WO2013060087A1

WO2013060087A1 - Polyhedral oligomeric silsesquioxane compound containing mercapto polyfunctional group, its composition, and soft template for imprinting

Info

Publication number: WO2013060087A1
Application number: PCT/CN2012/000319
Authority: WO
Inventors: 林宏; 姜学松; 印杰; 锻治诚
Original assignee: 上海交通大学; 日立化成工业株式会社
Priority date: 2011-10-27
Filing date: 2012-03-15
Publication date: 2013-05-02
Also published as: CN103087087B; JP2015501296A; CN103087087A

Abstract

Provided are a polyhedral oligomeric silsesquioxane compound containing mercapto polyfunctional group shown as general formula (1), its composition used for preparing the soft template for imprinting and the imprinting process, wherein R₁ is -CH₂-CH₂-CH₂-SH, and m represents the integer of 3 to 12; R₂ is unsubstituted or substituted alkyl group, unsubstituted or substituted alkoxy, unsubstituted or substituted ester group, and unsubstituted or substituted aryl group respectively, and the said substituent group is halogen; n represents the integer of 1 to 12. The composition is a high hydrophobic photoresist. When the composition is applied to prepare nanoimprinting template, a high precision structure can be achieved and the recycling rate of the template may be improved.

Description

Thiol-based polyfunctional low-poly polysiloxane compounds and compositions thereof and embossed soft templates

FIELD OF THE INVENTION The present invention relates to the field of micro/nano processing in microelectronics and nanoelectronics, and relates to a polyfunctional polysiloxane-containing polysiloxane compound (referred to as "low poly polysiloxane compound" simply as "Polyhedral" Ol igomeric Si lsesquioxane, abbreviated as POSS") and its composition for preparing embossed soft stencils and embossed soft stencils. BACKGROUND Nanoimprint lithography is considered to be one of the most promising next-generation lithography technologies. Based on its mechanical imprinting principle, nanoimprint technology can achieve graphics resolution beyond the limitations of light diffraction or particle beam scattering in other traditional technologies, with low cost, high resolution, high productivity and so on. Among them, the template is the biggest difference between nanoimprint lithography (NIL) and traditional optical lithography. The template as the initial carrier of the embossed feature directly determines the quality of the embossed pattern, and achieves high quality. For embossing replicas, high quality stamping stencils are required. Unlike the masks used in traditional optical lithography (4 X), nanoimprint lithography uses the 1 X template, which faces greater challenges in stencil making, inspection and repair techniques. At present, the fabrication of templates has become the biggest technical bottleneck of NIL, and with the deepening of nanoimprint lithography research and the expanding application fields, the manufacture of NIL templates will become more and more important and face more severe challenges. . Therefore, the fabrication of templates has become one of the most important research hotspots in nanoimprint lithography, especially the fabrication of 3D templates, large-area templates and high-resolution templates, and the inspection and repair of template defects are the most urgent in the future and in the future. Demand, the most important research hotspots and challenges. The traditional embossed carrier template is made of quartz, which is not only expensive, but also extremely fragile. After repeated work, the etchant is easily adhered to the surface of the stencil. These residual cured polymers can easily damage the replication precision of the structure. At the same time, after the template is used for many times, it needs to be refluorinated, and the multiple treatments have a destructive effect on the material structure itself. Therefore, there is an urgent need for new materials to replace quartz-based templates, saving costs and increasing template utilization. Many researches at present The team is dedicated to the study of soft stencils. Soft stencils refer to substrates made of soft materials. They are usually made of photoresist as a prepolymer. They are patterned on the surface by imprinting, and then cured by heat or UV. Photocuring to obtain a polymer soft template with a reverse replication pattern. Compared with the hard template, the soft template not only has a simple preparation process, but also greatly saves cost; at the same time, due to its soft matrix, it can replace the disadvantage that the hard material cannot be bent, and the quality of the imprint is greatly improved. A search of the prior art found that the most successful commercialization of the currently used imprinted photoresist product for soft stencil fabrication is polydimethylsiloxane (PDMS). PDMS is a polymer material widely used in fields such as microfluidics. It is low in cost, simple to use, has good adhesion to silicon wafers, and has good chemical inertness, so it is often used in chip packaging and other fields. Lower surface energy due to its good light transmission

(21.6raJ/cra ³ ) and shrinkage, as well as its excellent solvent resistance, make PDMS materials a hot spot in soft template production in recent years. However, the viscosity of PDMS glue is large, the mechanical properties of the film after curing are relatively poor, and it is not resistant to abrasion. In particular, high-precision, high-resolution graphics cannot be produced (after the graphic structure is less than 200 ships, the PDMS template structure is easily broken and deformed) , making further application of this material limited. With the development of lithography technology, the precision requirements are getting higher and higher. At present, the average line width of the characteristic lines on the large-scale integrated circuit chip has reached 45 nm, and many companies in the world are still marching toward smaller line sizes. Obviously, PDMS materials as soft templates have not adapted to the requirements of soft film technology. In recent years, thiol/olefinic UV photoresists have shown a larger application scenario due to the high efficiency, rapid response and mild reaction conditions of the click chemistry. The mercapto/olefin-based ultraviolet photopolymerization reaction refers to a radical polymerization of a monomer having two or more mercapto groups (-SH) and a monomer having an unsaturated carbon-carbon double bond (-C=C-). Compared with the ultraviolet (meth) acrylate self-polymerization reaction, since the comonomer containing fluorenyl group is introduced into the system, the polymerization mechanism is changed in essence, and the photopolymerization reaction is changed from free-radical chain self-polymerization to radical gradualization. Copolymerization, so that the molecular weight of the polymer is gradually increased, the gelation phenomenon is delayed, the oxygen inhibition effect is effectively reduced, the conversion rate of the double bond is greatly improved, and the volume shrinkage of the polymer is reduced. Moreover, the amount of photoinitiator required for photopolymerization of mercapto/olefin monomers is very small, or even unnecessary, so it is possible to use light curing to prepare thicker parts. In order to improve and improve the mechanical properties of the polymer, inorganic fillers are usually added. However, due to the incompatibility of the inorganic particles themselves with the polymer precursor, excessive doping causes the system to be phase-separated, greatly affecting the properties of the material. Recently, research on new types of silicone polymer materials has received increasing attention. Among them, POSS (Polyhedral Oligomeric Silsesquioxane) is a widely used class of silicones, The basic composition is composed of a Si-0 bond, and the side chain is a variety of organic groups bonded to a silicon atom. Therefore, the structure of the silicone material contains both an organic group and an inorganic skeleton. Since the P0SS monomer is soluble in the process of mixing, it can be considered as a polymer which is formed in the true sense of molecular level dispersion, which has many characteristics that cannot be achieved by nanomaterial additives: P0SS skeleton is dispersed in the nanometer scale in the polymerization. The substrate has the advantages of low density, good monodispersity, no moisture absorption, and high thermal stability; its excellent compatibility overcomes the problem of weak phase interface of the composite during blending. Organic polymer polymerization can produce organic/inorganic nanocomposites. Due to the presence of inorganic nanophases, the material has a great leap in performance, and has become an important means of preparing high-performance and functional materials. It is the most dynamic and dynamic field in materials science.

US Patent No. 007691275B2 describes and discloses a P0SS compound containing an active hydrogen functional group, and combines the P0SS compound and a monomer of a double bond functional group to form an imprinted photoresist composition, further passing ultraviolet nanoimprinting. Form nanopatterns. Patent US20110062619A1 describes and discloses a process for preparing a methoxysilane-containing P0SS compound, and this P0SS compound is used in nanoimprinting by thermal polymerization. Patent US20080166871A1 describes and discloses a P0SS containing an acrylate or epoxy functional group, and forms the P0SS compound with other diluents and photoinitiators to form an imprinted photoresist composition, and further forms a nanometer by ultraviolet nanoimprinting. Graphics. It is apparent that in the prior art, the P0SS compound is an essential component of the embossing composition, and the mechanical properties, thermal properties, etching resistance and the like of the polymer film can be remarkably improved. However, in the prior art, there are relatively few studies on the use of P0SS compounds for the manufacture of imprinted soft templates, and at the same time based on some defects of the existing ultraviolet photoresists, such as acrylate photoresists, even if P0SS compounds are introduced, Avoiding the disadvantages of oxygen inhibition, resulting in edge defects on the surface of the pattern, and low shrinkage of acrylates, thus affecting the precision of the soft template; epoxy resin, due to its higher The surface energy, usually not directly used as a soft template, requires modification of the fluorine-containing groups on the surface of the pattern to reduce the surface energy, which is cumbersome. At the same time, due to the low moisture resistance of the epoxy resin, the defect of heat-induced yellowing will inevitably lead to a limited limitation on the number of times the soft mold plate is used. SUMMARY OF THE INVENTION The present invention is directed to the above-mentioned deficiencies of the prior art by using a fluorenyl-containing low polypolysiloxane compound.

