvent evaporates.

There is no restriction | limiting in particular as such an organic solvent, According to the objective, it can select suitably, For example, glycol ether esters, glycol ethers, esters, ethers, ketones, cyclic esters, alcohols , Etc.
These organic solvents may be used individually by 1 type, and may use 2 or more types together.

The glycol ether esters are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethyl cellosolve acetate, methyl cellosolve acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. It is done.
The glycol ether is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include ethyl cellosolve, methyl cellosolve, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether and the like. It is done.
There is no restriction | limiting in particular as said ester, According to the objective, it can select suitably, For example, ethyl lactate, butyl acetate, amyl acetate, ethyl pyruvate, etc. are mentioned.
There is no restriction | limiting in particular as said ethers, According to the objective, it can select suitably, For example, anisole etc. are mentioned.
There is no restriction | limiting in particular as said ketones, According to the objective, it can select suitably, For example, 2-heptanone, cyclohexanone, etc. are mentioned.
There is no restriction | limiting in particular as said cyclic ester, According to the objective, it can select suitably, For example, (gamma) -butyrolactone etc. are mentioned.
There is no restriction | limiting in particular as said alcohol, According to the objective, it can select suitably, For example, methanol, ethanol, propanol, isopropanol, a butanol, etc. are mentioned.

-Other ingredients-
There is no restriction | limiting in particular as long as the said other component does not impair the effect of this invention, According to the objective, it can select suitably, Well-known various additives are mentioned. The known various additives are not particularly limited and may be appropriately selected depending on the purpose. For example, when the purpose is to improve the solubility and coating properties of the composition, a crosslinking agent and an acid generator Agents, surfactants and the like.

-Crosslinking agent-
The crosslinking agent is not particularly limited as long as it has a function of crosslinking the resin, and can be appropriately selected according to the purpose. Examples thereof include an amino crosslinking agent.
There is no restriction | limiting in particular as said amino type crosslinking agent, According to the objective, it can select suitably, For example, a melamine derivative, a urea derivative, a uril derivative, etc. are mentioned suitably. These may be used alone or in combination of two or more.

There is no restriction | limiting in particular as said melamine derivative, According to the objective, it can select suitably, For example, alkoxymethylmelamine, these derivatives, etc. are mentioned.
The urea derivative is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include urea, alkoxymethylene urea, N-alkoxymethylene urea, ethylene urea, ethylene urea carboxylic acid, and derivatives thereof. Is mentioned.
The uril derivative is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include benzoguanamine, glycoluril, and derivatives thereof.

  There is no restriction | limiting in particular as content of the said crosslinking agent, According to the objective, it can select suitably, For example, 0.5 mass%-50 mass% are preferable with respect to content of the said resin, Furthermore, 1 mass%-40 mass% are more preferable. When the content is less than 0.5% by mass, the crosslinking reaction with respect to the resin may not sufficiently proceed. When the content exceeds 50% by mass, the crosslinking reaction may reach the upper or lower resist film. is there.

The cross-linking agent dissolves the resist sensitizing film in the resist solvent contained in the resist composition when the resist composition is spin-coated on the resist sensitizing film to form a resist film described later. Not to be added.

-Acid generator-
The acid generator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include aliphatic sulfonic acids, aliphatic sulfonates, aliphatic carboxylic acids, aliphatic carboxylates, and aromatic sulfones. Examples thereof include thermal acid generators such as acids, aromatic sulfonates, aromatic carboxylic acids, aromatic carboxylates, metal salts, phosphate esters, and nitrobenzyl tosylate.
These acid generators may be used alone or in combination of two or more.

The thermal acid generator is not particularly limited and may be appropriately selected depending on the intended purpose. For example, methyl benzenesulfonate, ethyl benzenesulfonate, propyl benzenesulfonate, methyl p-toluenesulfonate, o- Methyl toluenesulfonate, ethyl p-toluenesulfonate, ethyl o-toluenesulfonate, methyl naphthalenesulfonate, ethyl 4-methoxybenzenesulfonate, 2-butoxyethyl p-toluenesulfonate, 2-phenoxybenzenebenzene Ethyl, benzyl 3-methoxycarbonylbenzenesulfonate, 2-nitroethyl benzenesulfonate, p-toluenesulfonate-3-acetaminopropyl, diethyl sulfate, di-n-propyl sulfate, di-n-butyl sulfate, bis ( 2-ethylhexyl) sulfuric acid, dill Rylsulfuric acid, distearyl sulfate, bis (2-phenethyl) sulfuric acid, bis (α-naphthylmethyl) sulfuric acid, dibenzylsulfuric acid, bis (2-butoxyethyl) sulfuric acid, bis (2-phenoxyethyl) sulfuric acid, bis (2-octyl) Thioethyl) sulfuric acid, bis [2- (4-tolyl) thioethyl] sulfuric acid, bis (4-nitroethyl) sulfuric acid, bis (2-chloroethyl) sulfuric acid, dicyclohexylsulfuric acid, bis (4-methylcyclohexyl) sulfuric acid, bis (4- Methoxycyclohexyl) sulfuric acid, bis (4-butylthiocyclohexyl) sulfuric acid, 2-nitrobenzyl tosylate, 2,4-dinitrobenzyl tosylate, 2,6-dinitrobenzyl tosylate, 4-nitrobenzyl tosylate, -trifluoro Methyl-6-nitrobenzyl 4-chlorobenzenesulfonate, 2-trifluoro Examples include olomethyl-6-nitrobenzyl 4-nitrobenzenesulfonate, aliphatic onium salts (for example, 2-butynyltetramethylenesulfonium hexafluoroantimonate), and the like.
There is no restriction | limiting in particular as content of the said thermal acid generator, Although it can select suitably according to the objective, It is 0.5 mass%-40 mass% with respect to content of the said resin, for example. It is preferable.

In addition to the thermal acid generator, a photoacid generator can be used.
The photoacid generator is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include onium salts, sulfonium salts, halogen-containing triazine compounds, sulfone compounds, aromatic sulfonate compounds, and N-hydroxyimide. And sulfonate compounds.

There is no restriction | limiting in particular as said onium salt, According to the objective, it can select suitably, For example, a diaryl iodonium salt, a triaryl selenonium salt, a triaryl sulfonium salt etc. are mentioned.
The diaryliodonium salt is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diphenyliodonium trifluoromethanesulfonate, 4-methoxyphenylphenyliodonium hexafluoroantimonate, and 4-methoxyphenylphenyliodonium trifluoromethane. Sulfonate, bis (4-tert-butylphenyl) iodonium tetrafluoroborate, bis (4-tert-butylphenyl) iodonium hexafluorophosphate, bis (4-tert-butylphenyl) iodonium hexafluoroantimonate, bis (4-tert -Butylphenyl) iodonium trifluoromethanesulfonate, and the like.
The triaryl selenonium salt is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include triphenyl selenonium hexafluorophosphonium salt, triphenyl selenonium borofluoride, triphenyl selenonium hexafluoro. And antimonate salts.
The triarylsulfonium salt is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include triphenylsulfonium hexafluorophosphonium salt, triphenylsulfonium hexafluoroantimonate salt, diphenyl-4-thiophenoxyphenyl. Examples thereof include sulfonium hexafluoroantimonate salt and diphenyl-4-thiophenoxyphenylsulfonium pentafluorohydroxyantimonate salt.

