JP2010245130A - Stamper and optical imprint lithography method using the same - Google Patents

Stamper and optical imprint lithography method using the same Download PDF

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JP2010245130A
JP2010245130A JP2009089611A JP2009089611A JP2010245130A JP 2010245130 A JP2010245130 A JP 2010245130A JP 2009089611 A JP2009089611 A JP 2009089611A JP 2009089611 A JP2009089611 A JP 2009089611A JP 2010245130 A JP2010245130 A JP 2010245130A
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stamper
transfer layer
light
meth
acrylate
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Norito Ikui
Yoshitomo Yasuda
慶友 保田
準人 生井
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Jsr Corp
Jsr株式会社
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Abstract

A stamper capable of easily removing a residue remaining on a concavo-convex pattern formed on a surface of a shape transfer layer after being separated from a stamper, and a photoimprint lithography method using the stamper.
A stamper 10a used in an optical imprint lithography method having a concavo-convex pattern 12 for transferring to a shape transfer layer provided on a substrate, wherein the concavo-convex pattern 12 has a light-shielding convex portion 121s. And a light-transmitting recess 122t. The present optical imprint lithography method includes a step of pressing the stamper 10a onto a shape transfer layer having a negative photocuring property, a step of exposing the shape transfer layer while the stamper 10a is pressed against the shape transfer layer, A step of separating the stamper 10a from the shaped transfer layer after exposure, and a step of cleaning the concavo-convex pattern formed on the shaped transfer layer after separation.
[Selection] Figure 1

Description

  The present invention relates to a stamper and an optical imprint lithography method using the stamper. More specifically, the present invention relates to a stamper having a light-shielding convex portion and a light-transmissive concave portion, a stamper having a light-transmissive convex portion and a light-shielding concave portion, a stamper using these stampers, and light using the stamper The present invention relates to an imprint lithography method.

In order to improve the integration degree and recording density of circuits such as semiconductor elements, a finer processing technique is required. As a fine processing technique, a photolithography technique using an exposure process can perform a fine processing of a large area at a time, but does not have a resolution below the wavelength of light. Accordingly, in recent years, photolithography technology using short-wavelength light of 193 nm (ArF), 157 nm (F 2 ), and 13.5 nm (EUV) has been developed. However, as the wavelength of light becomes shorter, the substances that can be transmitted at that wavelength are limited.
On the other hand, in methods such as electron beam lithography and focused ion beam lithography, the resolution does not depend on the wavelength of light and a fine structure can be created, but poor throughput is a problem.
On the other hand, as a technique for creating a fine structure with a wavelength equal to or less than the wavelength of light at a high throughput, a stamper on which a predetermined fine uneven pattern is created in advance by electron beam lithography or the like is pressed against a resist-coated substrate, There is known an imprinting method for transferring a film onto a resist film on a substrate (for example, see Non-Patent Documents 1 and 2 and Patent Documents 1 and 2).

US Pat. No. 5,772,905 US Pat. No. 5,956,216 JP 2008-162190 A

S. Wy. S. Y. Chou, "Nano Imprint Lithography technology" Applied Physics Letters, Vol. 76, 1995, p. 3114

In the imprint method, after separating the stamper from the shaped transfer layer, a clearer pattern can be obtained by removing the residue between the patterns formed on the shaped transfer layer (that is, the concave portions of the concavo-convex pattern). . However, in the photoimprint lithography method that performs photocuring, there is a problem that it is difficult to remove residues that have been cured between patterns, and a technique that can easily remove residues is required.
The present invention has been made in view of the above circumstances, and a stamper capable of easily removing a residue remaining on a concavo-convex pattern formed on a surface of a shape-transferred layer after being separated from the stamper, and the stamper It is an object of the present invention to provide a photoimprint lithography method used.

That is, the present invention is as follows.
<1> A stamper used in an optical imprint lithography method having a concavo-convex pattern for transferring to a shape transfer layer provided on a substrate,
The concavo-convex pattern has a light-shielding convex portion and a light-transmitting concave portion.
<2> (a) a pressure-contacting step in which the stamper according to the above <1> is pressure-contacted to the shape-transferred layer having negative photocuring property;
(B) an exposure step of exposing the shaped transfer layer in a state where the stamper is in pressure contact with the shaped transfer layer;
(C) a separation step of separating the stamper and the shaped transfer layer after exposure;
(D) A cleaning process for cleaning the concavo-convex pattern formed on the shaped transfer layer after the separation.
<3> A stamper used in an optical imprint lithography method having a concavo-convex pattern for transferring to a shape transfer layer provided on a substrate,
The concavo-convex pattern has a light-blocking concave portion and a light-transmitting convex portion.
<4> (a) a pressure-contacting process in which the stamper according to <3> is pressure-contacted to the shape-transferred layer having positive photocurability;
(B) an exposure step of exposing the shaped transfer layer in a state where the stamper is in pressure contact with the shaped transfer layer;
(C) a separation step of separating the stamper and the shaped transfer layer after exposure;
(D) A cleaning process for cleaning the concavo-convex pattern formed on the shaped transfer layer after the separation.

According to the stamper having the light-shielding convex portion and the light-transmitting concave portion of the present invention, it is possible to easily clean the concave-convex pattern transferred and formed on the surface of the shape transfer layer separated from the stamper. it can. In particular, since the residue of the recess is not photocured, it can be easily removed, and the resulting uneven pattern can be made clearer.
According to the optical imprint lithography method using the stamper having the light-shielding convex portion and the light-transmitting concave portion according to the present invention, the uneven pattern transferred and formed on the surface of the shape transfer layer separated from the stamper Can be easily cleaned. In particular, since the residue of the recess is not photocured, it can be easily removed, and the resulting uneven pattern can be made clearer.
According to the stamper having a light-shielding concave portion and a light-transmitting convex portion according to the present invention, it is possible to easily clean the concave-convex pattern transferred and formed on the surface of the shape transfer layer separated from the stamper. it can. In particular, since the residue of the recess is not photocured, it can be easily removed, and the resulting uneven pattern can be made clearer.
According to the optical imprint lithography method using the stamper having the light-shielding concave portion and the light-transmitting convex portion according to the present invention, the concave-convex pattern transferred and formed on the surface of the shape-transferred layer separated from the stamper Can be easily cleaned. In particular, since the residue of the recess is not photocured, it can be easily removed, and the resulting uneven pattern can be made clearer.

It is typical sectional drawing which shows an example of the stamper of this invention. It is typical sectional drawing which shows the light-shielding part and translucent part in an example of the stamper of this invention. It is explanatory drawing which shows the manufacturing method of an example of the stamper of this invention. It is explanatory drawing which shows the optical imprint lithography method using an example of the stamper of this invention. It is typical sectional drawing which shows the other example of the stamper of this invention. It is typical sectional drawing which shows the light-shielding part and the translucent part in the other examples of the stamper of this invention. It is explanatory drawing which shows the manufacturing method of the other example of the stamper of this invention. It is explanatory drawing which shows the optical imprint lithography method using the other example of the stamper of this invention. It is a typical perspective view explaining an uneven | corrugated pattern.

  Hereinafter, embodiments of the present invention will be described in detail with reference to FIGS. In the present specification, “(meth) acryl” means acryl and methacryl, and “(meth) acrylate” means acrylate and methacrylate.

[1] Stamper The first stamper 10a (see FIG. 1) of the present invention is a stamper used in an optical imprint lithography method having a concavo-convex pattern 12 for transferring to a shape transfer layer provided on a substrate. The concavo-convex pattern 12 has a light-shielding convex portion 121s and a light-transmitting concave portion 122t (hereinafter also referred to as “first stamper”).

  The second stamper 10b (see FIG. 5) of the present invention is a stamper used in an optical imprint lithography method having a concavo-convex pattern 12 for transferring to a shape transfer layer provided on a substrate. The pattern 12 includes a light-blocking concave portion 122s and a light-transmitting convex portion 121t (hereinafter also referred to as “second stamper”).

  In the following, the light-shielding convex portion 121s is referred to as “light-shielding convex portion”, the light-transmitting concave portion 122t is referred to as “translucent concave portion”, and the light-transmissive convex portion 121t is referred to as “light-transmitting”. 122 s having the light-shielding property and the light-shielding concave portion 122s. Furthermore, the first stamper 10 a and the second stamper 10 b are collectively referred to as “stamper” 10.

  The “photoimprint lithography” refers to transferring the concavo-convex pattern 12 of the stamper 10 (10 a and 10 b) to the shape transfer layer 30 provided on the substrate 20 and transferring the concavo-convex pattern 31 to the shape transfer layer 30. In forming a concavo-convex pattern of a stamper (a pattern in which a concavo-convex shape is reversed), an imprint method and a photolithography method are used in combination. That is, an imprint method in which the stamper 10 is pressed against the shape transfer layer 30 and the uneven pattern 12 on the surface of the stamper 10 is transferred to the shape transfer layer 30, and the stamper 10 is transmitted while the pressure contact state is maintained. The concavo-convex pattern 31 is formed on the surface of the morphological transfer layer 30 by using a photolithographic method in which the morphological transfer layer 30 is photocured by exposure and the shape of the transferred concavo-convex pattern is fixed. It is.

The “stamper (10)” has a concavo-convex pattern 12 on the surface for transferring to the shape transfer layer 30. Further, the first stamper 10a of the present invention has a light-shielding convex portion 121s and a light-transmissive concave portion 122t, and the second stamper 10b has a light-shielding concave portion 122s and a light-transmissive concave portion 121t, One of the recesses is light-shielding.
That is, as illustrated in FIG. 2, when exposure is performed through the first stamper 10a, light is not transmitted through the light-shielding convex portion 121s or the light transmission amount is less than that of the light-transmissive concave portion 122t. On the other hand, the light transmission amount in the light transmitting concave portion 122t is larger than that in the light shielding convex portion 121s. Similarly, as illustrated in FIG. 6, when exposure is performed via the second stamper 10b, light is not transmitted through the light-shielding concave portion 122s or the amount of transmitted light is less than that of the light-transmissive convex portion 121t. On the other hand, the light transmission amount of the light transmitting convex portion 121t is larger than that of the light blocking concave portion 122s.

Therefore, when the shape transfer layer 30 is exposed through the stamper 10, the portion of the shape transfer layer 30 where the light-shielding convex portion 121s of the first stamper 10a is pressed and the light-shielding concave portion of the second stamper 10b. Each of the portions where 122s is pressed is shielded from light, and this portion is not cured, or the progress of curing is delayed as compared with the other portions, and this portion can be cleaned and removed more easily.
In particular, as illustrated in FIGS. 4 and 8, the removability of the residue 40 of the shape transfer layer 30 remaining in the recess 312 of the uneven pattern 31 formed by transferring to the shape transfer layer 30 is excellent. By removing the residue 40, the uneven pattern 31 having better resolution can be formed on the surface of the shape transfer layer 30.