(POSS-SH for short) The thiol end group grafts a low surface energy organic functional group, combining the advantages of thiol click chemistry and P0SS fluoride to develop a novel compound for the preparation of embossed soft stencils and violet photoresist. Group Compound. The soft template prepared by the photoresist composition has low surface tension, high mold release efficiency, high mechanical strength, and the present invention further applies the soft template to commercial ultraviolet photoresist imprinting, and obtains good mold release. Effects and a wide range of high-definition graphics structures. The photoresist provided by the invention can be used not only as a soft template in the imprint technique, but also as a sacrificial layer in the imprint technique due to the high resistance to oxygen etching. The invention is achieved by the following technical solutions:

The present invention provides a fluorenyl-containing polyfunctional fluorene-containing polysiloxane compound represented by the formula (1), m · (SiO^CH^HsCHsSRa ) n (1) wherein R - CH ₂ -CH ₂ - C3⁄4 -SH, m represents an integer of from 3 to 12; R ₂ is an unsubstituted or substituted fluorenyl group, an unsubstituted or substituted ester group, and an unsubstituted or substituted aryl group, respectively. The substituent is a halogen atom or a silicon atom, and n represents an integer of 1 to 12. The present invention also provides a method according to the above, wherein R ₂ is an unsubstituted or substituted Ci—Cw alkyl group, an unsubstituted or substituted C ₃ -C ₁₅ ester group or none. C ₆ - C ₂ substituted or substituted with a substituent. The aromatic group, the substituent is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or a silicon atom.

The present invention also provides a technical solution based on the above technical solution, wherein the C ₃ - C ₁₅ ester group is a C ₃ - C ₁₅ ester group substituted by fluorine. The present invention also provides a solution based on the above, wherein the fluorine-substituted C ₃ - C ₁₅ ester group is propionic acid 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8, 8-trifluorooctyl ester or 2-methyl-propionic acid

Technical solution for 2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7-dodefluoroheptyl ester. The present invention also provides a technical solution based on the above technical solution, wherein the C ₆ -C _2Q aryl group is a phenethyl group. The present invention also provides a Ci- based on the above technical solution. The thiol group is replaced by fluorine. A technical solution for alkyl groups. The present invention also provides a method according to the above, wherein the fluorine is substituted. The fluorenyl group is a technical solution of 1, 1, 1 , 2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8-heptadefluoro-fluorenyl.

The present invention provides a composition for preparing a soft template in an imprinting process, comprising the compound shown above. The present invention also provides a composition based on the soft template described above, further comprising a composition of a compound of the formula (2), a crosslinking agent and a soft template of a photoinitiator,

CHR CR^ (2) Ri, R ₂ and R ₃ in the formula (2) are each a hydrogen atom, a d-alkyl group, and d-C ₂ . Alkoxy, C ₆ - C ₂ . Aromatic groups, C, - C ₂ .酉基, C ₃ -C ₂ . Cyclodecyl, C ₃ -C ₂ . The imide group, the formula (2) may be substituted by a halogen atom or a silicon atom. The present invention also provides a composition based on the soft template described above, wherein the compound of the formula (2) is selected from the group consisting of C ₃ -C ₁₅ olefins, C ₃ - C ₁₅ vinyl ethers, C ₃ - C ₁₅ vinyl groups Amide, C ₃ -C ₂ . (Meth)acrylate, a composition in which the substituent is a fluorine atom or a soft template of a silicon atom. The present invention also provides a composition based on the soft template, the C ₃ - C ₁₅ olefins selected from 1-butene, 1-hexene, 1-heptene, perfluoro-hexene, heptene, or perfluoro a fluorofluoroheptene; the C ₃ -C ₁₅ vinyl ether is selected from the group consisting of vinyl ethyl ether, vinyl butyl ether, vinyl hexane glycol ether, 2, 2, 2-trifluoroethyl vinyl ether or 2-perfluoro Propoxy perfluoropropyl trifluorovinyl ether; said C ₃ - C ₂ . (Meth)acrylate is selected from crotonate, benzyl methacrylate, phenoxyethylene glycol acrylate, 1H, 1H, 2H, 2H-perfluorooctyl acrylate, 1H, 1H, 2H, 2H a composition of perfluorodecyl acrylate or a soft template of 1H, 1H, 7H-dodecafluoroheptyl methacrylate. The present invention also provides a composition based on the soft template described above, wherein the compound of the formula (2) is benzyl methacrylate, 1H, 1H, 2H, 2H-perfluorooctyl acrylate, 1H, 1H, A composition of a soft template of 2H, 2H-perfluorononanol acrylate. The present invention also provides a composition based on the soft template described above, wherein the crosslinking agent is selected from the group consisting of 1, 4-butadiene, 2,5-dimethyl-1,5-hexadien-3-ol, Perfluorohexadiene, 1,3-diethylene-1,1,3,3-tetramethyldisiloxane, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, dipropylene glycol Diacrylate, 1,6-bis(acryloyloxy)-2, 2, 3, 3, 4, 4, 5, 5-octafluorohexane, 1,5-bis(acryloyloxy)-2 , 2, 3, 3, 4, 4- A composition of a soft template of hexafluoropentane, trimethylolpropane trimethacrylate, trimethylolpropane triacrylate. The present invention also provides a composition based on the soft template described above, wherein the compound of the formula (1) is 5 to 65 mass%, the compound of the formula (2) is 10 to 60 mass%, and the crosslinking agent is 5 The composition of the soft template is 5% by mass, and the photoinitiator is 0.3 to 3 mass%, and the sum of the masses of the components is 100%. The present invention provides an embossed soft template formed from the above-described ultraviolet photoresist composition. The invention provides a method for preparing an embossed soft template, which comprises the following steps:

(1). Modified substrate quartz plate (3);

(2) The embossed UV photoresist (2) of the composition of any one of claims 8 to 14 is spin-coated on the surface of the modified quartz plate (3) under the following conditions: at 300 rpm After rotating the film for 10 seconds,

The film was rotated at 3000 rpm for 20 seconds to obtain a film thickness of 750 ± 5 nm _;

(3). The quartz plate (3) with the UV photoresist (2) is brought into contact with the quartz template (1), placed in an imprinting machine, evacuated for 3 minutes, and 100 N is applied to the quartz template (1). The pressure, UV exposure for 3 minutes, after the photoresist was cured, demolded, and then aging for 1 hour at 10 CTC, the aged polymer was used as an embossed soft template to form a soft template (4). The present invention provides a process for imprinting a photoresist and an embossed pattern obtained by using the above-described soft mold.

The composition system using the compound of the formula (1) and the compound of the formula (2) is transparent, uniform, stable, and has good storage properties, and is also desirable because it has a low viscosity and is convenient for spin coating. Applied to the imprint process operation, the damage to the quartz template is reduced.

In addition, the composition can also be applied to the preparation of embossed soft stencils, and the embossed soft stencil produced has a large static water contact angle, so that it has superior hydrophobic properties. In addition, because of its small surface energy, it has high mold release property, and the pattern of the quartz plate can be well reproduced on the soft template. At the same time, the soft template can be used to imprint the defect-free surface. No peeling, structurally complete graphics, the soft template has excellent technical effects. In addition, the embossed soft template prepared by the composition has high mechanical strength, is convenient for repeated embossing and does not need to be modified again, and improves the use of the soft template. Compared with the soft stencil made by the existing photoresist, the remarkable technical effects are mainly reflected in:

1. The photoresist has a low viscosity, which is convenient for spin coating and imprint process operations.

2. The soft template has high mechanical strength and wear resistance, which improves the use rate of the template.

3. The low surface energy of the soft template helps to improve the demolding efficiency, and the surface of the template does not need further modification. The obtained embossed pattern has no defects, no peeling on the surface and complete structure. DRAWINGS

Figure 1 is a structural diagram of the compounds synthesized in the columns 1-5 and corresponding nuclear magnetic hydrogen diagrams: Figure 1 (a): P0SS-SH;

Figure 1 (b): POSS - SCFA ₆ - SH;

Figure 1 (c): P0SS-SDCFA ₆ -SH _;

Figure 1 (d): P0SS-SS-SH;

Figure 1 (e): P0SS-SPFDE ₈ -SHo

Figure 2 is a process flow for soft stencil fabrication and imprinting of a conventional commercial photoresist.

Figures 3(a), (c) and (e) show the different structural patterns of the quartz template 1 respectively: (&) 3.00μπι lattice, (c) 350nm lattice, (e) 700nm grating;

3(b), (d) and (f) respectively utilize the quartz template 1 having Figs. 3(a), (c) and (e) and the ultraviolet photoresist JTHC-B- in the following examples. 1 Corresponding figures of the soft template prepared by the composition: (b) 3·00 μιη dot matrix, (d) 350 nm dot matrix, (f) 700 nm grating.

Figure 4 is an SEM image, respectively: Figure 4 (a) 200 nm lattice quartz template 1; Figures 4 (b), 4 (c) are the JTHC-B-2 ultraviolet photoresist composition of the following examples, The pattern of the soft template 4 prepared by the commercial glue Sylgardl 84 composition through the template 1 (Fig. 4 (a)); Fig. 4 (d) and Fig. 4 (e) are the two types of soft templates prepared in the above-mentioned, respectively. The commercial glue watershed 11120, the pattern of the imprinted polymeric film 7 obtained after the demolding is cured.

Figure 5 is a soft template 4 embossed commercial glue Watershed 11120 of different structures and sizes prepared by using the UV photoresist JTHC-B-2 composition of the following examples, which is obtained by patterning after curing. SEM image of the cured film 7: (a) 350, grating, (b) 700 nm dot matrix.

Figure 6 is a (a) pattern of a soft template prepared by using the ultraviolet photoresist JTHC-B-2 composition of the following examples, and (b) and (c) are respectively the ultraviolet rays of the following examples. Soft template prepared from photoresist JTHC-B-2 composition and soft template prepared from commercial gum Sylgard 184 composition in embossed commercial adhesive Watershed 1 1120, AFM chart after 10 uses.