The sulfonium salt is not particularly limited and may be appropriately selected depending on the intended purpose. For example, triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium trifluoromethanesulfonate, 4-methoxyphenyl Diphenylsulfonium hexafluoroantimonate, 4-methoxyphenyldiphenylsulfonium trifluoromethanesulfonate, p-tolyldiphenylsulfonium trifluoromethanesulfonate, 2,4,6-trimethylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-tert-butylphenyldiphenylsulfonium trifluoromethane Sulfonate, 4-phenylthiophenyl diphenyls Honium hexafluorophosphate, 4-phenylthiophenyldiphenylsulfonium hexafluoroantimonate, 1- (2-naphthoylmethyl) thiolanium hexafluoroantimonate, 1- (2-naphthoylmethyl) thiolanium trifluoromethanesulfonate, 4-hydroxy Examples include -1-naphthyldimethylsulfonium hexafluoroantimonate and 4-hydroxy-1-naphthyldimethylsulfonium trifluoromethanesulfonate.

  The halogen-containing triazine compound is not particularly limited and may be appropriately selected depending on the intended purpose. For example, 2-methyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2, 4,6-tris (trichloromethyl) -1,3,5-triazine, 2-phenyl-4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-chlorophenyl) -4, 6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxyphenyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-methoxy- 1-naphthyl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (benzo [d] [1,3] dioxolan-5-yl) -4,6-bis (trichloromethyl) ) -1,3, 5-triazine, 2- (4-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (3,4,5-trimethoxystyryl) -4,6-bis (Trichloromethyl) -1,3,5-triazine, 2- (3,4-dimethoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2,4-dimethoxy) Styryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (2-methoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-Butoxystyryl) -4,6-bis (trichloromethyl) -1,3,5-triazine, 2- (4-pentyloxystyryl) -4,6-bis (trichloromethyl) -1,3,5 -Triazine, etc. That.

  The sulfone compound is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include diphenyldisulfone, di-p-tolyldisulfone, bis (phenylsulfonyl) diazomethane, bis (4-chlorophenylsulfonyl) diazomethane, Bis (p-tolylsulfonyl) diazomethane, bis (4-tert-butylphenylsulfonyl) diazomethane, bis (2,4-xylylsulfonyl) diazomethane, bis (cyclohexylsulfonyl) diazomethane, (benzoyl) (phenylsulfonyl) diazomethane, phenyl And sulfonylacetophenone.

There is no restriction | limiting in particular as said aromatic sulfonate compound, According to the objective, it can select suitably, For example, (alpha) -benzoyl benzyl p-toluenesulfonate (popular name benzoin tosylate), (beta) -benzoyl-beta-hydroxyphenethyl p -Toluenesulfonate (commonly known as α-methylolbenzoin tosylate), 1,2,3-benzenetriyl trismethanesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, 2-nitrobenzyl p-toluenesulfonate, 4-nitrobenzyl p-toluenesulfonate, and the like.

  The sulfonate compound of N-hydroxyimide is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include N- (phenylsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) succinimide, N -(P-chlorophenylsulfonyloxy) succinimide, N- (cyclohexylsulfonyloxy) succinimide, N- (1-naphthylsulfonyloxy) succinimide, N- (benzylsulfonyloxy) succinimide, N- (10-camphorsulfonyloxy) succinimide, N- (trifluoromethylsulfonyloxy) phthalimide, N- (trifluoromethylsulfonyloxy) -5-norbornene-2,3-dicarboximide, N- (trifluoromethylsulfonyl) Oxy) naphthalimide, N-(10- camphorsulfonic sulfonyloxy) naphthalimide, and the like.

  Among these, a triarylsulfonium salt, a diaryliodonium salt, and a triarylselenonium salt are preferable because they have a high quantum yield and can be detached from the film as a gas after decomposition.

--Surfactant--
The surfactant is not particularly limited and may be appropriately selected depending on the intended purpose.For example, a nonionic surfactant, a cationic surfactant, an anionic surfactant, an amphoteric surfactant, Etc. These may be used alone or in combination of two or more. Among these, nonionic surfactants are preferable in that they do not contain metal ions.

  The nonionic surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alkoxylate surfactants, fatty acid ester surfactants, amide surfactants, alcohols Surfactant, ethylenediamine surfactant, and the like. Specific examples of these include polyoxyethylene-polyoxypropylene condensate compounds, polyoxyalkylene alkyl ether compounds, polyoxyethylene alkyl ether compounds, polyoxyethylene derivative compounds, sorbitan fatty acid ester compounds, glycerin fatty acid ester compounds, Primary alcohol ethoxylate compound, phenol ethoxylate compound, nonylphenol ethoxylate, octylphenol ethoxylate, lauryl alcohol ethoxylate, oleyl alcohol ethoxylate, fatty acid ester, amide, natural alcohol, ethylenediamine, Secondary alcohol ethoxylate type and the like.

  The cationic surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include alkyl cationic surfactants, amide type quaternary cationic surfactants, and ester type quaternary cationic types. And surfactants.

  The anionic surfactant is not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include fatty acids, higher alcohol sulfates, sulfates of liquid fatty oils, aliphatic amines and aliphatic amides. Sulfates of aliphatic alcohols, phosphate esters of aliphatic alcohols, sulfonates of dibasic fatty acid esters, sulfonates of aliphatic amides, alkylallyl sulfonates, formalin condensed naphthalene sulfonates, and the like.

  There is no restriction | limiting in particular as said amphoteric surfactant, According to the objective, it can select suitably, For example, an amine oxide type surfactant, a betaine type surfactant, etc. are mentioned.

  The content of the surfactant in the resist sensitizing film forming material can be appropriately determined according to the type and content of each component.

(Method for manufacturing semiconductor device)
The method of manufacturing a semiconductor device of the present invention includes at least a resist sensitizing film forming step, a resist film forming step, a resist pattern forming step, and a patterning step, and further includes other steps that are appropriately selected as necessary. Including.

-Resist sensitized film formation process-
The resist sensitized film forming step is a step of forming a resist sensitized film by applying a resist sensitized film forming material on a surface to be processed (base material) or a resist film. Note that “on the substrate” means “in contact with the substrate surface” to “above the substrate”, and “on the resist film” means “in contact with the resist film surface” to “above the resist film”. Means.
There is no restriction | limiting in particular as this application | coating method, According to the objective, it can select suitably, For example, a spin coat method etc. are mentioned suitably. In the case of the spin coating method, the rotation speed of the spin coater is, for example, preferably 100 rpm to 10,000 rpm, more preferably 800 rpm to 5,000 rpm, and the spin coating time is, for example, about 1 second to 10 minutes. Preferably, it is more preferably 1 second to 90 seconds.
The thickness of the applied resist sensitizing film is not particularly limited and may be appropriately selected depending on the intended purpose.
The surface to be processed (base material) is not particularly limited and can be appropriately selected according to the purpose. Examples thereof include a semiconductor substrate surface in an electronic device such as a semiconductor device, an alloy substrate surface in a magnetic head, and the like. Can be mentioned. Specifically, a substrate such as a silicon wafer or an AlTiC wafer, various oxide films, and the like are preferable.

