KR100634846B1 - Inorganic polymer negative photoresist - Google Patents

Abstract

Inorganic polymer type of negative photoresist composition is provided to produce ceramic pattern/structure of two or three-dimensional microfine inorganic polymer employed in lithography process by chemically introducing various photo-sensitive functional group in the inorganic polymer and embodying rapid cross-linking the polymer with UV at ordinary temperature. The photo-polymerization type of negative photoresist reformed polymer is generated by reaction of a polymer containing a repeating unit represented by the formula(1) with any one compound represented the formula(2). In the formula(1), Ra, Rb and Rc are independently selected from H, ORd, NHRd, vinyl or linear or branched lower alkyl group with 1-10 carbon atoms; Rd is H or linear or branched lower alkyl group having 1-10 carbon atoms; n, m and k are integers of 1 to 200, and in the formula(2), the compound is one compound selected from: (a) acryl compound; (b) epoxy compound; (c) vinyl compound; and (d) cinnamoyl compound. The negative photoresist composition comprises the negative photoresist reformed polymer, organic solvent and photo-initiator.

Description

Inorganic Polymer Negative Photoresist Composition

1 is a ¹ H NMR spectrum of a photoresist polymer according to Synthesis Example 1 of the present invention.

2 is a ¹ H NMR spectrum of a photoresist polymer according to Synthesis Example 2 of the present invention.

3 is a photoresist pattern photograph formed using the photoresist composition according to Example 3 of the present invention.

4 is a photoresist pattern photograph formed by using a two-photon absorption method of a photoresist composition according to a fourth embodiment of the present invention.

A general organic polymer photoresist is a photosensitive sacrificial material that is finally completely removed as a tool material of a photolithography process for transferring a mask pattern onto a silicon wafer in the manufacture of a microcircuit of a semiconductor device.

However, in the present invention, the inorganic polymer negative photosensitive photoresist composition is a photolithography process using an ultraviolet (UV) light source to produce a specific pattern and microstructure is the same as the organic polymer photoresist but is not removed as a sacrificial layer after pattern transfer. As the cured inorganic polymer structure is ultimately transferred to ceramic patterns and microstructures through pyrolysis, it is utilized as a ceramic component of a micro device requiring chemical resistance, heat resistance, and abrasion resistance (tribolology). The inorganic polymer pyrolysis method is similar to the principle of obtaining carbon fiber by pyrolysis of organic polymer such as polyacrylonitrile (PAN). That is, a metal such as Si forms a main chain, and organic atoms have been utilized as a ceramic synthesis method in which organic atoms are thermally decomposed and transferred to ceramics attached to main chains and branches.

Since the inorganic polymer negative photosensitive photoresist composition has solubility and meltability compared to the conventional ceramic powder process, it is easy to control viscosity and has good wettability, so that molecular level mixing is possible and moldability is improved. It has the advantage that it can be applied as the base material of fiber, large area coating, composite material. In addition, powder molding should be sintered at 1600 ℃ or higher after completely removing the organic binder, but the inorganic polymer can overcome the problems and disadvantages of the existing ceramic process because it can obtain a uniform ceramic at relatively low temperature of 1000 ℃ through crosslinking reaction. Known as a new ceramic manufacturing process. (Journal of the American Ceramic Society, vol. 75, 1300, 1992. United States Patent, 4,336,215 1982)

Inorganic polymers have been studied since the mid-1970s and Nippon Carbon Co. developed and marketed SiC fibers (trade name: Nicalon) in the 1980s, and various inorganic polymer precursors have been synthesized to produce ceramic fibers, coatings, and ceramic It has been used as a composite material. Oxide-based ceramics using various sol-gel processes are widely used as electronic and structural materials, while SiC and Si ₃ N ₄ ceramics made from inorganic polymers are in commercialization stages in some parts such as fibers. However, in order to secure economic viability as an inorganic precursor, it is necessary to replace the existing ceramic manufacturing process or to develop a high value-added ceramic application and to develop a suitable process.

Synthesis of organic polymers with photocrosslinking properties has been developed for a very long time and utilized in various fields, and their practicality has been proved, but photocrosslinkable inorganic polymers have been partially commercialized only for siloxane polymers. Ceramic Society, vol. 125, 4060, 2003) Despite the significant development history of inorganic polymer precursors for the production of silicon carbide or silicon nitride, it is surprising that there has been no development of photocurable inorganic polymers as ceramic precursors.