Label description:

1, quartz template, 2, UV imprinted photoresist, 3, quartz, 4, soft template, 5, commercial lithography, 6, silicon substrate, 7, commercial adhesive film with graphics. detailed description

The present invention provides a fluorenyl-containing polyfunctional group-containing low-poly polysiloxane compound represented by the formula (1), (SiO^R m · (SiO _{L 5} CH ₂ CH ₂ CH ₂ SR ₂ ) n (1) wherein is _{_{- CH 2 - C -CH 2 -}} SH, m represents an integer of 3~12; R ₂ are unsubstituted or substituted alkyl with the substituent group, substituted or unsubstituted ester group, and a substituted or unsubstituted An aromatic group substituted with a substituent, wherein the substituent is a halogen atom or a silicon atom, and η represents an integer of 1 to 12. The above are respectively an unsubstituted or substituted d-fluorenyl group, an unsubstituted or substituted group. a substituted C ₃ -C ₁₅ ester group or a C ₆ -C ₂ aryl group which is unsubstituted or substituted with a substituent, and the substituent is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or a silicon atom. C ₃ - C ₁₅ ester group is preferably a fluorine-substituted C ₃ - C ₁₅ ester group, the fluorine-substituted C ₃ -C ₁₅ acid ester is a 3, 3, 4, 4, 5, 5 , 6, 6, 7, 7, 8, 8, 8 -tridecafluorooctyl or 2-methyl-propionic acid

2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7-dodefluoroheptyl ester. Said C ₆ - C ₂ . The aromatic group is phenethyl. Said. The fluorenyl group is d- substituted by fluorine. An alkyl group; said dC substituted by fluorine. The alkyl group is 1, 1, 1, 2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8-heptadecyfluorenyl. The present invention relates to a process for preparing a fluorenyl-containing polyfunctional low polypolysiloxane compound represented by the general formula (1), which method comprises the following steps in sequence:

Step (1) can be prepared according to the following recognized technique ^[1 ' ^2] :

That is, a silicon germanium monomer or a mixture thereof, concentrated hydrochloric acid is sequentially added to a one-necked flask equipped with a magnetic stirrer, and then dissolved in a certain amount of methanol solvent, and after refluxing for a while, the mixture is allowed to stand, and then filtered. The supernatant liquid is obtained as a milky white product, and the milky white product is dissolved in dichloromethane, and then added. The methanol solvent was allowed to settle, and after repeated three times, the solvent was evaporated by rotary evaporation, and the solvent was evaporated to obtain a purified fluorenyl-containing low-poly polysiloxane compound (P0SS-SH for short).

The silane monomer or a mixture thereof used in the foregoing step is (3-mercaptopropyl)trimethoxysilane (TPS), (3-mercaptopropyl)trimethoxysilane (TPS) and n-octyltriethoxy a mixture of silicon germanium (0TES)., a mixture of (3-mercaptopropyl)trimethoxysilane (TPS) and phenyltrimethoxysilane (PTMS), (3-mercaptopropyl)trimethoxysilane (TPS) A mixture with 1, 1, 1, 2, 2, 3, 3, 4, 4, 5, 6, 7-dodecafluorodecyltrimethoxysilane (FPTES).

The heating and refluxing means: refluxing at 50-100 ° C for 24-40 hours.

The concentrated hydrochloric acid has a mass concentration range of 35-37%.

[1] H. Z. Liu, S. X. Zheng, K. M. Nie, Macromolecules 2005, 38, 5088-5097.

[2] A. F. Luo, X. S. Jiang, H. Lin, J. Yin, J. Mater. Chem. , 2011 , D0I : 10. 1039/cljral l425e.

Step (2): sequentially adding the thiol-containing low-polysiloxane compound (POSS-SH) prepared above with a double bond-containing monomer and a photoinitiator to a closed reagent bottle with a magnetic stirrer Then, a small amount of dichloromethane solvent is added to dissolve, and the reaction is stirred under ultraviolet light at room temperature. After the reaction is completed, the clear solution obtained by the reaction is sedimented with n-hexane, and after standing for a while, the supernatant liquid is filtered off to obtain a liquid viscosity. Thick sediment. The liquid viscous sediment is dissolved with a small amount of methylene chloride, and the excess hexane is added to carry out product sedimentation. After repeated three times, the finally obtained liquid viscous sediment is subjected to rotary evaporation, and the solvent is evaporated to obtain a general formula (1). a purified product of the compound.

The solvent used in this step may also be one or a mixture of dichloromethane, chloroform, tetrahydrofuran, and toluene. Preferred is dichloromethane, chloroform.

The double bond-containing monomer is selected from a C ₃ -c ₁₅ olefin which is unsubstituted or substituted by a substituent, a C ₃ -c ₁₅ vinyl ether which is unsubstituted or substituted by a substituent, is unsubstituted or substituted by a substituent. c ₃ -c ₂ . (Methyl) acrylate compound. The substituent is a fluorine, chlorine, bromine, iodine atom or a silicon atom, preferably a fluorine atom.

The unsubstituted or substituted C ₃ -C ₁₅ olefin, preferably 1H, 1H, 2H-perfluoro-1-decene, 1H, 1H, 2H-perfluoro-1-hexene, styrene , p-methylstyrene or 2, 3, 4, 5, 6-pentafluorostyrene.

The unsubstituted or substituted C ₃ -C ₁₅ vinyl ether, preferably 2, 2, 2-trifluoroethyl vinyl ether, 2-perfluoropropoxy perfluoropropyl trifluorovinyl ether . The unsubstituted or substituted c ₃ - c ₂ . (meth) acrylate compound, preferred

1H, 1H, 2H, 2H-perfluorononanol acrylate, 1H, 1H, 2H, 2H-perfluorooctyl acrylate or 1H, 1H, 7H-decafluoroheptyl methacrylate. .

The double bond-containing monomer is preferably styrene, 1H, 1H, 2H-perfluoro-1-nonene, 1H, 1H, 2H, 2H-perfluorooctyl acrylate or 1H, 1H, 7H-ten Difluoroheptyl methacrylate.

The photoinitiator is selected from a hydrogen abstraction type or a cleavage type free radical photoinitiator: 1-hydroxycyclohexyl phenyl ketone, benzophenone, isopropyl thioxanthone (abbreviation: ITX), 2, 4 , one or a combination of 6-trimethylbenzophenone, a-hydroxydecyl benzophenone, benzyl diformaldehyde acetophenone or α-aminoalkyl benzophenone (abbreviation . 1-907) It is preferably a combination of α-aminomercaptophenone and isopropyl thioxanthone.

The mass concentration range of the photoinitiator is: 0. 3-3 %;

The time range of the ultraviolet light is: 4-24 hours;

The ultraviolet band: 300-400 nm _;

The molar ratio of the compound P0SS-SH to the content of the double bond-containing monomer is: 1: 1-1: 8. A second invention of the present invention provides an ultraviolet resist composition comprising the compound of the above formula (1) and the compound of the formula (2),

CHRfCR^ (2)

And in the formula (2) are a hydrogen atom, d-C _2Q fluorenyl group, and dC _{2 , respectively} . Alkoxy, C ₆ - C ₂ . Aromatic group, d-C ₂ . Ester group, C ₃ -C ₂ . a cyclodecyl group, a C ₃ -C _2Q imide group, and the formula (2) may be substituted by a halogen atom or a silicon atom. The compound of the formula (2) is selected from the group consisting of C ₃ -C ₁₅ olefins, C ₃ -C ₁₅ vinyl ethers, C ₃ -C ₁₅ vinyl amides, C ₃ -C ₂ . (Meth) acrylate, the substituent being a fluorine atom or a silicon atom. The _3- ( ₁₅ olefin) is selected from 1-butene, 1-hexene, 1-heptene, perfluorohexene, perfluoroheptene or PFH; the C ₃ - C ₁₅ vinyl ether is selected From vinyl ethyl ether, vinyl butyl ether, vinyl hexane glycol ether, 2, 2, 2-trifluoroethyl vinyl ether or 2-perfluoropropoxy perfluoropropyl trifluorovinyl ether; ₃ - C ₂ (meth) acrylate selected from crotonate, benzyl methacrylate, phenoxyethylene glycol acrylate, 1H, 1H, 2H, 2H-perfluorooctyl acrylate, 1H, 1H, 2H, 2H-perfluorononanol acrylate or 1H, 1H, 7H-dodecafluoroheptyl methacrylate. The compound of the formula (2) in the ultraviolet photoresist composition is Benzyl methacrylate, 1H, 1H, 2H, 2H-perfluorooctyl acrylate, 1H, 1H, 2H, 2H-perfluorononanol acrylate.

The ultraviolet photoresist composition further contains a crosslinking agent and a photoinitiator.

The crosslinking agent in the ultraviolet photoresist composition is selected from a double bond having a functional group of not less than two

C ₃ -C ₁₅ olefin, C ₃ - C ₂ . Acrylate and C ₃ -C ₂ . The methacrylate compound may have a plurality of hetero atom substituents such as a halogen atom or a silicon atom, if necessary. A fluorine atom or a silicon atom is preferred.