-Resist film formation process-
The resist film forming step is a step of forming a resist film by applying a resist composition on the surface to be processed (base material) or the resist sensitized film.
The resist composition includes a resin (eg, t-butoxycarbonyl (t-Boc) -modified poly p-hydroxystyrene), a photoacid generator (eg, diphenyliodonium nonafluorobutanesulfonate), and an additive (eg, hexylamine). And at least a solvent (for example, propylene glycol monomethyl ether acetate).

-Resist pattern formation process-
The resist pattern forming step is a step of forming a resist pattern by exposing and developing the resist film, or the resist film and the resist sensitizing film.

--Exposure--
The exposure can be suitably performed by a known exposure apparatus, and is performed by selectively irradiating the resist film with exposure light. When the photoacid generator is contained in the resist composition, the photoacid generator in the resist composition in the exposed region is decomposed to generate an acid by irradiation with the exposure light, thereby generating a resist composition. A curing reaction of the product occurs and a pattern latent image is formed. Further, depending on the constituent material of the resist composition, the exposure may be performed after the heating step described later.

  Irradiation of the exposure light is selectively performed on a partial region of the resist film, so that the solubility and polarity change in the partial region. An unreacted region other than a partial region where the polarity has changed remains (in the case of a positive resist) or is removed (in the case of a negative resist) to form a resist pattern.

  There is no restriction | limiting in particular as said exposure light, Although it can select suitably according to the objective, An ultraviolet-ray, an excimer laser beam, an ionizing radiation (an electron beam, a focused ion beam, a positron beam, an alpha ray, a beta ray, a microparticle) At least one kind of charged particle beam selected from X-rays, π-particle beams, X-rays, proton beams, deuteron beams, and heavy ion beams), and active energy beams such as X-rays, electron beams, and focused ion beams. More preferred is an electron beam. When an electron beam is used as exposure light, the sensitivity of the resist composition can be significantly improved.

--Development--
In the development, after the exposed (not exposed) region of the resist film is cured, the uncured region is removed.

  There is no restriction | limiting in particular as a removal method of the said unhardened area | region, According to the objective, it can select suitably, For example, the method of removing using a developing solution etc. are mentioned.

  There is no restriction | limiting in particular as said developing solution, Although it can select suitably according to the objective, Water, alkaline aqueous solution, etc. are preferable at the point which can reduce the load to an environment.

  There is no restriction | limiting in particular as an alkali in the said alkaline aqueous solution, According to the objective, it can select suitably, For example, inorganic alkalis, such as sodium hydroxide, potassium hydroxide, sodium silicate, ammonia; Ethylamine, propylamine, etc. Primary amines; secondary amines such as diethylamine and dipropylamine; tertiary amines such as trimethylamine and triethylamine; alcohol amines such as diethylethanolamine and triethanolamine; tetramethylammonium hydroxide, tetraethylammonium hydroxide, And quaternary ammonium hydroxides such as triethylhydroxymethylammonium hydroxide and trimethylhydroxyethylammonium.

  Further, for example, a water-soluble organic solvent such as methyl alcohol, ethyl alcohol, propyl alcohol, and ethylene glycol, a surfactant, a resin dissolution inhibitor, and the like can be added to the alkaline aqueous solution as necessary. . As the surfactant, those described in the resist sensitizing film forming material can be used.

  In addition, the resist pattern forming process is capable of easily and efficiently forming a fine resist pattern with high sensitivity, high resolution and low cost without pattern loss or dimensional variation. Various resist patterns such as line & space It is suitable for forming patterns, hole patterns (for contact holes, etc.), pillar (column) patterns, trench (groove) patterns, line patterns, and the like. The resist pattern formed by the resist pattern forming step can be used as, for example, a mask pattern, a reticle pattern, and the like, such as a metal plug, various wirings, a magnetic head, an LCD (liquid crystal display), a PDP (plasma display panel), It can be suitably used for the manufacture of functional parts such as SAW filters (surface acoustic wave filters), optical parts used for connection of optical wiring, fine parts such as microactuators, and semiconductor devices. It can use suitably for a manufacturing method.

-Patterning process-
The patterning step is a step of patterning the surface to be processed by etching using the resist pattern as a mask (using as a mask pattern or the like).
There is no restriction | limiting in particular as the said etching method, According to the objective, it can select suitably according to the objective, For example, selective vapor deposition and dry etching are mentioned suitably. The etching conditions are not particularly limited and can be appropriately selected depending on the purpose.
In the patterning process, by performing selective vapor deposition or etching using the resist pattern formed in the resist pattern forming process as a mask, a fine processing pattern made of a material such as a metal having a constant line width is obtained. A device can be manufactured. For example, a semiconductor device having a wiring with a line width of about 50 nm can be manufactured.

-Other processes-
There is no restriction | limiting in particular as said other process, According to the objective, it can select suitably, For example, a heating process, a removal process, etc. are mentioned.

-Heating process-
The heating step is a step of heating the resist sensitizing film forming material.
In the heating step, the applied resist sensitizing film forming material is preferably baked (heated and dried) during or after the coating step.
Conditions and methods such as heating temperature and heating time in the heating step are not particularly limited as long as the resist sensitizing film forming material is not decomposed, and can be appropriately selected according to the purpose. There is no restriction | limiting in particular as said heating temperature, Although it can select suitably according to the objective, For example, about 50 to 300 degreeC is preferable, Furthermore, 70 to 270 degreeC is more preferable, and 100 to 250 degreeC is more preferable. Particularly preferred.
When the heating temperature is less than 50 ° C., drying of the solvent may not proceed sufficiently, and when it exceeds 300 ° C., the resin may be thermally decomposed.
There is no restriction | limiting in particular as the heating time in the said heating process, Although it can select suitably according to the objective, For example, about 10 seconds-5 minutes are preferable, and also 30 seconds-90 seconds are more preferable.

-Removal process-
The removing step is a step of removing the resist sensitizing film.
There is no restriction | limiting in particular as the removal method of the said resist sensitizing film, According to the objective, it can select suitably, For example, washing, image development, an etching, etc. are mentioned.
Among these, water washing and development are preferable from the viewpoint of simplicity. There is no restriction | limiting in particular as a developing solution used in the case of the said image development, According to the objective, it can select suitably, For example, an anisole / xylene (weight ratio 70/30) liquid mixture etc. are mentioned.
Here, the resist sensitizing film provided under the resist is preferably insoluble in the developing solution for the resist film in that the removed portion can be easily controlled. If the resist sensitizing film dissolves in the resist film developer, the developer may ooze out from the resist film into the resist sensitizing film during development of the resist film, and unintended portions may be developed. Because there is sex.