At present, most inorganic polymers are transferred to ceramics through a long heat crosslinking process using various catalysts and additives such as dehydrogenation reactions between SiH / vinyl functional groups or SiH / NH functional groups. In addition, a case has been reported in which SiC-based patterns and structures were prepared using a simple mixture of an inorganic polymer and a radical initiator (American Ceramic Society Bulletin, Vol. 80, No. 5 25-29, 2001). Since the crosslinking reaction rate is very slow and requires a photocrosslinking time of several minutes (about 10 minutes) or more, it is impossible to apply a normal photolithography process and thus it is low in application as a photoresist.

To date, examples of fabricating silicon carbide (SiC) -based ceramics, silicon carbide (SiOC), and silicon nitride (Si ₃ N ₄ ) -based ceramic patterns and structures using a negative inorganic polymer photolithography process to a size less than a micron meter None reported.

Accordingly, the present invention is to provide a novel inorganic polymer negative photoresist polymer and its composition to be applicable to a variety of applications,

     The present invention aims to provide an inorganic polymer negative photoresist composition that can be used in various lithography processes to manufacture two-dimensional, three-dimensional fine inorganic polymers and ceramic patterns / structures having a maximum size of 1 cm and a minimum of 10 nm. .

      In addition, an object of the present invention is to provide a method for forming a photoresist ceramic pattern using the photoresist composition and a structure produced by such a method.

In addition, the present invention synthesizes and develops inorganic polymers having rapid photocrosslinking properties by ultraviolet rays or electron beams, and by mixing them with various crosslinking initiators and additives to prepare inorganic polymeric negative photoresist compositions having optimal crosslinking properties. In addition, by using this to manufacture a ceramic pattern and microstructure having a stable physical properties to develop new applications in the future.

In order to solve the above problems, in the present invention, various photosensitive functional groups are chemically introduced into the inorganic polymer to implement a rapid crosslinking reaction by ultraviolet rays at room temperature.

     For the inorganic polymer negative photoresist polymer having such a function and the composition thereof, the polymer structure of the present invention comprises an inorganic polymer including the following repeating units.

[Formula 1]

또는

or

Wherein R _a , R _b and R _c are independently selected from H, OR _d , NHR _d , vinyl or a C ₁ to C ₁₀ straight or branched lower alkyl group, and R _d is H or C ₁ to C _A linear or branched lower alkyl group of 10, n, m and k are integers from 1 to 200, and the polymer polymer composed of repeating units of the above formula also includes an inorganic polymer having a primary amine group at the chain end.)

Inorganic polymer containing the repeating unit contains at least one functional group selected from -H, -OH, -OR, -NHR, vinyl group or alkyl group in the middle or terminal of the polymer, containing a photocurable reactor The photocurable reactor is introduced by condensation reaction with hydrogen, hydrogenation or addition insertion reaction. Photocurable reactors to be introduced are acrylated, urethane acrylated, cinnamoyl, epoxy, vinyl, vinylylstyrene, and the like. The inorganic polymer polymer functionalized by the reactor is synthesized.

The reaction product is a siloxane polymer having a negative photoresist property capable of UV crosslinking and a silazane polymer, and thus, silicon oxide (SiOC) and silicon nitride (Si 3 N 4) -based ceramics can be manufactured.

The photocrosslinking mechanism in which the inorganic polymer composition synthesized as described above is subjected to ultraviolet rays and crosslinks is photocrosslinked by radical polymerization, photocrosslinked by cation polymerization, and photocrosslinked polymerization including a noble metal such as platinum or rhodium. There are three methods of the method, and the present invention belongs to the technical scope of the present invention, which is prepared by any of the three types of photocrosslinking polymerization methods, and the following will be described in detail for the photopolymerization method.

First, the polymerization having crosslinking characteristics by radical mechanisms includes acrylated inorganic polymer, urethane acrylated inorganic polymer, thiol-ene olygomer, and cinnamic acid. (cinnamic acid) substituted inorganic polymer polymer, cinnamilidene acid substituted inorganic polymer polymer, beta-cyanatostyryl acrylic acid substituted inorganic polymer polymer, and the like.

Photoinitiators of the radical mechanism include benzoin ether, benzoth ether, diethoxy acetophenone, dioctanoate dibutyletain, benzoin, xanthone, tea Oxanthone, isopropyltloxanthone, benzophenone, quinone, and siloxane containing benzophenone. In addition, the reaction rate is fast, and thiol propyl dimethyl siloxane (thiolpropyl dimethyl siloxane), which is not sensitive to moisture, undergoes cross-linking reaction of vinyl or acrylate polymer with benzophenone by ultraviolet rays.