  The light shielding convex portion 121s and the light shielding concave portion 122s (hereinafter collectively referred to as “light shielding portion”) are also referred to as the light transmitting concave portion 121t and the light transmitting convex portion 121t (hereinafter collectively referred to as “translucent portion”). The light transmittance of the light-shielding portion may be 0% with respect to light intended for light shielding, but may exceed 0%. The light transmittance of the light-shielding part is usually 0 to 50%, preferably 0 to 20%, more preferably 0 to 1%. On the other hand, the light transmittance of the translucent part is usually 70% or more, preferably 75 to 100%, more preferably 80 to 100%, and particularly preferably 90 to 100% with respect to light intended for transmission. .

The light for the purpose of light shielding and the light for the purpose of transmission are not particularly limited as long as they are light having a wavelength used for photocuring, and are included in the size of the target concavo-convex pattern and the shape transfer layer. It can be suitably selected according to the characteristics of the photosensitive agent to be used. Among them, the light transmittance is preferably for visible light (wavelength 360 to 830 nm), particularly preferably for light having a shorter wavelength of 360 to 660 nm, and particularly for ultraviolet light of 365 nm. It is preferable.
In addition, the said light transmittance in a light-shielding part and a translucent part is the value measured with the ultraviolet visible spectrophotometer (The JASCO Corporation make, type "JASCO V7100").

The light-shielding material constituting the light-shielding part is not particularly limited as long as it has a light-shielding property with respect to exposure light used for exposure. Examples of materials excellent in light-shielding property in the ultraviolet region include metal materials and ceramic materials. Etc. These may use only 1 type and may use 2 or more types together. Of these, metal materials are preferred.
As metal materials, Cu (copper), Ti (titanium), Au (gold), Ag (silver), Ni (nickel), Cr (chromium), Ta (tantalum), Pd (palladium), Pt (platinum), Examples include W (tungsten), Ti (titanium), Co (cobalt), Sn (tin), In (indium), Zn (zinc), Al (aluminum), Pb (lead), and alloys thereof. Among these, Cr and Ni are preferable from the viewpoints of light shielding properties and moldability. Further, from the viewpoint of suppressing the adhesion of metal ions to the shape transfer layer, it is preferably composed of a stable material that is difficult to be ionized, such as Au, Ag, Al, Cr, Ta, Ni, and alloys thereof. Is preferred.
In addition, when forming a light-shielding part using these metal materials, it is preferable to form in thickness 5 nm or more at least. This thickness is more preferably 5 to 200 nm, and further preferably 5 to 70 nm.

The shape of the convex part 121 (121s and 121t) and the concave part 1222 (122s and 122t) of each of the light transmitting part and the light shielding part is not particularly limited, and may be any shape. For example, a ridge (reference numeral 51 in FIG. 9), a ridge having two or more steps (reference numeral 52 in FIG. 9), a convex island-shaped part (reference numeral 53 in FIG. 9), and a protrusion (reference numeral 54 in FIG. 9). , A concave line (reference numeral 55 in FIG. 9), a concave line having two or more steps (reference numeral 56 in FIG. 9), a concave island-shaped part (reference numeral 57 in FIG. 9), a bottomed hole ( For example, a recess such as reference numeral 58) in FIG.
Although the size (width, depth, etc.) of the projections and recesses is not particularly limited, the width is usually 10 μm or less, particularly 10 to 1000 nm, and more preferably 10 to 500 nm. In particular, it can be 10 to 100 nm. That is, for example, as shown in FIGS. 1 and 5, the width at the convex portion means the width w 1 of the tip portion, and the width at the concave portion means the opening width w 2 .
In the second stamper 10b, in order to prevent exposure light from leaking, light is blocked on the side surface of the translucent convex portion 121t (that is, the inner side surface of the light-shielding concave portion) within a range that does not affect pattern formation on the shape transfer layer. You may have sex.

The formation method of these convex part 121 and the recessed part 122 is not specifically limited, What kind of method may be used.
The first stamper 10a (see FIG. 1) can be formed by, for example, the method illustrated in FIG.
A plating resist layer forming step of forming a plating resist layer 14 on the surface of the translucent electrode layer 13 of the substrate 11 on which the translucent electrode layer 13 is disposed;
A patterning step of patterning the plating resist layer 14 by a photolithography method (performed so that the translucent electrode layer 13 under the plating resist layer 14 is exposed by patterning);
A plating step of energizing the translucent electrode layer 13 and depositing a metal material in the concave portion 141 of the patterned plating resist layer 14 by electrolytic plating;
A plating resist layer removing step of removing the plating resist layer 14 used (removal by a solvent and / or burning by heating, etc.), and the first stamper 10a can be obtained.

On the other hand, the second stamper 10b (see FIG. 5) can be formed by, for example, the method illustrated in FIG. That is,
A plating resist layer forming step of forming a plating resist layer 14 on the surface of the translucent electrode layer 13 of the substrate 11 on which the translucent electrode layer 13 is disposed;
A patterning step of patterning the plating resist layer 14 by a photolithography method (performed so that the translucent electrode layer 13 under the plating resist layer 14 is exposed by patterning);
By energizing the translucent electrode layer 13 and depositing a metal material in the concave portion 141 of the patterned plating resist layer 14 by electrolytic plating, the concave portion can be maintained by depositing it lower than the height of the convex portion of the plating resist layer. 2), a second stamper 10b can be obtained. In the second stamper, the plating resist layer functions as the translucent convex portion 121t.

The substrate 11 only needs to have translucency while having mechanical properties as a stamper. From such a viewpoint, the material constituting the substrate 11 is preferably a translucent inorganic material (usually a nonmetallic inorganic material). As this translucent inorganic material, a quartz material {quartz (single crystal, polycrystal), various glasses (quartz glass, fluoride glass, calcium phosphate glass, borate glass, borosilicate glass, etc.) }, Silicon, spinel, corundum, sapphire and the like. These may use only 1 type and may use 2 or more types together. Among these, a quartz material is preferable from the viewpoint of excellent translucency, and quartz (SiO 2 ) is particularly preferable because of excellent thermal shock resistance.

The substrate 11 may be composed of only one layer or may be composed of two or more layers. Furthermore, each layer may consist of layers of the same material, or may consist of layers of different materials.
Moreover, although the thickness of the base | substrate 11 is not limited, Usually, they are 0.01 micrometer-1000 micrometers.
Further, the degree of translucency of the substrate 11 is not particularly limited, but the reference light transmittance with respect to the light-shielding part and the translucent part is usually 70% or more. Further, this preferable light transmittance is particularly preferable when ultraviolet light (particularly, 365 nm ultraviolet light) is selected as the radiation.

The translucent electrode layer 13 is a translucent conductive layer formed on the surface of the base 11 of the stamper 10. By providing the translucent electrode layer 13, the plating process can be performed, and an exposure process to be described later can be performed when the stamper 10 is used for optical imprint lithography.
Examples of the material constituting the translucent electrode layer 13 include oxide semiconductor materials. That is, for example, indium oxide-based materials {indium tin oxide (ITO), indium zinc oxide, indium magnesium oxide, fluorine-containing indium tin oxide, etc.}, zinc oxide, zinc oxide-based materials (Al, Co, Fe, In, Sn and Zinc oxide containing at least one of Ti), tin oxide, tin oxide-based material {antimony-containing tin oxide (ATO), fluorine-containing tin oxide (FTO), etc.}, titanium oxide-based material (niobium-added titanium dioxide, etc.) ) And the like. Among these, in terms of excellent translucency, indium tin oxide, indium zinc oxide, tin oxide, zinc oxide, niobium-added titanium dioxide, and the like are preferable.

The translucent electrode layer 13 may be composed of only one layer or may be composed of two or more layers. Furthermore, each layer may consist of layers of the same material, or may consist of layers of different materials. Moreover, the film thickness of the translucent electrode layer 13 is not particularly limited, but is usually 0.1 to 1000 nm, preferably 0.1 to 100 nm, and more preferably 0.1 to 50 nm.
Furthermore, the degree of translucency of the translucent electrode layer 13 is not particularly limited, but is usually 70% or more in the reference light transmittance with respect to the light-shielding part and the translucent part. Further, this preferable light transmittance is particularly preferable when ultraviolet light (particularly, 365 nm ultraviolet light) is selected as the radiation.

  The plating resist layer 14 is a layer for preventing deposition of plating when depositing plating (which becomes the light-shielding convex portion 121s) on the surface of the translucent electrode layer 13 (during the plating step). This plating resist layer 14 is used by forming a recess 141 for depositing plating by patterning as described above. Although the formation method is not particularly limited, it is usually based on an optical lithography method.

The plating resist layer may be formed in any way, but is usually formed by applying a composition for plating resist layer (heat treatment can be performed after application). Any plating resist layer composition may be used. For example, a polymer (A) containing a structural unit represented by the following formula (1) and a structural unit represented by the following formula (2): A plating resist layer composition containing a compound (B) having at least one ethylenically unsaturated double bond and a radiation-sensitive radical polymerization initiator (C) can be used.
Wherein (1), R 1 represents a hydrogen atom or a methyl group, R 2 represents at least one of the hydrogen atoms of the straight-chain, cyclic or aromatic hydrocarbon groups, or these groups having 6 to 12 carbon atoms Represents a substituted hydrocarbon group substituted with a hydrocarbon group, R 3 represents a — (C n H 2n ) — group, m is an integer of 1 to 10, and n is an integer of 2 to 4. ]
[In formula (2), R 1 represents a hydrogen atom or a methyl group. ]

By including the structural unit represented by the formula (1) in the polymer (A), the adhesion between the plating resist layer and the lower layer is improved as compared with the case where the structural unit is not included, and the plating solution is a plating resist. Exudation between the layer and the lower layer can be prevented.
In addition, since the polymer (A) includes the structural unit represented by the formula (2), the swelling resistance of the plating resist layer to the plating solution is improved as compared with the case where the structural unit is not included. It is possible to prevent floating and peeling from the lower layer. Furthermore, there is an effect of improving the resolution by suppressing the crosslinking density of the plating resist layer.
The sum total of the structural units represented by the formula (1) in the polymer (A) is usually 1 to 40% by mass, and preferably 10 to 30% by mass. Furthermore, the sum total of the structural unit represented by the said Formula (2) in a polymer (A) is 1-30 mass% normally, and 10-20 mass% is preferable. In each range, the polymer (A) having a large molecular weight can be obtained, and the swelling resistance to the plating solution is further improved.

Of R 2 in the formula (1), examples of the straight chain having 6 to 12 carbon atoms include a hexyl group, a heptyl group, an octyl group, and a nonyl group. Among the R 2 , the cyclic hydrocarbon group having 6 to 12 carbon atoms is a cycloalkyl group (cyclohexyl group, cycloheptyl group, cyclooctyl group, etc.) or a group derived from a bridged hydrocarbon (adamantane, bicyclo [2. 2.1] heptane, tetracyclo [6.2.1.1 3,6 .0 2,7] dodecane, tricyclo [5.2.1.0 2, 6] decane, etc.) and the like. Among R 2 , the aromatic hydrocarbon group having 6 to 12 carbon atoms includes phenyl group, o-tolyl group, m-tolyl group, p-tolyl group, 4-t-butylphenyl group, 1-naphthyl group, benzyl Groups and the like. Furthermore, examples of the hydrocarbon group that can be substituted for each of the groups in R 2 include a methyl group and an ethyl group.