By forming a resist sensitizing film containing a metal salt and resin on the base material of the resist, it is possible to improve the apparent resist sensitivity, and to suppress the penetration of electrons into the base material. In addition, the electrons that bounce off the resist from the base material can be suppressed, and the influence of backscattering can be greatly reduced.

In addition, by forming a resist sensitizing film containing a metal salt and a resin on the upper part of the resist formed on the base material, electron scattering in the resist sensitizing film is promoted in electron beam exposure, and resist reaction. Since the contributing electrons increase, the apparent resist sensitivity can be improved.
(Example)

  Examples of the present invention will be described below, but the present invention is not limited to the following examples.

(Examples 1-21 and Comparative Examples 1-5)
-Preparation of resist sensitizing film forming material-
Resist sensitized film forming materials having the compositions shown in Table 1 were prepared.

In addition, the unit of the numerical value in the parenthesis in Table 1 represents “part by mass”.
In the column of “Metal Salt” in Table 1, “A-1” represents cesium carbonate (manufactured by Kanto Chemical Co., Ltd.), and “A-2” represents barium acetate (manufactured by Kanto Chemical Co., Ltd.). "A-3" represents rubidium carbonate (manufactured by Kanto Chemical Co., Ltd.), "A-4" represents strontium chloride (manufactured by Kanto Chemical Co., Ltd.), and "A-5" It represents potassium carbonate (manufactured by Kanto Chemical Co., Ltd.), and “A-6” represents calcium acetate (manufactured by Kanto Chemical Co., Ltd.).
In the column of “Resin” in Table 1, “B-1” represents polymethyl methacrylate (manufactured by Sigma-Aldrich Japan), and “B-2” represents poly-p-hydroxystyrene (Nippon Soda ( "B-3" represents a 3-amino-4-methoxybenzenesulfonic acid polymer (synthesized by the method described in paragraph "0064" in JP-A-8-109351), and “B-4” represents 30% acetalized polyvinyl alcohol.
In the column of “Crosslinking agent” in Table 1, “C-1” represents hexamethoxymethylmelamine (manufactured by Tokyo Chemical Industry Co., Ltd.), and “C-2” represents N, N′-dimethoxymethyldimethoxyethylene. Yulia (manufactured by Sanwa Chemical Co., Ltd.), and “C-3” represents tetramethoxymethyl glycoluril (manufactured by Tokyo Chemical Industry Co., Ltd.).
“D-1” in the column of “thermal acid generator” in Table 1 represents 2-nitrobenzyl tosylate (manufactured by Midori Chemical Co., Ltd.).
In the column of “Solvent” in Table 1, “E-1” represents anisole (manufactured by Kanto Chemical Co., Ltd.), “E-2” represents ethyl lactate (manufactured by Kanto Chemical Co., Ltd.), “ “E-3” represents water, and “E-4” represents isopropyl alcohol (manufactured by Kanto Chemical Co., Inc.).

  About the formation of the following resist sensitizing films, the preparation of the resist composition and the formation of the resist pattern, “Examples 1 to 19 and Comparative Examples 1 to 3” and “Examples 20 to 21 and Comparative Examples 4 to 5” They will be explained separately.

(Examples 1-19 and Comparative Examples 1-3)
-Formation of resist sensitized film-
The resist sensitizing film forming material prepared at the mixing ratio shown in Table 1 has, for example, a part of tungsten wiring, a thickness of about 300 nm at a position of about 200 nm deep from the substrate surface, and a wiring occupation ratio of about 25. After being applied to a silicon substrate embedded in% by spin coating, baking is performed at the baking temperature shown in Table 1 to form a film (resist sensitized film). The thickness of the film (resist sensitized film) was set to 1000 mm by adjusting the spin rotation speed unless otherwise specified.

  In Example 6, a homogeneous film was not formed due to white turbidity. In Example 13, a homogeneous film was not formed by the thermal decomposition of the constituent materials.

-Preparation of resist composition-
A resist composition having the following composition may be prepared.
Resin: 30% t-Butoxycarbonyl (t-Boc) -modified poly p-hydroxystyrene (Maruzen Petrochemical Co., Ltd.) 100 parts by weight Photoacid generator: Diphenyliodonium nonafluorobutanesulfonate (Midori Chemical Co., Ltd.) ) ... 5 parts by mass Additive: Hexylamine (Kanto Chemical Co., Ltd.) ... 0.5 parts by mass Solvent: Propylene glycol monomethyl ether acetate (Kanto Chemical Co., Ltd.) ... 700 parts by mass

-Formation of resist pattern-
On the film (resist sensitized film), for example, the resist (chemically amplified resist) composition may be applied by spin coating and then baked at 110 ° C. for 120 seconds.
Next, with respect to the substrate on which the resist film is formed on the film (resist sensitized film), for example, using an electron beam exposure machine (ELS-5700 manufactured by Elionix Co., Ltd.) with an acceleration voltage of 50 keV, the exposure amount A plurality of line patterns having a width of 50 nm can be drawn by changing the above stepwise. After drawing, for example, baking can be performed at 110 ° C. for 90 seconds, and development can be performed with a 2.38% aqueous tetramethylammonium hydroxide solution for 60 seconds.
The line width of the line pattern formed by the above method is measured with a scanning electron microscope (S-4500, manufactured by Hitachi, Ltd.), and the exposure amount at which the pattern is formed with a line width of 50 nm is defined as sensitivity. To do.
Table 2 shows the sensitivities of Examples 1 to 19 and Comparative Examples 1 to 3.
In addition, you may change suitably about the film thickness of the film (resist sensitized film) of Examples 1-3 by adjustment of spin rotation.

(Examples 20 to 21 and Comparative Examples 4 to 5)
-Preparation of resist composition-
A resist composition having the following composition is prepared.
Resin: 30% t-Butoxycarbonyl (t-Boc) -modified poly p-hydroxystyrene (Maruzen Petrochemical Co., Ltd.) 100 parts by weight Photoacid generator: Diphenyliodonium nonafluorobutanesulfonate (Midori Chemical Co., Ltd.) ) ... 5 parts by mass Additive: Hexylamine (Kanto Chemical Co., Ltd.) ... 0.5 parts by mass Solvent: Propylene glycol monomethyl ether acetate (Kanto Chemical Co., Ltd.) ... 700 parts by mass

-Formation of resist sensitized film-
For example, the prepared resist composition is spin-coated on a silicon substrate in which a part of the tungsten wiring is embedded at a position of about 200 nm deep from the substrate surface with a thickness of about 300 nm and a wiring occupation ratio of about 25%. Apply. Thereafter, for example, a resist film is formed by baking at 110 ° C. for 120 seconds, and a resist sensitizing film forming material prepared at a mixing ratio shown in Table 1 is spin-coated on the resist film. Apply by the method. Furthermore, baking can be performed at the baking temperature shown in Table 1 to form a film (resist sensitized film).
The thickness of the coating (resist sensitizing film) was set to 1000 mm by adjusting the spin rotation speed.