Next, polymers having crosslinking properties by cationic mechanisms include epoxy inorganic polymers, vinyl inorganic polymers, styrenic inorganic polymers, and the like. Photoinitiators of the cationic mechanism include aryl diazonium anion salts (ArN ₂ ⁺ Z ⁻ ), which are sometimes moisture sensitive. Z is boron flow rate (BF ₄ ^-) as the nucleophile anion, ferric chlorate (FeCl ₄ ^-), phosphonic sulphonic flow rate (PF ₆ ^-), anti-monik flow rate (SbF ₆ ^-), Al Scenic flow rate (AsF ₆ ^-), carbonyl sulfonate as a triple (CF ₃ SO ₃ ^- and the like) ^-), perchlorate (ClO _4. Onium salts ^{_{(onium salt; Ar 2 I +}} Z -) is more effective as the cationic initiator, diaryl iodo salt (diaryl iodnium salt), diaryl-Chloro salt (diaryl chloronium salt), diaryl-Bromo salt (diaryl bromonium salt), triaryl sulfonium salt, and the like. That is typically used more as bis (p-dodecylphenyl) iodo iodonium anti monik flow rate _{((C 12 H 25 Ø)} 2 I + SbF 6 -), bis (p-butylphenyl) iodo iodonium al Scenic and the like flow rate ^{_{((BuØ) 2 I + AsF}} 6 - -), triphenyl sulfonium anti monik flow rate ^{_{(Ø 3 S + SbF 6)}} .

Finally, crosslinked polymers containing silicon hydride (Si-H) / silicone vinyl (Si-vinyl) functional groups, including noble metals such as platinum or rhodium. In this case, photosensitive initiators and other additives suitable for each mechanism are suitably used to crosslink by light or electron beam to act as negative photoresist.

In the present invention, UV (UV) cross-linkable inorganic polymers are developed to utilize 2D and 3D of maximum 1cm, minimum 10nm size by using already developed devices such as UV lithography imprinting lithography process that is photolithography or lithography equipment. It includes the development of a process for manufacturing patterns and structures, and also includes a process for mass production of ceramic patterns having excellent high temperature stability, friction, and wear characteristics according to subsequent heat treatment processes. This will be used in the manufacture of applications that can be used in MEMS (Micro Electro Mechanical Systems) devices by establishing a mass production technology of ceramic patterns and structures of various shapes.

In particular, the two-photon absorption photopolymerization method using laser is known to produce high-precision three-dimensional structures without expensive semiconductor processing equipment and masks, and there have been examples of applying them in the manufacture of organic polymers and PDMS (polydimethysiloxane) molds (Applied Physic B. Vol. 77, 485, 2003), which have not been applied to the manufacture of fine ceramic patterns and structures. Stereolithography using two-photon-absorbing dyes allows the fabrication of structures with nanoscale precision by limiting the area of photopolymerization by absorbing two long-wavelength photons to a small focal size of at least 100 nm. It is also possible to manufacture complex three-dimensional structures using bitmap picture files. (Applied Physic A. Vol 73, 561, 2001)

An overview of the steps up to the manufacture of the ceramic pattern and structure using the inorganic polymer photoresist synthesized in the present invention is as follows.

first. Inorganic polymers with photosensitive functional groups are synthesized, and the synthesized inorganic polymers are then subjected to various lithography processes such as stereolithography, imprinting lithography, as well as photolithography. In preparing the crosslinked inorganic polymer pattern and structure having excellent solvent resistance and heat resistance compared to the organic plastic pattern, it can be applied to various micro devices. After the fine pattern is formed, a heat treatment process is performed at 600 to 1200 ° C. under an inert atmosphere such as nitrogen and argon to finally form silicon carbide (SiC), silicon carbide (SiOC), and silicon nitride (Si ₃ N ₄ ) ceramics. Patterns and structures can be obtained.

Specifically, the inorganic polymer thin film is applied to a substrate material for producing a microelement, such as a silicon wafer, and then the coated substrate is heated to evaporate the solvent in the photoresist film. The coated surface of the heated substrate is then exposed by imaging to cause chemical deformation. Visible light, ultraviolet (UV) light, electron beams, X-rays, and the like are imaging rays commonly used in microlithography processes. After the exposure process, the substrate is treated with a developer to dissolve and remove the non-exposed portions of the coated surface of the substrate. Manufacture of silicon carbide (SiC), silicon carbide (SiOC), silicon nitride (Si ₃ N ₄ )) ceramic patterns and structures by using the prepared polymer pattern and the structure itself, or additionally by heat treatment up to 1200 ℃ in an inert atmosphere. do. In addition, by utilizing a variety of existing exposure or non-exposure lithography process, it is possible to manufacture two-dimensional, three-dimensional patterns and structures of various sizes. As described above, manufacturing a specific pattern and a microstructure by a photolithography process using an ultraviolet (UV) light source is the same as that of an organic polymer photoresist and may be used as a sacrificial layer depending on the purpose. When the microstructure pattern is formed by the process according to the present invention, it is a very economical process compared to the expensive process of manufacturing the microstructure by the conventional silicon wafer and glass by various micromachining processes.