  Examples of the monomer that introduces the structural unit of the formula (1) into the polymer (A) include phenoxydiethylene glycol (meth) acrylate, phenoxytriethylene glycol (meth) acrylate, phenoxytetraethylene glycol (meth) acrylate, and phenoxydi. Propylene glycol (meth) acrylate, phenoxytripropylene glycol (meth) acrylate, and phenoxytetrapropylene glycol (meth) acrylate are preferable, and phenoxydiethylene glycol acrylate, phenoxytriethylene glycol acrylate, and phenoxytetraethylene glycol acrylate are preferable.

  Examples of the monomer for introducing the structural unit of the formula (2) into the polymer (A) include hydroxyl group-containing aromatic vinyl such as o-hydroxystyrene, p-hydroxystyrene, m-hydroxystyrene, and p-isopropenylphenol. Compounds. These may use only 1 type and may use 2 or more types together. Among these, p-hydroxystyrene and p-isopropenylphenol are preferable and p-isopropenylphenol is more preferable because of excellent resistance to long-term plating treatment.

  The polymer (A) can contain structural units introduced from other monomers in addition to the structural units represented by the formula (1) and the formula (2). Other monomers include aromatic vinyl compounds (styrene, α-methylstyrene, p-methylstyrene, p-methoxystyrene, etc.), heteroatom-containing alicyclic vinyl compounds (N-vinylpyrrolidone, N-vinyl). Caprolactam, etc.), cyano group-containing vinyl compounds (acrylonitrile, methacrylonitrile, etc.), conjugated diolefins (1.3-butadiene, isoprene, etc.), carboxyl group-containing vinyl compounds (acrylic acid, methacrylic acid, etc.), (meth) Acrylic acid esters {alkyl (meth) acrylate, hydroxyalkyl (meth) acrylate, polyalkylene glycol mono (meth) acrylate, glycerol mono (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth ) Acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, etc.}, and, p- hydroxyphenyl (meth) acrylamide. These may use only 1 type and may use 2 or more types together.

The compound (B) having at least one ethylenically unsaturated double bond is a liquid or solid compound at room temperature having at least one ethylenically unsaturated group in the molecule. As the compound (B), 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) Acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, isoamyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) Acrylate, octyl (meth) acrylate, isooctyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth) acrylate, isodecyl (meth) Acrylate, undecyl (meth) acrylate, dodecyl amyl (meth) acrylate, lauryl (meth) acrylate, octadecyl (meth) acrylate, stearyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, butoxyethyl (meth) acrylate, ethoxydiethylene glycol (Meth) acrylate, benzyl (meth) acrylate, cyclohexyl (meth) acrylate, phenoxyethyl (meth) acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, methoxyethylene glycol (meth) acrylate, ethoxyethyl (Meth) acrylate, methoxypolyethylene glycol (meth) acrylate, phenoxypolyethylene Glycol (meth) acrylate, phenoxy polypropylene glycol (meth) acrylate, methoxy polypropylene glycol (meth) acrylate, tricyclo [5.2.1.0 2,6] decadienyl (meth) acrylate, tricyclo [5.2.1. 0 2,6 ] decanyl (meth) acrylate, tricyclo [5.2.1.0 2,6 ] decenyl (meth) acrylate, isobornyl (meth) acrylate, bornyl (meth) acrylate, diacetone (meth) acrylamide, isobutoxy Methyl (meth) acrylamide, N-vinyl pyrrolidone, N-vinyl caprolactam, N, N-dimethyl (meth) acrylamide, tert-octyl (meth) acrylamide, dimethylaminoethyl (meth) acrylate, diethyl alcohol Minoethyl (meth) acrylate, 7-amino-3,7-dimethyloctyl (meth) acrylate, dimethyl maleate, diethyl maleate, dimethyl fumarate, diethyl fumarate, ethylene glycol monomethyl ether (meth) acrylate, ethylene glycol monoethyl Examples include ether (meth) acrylate, glycerol (meth) acrylate, acrylic acid amide, methacrylic acid amide, and (meth) acrylonitrile. These may use only 1 type and may use 2 or more types together.

  Furthermore, as the (meth) acrylate compound, trimethylolpropane tri (meth) acrylate, ethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,4-butanediol Di (meth) acrylate, butylene glycol di (meth) acrylate, propylene glycol di (meth) acrylate, trimethylolpropane di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) Acrylate, tris (2-hydroxyethyl) isocyanurate tri (meth) acrylate, tris (2-hydroxyethyl) isocyanurate di (meth) acrylate, tricyclodecane dimethanol Di (meth) acrylate, epoxy (meth) acrylate obtained by adding (meth) acrylic acid to diglycidyl ether of bisphenol A, bisphenol A di (meth) acryloyloxyethyl ether, bisphenol A di (meth) acryloyloxyethyloxyethyl Ether, bisphenol A di (meth) acryloyloxymethyl ethyl ether, tetramethylolpropane tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipenta Examples include erythritol hexa (meth) acrylate. These may use only 1 type and may use 2 or more types together.

  A commercially available product can be used as it is as the ethylenically unsaturated compound (B). Specifically, Aronix M-210, M-309, M-310, M-400, M-7100, M-8030, M-8060, M-8100, M-8050, M-9050, Same M-240, Same M-245, Same M-6100, Same M-6200, Same M-6250, Same M-6300, Same M-6400, Same M-6500 (above, manufactured by Toagosei Co., Ltd.), KAYARAD R-551, R-712, TMPTA, HDDA, TPGDA, PEG400DA, MANDA, HX-220, HX-620, R-604, DPCA-20, DPCA-30, DPCA -60, DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.), Biscote # 295, 300, 260, 312, 335HP, 360, GPT, 3PA, 400 (manufactured by Osaka Organic Chemical Industry Co., Ltd.), and the like. These may use only 1 type and may use 2 or more types together.

A compound (B) is 30-80 mass parts normally with respect to 100 mass parts of polymers (A), and 40-70 mass parts is preferable. Within this range, the exposure sensitivity of the resulting plating resist layer is good, and further, the compatibility with the polymer (A) is excellent, and the storage stability of the composition is improved.
The initiator (C) is a component that initiates polymerization of the compound (B) by generating radicals upon irradiation with radiation (including ultraviolet rays, visible rays, far ultraviolet rays, X-rays, and electron beams). Content of this initiator (C) is 1-40 mass parts normally with respect to 100 mass parts of polymers (A), 5-30 mass parts is preferable, and 10-20 mass parts is more preferable.

It is preferable that at least a biimidazole compound is included as the initiator (C). Examples of the biimidazole compound include 2,2′-bis (2,4-dichlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole, 2,2′-bis (2 -Chlorophenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis (2,4-dichlorophenyl) -4,5,4', 5'-tetra Phenyl-1,2′-biimidazole, 2,2′-bis (2,4-dimethylphenyl) -4,5,4 ′, 5′-tetraphenyl-1,2′-biimidazole, 2,2 ′ -Bis (2-methylphenyl) -4,5,4 ', 5'-tetraphenyl-1,2'-biimidazole, 2,2'-diphenyl-4,5,4', 5'-tetraphenyl- 1, 2'-biimidazole and the like. These may use only 1 type and may use 2 or more types together.
The content of the biimidazole compound is usually 1 to 30 parts by weight, preferably 1 to 20 parts by weight, and more preferably 1 to 10 parts by weight with respect to 100 parts by weight of the polymer (A). Within this range, the exposure sensitivity of the plating resist layer to be obtained is good, and furthermore, a straight pattern having excellent radiation transparency and no gaps can be formed.

  In addition to the biimidazole compound, other compounds can be used in combination as the initiator (C). Other initiators (C) include 2,2-dimethoxy-1,2-diphenylethane-1-one, 4,4′-bis (diethylamino) benzophenone, 2-benzyl-2-dimethylamino-1- ( 4-morpholinophenyl) -butanone-1, 2-methyl-1- [4- (methylthio) phenyl] -2-monforinopropanone-1, and the like. These may use only 1 type and may use 2 or more types together. Moreover, as this other initiator (C), the following commercial item can be used. That is, Irgacure 369 (manufactured by Ciba Specialty Chemicals Co., Ltd.), Irgacure 907 (manufactured by Ciba Specialty Chemicals Co., Ltd.) and the like can be mentioned. These may use only 1 type and may use 2 or more types together.

  The said composition for plating resist layers can contain another component other than a polymer (A), a compound (B), and an initiator (C). Another component includes an organic solvent (D). Examples of the organic solvent (D) include polyhydric alcohol alkyl ethers (ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, etc.), polyhydric alcohol alkyl ether acetates (ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, etc.) ), Esters (ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, ethyl 2-hydroxypropionate, ethyl lactate, etc.) and ketones such as diacetone alcohol are preferred. These may use only 1 type and can use 2 or more types together.

  Furthermore, the composition for a plating resist layer can contain a thermal polymerization inhibitor. Thermal polymerization inhibitors include pyrogallol, benzoquinone, hydroquinone, methylene blue, tert-butylcatechol, monobenzyl ether, methylhydroquinone, amylquinone, amyloxyhydroquinone, n-butylphenol, phenol, hydroquinone monopropyl ether, 4,4 ′-( 1-methylethylidene) bis (2-methylphenol), 4,4 ′-(1-methylethylidene) bis (2,6-dimethylphenol), 4,4 ′-[1- [4- (1- (4 -Hydroxyphenyl) -1-methylethyl) phenyl] ethylidene] bisphenol, 4,4 ', 4 "-ethylidenetris (2-methylphenol), 4,4', 4" -ethylidenetrisphenol, 1,1,3 -Tris (2,5-dimethyl-4-hydroxyphenyl)- - phenyl propane. These may use only 1 type and can use 2 or more types together. The amount of the thermal polymerization inhibitor used is preferably 5 parts by mass or less with respect to 100 parts by mass of the polymer (A).

The plating resist layer composition may contain a surfactant. By containing the surfactant, it is possible to improve coating properties, antifoaming properties, leveling properties and the like.
As the surfactant, a commercially available compound can be used as it is. That is, for example, FTX-204D, FTX-208D, FTX-212D, FTX-216D, FTX-218, FTX-220D (above, manufactured by Neos Co., Ltd.), BM-1000, BM-1100 (above, BM Chemie), MegaFac F142D, F172, F173, F183 (above, manufactured by Dainippon Ink and Chemicals), Florard FC-135, FC-170C, FC-430, FC-431 (Above, manufactured by Sumitomo 3M Limited), Surflon S-112, S-113, S-131, S-141, S-145 (above, manufactured by Asahi Glass Co., Ltd.), SH-28PA, -190 -193, SZ-6032, SF-8428 (above, manufactured by Toray Dow Corning Silicone Co., Ltd.) and the like. . These may use only 1 type and can use 2 or more types together. The amount of the surfactant used is preferably 5 parts by mass or less with respect to 100 parts by mass of the polymer (A).