-Formation of resist pattern-
Next, with respect to the substrate on which the coating film (resist sensitized film) is formed on the resist film, for example, an exposure amount using an electron beam exposure machine (ELS-5700 manufactured by Elionix Co., Ltd.) with an acceleration voltage of 50 keV is used. By changing stepwise, a plurality of line patterns having a width of about 50 nm can be drawn. After drawing, for example, baking can be performed at 110 ° C. for 90 seconds, and development can be performed with a 2.38% aqueous tetramethylammonium hydroxide solution for 60 seconds.
The line width of the line pattern formed by the above method is measured with, for example, a scanning electron microscope (S-4500, manufactured by Hitachi, Ltd.), and the exposure amount at which the pattern is formed with a line width of 50 nm is sensitivity. It is defined as
Table 2 shows the sensitivities of Examples 20 to 21 and Comparative Examples 4 to 5.
In the development process, the resist sensitized film is dissolved and removed in a 2.38% tetramethylammonium hydroxide aqueous solution.

In Examples 1 to 6, the exposure amount for forming a pattern with a line width of 50 nm is smaller than that of Comparative Example 1, and in the formation of a line width pattern of 50 nm that requires high resolution of the resist, the sensitivity Can be seen to be large.
In Examples 7 to 18, the amount of exposure for forming a pattern with a line width of 50 nm is smaller than that of Comparative Example 2, and sensitivity is required in the formation of a line width pattern of 50 nm that requires high resist resolution. Can be seen to be large.
In Example 19, the amount of exposure for forming a pattern with a line width of 50 nm is smaller than that of Comparative Example 3, and the sensitivity is high in the formation of a 50 nm line width pattern that requires higher resolution of the resist. I understand that.
In Example 20, the exposure amount for forming a pattern with a line width of 50 nm is smaller than that of Comparative Example 4, and the sensitivity is high in the formation of a 50 nm line width pattern that requires high resolution of the resist. I understand that.
In Example 21, compared with Comparative Example 5, the amount of exposure for forming a pattern with a line width of 50 nm is small, and the sensitivity is high in the formation of a line width pattern of 50 nm that requires high resist resolution. I understand that.

In Examples 1 to 6, the sensitivity ratio (no W-embedding / W-embedded substrate) is smaller than in Comparative Example 1, and it can be seen that the influence of backscattering is small.
In Examples 7 to 18, the sensitivity ratio (no W-embedding / W-embedded substrate) is smaller than in Comparative Example 2, and it can be seen that the influence of backscattering is small.
In Example 19, the sensitivity ratio (no W embedded / W embedded substrate) is smaller than in Comparative Example 3, and it can be seen that the influence of backscattering is small.
In Example 20, the sensitivity ratio (no W embedded / W embedded substrate) is smaller than that in Comparative Example 4.
In Example 21, the sensitivity ratio (no W embedded / W embedded substrate) is smaller than that of Comparative Example 5.

  In Example 10, the resist film is not uniformly formed because a part of the undercoat is dissolved during the resist film formation.

  From Examples 10 to 13, it can be seen that the baking temperature of the resist sensitized film is preferably 50 ° C to 300 ° C, more preferably 70 ° C to 270 ° C.

In Comparative Example 1 and Examples 1 to 13, a positional deviation of 20 to 100 nm occurred from the wafer reference position due to charging. However, in Comparative Examples 3 to 4 and Examples 19 to 20, the positional deviation was 5 nm or less. there were. This is considered to be due to the use of conductive resin (B-3) as the resin for the resist sensitizing film.
The wafer reference position refers to a cross-shaped step pattern formed in advance on a substrate by resist patterning and dry etching using an ArF excimer laser exposure machine. Further, the amount of positional deviation from the wafer reference position was measured with an overlay measuring device manufactured by KLA, and the average value thereof was taken as the amount of positional deviation.

  Moreover, the film (resist sensitized film) of Comparative Example 1 and Examples 1 to 6 can be removed by a mixed solution of anisole / xylene (for example, weight ratio 70/30) in addition to normal dry etching.

(Example 22)
-Flash memory and its manufacture-
Example 22 is an example of a method for manufacturing a semiconductor device of the present invention using the resist sensitizing film forming material of the present invention. In Example 22, the following resist films 26, 27, 29 and 32 may be resist films to which the resist sensitizing film forming material of the present embodiment is applied. Specifically, as the resist film, the resist composition used in Examples 1 to 21 may be used with a resist sensitized film formed using the resist sensitized film forming material of the present embodiment as a base. . In addition, these resist sensitized films and resist compositions are formed by the same method as in Examples 1 to 21.
The resist films 26, 27, 29, 32, and 43 may include resist films 26a, 27a, 29a, 32a, and 43a and resist sensitized films 26b, 27b, 29b, 32b, and 43b.

  1 and 2 are top views (plan views) of a FLASH EPROM called a FLOTOX type or an ETOX type. 3A to 3I are cross-sectional schematic diagrams for explaining an example relating to a manufacturing method of the FLASH EPROM. 3A to 3I are memory cell portions (first element regions), and a cross section in the gate width direction (X direction in FIGS. 1 and 2) of a portion where a MOS transistor having a floating gate electrode is formed. (A direction cross section) Schematic diagram, central view is the memory cell portion of the same part as the left view, and cross section (B direction cross section) in the gate length direction (Y direction in FIGS. 1 and 2) orthogonal to the X direction ) Schematic diagram, right diagram is a schematic diagram of a section (cross-section in the A direction in FIGS. 1 and 2) of a portion where a MOS transistor is formed in the peripheral circuit portion (second element region).

First, as shown in FIG. 3A, for example, a field oxide film 23 made of a SiO ₂ film is selectively formed in an element isolation region on a p-type Si substrate (semiconductor substrate) 22. After that, for example, the first gate insulating film 24a in the MOS transistor in the memory cell portion (first element region) is formed by SiO ₂ film by thermal oxidation so that the thickness becomes, for example, 100 to 300 mm (10 to 30 nm). Also good. In a separate step, for example, the peripheral circuit section thickness of the second gate insulating film 24b in the MOS transistor (second element region) is eg, SiO by thermal oxidation so that 100 Å to 500 Å (10 to 50 nm) ₂ You may form with a film | membrane. When the first gate insulating film 24a and the second gate insulating film 24b have the same thickness, an oxide film may be formed simultaneously in the same process.

Next, in order to form a MOS transistor having an n-type depletion type channel in the memory cell portion (left and center views in FIG. 3A), the peripheral circuit portion (in FIG. 3A) is formed for the purpose of controlling a threshold voltage. The right figure) may be masked by the resist film 26. Then, phosphorus (P) or arsenic (As) with a dose amount of 1 × 10 ¹¹ to 1 × 10 ¹⁴ cm ⁻² is introduced as an n-type impurity into a channel region immediately below the floating gate electrode by an ion implantation method, The first threshold control layer 25a may be formed. Note that the dose amount and the conductivity type of the impurity at this time can be appropriately selected depending on whether the depletion type or the accumulation type is used.