The crosslinking agent in the ultraviolet photoresist composition is selected from the group consisting of 1, 4-butadiene, 2,5-dimethyl-1, 5-hexadien-3-ol, and perfluorohexane Alkene, 1,3-diethylene-1,1,3,3-tetramethyldisiloxane, neopentyl glycol diacrylate, 1,6-hexanediol diacrylate, dipropylene glycol diacrylate, 1,6-bis(acryloyloxy)-2,2,3,3,4,4,5,5-octafluorohexanyl, 1,5-bis(acryloyloxy)-2, 2, 3 , 3, 4, 4-hexafluoropentafluorene, trishydroxymethylpropionate trimethacrylate, trimethylolpropane triacrylate (TMPTA). Preferred is 1, 3-diethylene-1,1,3,3-tetramethyldisiloxane, trimethylolpropane triacrylate or 1,6-bis(acryloyloxy)-2. 2, 3, 3, 4, 4, 5, 5-octafluorohexane.

The photoinitiator is a hydrogen abstraction type or a cleavage type free radical photoinitiator selected from the group consisting of 1-hydroxycyclohexyl phenyl ketone, benzophenone, isopropyl thioxanthone (ITX), 2, 4, 6 Or one or a combination of trimethyl benzophenone, α-hydroxyalkylphenone, benzyl diformaldehyde acetophenone or ct-amine decyl ketone (1-907), preferably α - Amino benzophenone (1-907).

Appropriate adjuvants can also be used as needed.

The content of each component in the ultraviolet photoresist composition is: in terms of mass%, the compound of the formula (1) is 5 to 65% by mass, and the compound of the formula (2) is 10 The sum of the mass of each component is 100. The mass of the photoinitiator is 0.3 to 3 mass%, and the sum of the masses of the components is 100.

The content of each component in the ultraviolet photoresist composition is: in terms of mass%, the compound of the formula (1) is 19 to 50% by mass, and the formula (2) The compound is 10 to 50% by mass, the crosslinking agent is 10 to 60% by mass, the photoinitiator is 0.3 to 1% by mass, and the sum of the masses of the components is 100.

The above ultraviolet photoresist composition is prepared by sequentially adding a compound of the formula (1), a compound of the formula (2), a crosslinking agent, a photoinitiator and a desired auxiliary agent to a magnetic stirrer. In a sealed reagent bottle, stir and mix well, dilute with anhydrous chloroform, and then use a filter to micro-filter to prepare an ultraviolet photoresist composition, and store it in the dark at low temperature for use.

The diluted mass concentration of the composition with anhydrous chloroform is: 5-20%;

The ultraviolet photoresist composition is clarified and transparent at a normal temperature of 15 to 30 稀释 when solvent-free dilution. Liquid. The invention also relates to a soft template and a method of manufacturing the same, which is illustrated in Figures 2(A)-(C):

(A). The imprinted UV photoresist 2 of the present invention is spin-coated on the surface of the modified quartz plate 3. The spin coating means that the film was rotated at 300 rpm for 10 seconds, and then the film was rotated at 3000 rpm for 20 seconds to obtain a film thickness of 750 ± 5 nm.

(B) The quartz piece 3 with the ultraviolet photoresist 2 was brought into contact with the quartz template 1 and placed in an imprinting machine. The nanopattern of the quartz template 1 was copied onto the imprinted photoresist 2 under pressure and cured by ultraviolet exposure.

(C). The cured quartz plate 3 with the nanopattern of the quartz template 1 is separated from the quartz template 1 (i.e., demolded) to obtain a soft template 4 having a pattern after curing. Then, the quartz piece 3 with the soft template 4 was further aged at 10 CTC for 3 hours, and used as an imprinted soft template (a combination of the soft template 4 and the quartz plate 3) after aging. The invention also relates to a process for soft stencil imprinting photoresist, as shown in Figures 2(D)-(F):

(D). Spin-coating the existing commercial photoresist 5 on the modified silicon substrate 6, which is: rotating the film at 300 rpm for 10 seconds, and then rotating the film at 5000 rpm for 20 seconds. The film thickness obtained was 500 ± 5 nm.

(E). The quartz plate 3 with the soft template 4 pattern prepared as described above is covered with the soft template 4 in the state of the commercial photoresist 5 as shown in Fig. 2(D). The photoresist 5 is placed in the stamping machine together with the silicon substrate 6. The nanopattern of the soft template 4 was reproduced on a commercial photoresist 5 and cured by ultraviolet exposure. .

(F). The quartz plate 3 with the soft template 4 pattern is detached from the silicon substrate 6 with 7 to obtain a commercial cured film 7 with a pattern, which is a process of soft stencil imprinting of the photoresist. Viscosity:

The viscosity of the UV photoresist composition is calculated by a trace Oswald viscometer at 25 ° C, by the flow time of the liquid sample and water, the sample density and the viscosity of the water. The specific calculation formula is as follows: Pi U

No Po k

Among them, P i and P. For UV photoresist density and water density,

t. The time required for the sample and water to flow through the same volume, respectively, if the viscosity of the reference liquid 0 is known to be at a certain temperature:! . And P _Q , and measured P i, to, ti can determine the viscosity of the sample at this temperature. '

Young's modulus and hardness:

The Young's modulus and hardness of the polymer film formed after curing were measured by an in situ nanomechanical test system (Hysitron TI-900 Tribolndenter; USA) at room temperature, taking the lowest value.

Static water contact angle:

The static water contact angle of the polymer film formed after curing is through the surface angle contactor

(SL200B; USA) obtained by measurement.

Surface energy:

The surface energy of the polymer film formed after curing can be measured by the method described in the following Document 3, that is, by using a surface angular contact meter (SL200B; USA), three different solvents are selected, and the contact angle is measured, and the pass angle is measured. The Young's equation calculates the surface energy of the material ^[4] .

[3] Wang Hui, Gu Yuhua, Qiu Guanzhou, Measurement of surface energy of polymer materials by contact angle method. Journal of Central South University (Natural Science Edition), 2006, 5, 942-947.

The method will be further described in detail below with reference to the accompanying drawings.

The following examples and comparative examples are illustrative of the invention and are not intended to limit the scope of the invention.

Examples of compounds:

Example 1 Preparation of a fluorenyl-containing low polypolysiloxane compound (P0SS-SH)

15.0 ml (3-mercaptopropyl)trimethoxysilane (TPS), 30 ml of concentrated hydrochloric acid (37% by mass) were placed in a one-necked flask equipped with a magnetic stirrer, and 350 ml of a methanol solvent was weighed and dissolved. The mixture was stirred and refluxed at 90 ° C for 24 hours, allowed to stand, and the supernatant liquid was filtered off to obtain a milky white product. The milky white product was dissolved in dichloromethane, and then excess methanol was added to precipitate the product, and after repeated three times, rotary distillation was carried out. Evaporating the solvent to obtain a purified product containing a fluorenyl-based low-poly polysiloxane compound (referred to as P0SS-SH) (please see 1 (a) ) o

Example 2 Preparation of cage octa((Y-mercaptopropyl)silsesquioxane (POSS-SCFA ₆ -SH for short) formed after grafting 1H, 1H, 2H, 2H-perfluorooctyl acrylate

POSS-SH and 1H, 1H, 2H, 2H-perfluorooctyl acrylate (CFA ₆ ) prepared in Example 1 were sequentially added to dichloromethane in a closed reagent bottle with a magnetic stirrer, wherein P0SS The molar ratio of -SH to CFA ₆ is 1:4, and the initiator 1-907 accounts for 5% of the total mass of the entire reaction system. The reaction was stirred under a UV light of 365 nm for 6 hours, and an excess of n-hexane was added to precipitate. After standing, the supernatant was filtered off, and the resulting transparent product was dissolved in dichloromethane, and an excess of hexamethylene precipitate was added. After the reaction was repeated three times, the solvent was evaporated to dryness by rotary evaporation to obtain a purified product of octadecyl (Y-mercaptopropyl)silsesquioxane (P0SS-SCFA ₆ -SH ) (see Fig. 1 (b)).

Example 3 Preparation of caged octameric (γ-mercaptopropyl)silsesquioxane (POSS-SDCFA ₆ - SH) formed by grafting 1H, 1H, 7H-dodecafluoroheptyl methacrylate

In the sealed reagent bottle with a magnetic stirrer, the P0SS-SH obtained in Example 1 was

1H, 1H, 7H-dodecafluoroheptyl methacrylate (DCFA _{6 for} short), added to the dichloromethane in the reagent bottle, wherein the molar ratio of P0SS-SH to DCFA ₆ is 1: 4, initiator 1-907 and ITX account for 5% of the total system quality. The reaction was stirred under a UV light of 365 nm for 6 hours, and then added with n-hexane to precipitate. After standing, the supernatant was filtered off, and the obtained transparent product was dissolved with methylene chloride, and an excess of hexamethylene was added thereto to cause sedimentation. After repeated three times, the solvent was evaporated to dryness by rotary evaporation to obtain purified product P0SS-SDCFA ₆ -SH (see Fig. 1 (c)).

Example 4 Preparation of caged octameric (Y-mercaptopropyl)silsesquioxane (referred to as P0SS-SS-SH) formed after grafting styrene

In a sealed reagent bottle with a magnetic stirrer, the POSS-SH, stupid ethylene obtained in Example 1 was sequentially added to the methylene chloride in the reagent bottle, wherein the molar ratio of POSS-SH to styrene was For 1:4, the initiator 1-907 and ITX account for 5% of the total mass of the system. The reaction was stirred under a UV light of 365 nm for 12 hours, and the precipitate was added to n-hexane. The supernatant was filtered off. After repeated three times, the solvent was evaporated to dryness to give the product POSS-SS-SH (see Figure 1 (d)). .