Further, the plating resist layer composition may contain an adhesion assistant. By containing an adhesion assistant, the adhesion between the plating resist layer and the lower layer (especially preferred when the substrate 11 is made of a quartz material) can be improved.
As the adhesion assistant, a functional silane coupling agent having a reactive substituent such as a carboxyl group, a methacryloyl group, an isocyanate group, or an epoxy group is preferable. Examples of this functional silane coupling agent include trimethoxysilylbenzoic acid, γ-methacryloxypropyltrimethoxysilane, vinyltriacetoxysilane, vinyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, and γ-glycidoxypropyl. Examples include trimethoxysilane and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. These may use only 1 type and can use 2 or more types together. The amount used is preferably 20 parts by mass or less with respect to 100 parts by mass of the polymer (A).

In addition to the translucent electrode layer 13, the stamper 10 of the present invention can include other layers. Other layers include release layers, ionization-suppressing layers, adhesion improving layers {layers that improve adhesion between various layers (such as an interlayer between a stamper and a translucent electrode layer)}, thermal diffusion layers, various optical layers Examples include functional layers {reflection suppression, refractive index control layer, light transmission improving layer (made of silicon oxide), etc.}, insulating layers, and the like. These various layers may use only 1 type and may use 2 or more types together. That is, for example, each layer may have only one layer or may have a multilayer structure of two or more layers. Moreover, when it has two or more types of 1 type of layers, it can also be set as the sandwich structure through which other types of layers were interposed between the same types of layers.
The thicknesses of these other layers are not particularly limited, but the thickness of each layer is usually 1 to 100 nm, preferably 1 to 50 nm, and particularly preferably 1 to 20 nm.

Of the other layers, the release layer is a layer for facilitating separation of the stamper and the shape transfer layer. When the release layer is provided, the release layer is preferably disposed on a part or the entire outer surface of the concave / convex pattern 12 included in the stamper 10.
As the release layer, a silane compound having a halogenated alkyl group is preferably used. When such a silane-based compound is used, a release layer composed of an organic monomolecular film that is self-assembled so that the halogenated alkyl group is located on the surface can be obtained.
Examples of the silane compound include (3,3,3-trifluoropropyl) trichlorosilane, (3,3,3-trifluoropropyl) trimethoxysilane, and (3,3,3-trifluoropropyl) triethoxysilane. , (Tridecafluoro-1,1,2,2-tetrahydrooctyl) trichlorosilane, (Tridecafluoro-1,1,2,2-tetrahydrooctyl) trimethoxysilane, (Tridecafluoro-1,1,2) , 2-tetrahydrooctyl) triethoxysilane, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) trichlorosilane, (heptadecafluoro-1,1,2,2-tetrahydrodecyl) trimethoxysilane, Heptadecafluoro-1,1,2,2-tetrahydrodecyl) triethoxysilane, (3,3 4,4,5,5,6,6,6-nonafluorohexyl) trichlorosilane, (3,3,4,4,5,5,6,6,6-nonafluorohexyl) trimethoxysilane, (3 , 3,4,4,5,5,6,6,6-nonafluorohexyl) triethoxysilane, perfluorodecyltrichlorosilane, octadecyltrichlorosilane, dimethyldichlorosilane and the like. These may use only 1 type and may use 2 or more types together. In addition, regardless of the presence or absence of the release layer, various release agents can be applied to the stamper surface.

Among the other layers, the ionization suppressing layer can be formed from a light-transmitting inorganic material. When the ionization suppression layer is provided, the ionization suppression layer is preferably disposed on a part or the entire surface of the concavo-convex pattern 12 of the stamper 10.
Examples of the light-transmitting inorganic material include nitrides, oxides, oxynitrides, and hydronitrides. Among these, examples of the nitride include silicon nitride, aluminum nitride, indium nitride, gallium nitride, tin nitride, boron nitride, chromium nitride, and silicon nitride carbide. Examples of the oxide include indium oxide, tin oxide, indium tin oxide, aluminum oxide, germanium oxide, silicon oxide, zinc oxide, zirconium oxide, titanium oxide, yttrium oxide, erbium oxide, cerium oxide, tantalum oxide, and hafnium oxide. It is done. Examples of the oxynitride include silicon oxynitride, tin oxynitride, boron oxynitride, aluminum oxynitride, indium oxynitride, gallium oxynitride, chromium oxynitride, and silicon oxynitride carbide. Examples of the hydrogenated nitride include aluminum hydrogenated nitride, hydrogenated indium nitride, hydrogenated gallium nitride, silicon hydrogenated nitride, hydrogenated tin nitride, hydrogenated boron nitride, hydrogenated chromium nitride, and hydrogenated silicon nitride carbide. It is done. These may use only 1 type and may use 2 or more types together.

Although the refractive index of this ionization suppression layer is not particularly limited, it is preferably 1.5 or more, more preferably 1.8 to 5.5, and particularly preferably 2.0 to 3.5. This refractive index is based on JIS K0062 (a method for measuring the refractive index of chemical products).
Further, the light transmittance of the ionization suppressing layer is preferably 70% or more, more preferably 75 to 100%, still more preferably 80 to 100%, and particularly preferably 90 to 100%. The standard of the light transmittance is as described above.

  The method of forming the translucent electrode layer 13 and the other layers is not particularly limited, but usually, a physical vapor deposition method such as a vapor deposition method, an ion plating method, a sputtering method, a molecular beam epitaxy method (MBE), and A dry process such as a chemical deposition method such as a CVD method, an MOCVD method, or a plasma CVD method is preferred. These processes may use only 1 type and may use 2 or more types together.

[2] Optical Imprint Lithography Method Hereinafter, the optical imprint lithography method of the present invention will be described in detail. The present invention includes two optical imprint lithography methods. The first imprint method described below uses the first stamper and the negative photocurable shape transfer layer, while the second imprint method. The method is different in that the second stamper and the positive type photocurable shape transfer layer are used, but these will be described together below.

  The first photo-imprint lithography method (see FIG. 4) of the present invention includes: (a) a pressure-contacting process PR1 in which the first stamper 10a is pressed against the shape-transferred layer 30 having a negative photocuring property; An exposure step PR2 for exposing the shape transfer layer 30 in a state where the stamper 10a is in pressure contact with the shape transfer layer 30, and (c) separation for separating the stamper 10a and the shape transfer layer 30 after exposure. A step PR3; and (d) a cleaning step PR4 for cleaning the concavo-convex pattern formed on the shaped transfer layer 30 after separation (hereinafter also referred to as “first imprint method”).

  The second photo-imprint lithography method (see FIG. 8) of the present invention includes (a) a pressure-contacting process in which the second stamper 10b is pressure-contacted to the shape transfer layer 30 having a positive photocuring property, and (b) the above-mentioned An exposure step PR2 for exposing the shape transfer layer 30 in a state where the stamper 10b is in pressure contact with the shape transfer layer 30, and (c) a separation step for separating the stamper 10b and the shape transfer layer 30 after exposure. PR3 and (d) a cleaning process PR4 for cleaning the uneven pattern formed on the shaped transfer layer 30 after separation (hereinafter also referred to as “second imprint method”).

  In the first imprint method, the “pressure contact process PR1” is a process in which a first stamper is pressed against a shape transfer layer having a negative photocuring property. In the second imprint method, positive light is used. In this step, the second stamper is pressed against the shape-transferred layer having curability.

The “shaped transfer layer 30” is a layer to which the concave / convex pattern 11 of the stamper 10 is pressed and transferred. The shape transfer layer 30 refers to a layer in all states in the process until it has a cured uneven pattern (that is, until it becomes a pattern layer). That is, a layer before the concavo-convex pattern is pressed, a layer where the concavo-convex pattern is pressed, a layer having a semi-cured concavo-convex pattern, and the like are included.
In addition, the shape transfer layer 30 is usually formed on the surface of the substrate 20 and formed with a concavo-convex pattern, for example, a semiconductor such as LSI, system LSI, DRAM, SDRAM, RDRAM, or D-RDRAM. It can be used as a film for an interlayer insulating film of an element, a resist film at the time of manufacturing a semiconductor element, and the like.

The shape-transferring layer 30 can be shared in each method except for the difference between the negative type and the positive type, and is usually obtained by coating the shape-transferring layer composition on a substrate to form a film. Although the component which comprises the composition for to-be-shaped transfer layers is not specifically limited, Usually, the curable polymer contains. Examples of the polymer include a silane polymer, a (meth) acrylic polymer, an epoxy polymer, an oxetane polymer, and a vinyl polymer. Of these, it is preferable to use a silane polymer.
That is, for example, after performing pattern formation on a shape-transfer layer obtained by forming a composition for a shape-transfer layer containing a silane polymer and a pore-forming agent on a substrate, Curing, and then removing the pore-forming agent from the obtained cured product (including semi-cured product) to obtain an interlayer insulating film (pattern layer) mainly composed of a silane polymer it can. It is particularly suitable for the purpose of forming an interlayer insulating film having a low relative dielectric constant.

The silane polymer is preferably a polymer obtained by hydrolytic condensation of a hydrolyzable silane compound. More specifically, a hydrolyzable silane compound represented by the following formula (1) (hereinafter simply referred to as “compound (1)”) and a hydrolyzable silane compound represented by the following formula (2) (hereinafter, It is preferably a polymer obtained by hydrolytic condensation of at least one hydrolyzable silane compound selected from “compound (2)”.
R a Si (OR 1 ) 4-a (1)
[In the formula (1), R represents a hydrogen atom, a fluorine atom, a linear or branched alkyl group having 1 to 5 carbon atoms, a cyano group, a cyanoalkyl group, or an alkylcarbonyloxy group, and R 1 represents 1 Represents a valent organic group, and a represents an integer of 1 to 3. ]
Si (OR 2 ) 4 (2)
In [the formula (2), R 2 represents a monovalent organic group. ]

Examples of the monovalent organic group in R 1 of the formula (1) include an alkyl group, an alkenyl group, an aryl group, an allyl group, and a glycidyl group.
Specific examples of the compound (1) include, for example, methyltrimethoxysilane, methyltriethoxysilane, methyltri-n-propoxysilane, methyltri-iso-propoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, dimethyldimethoxysilane. Dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane and the like are preferable. In addition, a compound (1) may be used individually by 1 type, and may use 2 or more types together.

As the monovalent organic group in R 2 of the formula (2), the monovalent organic group in R 1 of the formula (1) can be applied as it is. However, it may be different may be the same as R 1 of formula R 2 and formula (2) (1).
Specific examples of the compound (2) include, for example, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, tetra-iso-propoxysilane, tetra-n-butoxysilane, tetra-sec-butoxysilane, tetra- Examples thereof include tert-butoxysilane and tetraphenoxysilane. Among these, tetramethoxysilane and tetraethoxysilane are preferable. In addition, a compound (2) may be used individually by 1 type, and may use 2 or more types together.