Next, in order to form a MOS transistor having an n-type depletion type channel in the peripheral circuit portion (the right diagram in FIG. 3B), a memory cell portion (the left diagram in FIG. The resist film 27 may be masked. Then, phosphorus (P) or arsenic (As) having a dose amount of 1 × 10 ¹¹ to 1 × 10 ¹⁴ cm ⁻² is introduced as an n-type impurity into a channel region immediately below the gate electrode by an ion implantation method. A two-threshold control layer 25b may be formed.

  Next, as the floating gate electrode of the MOS transistor in the memory cell portion (the left diagram and the central diagram in FIG. 3C) and the gate electrode of the MOS transistor in the peripheral circuit portion (the right diagram in FIG. 3C), a thickness of, for example, 500 to A first polysilicon film (first conductor film) 28 having a thickness of 2,000 mm (50 to 200 nm) may be formed on the entire surface.

  Thereafter, as shown in FIG. 3D, for example, the first polysilicon film 28 is patterned by a resist film 29 formed as a mask, and the floating gate electrode in the MOS transistor of the memory cell portion (the left diagram and the central diagram in FIG. 3D). 28a may be formed. At this time, as shown in FIG. 3D, patterning for defining the X direction so as to have a final dimension width is performed, and patterning for defining the Y direction is not performed, and the region that becomes the S / D region layer is the resist film 29. Can remain covered.

Next, as shown in the left diagram and the central diagram in FIG. 3E, after removing the resist film 29, the capacitor insulating film 30a made of a SiO ₂ film is formed so as to cover the floating gate electrode 28a with a thickness of about You may form by thermal oxidation so that it may become 200-500 mm (20-50 nm). At this time, a capacitor insulating film 30b made of a SiO ₂ film may also be formed on the first polysilicon film 28 in the peripheral circuit portion (the right diagram in FIG. 3E). Here, the capacitor insulating films 30a and 30b are formed of only the SiO ₂ film, but may be formed of a composite film in which two or _three SiO ₂ films and Si ₃ N ₄ films are laminated.

  Next, as shown in FIG. 3E, the second polysilicon film (second conductor film) 31 serving as the control gate electrode is covered with the floating gate electrode 28a and the capacitor insulating film 30a, for example, with a thickness of 500, for example. You may form so that it may become -2,000 cm (50-200 nm).

  Next, as shown in FIG. 3F, for example, the memory cell part (the left figure and the middle figure in FIG. 3F) is masked with a resist film 32, and the second polysilicon in the peripheral circuit part (the right figure in FIG. 3F) is masked. The film 31 and the capacitor insulating film 30b can be sequentially removed by etching, and the first polysilicon film 28 can be exposed.

  Next, as shown in FIG. 3G, for example, the second polysilicon film 31, the capacitor insulating film 30a of the memory cell portion (the left figure and the middle figure in FIG. 3G), and the patterning that defines the X direction are only performed. The 1 polysilicon film 28a can be patterned using the resist film 32 as a mask to define the Y direction so that the final dimension of the first gate portion 33a is obtained. In this process, a stack of a control gate electrode 31a / capacitor insulating film 30c / floating gate electrode 28c having a width of about 1 μm in the Y direction is formed, and the first polysilicon film 28 in the peripheral circuit portion (the right diagram in FIG. 3G) is formed. On the other hand, by using the resist film 32 as a mask, patterning is performed so that the final dimension of the second gate portion 33b is obtained, thereby forming a gate electrode 28b having a width of about 1 μm.

Next, using the stack of the control gate electrode 31a / capacitor insulating film 30c / floating gate electrode 28c of the memory cell portion (left and center views in FIG. 3H) as a mask, the Si substrate 22 in the element formation region is, for example, dosed. An amount of 1 × 10 ¹⁴ to 1 × 10 ¹⁶ cm ⁻² of phosphorus (P) or arsenic (As) can be introduced by an ion implantation method. In this process, n-type S / D (source / drain) region layers 35a and 35b are formed, and the gate electrode 28b of the peripheral circuit portion (the right diagram in FIG. 3H) is used as a mask to form a Si substrate in the element formation region. 22 is doped with phosphorus (P) or arsenic (As) having a dose amount of 1 × 10 ¹⁴ to 1 × 10 ¹⁶ cm ⁻² as an n-type impurity by ion implantation to form S / D region layers 36a and 36b. Can do.

  Next, for example, the first gate portion 33a of the memory cell portion (the left diagram and the central diagram in FIG. 3I) and the second gate portion 33b of the peripheral circuit portion (the right diagram in FIG. 3I) are subjected to interlayer insulation using a PSG film. The film 37 may be formed so as to have a thickness of about 5,000 mm (500 nm).

Thereafter, for example, contact holes 38a and 38b and contact holes 39a and 39b are formed in the interlayer insulating film 37 formed on the S / D region layers 35a and 35b and the S / D region layers 36a and 36b. Electrodes 40a and 40b and S / D electrodes 41a and 41b may be formed.
As described above, as shown in FIG. 3I, a FLASH EPROM is manufactured as a semiconductor device.

  In the FLASH EPROM, the second gate insulating film 24b of the peripheral circuit portion (the right figure in FIGS. 3A to 3I) is formed and then covered with the first polysilicon film 28 or the gate electrode 28b (FIGS. 3A to 3D). Therefore, the thickness of the second gate insulating film 24b remains as it was when it was first formed. Therefore, the thickness of the second gate insulating film 24b can be easily controlled, and the conductivity type impurity concentration for controlling the threshold voltage can be easily adjusted.

  In this embodiment, the first gate portion 33a is formed by first patterning with a predetermined width in the gate width direction (X direction in FIGS. 1 and 2) and then in the gate length direction (in FIGS. 1 and 2). The final predetermined width may be obtained by patterning in the Y direction, but conversely, after patterning with the predetermined width in the gate length direction (Y direction in FIGS. 1 and 2), the gate width direction (FIGS. 1 and 2). The final predetermined width may be obtained by patterning in the X direction).