Example 5 Preparation of caged octameric (Y-mercaptopropyl)silsesquioxane (POSS-SPFDE ₈ -SH) formed by grafting 1H, 1H, 2H-perfluoro-1-nonene

In the sealed reagent bottle with a magnetic stirrer, the P0SS-SH obtained in Example 1 was 1H,1H,2H-perfluoro-1-pyrene (PFDE _{8 for} short), added to the dichloromethane in the reagent bottle, wherein the molar ratio of P0SS-SH to PFDE ₈ is 1:4, initiator 1-907 And IT accounted for 5% of the total system quality, and the light was reacted for 6 hours under a 365 nm UV lamp. After adding hexamidine, the supernatant was filtered off. After repeated three times, the solvent was evaporated to dryness to obtain the product P0SS-SPFDE ₈ - SH. (See Figure 1 (e)).

Examples of compositions:

Example 6 Ultraviolet photoresist composition for imprinting soft template preparation JTHC-B-1

The POSS-SCFA ₆ - SH 0. 30g, 1H, 1H, 2H, 2H-perfluorooctyl acrylate (CFAs) of Example 2 was weighed out. 40g, 1,6-bis(acryloyloxy)-2 , 2, 3, 3, 4, 4, 5, 5-octafluorohexanide 0. 30g, photoinitiator 1-907 0. 005g, and added to the reagent bottle one by one, stir and mix. The obtained mixture was subjected to microfiltration using a 0.25 μm filter, and the obtained UV-ray resist composition of the filtrate was diluted with anhydrous chloroform to a mass concentration of 20%, and stored in the dark for storage.

Example 7 Ultraviolet photoresist composition for imprinting soft template preparation JTHC-B-2

Weigh POST-SCFA ₆ -SH 0. 30g, 1H, 1H, 2H, 2H-perfluorooctyl acrylate (CFA ₆ ) 0. 10g, 1,6-bis(acryloyloxy)-2, 2 , 3,3, 4, 4,5, 5-octafluorohexanide 0. 60g, photoinitiator 1-907 0. 003g, one by one, added to the reagent bottle, stirred and mixed evenly. The obtained mixture was subjected to microfiltration using a 0.25 μm filter, and the obtained UV-ray resist composition of the filtrate was diluted with anhydrous chloroform to a mass concentration of 20%, and stored in the dark for storage.

Example 8 Ultraviolet photoresist composition for imprinting soft template preparation JTHC-B-3

2克, Photoinitiator, P0SS-SCFA ₆ - SH 0. 5g, benzyl methacrylate (BMA) monomer 0. 3g, crosslinker trimethylolpropane trimethacrylate (TMPT) 0. 2g, photoinitiator 1-907 0. 010g, added to the reagent bottle one by one, stir and mix well. The obtained mixture was subjected to microfiltration using a 0.25 μm filter, and the obtained UV-ray resist composition of the filtrate was diluted with anhydrous chloroform to a mass concentration of 20%, and stored in the dark for storage.

Example 9 Ultraviolet photoresist composition for imprinting soft template preparation JTHC-B-4

Weigh POST-SDCFA ₆ - SH 0. 50g, monomer vinyl butyl ether 0. 40g, crosslinker 1, 6 - bis(acryloyloxy)-2, 2, 3, 3, 4, 4, 5, 5-octafluorohexane 0. 10g, photoinitiator 1-907 0. 010g, one by one, added to the reagent bottle, stirred and mixed evenly. The obtained mixture was subjected to microfiltration using a 0.25 μm filter, and the obtained UV-ray resist composition of the filtrate was diluted with anhydrous chloroform to a mass concentration of 20%, and stored in the dark for storage. Example 10 Ultra-violet photoresist composition JTHC-B-5 for embossing was weighed POSS-SS-SH 0. 5g, 1H, 1H, 2H, 2H-perfluorononanol acrylate ( Cg ₈ ) monomer 0. 3g, cross-linking agent 1,3-diethylene-1, 1,3,3-tetramethyldisiloxane oxime 0. 2g, photoinitiator 1-907 0. 005g, one by one Into the reagent bottle, stir and mix well. The obtained mixture was subjected to microfiltration using a 0.25 μm filter, and the obtained UV-ray resist composition of the filtrate was diluted with anhydrous chloroform to a mass concentration of 20%, and stored in the dark for storage.

Example 11 Ultraviolet photoresist composition for imprinting soft template preparation JTHC-B - 6

5克, Crosslinker 1,6-bis(acryloyloxy), respectively, weighed POSS-SPFDE8-SH 0. 2g, 1H, 1H, 2H, 2H-perfluorononanol acrylate (CFA ₈ ) monomer 0. 5g, crosslinker 1, 6-bis(acryloyloxy) -2, 2, 3, 3, 4, 4, 5, 5-octafluorohexanide 0. 3g, photoinitiator 1-907 0. 005g, one by one, added to the reagent bottle, stirred and mixed evenly. The obtained mixture was subjected to microfiltration using a 0.25 μm filter, and the obtained UV-ray resist composition of the filtrate was diluted with anhydrous chloroform to a mass concentration of 20%, and stored in the dark for storage. A comparative example of changing the composition of the composition:

Comparative Example 1 Composition JTHC-A-1

5克, Photoinitiator 1 The POSS-SH 0. 3g, benzyl methacrylate 0. 5g, crosslinker trimethylolpropane trimethacrylate (TMPT) 0. 2g, photoinitiator 1 -907 0. 010g , added to the reagent bottle one by one, stir and mix well. The mixed UV photoresist composition was weighed and dried with anhydrous chloroform to a mass concentration of 5%. The photoresist of the present invention was microfiltered using a 0.25 micron filter, and stored in the dark and frozen to form an ultraviolet photoresist composition JTHC-A-1.

Comparative Example 1 differs from the embodiment of the present invention in that it does not contain any fluorine-containing component in the composition of this comparative example.

Comparative Example 2 Composition JTHC-A-2

The P0SS-SH 0. 3g, 1H, 1H, 2H, 2H-perfluorooctyl acrylate (CFA ₆ ) obtained in Example 1 was weighed separately. 0.4 g, 1,6-bis(acryloyloxy) )- 2,2,3,3,4, 4,5, 5-octafluorohexanide 0. 30g, photoinitiator 1-907 0. 003g, one by one, added to the reagent bottle, stirred and mixed uniformly to form JTHC- A-2.

The system after mixing is turbid and opaque, and phase separation occurs.

Comparative Example 2 differs from the embodiment provided by the present invention in that no grafted fluorine-containing groups are used. Comparative Example 3 Composition JTHC-A-3

4克,光。 Light, tetramethyl (meth) propyl methacrylate (TMPT) 0. 2g, light Initiator 1-9070. 010g, one by one, added to the reagent bottle, stirred and mixed evenly. The mixed composition was weighed to 1. 0 g, which was diluted with anhydrous chloroform to a mass concentration of 5%. The photoresist of the present invention was microfiltered using a 0.25 micron filter and stored in the dark to form an ultraviolet photoresist composition JTHC-A-3.

Comparative Example 3 differs from the embodiment 8 provided by the present invention in that POSS-SCFA ₆ -SH was replaced with tetrakis(3-mercaptopropionic acid) pentaerythritol ester (PTMP).

Comparative Examples of Existing Compositions for Use as Soft Formwork Manufacture: Commercial gum compositions and thiol/olefinic UV photoresist compositions reported in the prior art:

Comparative Column 4 Commercial Gum Dow Corning Sylgard 184 (Polydimethylsiloxane, PDMS for short) composition

Dow Corning SYLGARD 184 Silicone Rubber is a two component kit consisting of liquid components, including essential components and curing agents. The base component and the curing agent are thoroughly mixed in a weight ratio of 10:1. Regardless of the thickness, the mixture will cure into a flexible, transparent elastomer for electronic/electrical packaging and potting applications. Currently, the composition is often used as a thermosetting silica gel for preparing a soft template, and is currently the most commonly used composition for soft template production.

Comparative Example 5 Ultraviolet Photoresist Composition SB4

According to the photoresist provided in the following Document 4 and its corresponding data, the main components include: tetrakis(3-mercaptopropionic acid) pentaerythritol ester (PTMP), tetraethylene glycol divinyl ether (W=300), photoinitiated The agent 2,2-dimethoxy-phenylethanone (DMPA) forms an SB4 ultraviolet photoresist.

[Document 4] L. M. Campos, I. Me inel, R. G. Guino, M. Schierhorn, N. Gupta, G. D. Stucky, C. J. Hawker. Adv. Mater. 2008, 20, 3728-3733.

Comparative Example 6 Ultraviolet Photoresist Composition SB5

According to the photoresist provided in the following Document 4 and its corresponding data, the main components include: tetrakis(3-mercaptopropionic acid) pentaerythritol ester (PTMP), polyethylene glycol diacrylate (W=700), light The initiator 2,2-dimethoxy-phenylethanone forms an SB5 ultraviolet photoresist.