  As the hydrolyzable silane compound constituting the silane polymer, only the compound (1) and the compound (2) may be used, but if necessary, the hydrolyzable silane represented by the following formula (3) A compound (hereinafter referred to as “compound (3)”) can be used in combination.

R 3 x (R 4 O) 3-x Si- (R 7) z -Si (OR 5) 3-y R 6 y ... (3)
[In the formula (3), R 3 to R 6 are the same or different and each represents a monovalent organic group, x and y are the same or different and represent a number of 0 to 2, and R 7 represents an oxygen atom or a phenylene group Or a group represented by — (CH 2 ) n — (wherein n is an integer of 1 to 6), and z represents 0 or 1. ]
This compound (3) may be used individually by 1 type, and may use 2 or more types together. As the monovalent organic group in R 3 to R 6 of the formula (3), the monovalent organic group in R 1 of the formula (1) can be applied as it is. However, it may be different may be respectively same as the R 1 of formula (3) R 3 to R 6 of formula (1).

  Among the compounds (3), as the compound (3) where z = 0 in the formula (3), hexamethoxydisilane, hexaethoxydisilane, 1,1,2,2-tetramethoxy-1,2-dimethyldisilane 1,1,2,2-tetraethoxy-1,2-dimethyldisilane, 1,1,2,2-tetramethoxy-1,2-diphenyldisilane, 1,2-dimethoxy-1,1,2,2 -Tetramethyldisilane, 1,2-diethoxy-1,1,2,2-tetramethyldisilane, 1,2-dimethoxy-1,1,2,2-tetraphenyldisilane, 1,2-diethoxy-1,1 2,2-tetraphenyldisilane and the like are preferable. These compounds (3) in which z = 0 can be used alone or in combination of two or more.

  Among the compounds (3), the compound (3) in which z = 1 in the formula (3) includes bis (trimethoxysilyl) methane, bis (triethoxysilyl) methane, 1,2-bis (tri Methoxysilyl) ethane, 1,2-bis (triethoxysilyl) ethane, 1- (dimethoxymethylsilyl) -1- (trimethoxysilyl) methane, 1- (diethoxymethylsilyl) -1- (triethoxysilyl) Methane, 1- (dimethoxymethylsilyl) -2- (trimethoxysilyl) ethane, 1- (diethoxymethylsilyl) -2- (triethoxysilyl) ethane, bis (dimethoxymethylsilyl) methane, bis (diethoxymethyl) Silyl) methane, 1,2-bis (dimethoxymethylsilyl) ethane, 1,2-bis (diethoxymethylsilyl) ethane, 2-bis (trimethoxysilyl) benzene, 1,2-bis (triethoxysilyl) benzene, 1,3-bis (trimethoxysilyl) benzene, 1,3-bis (triethoxysilyl) benzene, 1,4- Bis (trimethoxysilyl) benzene, 1,4-bis (triethoxysilyl) benzene and the like are preferable. These compounds (3) where z = 1 may be used alone or in combination of two or more.

When the total of all the structural units contained in the silane polymer is 100 mol%, the content ratio of the structural unit derived from the compound (1) is preferably 30 to 100 mol%, and 60 to 100 Mole% is more preferable, and 70 to 100 mol% is still more preferable. If it is 30 to 100 mol%, the balance between the process margin during the curing treatment and the physical properties of the cured product can be improved.
Moreover, it is preferable that the content rate of the structural unit derived from a compound (2) is 0-70 mol%, 0-40 mol% is more preferable, 0-30 mol% is still more preferable. When the content is 0 to 70 mol%, the balance between the process margin during the curing process and the physical properties of the cured product can be improved.
Furthermore, the total content of the structural unit derived from the compound (1) and the structural unit derived from the compound (2) is preferably 100 mol% or less, more preferably 30 to 100 mol%, and more preferably 60 to 100 mol. % Is more preferable. In 30-100 mol%, the effect by including the structural unit derived from each compound of the compound (1) and compound (2) in a silane polymer in uneven | corrugated pattern formation can be acquired more effectively.
Moreover, it is preferable that the content rate of the structural unit derived from a compound (3) is 50 mol% or less, 0-40 mol% is more preferable, 0-30 mol% is still more preferable. If it is 50 mol% or less, the compound (1) and the compound (2) in the concavo-convex pattern formation do not hinder the effect of including the structural units derived from the compounds (1) and (2) in the silane polymer. 3) The effect including the derived structural unit can be obtained more effectively.

  It is preferable that the polystyrene conversion weight average molecular weight (Mw) by the gel permeation chromatography (GPC) of the said silane type polymer is 1000-100000, More preferably, it is 1000-10000. When the Mw is 1000 to 100,000, it is possible to achieve both excellent applicability and high storage stability while suppressing unnecessary gelation before curing.

The silane polymer can be obtained by hydrolytic condensation reaction using a hydrolyzable silane compound {the compounds (1) to (3)} as a starting material.
In preparing this silane polymer, [1] a mixture of compounds (1), (2) and (3) may be subjected to a hydrolytic condensation reaction, and [2] hydrolyzate of each compound and its mixture A hydrolytic condensation reaction or a condensation reaction may be performed using at least one of the condensates, a hydrolyzate of a mixture of selected compounds, and at least one of the condensates.
In order to adjust the curing characteristics, silsesquioxanes having a crosslinking group such as octa [(1,2-epoxy-4-cyclohexyl) dimethylsiloxy] silsesquioxane, octa [(3-glycidoxy Propyl) dimethylsiloxy] silsesquioxane or the like may be added.
Moreover, after performing a hydrolysis condensation reaction, it is preferable to perform the removal process of reaction by-products, such as lower alcohols, such as methanol and ethanol, for example. Thereby, since the purity of the organic solvent is increased, it is possible to obtain more excellent coating properties and excellent storage stability.
The silane polymer in the present invention may be used after being isolated from the polymer solution, or may be used as it is. In addition, when using as a polymer solution, the solvent substitution of the below-mentioned solvent (C) may be carried out as needed.

As the pore-forming agent, various organic components that can be removed by heating (evaporation, sublimation, burning, reaction vaporization, etc.) can be used. Examples of the organic component include (meth) acrylic polymers, polymers having a polyalkylene oxide structure, polymers having a sugar chain structure, vinylamide polymers, aromatic vinyl compound polymers, dendrimers, polyimides, polyamic acids , Polyarylene, polyamide, polyquinoxaline, polyoxadiazole, fluorine-based polymer, and the like. Among these, a (meth) acrylic polymer and a polymer having a polyalkylene oxide structure are preferable, and a (meth) acrylic polymer is particularly preferable.
These organic components may use only 1 type and may use 2 or more types together.

  Of these, the (meth) acrylic polymer is a polymer obtained using a (meth) acrylic monomer. Examples of the (meth) acrylic monomer include monofunctional acrylate and polyfunctional acrylate, acrylic acid, N-vinylpyrrolidone, N-vinylcaprolactam, vinylimidazole, vinylpyridine, N, N-diethyl (meth) ) Acrylamide, N, N-dimethylaminopropyl (meth) acrylamide, hydroxybutyl vinyl ether, lauryl vinyl ether, cetyl vinyl ether, 2-ethylhexyl vinyl ether, diacetone (meth) acrylamide, isobutoxymethyl (meth) acrylamide, N, N-dimethyl ( (Meth) acrylamide, t-octyl (meth) acrylamide, and the like can be used. These may use only 1 type and may use 2 or more types together.

The (meth) acrylic polymer as the pore-forming agent includes, among the various monomers, particularly isobutyl methacrylate, tetrahydrofurfuryl methacrylate, hydroxyethyl (meth) acrylate, hydroxyadamantyl (meth) acrylate, γ-Butylactyl (meth) acrylate and norbornane carbolactyl (meth) acrylate are preferred.
Furthermore, the polystyrene equivalent weight average molecular weight (Mw) by gel permeation chromatography (GPC) of this (meth) acrylic polymer is preferably 1000 to 100,000, more preferably 1000 to 50000, and more preferably 1000 to 15000. preferable. When this Mw is 1000 to 15000, it can be mixed with a particularly good compatibility in a composition for a shape-transferring layer intended to form an interlayer insulating film having a low relative dielectric constant.

  Examples of the polymer having a polyalkylene oxide structure include a polymethylene oxide structure, a polyethylene oxide structure, a polypropylene oxide structure, a polytetramethylene oxide structure, and a polybutylene oxide structure. Specifically, polyoxymethylene alkyl ether, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene sterol ether, polyoxyethylene lanolin derivative, ethylene oxide derivative of alkylphenol formalin condensate, polyoxyethylene poly Oxypropylene block copolymer, ether type compounds such as polyoxyethylene polyoxypropylene alkyl ether, polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, polyoxyethylene fatty acid alkanolamide sulfate, etc. Ether ester type compound, polyethylene glycol fatty acid ester, ethylene glycol fatty acid Ester, fatty acid monoglycerides, polyglycerol fatty acid esters, sorbitan fatty acid esters, propylene glycol fatty acid esters, ether-ester type compounds such as sucrose fatty acid esters.

Moreover, as said polyoxyethylene polyoxypropylene block copolymer, the compound which has the following block structure is mentioned.
− (X ′) 1 − (Y ′) m
− (X ′) 1 − (Y ′) m − (X ′) n
[Wherein, X ′ represents a group represented by —CH 2 CH 2 O—, Y ′ represents a group represented by —CH 2 CH (CH 3 ) O—, and l represents 1 to 90, m Represents a number from 10 to 99, and n represents a number from 0 to 90. ]

Examples of the polymer having a polyalkylene oxide structure as the pore-forming agent include polyoxyethylene alkyl ethers, polyoxyethylene polyoxypropylene block copolymers, polyoxyethylene polyoxypropylene alkyl ethers, among the above-mentioned various polymers. Ether type compounds such as polyoxyethylene glycerin fatty acid ester, polyoxyethylene sorbitan fatty acid ester, and polyoxyethylene sorbitol fatty acid ester are preferred. These may use only 1 type and may use 2 or more types together.
Furthermore, it is preferable that the polystyrene conversion weight average molecular weight (Mw) by the gel permeation chromatography (GPC) of the polymer which has this polyalkylene oxide structure is 1000-100000, 1000-50000 are more preferable, 1000-15000 are Further preferred. When this Mw is 1000 to 15000, it can be mixed with a particularly good compatibility in a composition for a shape-transferring layer intended to form an interlayer insulating film having a low relative dielectric constant.