The manufacturing example of the FLASH EPROM shown in FIGS. 3J to 3L is the same as the above example except that the steps shown in FIG. 3E in Example 22 are changed as shown in FIGS. 3J to 3L. That is, as shown in FIG. 3J, on the second polysilicon film 31 in the memory cell portion (left and center views in FIG. 3J) and on the first polysilicon film 28 in the peripheral circuit portion (right view in FIG. 3J). Further, a refractory metal film (fourth conductor film) 42 made of a tungsten (W) film or a titanium (Ti) film may be formed so as to have a thickness of about 2,000 mm (200 nm). The point which provided the polycide film differs from the said Example. The steps after FIG. 3J, that is, the steps shown in FIGS. 3K to 3L may be performed in the same manner as in FIGS. 3G to 3I. The description of the same steps as those in FIGS. 3G to 3I is omitted, and in FIGS. 3J to 3L, the same components as those in FIGS. 3G to 3I are denoted by the same symbols.
As described above, as shown in FIG. 3L, a FLASH EPROM can be manufactured as a semiconductor device.
In FIG. 3K, reference numeral 43 denotes a resist film, 44a denotes a first gate portion, and 44b denotes a second gate portion. Further, in FIG. 3L, 45a, 45b, 46a, 46b indicate S / D (source / drain) region layers, 47 indicates an interlayer insulating film, 48a, 48b, 49a, 49b indicate contact holes, 50a, Reference numerals 50b, 51a, 51b denote S / D (source / drain) electrodes.

In this FLASH EPROM, since the refractory metal films (fourth conductor films) 42a and 42b are provided on the control gate electrode 31a and the gate electrode 28b, the electric resistance value can be further reduced.
Here, although the refractory metal films (fourth conductor film) 42a and 42b are used as the refractory metal film (fourth conductor film), a refractory metal silicide film such as a titanium silicide (TiSi) film is used. May be used.

The manufacturing example of the FLASH EPROM shown in FIGS. 3M to 3O is the same as that of the above-described twenty-second embodiment. For example, the second gate portion 33c of the peripheral circuit portion (second element region) (the right diagram in FIG. The first polysilicon film 28b (first conductor film) / SiO ₂ film 30d (capacitor insulating film) in the same manner as the first gate portion 33a of the portion (first element region) (left and center views in FIG. 3M) / The second polysilicon film 31b (second conductor film) may be used. As shown in FIG. 3N or FIG. 3O, the second embodiment is the same as the first embodiment except that the gate electrode is formed by short-circuiting the first polysilicon film 28b and the second polysilicon film 31b.

Here, as shown in FIG. 3N, the first polysilicon film 28b (first conductor film) / SiO ₂ film 30d (capacitor insulating film) / second polysilicon film 31b (second conductor film) is penetrated. The opening 52a may be formed at a location different from the second gate portion 33c shown in FIG. 3M, for example, on the insulating film 54, for example. By embedding a third conductor film, for example, a refractory metal film 53a such as a W film or a Ti film in the opening 52a, the first polysilicon film 28b and the second polysilicon film 31b can be short-circuited. Further, as shown in FIG. 3O, an opening 52b that penetrates the SiO ₂ film 30d (capacitor insulating film) / second polysilicon film 31b (second conductor film) is formed, and a lower layer is formed at the bottom of the opening 52b. The first polysilicon film 28b can be exposed. After that, the first polysilicon film 28b and the second polysilicon film 31b can be short-circuited by embedding a third conductor film, for example, a refractory metal film 53b such as a W film or a Ti film in the opening 52b. .

In this FLASH EPROM, since the second gate portion 33c of the peripheral circuit portion has the same structure as the first gate portion 33a of the memory cell portion, the peripheral circuit portion is simultaneously formed when the memory cell portion is formed. It can be formed, and the manufacturing process can be simplified and efficient.
Although the third conductor film 53a or 53b and the refractory metal film (fourth conductor film) 42 are separately formed here, they may be formed simultaneously as a common refractory metal film. Good.

(Example 23)
-Manufacture of magnetic heads-
Example 23 relates to the manufacture of a magnetic head as an application example of a resist pattern of a resist film formed using a resist sensitized film formed using the resist sensitized film forming material of this embodiment as a base. In Example 23, the following resist pattern R2A is a resist pattern to which the sensitized film forming material of the present embodiment is applied. For example, the resist film may be the resist composition used in Examples 1 to 21 with the resist sensitized film formed using the resist sensitized film forming material of the present embodiment as a base. Good. These resist sensitizing films and resist films are resist patterns formed by irradiating a resist film formed by the same method as in Examples 1 to 21 with an electron beam.
Note that the resist film R2 and the resist pattern R2A may include a resist film R2a and a resist sensitized film R2b.

The manufacturing process of the thin film magnetic head using the fine pattern forming material and the fine pattern forming method of the present invention will be described with reference to FIGS. 4A to 4G.
Referring to FIG. 4A, first, a lower magnetic shield layer 131 made of a NiFe alloy is formed on an Al ₂ O ₃ —TiC substrate (not shown) through an Al ₂ O ₃ film (not shown) by an electrolytic plating method. can do. The spin valve structure film 115L may be formed by a sputtering method through the Al ₂ O ₃ gap spacer layer 131A.

  Next, in the step of FIG. 4B, for example, the magnetoresistive element 115 may be formed by patterning the spin valve structure film 115L into a predetermined shape having a width of about 300 nm using the resist pattern R1 as a mask. 4B, a hard bias film 116 made of CoCrPt may be formed by sputtering using the resist pattern R1 as a mask, and hard bias patterns 116A and 116B may be formed on both sides of the magnetoresistive element 115. .

  Next, in the step of FIG. 4C, for example, the resist pattern R1 is removed, the CoCrPt film 116 deposited on the top of the resist pattern R1 is removed, and the hard bias on both sides of the magnetoresistive effect element 115 is formed on the entire surface. The organic polymer film 117 may be formed so as to include the patterns 116A and 116B.

  In the step of FIG. 4C, for example, a resist film R2 may be applied to a thickness of, for example, 500 nm on the organic polymer film 117 using a commercially available resist for KrF, for example, UV-6 manufactured by Shipley.

  Next, in the step of FIG. 4D, for example, an electron beam with an acceleration voltage of 50 KeV and a KrF excimer laser with a wavelength of 248 nm are used as an exposure light source, the magnetoresistive effect element portion is an electron beam, and the other wide exposure area portions are KrF The resist pattern R2A may be formed to have a width of, for example, 150 nm by exposure and development using a TMAH solution. By this development processing, the organic polymer film 117 is simultaneously etched, and an organic polymer layer pattern 117A having the same width as the resist pattern R2A can be formed immediately below the resist pattern R2A. As a result, a lift-off mask pattern 120 composed of the resist pattern R2A and the organic polymer film pattern 117A is formed on the magnetoresistive element 115.

  Next, in the step of FIG. 4E, for example, a lift-off mask pattern 120 made of the resist pattern R2A and the organic polymer film 117A may be formed on the magnetoresistive element 115 by a slimming process.

  4E, for example, the etching rate ratio between the resist pattern R2A made of a resist film and the organic polymer film pattern 117A may have a value of 1: 1.2. An undercut 117B is formed after the slimming process.

  When the resist pattern R2A has a width of about 100 nm and the organic polymer film pattern 117A has a width of about 90 nm, an undercut 117B of about 5 nm can be formed on both sides of the pattern 117A.