[Document 4] LM Campos, I. Me inel, RG Guino, M. Schierhorn, N. Gupta, GD Stucky, CJ Hawker. Adv. Mater. 2008, 20, 3728-3733. Comparative Example 7 UV photoresist composition SB6

According to the photoresist provided in the following document 4 and its corresponding data, the main components include: tetrakis(3-mercaptopropionic acid) pentaerythritol ester (PTMP), polyethylene glycol diacrylate (W=700), light The initiator 2,2-dimethoxy-phenylethanone forms an SB6 ultraviolet photoresist.

[Document 4] L. M. Campos, I. Me ine l , R. G. Guino, M. Schierhorn, N. Gupta, G. D. Stucky, C. J. Hawker. Adv. Mater. 2008, 20, 3728-3733.

Comparative Example 8 UV photoresist composition T2

According to the photoresist provided in the following Document 5 and its corresponding data, the main components include: tetrakis(3-propionylpropionic acid) pentaerythritol ester (ΡΤΜΡ), 2,2-di-acryloyloxymethyl-butyl acrylate The photoinitiator 2,2-dimethoxy-phenylethanone forms a Τ2 ultraviolet photoresist.

[Document 5] E. C. Hagberg, M. Malkoch, Y. Ling, C. J. Hawker, K. R. Carter. Nano Lett. 2007, 7, 233-237. Example of imprint process:

Example 12 Preparation of Soft Template and UV Imprinting Process Using UV Photoresist Composition JTHC-B-1

Using the ultraviolet photoresist composition JTHC-B-1 provided in Example 6 as the ultraviolet photoresist 2 in FIG. 2, a soft template was prepared by the following method, and used as an imprinted soft template for the imprint process. as shown in picture 2:

1. As shown in Fig. 2(A), the substrate quartz plate 3 and the silicon wafer 6 are modified: the quartz plate 3 and the silicon wafer 6 to be modified are placed in a volume of 98% H ₂ S0 _{4 :} 30% H ₂ 0 ₂ It is treated at a temperature of 150 ° C for 3-7 hours in a mixed solution of 3:1. Acetone and alcohol were washed several times, dried, and then vacuum dried at 120 Torr for 8-12 hours. The dried substrate quartz plate 3 and the silicon wafer 6 were immersed in a mass fraction of 0.2% 3-(trimethoxysilyl) propyl-2-methyl-2-acrylate (MAPTES). In a water toluene solution, seal and store for 4-6 hours. The substrate quartz plate 3 and the silicon wafer 6 were washed with acetone, and nitrogen was blown dry for use, thereby completing the process of modifying the substrate quartz plate 3 and the silicon wafer 6.

甩 Coating on the modified substrate quartz plate 3 by a spin coating process: Using the ultraviolet photoresist JTHC-B-1 provided in Example 6 as the imprinting photoresist 2, the coating film is rotated under the following conditions: 300 rpm, time 10 seconds; high speed 3000 rpm, time 20 seconds, film thickness 750 ± 5 nm.

2. As shown in Fig. 2 (B), the quartz plate 3 with the ultraviolet photoresist 2 is connected to the quartz template 1. Touch and put them together in the press. Vacuum was applied for 3 minutes, and a pressure of 100 N was applied to the quartz template 1 and exposed to an ultraviolet lamp of 365 nm for 3 minutes.

3. As shown in FIG. 2(C), the cured quartz plate 3 with the quartz template 1 and the nano-patterned quartz plate 3 are detached from the detached quartz template 1 (ie, demolded), and a soft template with a pattern after curing can be obtained. 4. Then, the quartz piece 3 with the soft template 4 was further aged at 100 Torr for 3 hours, and used as an embossing template after aging.

4. As shown in FIG. 2(D), the existing commercial photoresist 5 is spin-coated on the modified silicon substrate 6. The spin coating refers to: rotating the film at 300 rpm for 10 seconds, and then The coating film was rotated at 5000 rpm for 20 seconds to obtain a film thickness of 500 ± 5 nm.

5. As shown in FIG. 2(E), the quartz plate 3 with the soft template 4 pattern obtained as described above is oriented to the commercial photoresist 5 with the soft template 4 as shown in FIG. 2(D). The soft template 4 is overlaid on the commercial photoresist 5, and placed in the stamping machine together with the silicon substrate 6. The nanopattern of the soft template 4 was reproduced on a commercial photoresist 5, vacuum was applied for 3 minutes, a pressure of 100 N was applied to the template, and exposure was performed by exposure to a 365 nm ultraviolet lamp for 3 minutes.

6. As shown in Fig. 2(F), the quartz plate 3 with the soft template 4 pattern and the silicon substrate 6 with the 7 are separated from the soft template 4 to obtain a patterned commercial adhesive cured film 7, which is soft. The process of embossing photoresist with a stencil.

Example 13 Preparation of Soft Template and Imprinting Using UV Photoresist JTHC-B-2

The rest of the steps were the same as in Example 12 except that the ultraviolet photoresist JTHC-B-2 of Example 7 was used.

Example 14 Preparation of Soft Template and Imprinting Using UV Photoresist JTHC-B-3

The rest of the steps were the same as in Example 12 except that the ultraviolet photoresist JTHC-B-3 of Example 8 was used.

Example 15 Preparation of Soft Template and Imprinting Using UV Photoresist JTHC-B-4

The rest of the steps were the same as in Example 12 except that the ultraviolet photoresist JTHC-B-4 of Example 9 was used.

Example 16 Preparation of Soft Template and Imprinting Using UV Photoresist JTHC-B-5

The rest of the steps were the same as in Example 12 except that the ultraviolet photoresist JTHC-B-5 of Example 10 was used.

Example 17 Preparation of Soft Template and Imprinting Using UV Photoresist JTHC-B-6

Except that the ultraviolet photoresist JTHC-B-6 of Example 11 was used, the remaining steps were the same as those of Example 12. Comparative Example 9 Preparation of Soft Template (C-1) by UV Photoresist JTHC-A-1

The rest of the steps were the same as in Example 12 except that the photoresist composition JTHC-A-1 formed in Comparative Example 1 was used, and the soft template (C-1) of Comparative Example 1 was formed. :

Comparative Example 10 Preparation of Soft Template from PTMP Ultraviolet Photoresist Composition (C-2)

The remaining steps were the same as in Example 12 except that the photoresist composition JTHC-A-3 formed in Comparative Example 3 was used, and the soft template (C-2) of Comparative Example 3 was formed.

Comparative Example 11 Commercial Adhesive Dow Corning Sylgard 184 (Polydimethylsiloxane, PDMS for short) Preparation of Soft Formwork (C-3)

In addition to using the commercial adhesive of Comparative Example 4, Dow Corning Sylgard 184 (PDMS) and in Example 12, Figure 2 (B), quartz sheet 3 with commercial gum Dow Corning Sylgard 184 (PDMS) Composition 2, with quartz The template 1 is brought into contact and placed together in the stamping machine. A vacuum was applied for 3 minutes, a pressure of 100 N was applied to the stencil, and heat curing was carried out at 10 CTC for 1 hour. In the step (C) of Fig. 2, after the mold was released, it was used as a soft template without further aging treatment, and the rest of the process flow was the same as in Example 12, and the soft template (C-3) of Comparative Example 4 was obtained.

Comparative Example 12 UV Photoresist Composition SB4 Preparation of Soft Template (C-4)

The rest of the procedure was the same as in Example 12 except that the ultraviolet resist composition SB4 of Comparative Example 5 was used, and the soft template (C-4) of Comparative Example 5 was formed.

Comparative Example 13 UV Photoresist Composition SB5 Preparation of Soft Template (C-5)

The rest of the procedure was the same as in Example 12 except that the ultraviolet resist composition SB5 of Comparative Example 6 was used, and the soft template (C-5) of Comparative Example 6 was formed.

Comparative Example 14 UV Photoresist Composition SB6 Preparation of Soft Template (C-6)

The remaining steps were the same as in Example 12 except that the UV resist composition SB6 of Comparative Example 7 was used, and a soft template (C-6) of Comparative 7 was formed.

Comparative Example 15 UV Photoresist Composition T2 Preparation of Soft Template (C-7)

The rest of the procedure was the same as in Example 12 except that the ultraviolet resist composition T2 of Comparative Example 8 was used, and the soft template (C-7) of Comparative Example 8 was formed.

The above compositions were summarized to form Table 1.