The shape-transferred layer contains a radiation-sensitive acid generator that generates an acid upon exposure (hereinafter also simply referred to as “photoacid generator”). By containing the photoacid generator, the acid generated from the photoacid generator promotes the crosslinking of the polymer, and as a result, the unevenness of the shape transfer layer progresses and the unevenness is excellent in mechanical properties. A pattern can be formed. This photoacid generator is exposed to radiation (for example, radiation such as visible light, ultraviolet rays, far ultraviolet rays, X-rays, and electron beam) (ArF excimer laser (wavelength 193 nm) or KrF excimer laser (wavelength 248 nm)). It is a component that generates an acid by the same).
Examples of the photoacid generator include onium salts such as sulfonium salts and iodonium salts, organic halogen compounds, and sulfone compounds such as disulfones and diazomethane sulfones. These may use only 1 type and can use 2 or more types together.

Specifically, triphenylsulfonium nonafluoro-n-butanesulfonate, triphenylsulfonium trifluoromethanesulfonate, triphenylsulfonium perfluoro-n-octanesulfonate, triphenylsulfonium 2-bicyclo [2.2.1] hept-2. - yl-1,1,2,2-tetrafluoroethanesulfonate, triphenylsulfonium 2- (3-tetracyclo [4.4.0.1 2,5 .1 7,10] dodecanyl) -1,1-difluoroethane Triphenylsulfonium salt compounds such as sulfonate, triphenylsulfonium N, N′-bis (nonafluoro-n-butanesulfonyl) imidate, triphenylsulfonium camphorsulfonate;

4-cyclohexylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-cyclohexylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-cyclohexylphenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-cyclohexylphenyldiphenylsulfonium 2-bicyclo [2. 2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-cyclohexyl-phenyl diphenyl sulfonium 2- (3-tetracyclo [4.4.0.1 2,5 .1 7, 10] dodecanyl) -1,1-difluoroethanesulfonate, 4-cyclohexyl-phenyl diphenyl sulfonium N, N'-bis (nonafluoro -n- butanesulfonyl) imidate 4-cyclohexyl-phenyl diphenyl sulfonium salt compounds such as 4-cyclohexyl-phenyl camphorsulfonate;

4-t-butylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyldiphenylsulfonium nonafluoro-n-butanesulfonate, 4-t-butylphenyldiphenylsulfonium perfluoro-n-octanesulfonate, 4-t-butylphenyl Diphenylsulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 4-t-butylphenyldiphenylsulfonium 2- (3-tetracyclo [4.4. 0.1 2,5 .1 7,10] dodecanyl) -1,1-difluoroethanesulfonate, 4-t-butylphenyl diphenyl sulfonium N, N'-bis (nonafluoro -n- butanesulfonyl) imidate, 4-t- Butylphenyl 4-t-butylphenyl diphenyl sulfonium salt compounds such as triphenylsulfonium camphorsulfonate;

Tri (4-t-butylphenyl) sulfonium trifluoromethanesulfonate, tri (4-t-butylphenyl) sulfonium nonafluoro-n-butanesulfonate, tri (4-t-butylphenyl) sulfonium perfluoro-n-octanesulfonate, Tri (4-t-butylphenyl) sulfonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, tri (4-t-butylphenyl) sulfonium 2 - (3-tetracyclo [4.4.0.1 2,5 .1 7,10] dodecanyl) -1,1-difluoroethanesulfonate, tri (4-t- butylphenyl) sulfonium N, N'-bis (nonafluoro -N-butanesulfonyl) imidate, tri (4-t-butylphenyl) sulfur Bromide tri (4-t- butylphenyl) such as camphorsulfonate sulfonium salt compound;

Diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluoro-n-butanesulfonate, diphenyliodonium perfluoro-n-octanesulfonate, diphenyliodonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2, 2-tetrafluoroethane sulfonate, diphenyliodonium 2- (3-tetracyclo [4.4.0.1 2,5 .1 7,10] dodecanyl) -1,1-difluoroethanesulfonate, diphenyliodonium N, N'-bis Diphenyliodonium salt compounds such as (nonafluoro-n-butanesulfonyl) imidate, diphenyliodonium camphorsulfonate;

Bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluoro-n-butanesulfonate, bis (4-t-butylphenyl) iodonium perfluoro-n-octanesulfonate, Bis (4-t-butylphenyl) iodonium 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, bis (4-t-butylphenyl) iodonium 2 - (3-tetracyclo [4.4.0.1 2,5 .1 7,10] dodecanyl) -1,1-difluoroethanesulfonate, bis (4-t- butylphenyl) iodonium N, N'-bis (nonafluoro -N-butanesulfonyl) imidate, bis (4-t-butylphenyl) io Bis (4-t- butylphenyl) such as camphorsulfonate iodonium salt compounds;

1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, (4-n-Butoxynaphthalen-1-yl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium 2-bicyclo [2.2. 1] Hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium 2- (3-tetracyclo [4.4. 0.1 2,5 .1 7,10 ] dodecanyl) -1,1-difluoroethanesulfonate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium N, N′-bis (nonafluoro-n-butanesulfonyl) imidate, 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothio 1- (4-n-butoxynaphthalen-1-yl) tetrahydrothiophenium salt compounds such as phenium camphorsulfonate;

1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium trifluoromethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium nonafluoro-n-butanesulfonate, (3,5-Dimethyl-4-hydroxyphenyl) tetrahydrothiophenium perfluoro-n-octanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 2-bicyclo [2.2. 1] Hept-2-yl-1,1,2,2-tetrafluoroethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium 2- (3-tetracyclo [4.4. 0.1 2,5 .1 7,10 ] dodecanyl) -1,1-difluoro Ethanesulfonate, 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium N, N′-bis (nonafluoro-n-butanesulfonyl) imidate, 1- (3,5-dimethyl-4-hydroxyphenyl) ) 1- (3,5-dimethyl-4-hydroxyphenyl) tetrahydrothiophenium salt compounds such as tetrahydrothiophenium camphorsulfonate;

N- (trifluoromethanesulfonyloxy) succinimide, N- (nonafluoro-n-butanesulfonyloxy) succinimide, N- (perfluoro-n-octanesulfonyloxy) succinimide, N- (2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethane sulfonyloxy) succinimide, N- (2- (3- tetracyclo [4.4.0.1 2,5 .1 7,10] dodecanyl) Succinimide compounds such as -1,1-difluoroethanesulfonyloxy) succinimide and N- (camphorsulfonyloxy) succinimide;

N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (nonafluoro-n-butanesulfonyloxy) bicyclo [2.2.1] hept -5-ene-2,3-dicarboximide, N- (perfluoro-n-octanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- ( 2-bicyclo [2.2.1] hept-2-yl-1,1,2,2-tetrafluoroethanesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy imide, N- (2- (3- tetracyclo [4.4.0.1 2,5 .1 7,10] dodecanyl) -1,1-difluoroethane-sulfonyloxy) bicyclo [2.2.1] hept Bicyclo [2.2.1] such as -5-ene-2,3-dicarboximide, N- (camphorsulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide. And hept-5-ene-2,3-dicarboximide compounds.
In addition, these photo-acid generators may use only 1 type, and may use 2 or more types together.

  From the viewpoint of ensuring sensitivity and resolution, the amount of the photoacid generator used is the weight contained in the composition constituting the shape-transferring layer (hereinafter simply referred to as “the composition for shape-transferring layer”). It is 0.1-30 mass parts normally with respect to 100 mass parts of unification (for example, the said silane polymer), 0.1-20 mass parts is preferable, and 0.1-15 mass parts is more preferable. In the preferable range, the sensitivity and resolution are excellent, transparency to radiation can be sufficiently obtained, and an uneven pattern can be obtained more easily.

In addition to the above-mentioned various components, the shape-transferring layer composition can contain a solvent.
As the solvent, it is preferable to use an organic solvent. Usually, the respective components are dissolved or dispersed in the organic solvent. The organic solvent is at least one selected from the group consisting of alcohol solvents, ketone solvents, amide solvents, ether solvents, ester solvents, aliphatic hydrocarbon solvents, aromatic solvents, and halogen-containing solvents. Is mentioned.
Among these solvents, it is preferable to use an organic solvent having a boiling point of less than 150 ° C. In particular, it is preferable to use one or more of alcohol solvents, ketone solvents and ester solvents.

  The amount of the solvent used is usually 100 to 3500 parts by mass and 200 to 3500 parts by mass with respect to 100 parts by mass of the polymer (for example, the silane polymer) contained in the composition for shape transfer layer. Part is preferable, and 400 to 3500 parts by mass is more preferable. In the preferred range, the in-plane uniformity of the shape-transferring layer is particularly excellent.

Furthermore, the composition for a shape-transferred layer can contain an acid diffusion inhibitor in addition to the various components.
The acid diffusion control agent is a component having an action of controlling unwanted diffusion of the acid generated from the photoacid generator in the shape transfer layer and suppressing an unintended chemical reaction in the non-irradiated region. By blending this acid diffusion control agent, it is possible to improve the resolution of the concavo-convex pattern formed on the surface of the shape-transferring layer and to suppress the line width change of the concavo-convex pattern.
The acid diffusion controller is preferably a nitrogen-containing organic compound whose basicity does not change by irradiation or heat treatment during the step of forming the concavo-convex pattern.

Examples of the nitrogen-containing organic compound include tertiary amine compounds, amide group-containing compounds, quaternary ammonium hydroxide compounds, and nitrogen-containing heterocyclic compounds.
Tertiary amine compounds include triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, Tri (cyclo) alkylamines such as tri-n-nonylamine, tri-n-decylamine, cyclohexyldimethylamine, dicyclohexylmethylamine, tricyclohexylamine; aniline, N-methylaniline, N, N-dimethylaniline, 2-methyl Aromatic amines such as aniline, 3-methylaniline, 4-methylaniline, 4-nitroaniline, 2,6-dimethylaniline, 2,6-diisopropylaniline, diphenylamine, triphenylamine, naphthylamine; triethanolamine, diethanol Alkanolamines such as niline; N, N, N ′, N′-tetramethylethylenediamine, N, N, N ′, N′-tetrakis (2-hydroxypropyl) ethylenediamine, 1,3-bis [1- (4 -Aminophenyl) -1-methylethyl] benzenetetramethylenediamine, 2,2-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- ( 4-aminophenyl) -2- (3-hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4-hydroxyphenyl) propane, 1,4-bis [1- (4-aminophenyl)- 1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene, bis (2-dimethylaminoethyl) ether , Bis (2-diethylaminoethyl) ether.