  4F, for example, by using the lift-off mask pattern 120 of the organic polymer film pattern 117A and the resist pattern R2A as a mask, the Ta film 133a, the Au film 133b, and the Ta film 133c are respectively 2 nm and 20 nm by sputtering, for example. Then, a readout electrode layer 133 having a Ta / Au / Ta stacked structure is deposited in order with a thickness of 2 nm. Accordingly, read electrode patterns 133A and 133B having the Ta / Au / Ta laminated structure can be formed on the hard bias patterns 116A and 116B and on both sides of the lift-off pattern 120, respectively.

  Next, in the step of FIG. 4G, the resist pattern R2A may be removed using, for example, acetone, and the electrode layer 133 deposited on the resist pattern R2A may be removed at the same time. Further, the organic polymer film pattern 117A may be removed using NMP (N-methylpyrrolidone).

Thereafter, for example, _Al 2 NiFe alloy layer _{134 O 3} through the gap spacer layer consisting constituting the upper magnetic shield layer and lower magnetic pole layer (see FIG. 5) is formed by electrolytic plating method, further _Al 2 _{O 3} A write gap layer made of may be formed.

  Next, in the process of FIG. 5, a first interlayer insulating film made of, for example, a resist film is formed, and a write coil 135 having a horizontal spiral pattern shape of, for example, a Cu layer is formed on the first interlayer insulating film by electrolytic plating. It may be formed. Further, write electrodes 136A and 136B may be provided at both ends of the write coil 135, and a resist film may be deposited so as to cover the write coil to form a second interlayer insulating film.

Further, a plating base layer made of a Ti film is provided on the entire surface of the second interlayer insulating film, and a NiFe film is selectively electroplated on the second interlayer insulating film using a resist mask formed thereon as a plating frame. By doing so, the top pole layer 137 and the write pole 138 at the tip may be formed.
Next, after removing the resist mask, the exposed portion of the plating base layer may be removed by ion milling using Ar ions. Next, after forming an Al ₂ O ₃ protective film on the entire surface, the substrate is cut to obtain a magnetic head slider in which a read head including the magnetoresistive effect element 115 and an inductive thin film magnetic head for writing are integrated. .
In FIG. 5, reference numeral 132 denotes a magnetoresistive element.

  As described above, in this embodiment, by using a resist, a magnetoresistive sensor having a fine core width can be manufactured in a simple process with high accuracy and with a high yield.

  The disclosed resist sensitizing film-forming material contains a metal salt, a resin, and a solvent, and can widen the range of selectivity of usable materials. Various patterning methods, semiconductor manufacturing methods, etc. The present invention can be preferably applied to the semiconductor device and the magnetic head of the disclosure.

22 Si substrate (semiconductor substrate)
23 field oxide film 24a first gate insulating film 24b second gate insulating film 25a first threshold control layer 25b second threshold control layer 26 resist film 26a resist film 26b resist sensitized film 27 resist film 27a resist film 27b resist sensitized film 28 First polysilicon film (first conductor film)
28a Floating gate electrode 28b Gate electrode (first polysilicon film (first conductor film))
28c Floating gate electrode 29 Resist film 29a Resist film 29b Resist sensitized film 30a Capacitor insulating film 30b Capacitor insulating film 30c Capacitor insulating film 30d SiO ₂ film (capacitor insulating film)
31 Second polysilicon film (second conductor film)
31a Control gate electrode 31b Second polysilicon film (second conductor film)
32 resist film 32a resist film 32b resist sensitized film 33a first gate portion 33b second gate portion 33c second gate portion 35a S / D (source / drain) region layer 35b S / D (source / drain) region layer 36a S / D region layer 36b S / D region layer 37 Interlayer insulating film 38a Contact hole 38b Contact hole 39a Contact hole 39b Contact hole 40a S / D electrode 40b S / D electrode 41a S / D electrode 41b S / D electrode 42 Refractory metal Film (fourth conductor film)
42a refractory metal film (fourth conductor film)
42b refractory metal film (fourth conductor film)
43 resist film 43a resist film
43b resist sensitized film 44a first gate portion 44b second gate portion 45a S / D (source / drain) region layer 45b S / D (source / drain) region layer 46a S / D (source / drain) region layer 46b S / D (source / drain) region layer 47 Interlayer insulating film 48a Contact hole 48b Contact hole 49a Contact hole 49b Contact hole 50a S / D (source / drain) electrode 50b S / D (source / drain) electrode 51a S / D ( Source / drain) electrode 51b S / D (source / drain) electrode 52a Opening 52b Opening 53a Third conductor film 53b Third conductor film 54 Insulating film 115 Magnetoresistive element 115L Spin valve structure film 116 Hard bias film 116A Hard bias pattern 116B Bias pattern 117 Organic polymer film 117A Organic polymer layer pattern 117B Undercut 120 Lift-off mask pattern 131 Lower magnetic shield layer 131A Gap spacer layer 132 Magnetoresistive element 133 Electrode layer 133A Electrode pattern 133B Electrode pattern 133a Ta film 133b Au film 133c Ta film 134 NiFe alloy layer 135 Write coil 136A Write electrode 136B Write electrode 137 Upper magnetic pole layer 138 Write magnetic pole R1 resist pattern R2 resist film R2a resist film R2b resist sensitized film R2A resist pattern

Claims (9)

It contains a metal salt, a resin containing at least one selected from polymethyl methacrylate, poly-p-hydroxystyrene, polyvinyl alcohol, and 3-amino-4-methoxybenzenesulfonic acid polymer, and a solvent. Electron beam resist sensitized film forming material. The material for forming an electron beam resist sensitized film according to claim 1, wherein the metal salt is one of an alkali metal salt and an alkaline earth metal salt. 3. The material for forming an electron beam resist sensitized film according to claim 1, wherein the metal salt contains at least one selected from potassium salt, calcium salt, rubidium salt, strontium salt, cesium salt and barium salt. . The material for forming an electron beam resist sensitizing film according to any one of claims 1 to 3, wherein the content of the metal salt is 1% by mass to 50% by mass with respect to the resin. The material for forming an electron beam resist sensitized film according to any one of claims 1 to 4, further comprising a crosslinking agent. The material for forming an electron beam resist sensitized film according to claim 5, wherein the crosslinking agent contains at least one selected from melamine derivatives, urea derivatives, and uril derivatives. The material for forming an electron beam resist sensitized film according to claim 1, further comprising an acid generator. A resist sensitized film forming step of forming a resist sensitized film by applying the electron beam resist sensitized film forming material according to any one of claims 1 to 7 on a work surface, and the resist sensitized film A resist film forming step of forming a resist film by applying a resist composition thereon, a resist pattern forming step of exposing the resist film with an electron beam and developing to form a resist pattern, and using the resist pattern as a mask And a patterning step of patterning the surface to be processed by etching. A resist film forming step of forming a resist film by applying a resist composition on a surface to be processed, and the electron beam resist sensitizing film forming material according to any one of claims 1 to 7 on the resist film. A resist sensitizing film forming step for forming a resist sensitizing film by coating, a resist pattern forming step for exposing the resist film and the resist sensitizing film with an electron beam and developing to form a resist pattern, and the resist And a patterning step of patterning the surface to be processed by etching using the pattern as a mask.