Table 1. Composition and content of each photoresist composition and properties after film formation Film-forming properties of photoresist composition of general formula (2) compounding agent (2)

Compound (wt%) compound (wt%) (wt%) (wt%)

1,6-di (propylene)

1H, 1H, 2H, 2 α -Amine thiol

POSS-acyloxy) - Example 6 H-Perfluorooctylbenzophenone Low surface energy, suitable for off

SCFA ₅ -SH 2,2,3,3,4,4,5

JTHC-B-1 based acrylate (1-907) mold, high mechanical properties

29.8%, 5-octafluorohexane

39.9% 0.5%

29.8%

1,6-di (propylene

1H, 1H, 2H, 2

POSS-acyloxy) - Example 7 H-Perfluorooctane 1-907 Low surface energy, suitable for off-

SCFA ₆ -SH 2,2,3,3,4,4,5

JTHC-B-2 based acrylate 0.3% mold, high mechanical properties

29.9%, 5-octafluorohexane

10.0%

59.8%

Trimethylol propyl

POSS- methacrylic acid 垸trimethyl propyl

Example 8 1-907 Low surface energy, suitable for off

SCFA ₆ -SH benzyl ester (BMA) enoate

JTHC-B-3 1.0% mold, high mechanical properties

49.5% 29.7% (TMPT)

19.8%

1,6-di (propylene

POSS-acyloxy) - Example 9 Vinyl butyl ether 1-907 Low surface energy, suitable for off

SDCFA6-SH 2,2,3, 3,4,4,5

JTHC-B-4 39.6% 1.0% mold, high mechanical properties

49.5%, 5-octafluorohexane

9.9%

1H, 1H, 2H, 2 1,3-diethylene - Example 10 POSS-SS-SH H-perfluoride 1,1,3,3-tetramethyl 1-907 Low surface energy, suitable for JTHC-B- 5 49.7% alcohol acrylate disiloxane 0.5% mold, high mechanical properties

29.9% 19.9%

1,6-di (propylene

1Η, 1Η, 2Η, 2

POSS-acyloxy) - Example 11 H-perfluoronucleus 1-907 low surface energy, suitable for off

SPFDE ₈ -SH 2,2,3,3,4,4,5

JTHC-B-6 alcohol acrylate 0.5% mold, high mechanical properties

19.9%, 5-octafluorohexanide

49.7 %)

29.9%

Trimethylol propyl

Methyl methacrylate

Comparative Example 1 POSS-SH 1-907 high surface energy, release benzyl ester enoate

JTHC-A- 1 29.7% 1.0% very difficult

49.5% (TMPT)

19.8%

1,6-di (propylene

1H, 1H, 2H, 2

Acyloxy) - Photoresist Heterogeneous, Comparative Example 2 POSS-SH H-Perfluoroxin 1-907

2,2,3,3,4,4,5 turbid, film-impermeable JTHC-A-2 29.9% alcohol acrylate 0.3%

,5-octafluorohexidine, 39.9%

29.9%

Trimethylol propyl

Four (3-mercaptopropyl

High surface energy of methacrylic acid trimethyl propyl hydride is not suitable. Comparative Example 3. Acid) Pentaerythritol 1-907

Benzyl ester enoate release, low mechanicality JTHC-A-3 ester (PTMP) 1.0%

49.5% (TMPT) can 29.7%

19.8%

Comparative example 4

Low surface energy, should be taken off

Mode, low mechanical property Corning Sylgard

Yes, the graphics are vulnerable to damage 184 Tetrakis(3-mercaptopropyltetraethylene glycol di 2,2-dimethyl

High surface energy, not suitable Comparative Example 5 Acid) Pentaerythritol Vinyl ether Oxy-phenyl

Demoulding, low mechanical composition SB4 ester (PTMP) (W=300) ethyl ketone

Can, graphic damage (DMPA) tetra (3-mercaptopropyl PEG)

High surface energy, not suitable for comparison 6 acid) pentaerythritol acrylate

DMPA release, low mechanical composition SB5 ester (PTMP) (W=300)

Yes, the pattern is easily damaged. Four (3-mercaptopropyl PEG)

High surface energy, not suitable. Comparative Example 7 Acid) Pentaerythritol Acrylate

DMPA release, low mechanical composition SB6 ester (PTMP) (W=700)

Yes, the pattern is easily damaged. Four (3-mercaptopropene acrylic acid 2, high surface energy, not suitable for comparison 8

Acid) pentaerythritol 2-di-acryloyl DMPA release, low mechanical composition T2

Ester (PTMP) oxymethyl-butyl ester, easy to damage graphics

The above-mentioned ultraviolet photoresist composition of the embodiment of the invention, the photoresist composition of the comparative example (commercial adhesive, thiol/olefinic ultraviolet photoresist ^[1 ' ^2] reported in the prior literature) and curing thereof The various films formed later (for example, the film 4 of Fig. 2(C)) were compared in physical properties, and the results are shown in Table 2.

Table 2

A successful UV photoresist composition must first ensure uniformity of the system, no phase separation before and after curing, good stability, and good storage performance. By comparison of the photoresist compositions of Comparative Example 2 and the examples, it can be seen that the composition of POSS-SH and the fluorine-containing acrylic monomer or fluorine-containing olefin is immiscible throughout the system, and significant phase separation occurs. It is obviously not suitable for the nanoimprinting system, and the fluorinated P0SS-SH of the present invention has good compatibility with the fluorine-containing monomer and the crosslinking agent, and all the implementation systems are transparent and uniform, and have good stability. Has good storage performance. At the same time, the UV photoresist provided by the invention has no phase separation behavior after curing, indicating that the cured polymer film has stable mechanical properties and uniform mechanical properties.

As shown in Table 2, the ultraviolet photoresist composition of the present invention has a lower viscosity than the commercial rubber Sylgard 184, so that the pressure required for the corresponding imprinting is relatively small, which is advantageous for low-cost printing and low pressure. It is beneficial to reduce the damage to the quartz template.

As shown in Table 2, the mechanical strength of the polymer film formed by curing the ultraviolet photoresist of the present invention Compared with the commercial photoresist Sylgard 184 and the UV photoresist compositions of Comparative Examples 5-8 (SB4-SB6 and T2), the Young's modulus and hardness are greatly improved due to the introduction of the rigid structure of P0SS, indicating the present invention. The provided UV photoresist composition can have strong mechanical properties if used as a soft stencil material.

Explain the drawings:

Figure 4 is an SEM image, respectively: Figure 4 (a) 200nm lattice quartz template 1; Figures 4 (b), 4 (c) are the JTHC-B-2 UV photoresist composition in the examples, respectively, commercial The pattern of the soft template 4 prepared by the template S1 (d) and Fig. 4 (e) are the two soft templates prepared by the above-mentioned composition of the gel Sylgard 184 composition (Fig. 4 (a)); 4 (b), 4 (c)) sequentially embossed the commercial glue watershed 11120, and cured the pattern of the imprinted polymeric film 7 obtained after demolding.

As can be seen from Figure 4 (c), the cured film of the commercial rubber Sylgard 184 soft template (Fig. 4 (c)) is embossed after demolding due to its small modulus (18 MPa) and hardness (2 IMPa). The resulting soft template (e.g., soft template 4) is clearly deformed and bent, and it is apparent that the softness of the commercial gum Sylgard 184 composition is required for a graphic imprinting process requiring high resolution and high aspect ratio. The template does not guarantee the accuracy of the original pattern. With the embossing pattern formed by the soft template of FIG. 4(c) (for example, the film 7 in FIG. 2), FIG. 4(e) has a large number of lattice-shaped broken arms remaining in the pattern grooves, indicating PDMS is used as a soft template, and the mechanical properties are far from sufficient. Structural fracture occurs during the demolding process, and the embossed pattern is deformed due to the deformation of the soft template pattern. With the embossing film of Fig. 4(d) formed by the soft template of Fig. 4(b), the soft stencil pattern produced by the invention is precise, and the mechanical properties are sufficient to ensure that the microstructure of the soft stencil is not torn, and at the same time ensure The accuracy of the copy.

The use of the ultraviolet photoresist composition of the present invention as a soft template is superior to the above mechanical properties, that is, its surface energy is low. It is well known that the smaller the surface energy of the soft stencil, the smaller the force between the soft stencil and the cured photoresist embossing film, and the more helpful the demolding. As shown in Table 2, the surface energy (53. OmJ/crn- ² ) of the UV-free photoresist JTHC-A-1 (Comparative Example 1) after curing is relatively large, and it cannot be removed at all during the experiment. mold. For the composition of the present invention, since the fluorine-containing group grafted on the POSS-SH is used, the surface energy of the polymer film after ultraviolet curing is remarkably lowered, and a good release effect is exhibited during the experiment. It is illustrated that the cured film of the ultraviolet photoresist composition formed using the compound of the present invention can be used as a soft template in the current nanolithographic preparation process due to its low surface energy. At the same time, the static hydration of the UV photoresist cured film formed by the thiol/olefin composition (SB4-SB6) reported in the existing literature ^[1 ' ^2] The comparison of the antenna angles shows that the UV photoresist cured film provided by the present invention is significantly larger, indicating that the ultraviolet photoresist provided by the present invention has superior hydrophobic properties after curing, and has a small surface tension and contributes to demolding.

By comparing the physical properties of the column 8 (JTHC-B-3) with the comparative example 3 (JTHC-A-3), it was found that the compound (1) P0SS-SCFA provided by the present invention was added in the case where the other components were the same. The composition of the _6- SH composition and the tetrakis(3-mercaptopropionic acid) pentaerythritol ester (PTMP), the resulting cured polymer film differs greatly in performance, and the mechanical properties of the film of Comparative Example 4 (Sylgard 184) For example, the surface energy and hardness are much less than the mechanical properties of the polymer film formed after the curing of the column 8 (JTHC-B-3), thereby further illustrating that the ultraviolet photoresist composition provided by the present invention is added. Inorganic organic hybrid particles (P0SS) have excellent mechanical properties, making them ideal for today's highly demanding nanoimprint processes.

As shown in Fig. 3, Figs. 3(a), (c) and (e) are different structural patterns of the quartz template 1 respectively: (a) 3.00 μιη lattice, (c) 350 nm lattice, (e) 700 nm grating; Figures 3 (b), (d) and (f) respectively utilize a quartz template 1 having Figures 3 (a), (c) and (e) and a UV photoresist JTHC-B-1 combination in the examples, respectively. The corresponding pattern of the soft template produced by the object: (b) 3.00μπι lattice, (d) 350nm lattice, (f) 700nm grating. As shown in the figure, the embossed pattern formed after the embossing process, that is, the pattern of FIG. 2(F) 7 is free from defects, the surface is not peeled off, and the structure is intact, because of its excellent technical effects, from which the present invention is provided. The soft stencil pattern of the photoresist composition is effectively replicated in a wide range, and the nano-sized pattern structure can be embossed in a large area, and has excellent reproducibility.