  Examples of the amide group-containing compound include Nt-butoxycarbonyldi-n-octylamine, Nt-butoxycarbonyldi-n-nonylamine, Nt-butoxycarbonyldi-n-decylamine, Nt-butoxycarbonyl. Dicyclohexylamine, Nt-butoxycarbonyl-1-adamantylamine, Nt-butoxycarbonyl-N-methyl-1-adamantylamine, N, N-di-t-butoxycarbonyl-1-adamantylamine, N, N -Di-t-butoxycarbonyl-N-methyl-1-adamantylamine, Nt-butoxycarbonyl-4,4'-diaminodiphenylmethane, N, N'-di-t-butoxycarbonylhexamethylenediamine, N, N , N ′, N′-Tetra-t-butoxycarbonylhexamethylenediamine N, N-di-t-butoxycarbonyl-1,7-diaminoheptane, N, N′-di-t-butoxycarbonyl-1,8-diaminooctane, N, N′-di-t-butoxycarbonyl- 1,9-diaminononane, N, N′-di-t-butoxycarbonyl-1,10-diaminodecane, N, N′-di-t-butoxycarbonyl-1,12-diaminododecane, N, N′-di -T-butoxycarbonyl-4,4'-diaminodiphenylmethane, Nt-butoxycarbonylbenzimidazole, Nt-butoxycarbonyl-2-methylbenzimidazole, Nt-butoxycarbonyl-2-phenylbenzimidazole, N -T-butoxycarbonyl-pyrrolidine, Nt-butoxycarbonyl-piperidine, Nt-butoxycarbonyl In addition to Nt-butoxycarbonyl group-containing amino compounds such as 4-hydroxy-piperidine, Nt-butoxycarbonyl-morpholine, formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone and the like.

Examples of the quaternary ammonium hydroxide compound include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, and tetra-n-butylammonium hydroxide.
Examples of nitrogen-containing heterocyclic compounds include imidazoles such as imidazole, 4-methylimidazole, 1-benzyl-2-methylimidazole, 4-methyl-2-phenylimidazole, benzimidazole, and 2-phenylbenzimidazole; pyridine, 2- Methylpyridine, 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, 2-methyl-4-phenylpyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 4- Pyridines such as hydroxyquinoline, 8-oxyquinoline and acridine; piperazines such as piperazine and 1- (2-hydroxyethyl) piperazine, as well as pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine and 3-piperidino 1,2-propanediol, morpholine, 4-methylmorpholine, 1,4-dimethylpiperazine, 1,4-diazabicyclo [2.2.2] octane.
In addition, these acid diffusion control agents may use only 1 type, and may use 2 or more types together.

  The amount of the acid diffusion controller used is usually 15 parts by mass or less (0.001 part by mass) with respect to 100 parts by mass of the polymer (for example, the silane polymer) contained in the composition for shape transfer layer. Part or more), preferably 10 parts by mass or less, and more preferably 5 parts by mass or less.

In addition to the various components, the composition for a shape-transferring layer can contain a surfactant.
A surfactant is a component that exhibits an effect of improving coating properties, striation and the like. As this surfactant, nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, fluorine surfactants, Examples include poly (meth) acrylate surfactants.
The amount of the surfactant used is usually 0.00001 to 1 part by mass with respect to 100 parts by mass of the polymer (for example, the silane polymer) contained in the composition for shape transfer layer. 0.00001-0.1 mass part is preferable and 0.00001-0.01 mass part is more preferable.

There is no particular limitation on the method of forming the shape transfer layer (the shape transfer layer before pressing the concave / convex pattern) using the composition for shape transfer layer. For example, it may be directly formed on a substrate by spin coating, casting coating, roll coating, or other methods, and a film formed in advance elsewhere is dried to form a sheet and cut into a required size. Then, it may be affixed on the substrate like a seal to form a shape-transferring layer, and other methods may be used.
The thickness of the shape-transferring layer (the shape-transferring layer in a state in which the solvent is removed when a solvent or the like is contained after film formation on the substrate) is not particularly limited. It is 01 μm or more (100 μm or less). The thickness is preferably 0.01 to 50 μm, more preferably 0.01 to 10 μm, and particularly preferably 0.01 to 1 μm. In the preferable range, excellent in-plane uniformity and high light transmittance of the shape transfer layer can be ensured.

The type of the substrate on which the shape transfer layer is formed is not particularly limited, and various types can be used. That is, for example, a wafer covered with a Si-containing layer such as Si, SiO 2 , SiN, SiC, or SiCN, or a lower layer in various semiconductor device manufacturing stages. Further, for example, as disclosed in Japanese Patent Publication No. 6-12452 (Japanese Patent Laid-Open No. 59-93448), a substrate on which an organic or inorganic antireflection film is formed may be used.

  Further, the pressure at the time of the pressure welding in the pressure welding process PR1 is not particularly limited, but is usually 0.1 MPa or more (100 MPa or less). This pressure is preferably 0.1 to 50 MPa, more preferably 0.1 to 30 MPa, and particularly preferably 0.1 to 20 MPa. Further, the pressure contact time is not particularly limited, but is usually 1 second or longer (600 seconds or shorter). The pressure contact time is preferably 1 to 300 seconds, more preferably 1 to 180 seconds, and particularly preferably 1 to 120 seconds.

The “exposure step PR2” is a step of exposing the shape transfer layer 30 while the stamper 10 is in pressure contact with the shape transfer layer 30. Further, this exposure is performed by transmitting through the stamper 10, whereby the light-shielding portion and the light-transmitting portion of the stamper 10 function as a pattern mask.
The exposure process PR2 accelerates the curing of the shape transfer layer 30, and the portion of the shape transfer layer under the light shielding portion (the light shielding convex portion of the first stamper and the light shielding concave portion of the second stamper), the transparent portion. There is a difference in the degree of curing between the light-transmitting portion (the light-transmitting recess of the first stamper and the light-transmitting recess of the second stamper). That is, the portion under the light-shielding convex portion of the first stamper in the negative shaped transfer layer does not proceed with curing more than the portion under the light-transmitting concave portion of the first stamper in the negative shaped transfer layer. It will be. Further, the portion under the light-transmitting convex portion of the second stamper in the positive shape-shaped transfer layer is less hardened than the portion under the light-shielding concave portion of the second stamper of the positive shape-shaped transfer layer. Become. By producing such a difference in the degree of curing, the residue can be easily removed in a cleaning process PR4 described later.

In the exposure step PR2, the shape transfer layer 30 may be completely cured or incompletely cured as described above, and the degree of curing is not particularly limited, and at least the transfer is performed when performing the separation step PR3. It is sufficient that curing is performed to such an extent that the shape of the uneven pattern thus formed can be maintained.
The type of radiation used for photocuring is not particularly limited. Radiation such as charged particle beams such as visible light, ultraviolet light, far ultraviolet light, X-rays, and electron beams {ArF excimer laser (wavelength 193 nm) or KrF excimer laser (wavelength 248 nm), etc. Can be used.

  The “separation process PR3” is a process of separating the stamper 10 from the shape transfer layer 30. Various conditions for separation are not particularly limited. That is, for example, the substrate 20 may be fixed and the stamper 10 may be moved away from the substrate 20 and separated, or the stamper 10 may be fixed and the substrate 20 moved away from the stamper 10 and separated. Well, both may be separated by pulling in the opposite direction.

The “cleaning process PR4” is a process of cleaning the concavo-convex pattern formed on the shaped transfer layer 30 after separation. By performing this step, a concavo-convex pattern 31 is formed on the shape transfer layer 30 as shown in FIGS.
In this cleaning process, an alkaline aqueous solution is usually used as a cleaning liquid, and the residue 40 is dissolved and removed. Examples of the cleaning liquid include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, and ethyl. Dimethylamine, triethanolamine, tetramethylammonium hydroxide, pyrrole, piperidine, choline, 1,8-diazabicyclo- [5.4.0] -7-undecene, 1,5-diazabicyclo- [4.3.0] An alkaline aqueous solution in which at least one alkaline compound such as -5-nonene is dissolved in water is preferable.
The concentration of the alkaline compound in the alkaline aqueous solution is usually 0.01 to 0.1% by mass.

Moreover, the said washing | cleaning liquid can contain an organic solvent and / or surfactant other than the said component. Examples of organic solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, 3-methylcyclopentanone, 2,6-dimethylcyclohexanone, and the like; methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol , N-butyl alcohol, tert-butyl alcohol, cyclopentanol, cyclohexanol, 1,4-hexanediol, 1,4-hexanedimethylol and other alcohols; tetrahydrofuran, dioxane and other ethers; ethyl acetate, n-acetate -Esters such as butyl and isoamyl acetate; aromatic hydrocarbons such as toluene and xylene; and phenol, acetonylacetone and dimethylformamide. These may use only 1 type and can use 2 or more types together.
The cleaning time with the cleaning liquid is appropriately selected depending on the composition of the shape-transferring layer and the amount of residue, but is usually 1 to 30 minutes. Moreover, after this washing | cleaning process, washing with water, drying, etc. can be performed as needed.

In the first imprint method and the second imprint method of the present invention, each of the steps may include other steps in addition to the steps described above. Another process includes a heat curing process.
In the case where this step is provided, it is preferably performed between the separation step PR3 and the cleaning step PR4 and / or after the cleaning step PR4. By providing this heat-curing step, the shape-transferred layer separated from the stamper 10 can be further cured, and further completely cured. Furthermore, when a hole forming agent is contained in the shape-transferred layer as described later, the hole forming agent can be removed to form holes.
When performing the heat curing, the heating atmosphere and the heating temperature are not particularly limited. For example, the heating and heating can be performed at 100 to 500 ° C. under an inert atmosphere or under reduced pressure, and further at 150 to 300 ° C. Can do. In this heating, a hot plate, an oven, a furnace, or the like can be used.

  Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples. Here, “part” and “%” are based on mass unless otherwise specified.

[Example 1] Production of first stamper In a flask equipped with a nitrogen-substituted dry ice / methanol reflux apparatus, 5.0 g of 2,2'-azobisisobutyronitrile and 150 g of ethyl lactate were charged, and a polymerization initiator was prepared. Stir until dissolved. To this solution, methacrylic acid (10 g), p-isopropenylphenol (15 g), isobornyl acrylate (40 g), n-butyl acrylate (5 g), tricyclo (5.2.1.0 2,6 ) decanyl Methacrylate (15 g) and phenoxytripropylene glycol acrylate (15 g) were charged, stirring was started gently, and the temperature was raised to 80 ° C. Thereafter, polymerization was carried out at 80 ° C. for 6 hours to obtain a polymer A.

  100 parts by mass of the obtained polymer A, 60 parts by mass of the first ethylenically unsaturated compound B (product name “Aronix M8100” manufactured by Toa Gosei Co., Ltd.), and the second ethylenically unsaturated compound B (Toa Gosei) 2,2′-bis (2-chlorophenyl) -4,5,4 ′, 5′-tetraphenyl-1 as a radiation-sensitive radical polymerization initiator C (product name “Aronix M320” manufactured by Co., Ltd.) , 2′-biimidazole (4 parts by mass), 2-methyl-1- [4- (methylthio) phenyl] -2-monforinopropanone-1 (10 parts by mass), 4,4′-bis (diethylamino) ) 0.3 parts by mass of benzophenone (0.2 parts by mass), surfactant (manufactured by Neos Co., Ltd., product name “FTX-218”), 150 parts by mass of ethyl lactate as a solvent, and stirred to obtain a uniform solution Adjust It was. This composition solution was filtered through a capsule filter having a pore size of 10 μm to obtain a composition for a plating resist layer.