Figure 5 is a soft template 4 embossed commercial glue Watershed 11120 of different structures and sizes prepared by using the UV photoresist JTHC-B-2 composition of the embodiment, and cured by demoulding to obtain a graphic commercial adhesive. SEM image of film 7: (a) 350 nm grating, (b) 700 nm lattice. As is apparent from Fig. 5, the cured film 7 obtained by using the composition of the present invention has no defects in the pattern, no peeling of the surface, and a complete structure, indicating that the composition of the present invention can be used as a soft template for imprinting. The nano-sized graphic structure is embossed in a large area while being effectively peeled off from the template.

It can also be seen from Fig. 4(d) and Fig. 5 (a and b) that the soft template formed by using the composition of the present invention can not only emboss patterns of different sizes, but also emboss patterns of different structures. Knowing that the glue is used as a soft template can meet the requirements of different sizes and different structural patterns in actual production.

Figure 6 is a (a) pattern of a soft template prepared by using the ultraviolet photoresist JTHC-B-2 composition of the examples, (b) and (c) respectively of the ultraviolet photoresist JTHC of the examples. The soft template prepared by the -B-2 composition and the soft template prepared from the commercial gum Sylgard 184 composition were printed on 10 times of commercial glue. AFM map after Watershed 11120. It can be seen from Fig. 6 (c) that the commercial glue Sylgard 184 is used as a soft template. After 10 times of application, the surface of the soft template becomes rough and the surface is gradually contaminated, which obviously affects the efficiency and pressure of the template. The integrity of the graphic structure formed after printing. As can be seen from Fig. 6(b), the surface structure of the soft template after 10 times of use is substantially unchanged and the structure is complete, compared with the pattern 6 (a) before use, indicating the ultraviolet photoresist provided by the present invention. The use of the composition as a soft template has excellent mold release efficiency and can improve the utilization of the soft form. The present invention relates to a compound of the formula (1), a compound using the compound of the formula (1), and the use of the composition as a soft template in an imprinting process, using the compound (1) and the formula The composition system of the compound (2) is uniform in transparency, good in stability, good in storage property, and also because it has a low viscosity and is convenient for spin coating, and can be ideally applied to an imprint process operation, and the pair is lowered. Damage to the quartz template.

In addition, the composition can also be applied to the preparation of embossed soft stencils, and the embossed soft stencils produced have a large static water contact angle, so that they have superior hydrophobic properties. In addition, because of its small surface energy, it has high mold release property, and the pattern of the quartz plate 1 can be well reproduced on the soft template, and at the same time, it can be expressed that the soft template can be imprinted without defects. The surface has no peeling and a structurally complete pattern, so the soft template has excellent technical effects. In addition, the embossed soft template prepared by the composition has high mechanical strength, is convenient for repeated embossing and does not need to be modified again, and improves the use rate of the soft stencil, and the existing photoresist Compared with the soft template produced, its remarkable technical effects are mainly reflected in:

3. The low surface energy of the soft template helps to improve the demolding efficiency, and the surface of the template does not need further modification. The obtained embossed pattern has no defects, no peeling on the surface and complete structure.

Claims

A fluorenyl-containing polyfunctional group-containing low-poly polysiloxane compound represented by the formula (1), (SiO _{L 5} Ri ) m · (Si0 _{1 5} CH ₂ CH ₂ C SR ₂ ) n (1)

among them! ^ Is _{_{_{- CH 2 - CH 2 -CH 2}}} - SH, m represents an integer of 3~12; R ₂ are unsubstituted or substituted alkyl with the substituent group, unsubstituted or substituted with an ester group and an unsubstituted Or an aromatic group substituted with a substituent, wherein the substituent is a halogen atom or a silicon atom, and n represents an integer of 1 to 12.

The compound according to claim 1, which is unsubstituted or substituted by a C _W alkyl group, an unsubstituted or substituted C ₃ -C ₁₅ ester group, or an unsubstituted or The C ₆ -C _2Q aryl group substituted by a substituent which is a fluorine atom, a chlorine atom, a bromine atom, an iodine atom or a silicon atom.

The compound according to claim 2, wherein the C ₃ -C ₁₅ ester group is a C ₃ -C ₁₅ ester group substituted by fluorine.

The compound according to claim 3, wherein the fluorine-substituted C ₃ -C ₁₅ ester group is propionic acid 3, 3, 4, 4, 5, 5, 6, 6, 7 , 7, 8, 8, 8-tridecafluorooctyl or 2-methyl-propionic acid

2, 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7-dodefluoroheptyl ester.

The compound according to claim 2, wherein the C ₆ - C _{2 is} . The aromatic group is a stupid ethyl group.

The compound according to claim 2, wherein the d-C,. Sulfhydryl is replaced by fluorine

Cio Academy.

The compound according to claim 6, wherein the d- is substituted by fluorine. The alkyl group is 1, 1 , 1 , 2 , 2, 3, 3, 4, 4, 5, 5, 6, 6, 7, 7, 8, 8-heptadecyfluorenyl.

A composition for preparing a soft template in an imprint process, comprising the compound of claim 1-7.

The composition according to claim 8, further comprising a compound of the formula (2), a crosslinking agent and a photoinitiator,

CHR CR ₂ R ₃ (2)

In the general formula (2), R ₂ and R ₃ are each a hydrogen atom and dC ₂ . Alkyl, dC ₂ . Alkoxy, C ₆ - C ₂ . An aryl group, (^(: ₂酉基, C ₃ -C ₂ . Cyclodecyl, C ₃ -C ₂ . imide group, the formula (2) may be a halogen atom or a silicon atom Replace.

The composition according to claim 9, wherein the compound of the formula (2) is selected from the group consisting of C ₃ -C ₁₅ olefins, C ₃ - C ₁₅ vinyl ethers, C ₃ -C ₁₅ ethylene Carboxamide, C ₃ -C ₂ . (Meth) acrylate, the substituent being a fluorine atom or a silicon atom.

The composition according to claim 10, wherein the C ₃ -C ₁₅ olefin is selected from the group consisting of 1-butene,

1-hexene, 1-heptene, perfluorohexene, perfluoroheptene or fluorohexylene; the c ₃ - c ₁₅ vinyl ether is selected from the group consisting of vinyl ethyl ether, vinyl butyl ether, vinyl hexan Alcohol ether, 2, 2, 2-trifluoroethyl vinyl ether or 2-perfluoropropoxy perfluoropropyl trifluorovinyl ether; said C ₃ - C ₂ . (Meth)acrylate is selected from crotonate, benzyl methacrylate, phenoxyethylene glycol acrylate, 1H, 1H, 2H, 2H-perfluorooctyl acrylate, 1H, 1H, 2H, 2H - Perfluorodecyl acrylate or 1H, 1H, 7H-dodecafluoroheptyl methacrylate.

The composition according to any one of claims 9 to 11, wherein the compound of the formula (2) is benzyl methacrylate, 1H, 1H, 2H, 2H-perfluorooctyl alcohol Acrylate, 1H, 1H, 2H, 2H-perfluorononanol acrylate.

The ultraviolet photoresist composition according to claim 9, wherein the crosslinking agent is selected from the group consisting of 1, 4-butadiene and 2,5-dimethyl-1,5-hexadiene. - 3-alcohol, perfluorohexadiene, 1,3-diethylene-1,1,3,3-tetramethyldisiloxane, neopentyl glycol diacrylate, 1,6-hexanediol Acrylate, dipropylene glycol diacrylate, 1,6-bis(acryloyloxy)-2,2,3,3,4,4,5,5-octafluorohexane, 1, 5-di(acryloyl) Oxy) -

2, 2, 3, 3, 4, 4-hexafluoropentafluorene, trishydroxymethylpropionate trimethacrylate, trishydroxymethylpropionate triacrylate.

The composition according to any one of claims 8 to 13, wherein the compound of the formula (1) is 5 to 65 mass%, and the compound of the formula (2) is 10 to 60 mass%, crosslinked. The agent is 5 to 45 mass%, the photoinitiator is 0.3 to 3 mass%, and the sum of the masses of the components is 100%.

An embossed soft stencil characterized by being formed by the ultraviolet ray resist composition according to any one of claims 8-14.

16. A method of preparing an embossed soft template, comprising the steps of:

(1). Modified substrate quartz plate (3);

(2) The embossed UV photoresist (2) of the composition of any one of claims 8 to 14 is spin-coated on the surface of the modified quartz plate (3) under the following conditions: After rotating the coating film for 10 seconds at rpm, the coating film was rotated at 3000 rpm for 20 seconds to obtain a film thickness of 750 ± 5 nm _.

(3). The quartz plate (3) with the UV photoresist (2) is brought into contact with the quartz template (1), placed in an imprinting machine, evacuated for 3 minutes, and 100 N is applied to the quartz template (1). Pressure, UV exposure for 3 minutes, to be photoresist After curing, demolding was carried out, and aging was continued for 1 hour at ioo °c. The aged polymer was used as an embossed soft template to form a soft template (4).

17. A process for imprinting a photoresist and an embossed pattern produced thereby, characterized in that the soft template of claim 15 is used.