  The composition for plating resist layer is spin-coated on a quartz substrate (reference numeral 11 in FIG. 3) provided with a transparent electrode made of 120 nm thick indium tin oxide (ITO, reference numeral 13 in FIG. 3) at 110 ° C. Was baked for 5 minutes to form a 5 μm plating resist layer (symbol 14 in FIG. 3). Irradiation with ultraviolet light through a pattern mask using an ultra-high pressure mercury lamp (1000 W), development with an aqueous 2.38% tetramethylammonium hydroxide solution (23 ° C., 60 seconds), washing with water, and drying As a result, a negative pattern having 50 μline / 50 μspace was obtained. Subsequently, the resulting negative pattern was irradiated with ultraviolet light for 5 minutes using an ultrahigh pressure mercury lamp (1000 W) to decompose the remaining radiation-sensitive radical polymerization initiator C.

The resulting quartz substrate (reference numeral 11 in FIG. 3) having the negative pattern (reference numeral 14 in FIG. 3) is subjected to electrolytic chrome plating, and the plating resist layer recess 141 has a thickness of 5 μm. Part). Thereafter, using a CMP method (chemical mechanical polishing method), the surface of the stamper is adjusted so that the in-plane height variation of the quartz substrate 11, the ITO film 13, and the light-shielding convex portion 14 made of chrome plating is 0.2 μm or less. Polishing and planarization were performed.
Thereafter, the negative stamp pattern is subjected to O 2 ashing (heated and burned out in the atmosphere), whereby the first stamper 10a having the light-shielding convex portion (121s in FIG. 1) and the translucent concave portion (122t in FIG. 1) is obtained. Obtained. On the obtained first stamper 10a, it is confirmed that a concave / convex pattern of 50 μline / 50 μspace is formed by observing with a scanning electron microscope (manufactured by Hitachi Instruments Service Co., Ltd., model “S9380”). did.
In addition, the light transmittance (ultraviolet visible spectrophotometer (manufactured by JASCO Corporation, model “JASCO V7100”)) of ultraviolet light of 365 nm was 0% for the light-shielding convex portion and 100% for the light-transmissive concave portion. .

[Example 2] Negative-type photoimprint lithography method using a first stamper (1) Preparation of resin composition having negative-type photocurability 20% aqueous solution of maleic acid 2 in a nitrogen-substituted quartz three-necked flask .14 g and ultrapure water 139.6 g were added and heated to 75 ° C. Next, a solution prepared by mixing 25.7 g (0.169 mol%) of tetramethoxysilane, 206.7 g (1.52 mol) of methyltrimethoxysilane, and 25.9 g of ethoxypropanol was dropped into the reaction vessel over 1 hour. And stirred at 75 ° C. for 2 hours. The reaction solution was returned to room temperature and concentrated under reduced pressure until the solid concentration was 25% to obtain 440 g of a silicon-containing resin solution containing a silicon-containing resin. The constituent monomer ratio (a: b) of the silicon-containing resin contained in this solution was 10:90 (mol%) in {(a: b)} in the above formula (3), and Mw was 8,500.

  Subsequently, 6 g of octa [(1,2-epoxy-4-cyclohexyl) dimethylsiloxy] silsesquioxane was added to 1 g of the obtained silicon-containing resin, and octa [(3-glycidoxypropyl) dimethylsiloxy] silsesquioxane. 3 g, 0.2 g triphenylsulfonium nonafluoro-n-butanesulfonate, 0.017 g Nt-butoxycarbonyl-2-phenylbenzimidazole, and the mixture added was dissolved in 24 g propylene glycol monomethyl ether acetate. Then, it filtered using the filter with a hole diameter of 0.1 micrometer, and obtained the resin composition (henceforth a "negative resin composition") which has negative photocurability.

(2) Formation of concavo-convex pattern on shaped transfer layer On the silicon wafer (symbol 20 in FIG. 4), the obtained negative resin composition is used as a shaped transfer layer composition having negative photocurability. This is applied by spin coating, and heated on a hot plate at 100 ° C. for 1 minute to form a 5 μm-thick negative photocuring shape transfer layer (reference numeral 30 in FIG. 4). did.

Light irradiation (60 seconds) was performed using a low-pressure mercury lamp (150 W) in a state where the first stamper 10a was pressed (4 MPa, 15 seconds) to the obtained shape-transfer layer (reference numeral 30 in FIG. 4) ( Pressure welding process PR1 and exposure process PR2).
Subsequently, after heating on a hot plate at 100 ° C. for 1 minute, the first stamper 10a was separated (separation process PR3).
Further, the substrate was washed with a 2.38% tetramethylammonium hydroxide aqueous solution (23 ° C., 60 seconds) (cleaning step PR4) to form a concavo-convex pattern (symbol 31 in FIG. 4).

  When the cross section of the obtained concavo-convex pattern (symbol 31 in FIG. 4) was observed with a scanning electron microscope trade name “S-4800” manufactured by Hitachi High-Technologies Corporation, a rectangular pattern of 50 μm line / 50 μm space was confirmed. No residue was observed in the concave portion of the concave-convex pattern (reference numeral 30 in FIG. 4).

[Example 3] Manufacture of a second stamper A quartz substrate (reference numeral 11 in FIG. 7) having an indium tin oxide (ITO) film (reference numeral 13 in FIG. 7) was prepared in the same manner as in Example 2 (1). A negative resin composition was used as a composition for a plating resist layer, and this was formed into a plating resist layer (reference numeral 14 in FIG. 7) having a negative photocurability with a thickness of 1 μm. Next, after KrF exposure through a pattern mask, development was performed using an aqueous 2.38% tetramethylammonium hydroxide solution (23 ° C., 60 seconds). Subsequently, it washed with water and dried, and the uneven | corrugated pattern of 450 nm line / 450 nm space was formed in the plating resist layer (code | symbol 14 of FIG. 7). Subsequently, gold plating is performed to form a gold film {corresponding to the light-shielding portion, symbol 122 (s) in FIG. 7} in the concave portion (reference numeral 141 in FIG. 7), and the light-shielding concave portion { The 2nd stamper 10b provided with the uneven | corrugated pattern (symbol 12 of FIG. 7) which has the code | symbol 122 (s)} of FIG. 7 and a translucent convex part {code | symbol 122 (t)} of FIG. 1] was obtained. The obtained second stamper 10b was observed with a scanning electron microscope (manufactured by Hitachi Instruments Service Co., Ltd., model “S9380”), and a concavo-convex pattern (symbol 12 in FIG. 7) of 450 nm line / 450 nm space was formed. It was confirmed.
In addition, the light transmittance (ultraviolet visible spectrophotometer (manufactured by JASCO Corporation, model “JASCO V7100”)) for ultraviolet light of 365 nm was 0% for the light-shielding concave portion and 100% for the light-transmissive convex portion. .

[Example 4] Positive-type photoimprint lithography method using a second stamper A positive-type radiation-sensitive resin composition (product name “M221Y” manufactured by JSR Corporation) is positively applied on a silicon wafer (reference numeral 20 in FIG. 8). This is used as a composition for a shape transfer layer having mold-type photocurability, and this is spin-coated and heated on a hot plate at 100 ° C. for 1 minute to have a positive-type photocurable film having a thickness of 1 μm. A shape transfer layer (reference numeral 30 in FIG. 8) was formed.

Light irradiation (60 seconds) was performed using a low-pressure mercury lamp (150 W) in a state where the second stamper 10b was pressed (10 MPa, 60 seconds) to the obtained shaped transfer layer (reference numeral 30 in FIG. 8) ( Pressure welding process PR1 and exposure process PR2).
Subsequently, after heating on a hot plate at 100 ° C. for 1 minute, the second stamper 10b was separated (separation process PR3).
Further, the substrate was washed with a 2.38% tetramethylammonium hydroxide aqueous solution (23 ° C., 60 seconds) (cleaning step PR4) to form an uneven pattern (symbol 31 in FIG. 8).

  The cross section of the resulting concavo-convex pattern (symbol 31 in FIG. 8) is observed with a scanning electron microscope (manufactured by Hitachi High-Technologies Corporation, model “S-4800”), and a rectangular concavo-convex pattern of 450 nm line / 450 nm space is formed. Confirmed that. Furthermore, no residue was observed in the recesses of the uneven pattern (reference numeral 31 in FIG. 8).

  In addition, in this invention, it can restrict to what is shown to said specific Example, It can be set as the Example variously changed within the range of this invention according to the objective and the use.

10 (10a and 10b); stamper, 11; substrate,
12; concavo-convex pattern, 121; convex part, 121s; light-shielding convex part, 121t; translucent convex part, 122; concave part, 122s; light-shielding concave part, 122t;
13; a translucent electrode layer;
14; plating resist layer, 141; recess of plating resist layer,
20; Substrate, 30; Shaped transfer layer, 31; Concave and convex pattern (transferred concavo-convex pattern), 312; Concave part of the shaped transfer layer, 40; Residue,
51; ridges, 52; ridges having two or more steps, 53; ridges, 54; protrusions, 55; ridges, 56; ridges having two or more steps, 57; Island, 58; bottomed hole,
PR1; pressure contact process, PR2; exposure process, PR3; separation process, PR4; cleaning process.

Claims (4)

  1. A stamper used in an optical imprint lithography method having a concavo-convex pattern for transferring to a shape transfer layer provided on a substrate,
    The concavo-convex pattern has a light-shielding convex portion and a light-transmitting concave portion.
  2. (A) a press-contacting step of press-contacting the stamper according to claim 1 to a shaped transfer layer having a negative photocuring property;
    (B) an exposure step of exposing the shaped transfer layer in a state where the stamper is in pressure contact with the shaped transfer layer;
    (C) a separation step of separating the stamper and the shaped transfer layer after exposure;
    (D) A cleaning process for cleaning the concavo-convex pattern formed on the shaped transfer layer after the separation.
  3. A stamper used in an optical imprint lithography method having a concavo-convex pattern for transferring to a shape transfer layer provided on a substrate,
    The concavo-convex pattern has a light-blocking concave portion and a light-transmitting convex portion.
  4. (A) a press-contacting step of press-contacting the stamper according to claim 3 to a shaped transfer layer having a positive photocurability;
    (B) an exposure step of exposing the shaped transfer layer in a state where the stamper is in pressure contact with the shaped transfer layer;
    (C) a separation step of separating the stamper and the shaped transfer layer after exposure;
    (D) A cleaning process for cleaning the concavo-convex pattern formed on the shaped transfer layer after the separation.
JP2009089611A 2009-04-01 2009-04-01 Stamper and optical imprint lithography method using the same Pending JP2010245130A (en)

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JP2012243777A (en) * 2011-05-13 2012-12-10 Fujikura Ltd Circuit board, imprint mold, and manufacturing method thereof
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JP2013135107A (en) * 2011-12-27 2013-07-08 Toshiba Mach Co Ltd Mold and method for molding article to be molded
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JP2017135413A (en) * 2013-09-18 2017-08-03 キヤノン株式会社 Method for manufacturing film, method for manufacturing optical part, method for manufacturing circuit board, method for manufacturing electronic part, and photocurable composition
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