Therefore, according to the present invention, it is possible to precisely control the composition and structure of ceramics by synthesizing and modifying inorganic polymers, and by combining various microcircuit manufacturing process technologies, new functional patterns can be developed and used for various microelements. Do. The ceramic device manufactured as described above can be utilized in the development of a micro device application technology having tribology characteristics with low failure rate by improving the efficiency and performance by minimizing the loss due to friction and wear.

In addition, inorganic polymer materials with excellent chemical and thermal stability, compared to various plastic materials with low chemical stability, such as swelling by organic solvents, have a lab on a chip and u-TAS for the reaction / detection of organic compounds. It can be applied to the desktop factory. In particular, the high thermal, chemical stability and wear resistance of non-oxide ceramics can be used in MEMS / NEMS and lab on a chip devices that can operate under high temperature and harsh environments. Furthermore, nano-scale ceramic ultra-fine patterning and structure manufacturing technology using inorganic polymers is expected to be a key process sector that can create future value.

The following describes the means for realizing the object of the present invention in more detail.

The present invention provides a negative photoresist polymer composition comprising a polymerizing repeating unit represented by the following Chemical Formula 1.

[Formula 1]

또는

or

Wherein R _a , R _b and R _c are independently selected from H, OR _d , NHR _d , vinyl or a C ₁ to C ₁₀ straight or branched lower alkyl group, and R _d is H or C ₁ to C _A linear or branched lower alkyl group of 10, n, m and k are integers from 1 to 200, and the polymer polymer composed of repeating units of the above formula also includes an inorganic polymer having a primary amine group at the chain end.)

     In the present invention, the compound that is modified by being substituted by the basic inorganic polymer chain of Chemical Formula 1 includes the compound of the following Chemical Formula 2.

[Formula 2]

(A) an acryl compound;

Wherein R is hydrogen or saturated hydrocarbon of C ₁ to C ₃ , R ′ is absent or is C ₁ to C ₂₀ saturated hydrocarbon, Y is hydroxy (OH), isocyanate (CNO), vinyl , Or halogen.)

(B) epoxy compounds;

(Wherein R 'is absent or is C ₁ to C ₂₀ saturated hydrocarbon, Y is hydroxy (OH), isocyanate (CNO), vinyl, halogen).

(C) vinyl compounds; or

(D) Cinnamoyl compounds.

(Wherein R 'is absent or is C ₁ to C ₂₀ saturated hydrocarbon, Y is hydroxy (OH), isocyanate (CNO), vinyl, halogen).

These reactors were polymerized by acrylated, urethane acrylated, cinnamoyl, epoxy, and vinyl functionalized polymers by condensation reaction, hydrogen siliconization reaction, addition insertion reaction, etc. Negative photoresist acrylated polymer, acrylated silazane polymer, urethane acrylated siloxane polymer, urethane acrylated silazane polymer, cinnamoyl siloxane polymer, cinnamoyl silazane Polymer, epoxy siloxane polymer, epoxy silazane polymer, vinyl siloxane polymer, vinyl silazane polymer.

The negative photoresist composition of the present invention provides the negative photoresist composition comprising the photoresist polymers and comprising an organic solvent and a photoinitiator.

The organic solvent may be any organic solvent commonly used in photoresist compositions, preferably tetrahydrofurane, toluene, benzene, propylene glycol monomethyl ether acetate glycol monomethyl ether acetate) is used at a ratio of 0 to 80% by weight relative to the polymer, to obtain a photoresist film of the desired thickness.

The photoinitiator uses a photoinitiator suitable for the method selected from photocrosslinking by radical polymerization, photocrosslinking by cation polymerization, and photocrosslinking polymerization method including noble metals such as platinum or rhodium, and specific compounds thereof As described above. Since the addition ratio of the photoinitiator used in the present invention is a range generally known in the art, further description is omitted.

The photoresist composition according to the present invention further contains a noble metal catalyst or a two-photon absorption dye selected from platinum or rhodium catalysts. The catalyst or two-photon absorbing dye becomes an essential component for causing a three-dimensional limited selective crosslinking reaction by two-photon absorption method during exposure. An example of the catalyst is cyclopentadienylmethyl trimethylplatinum, and an example of the two-photon absorption dye is TP-Flu-TP2, which is known in the art, and thus, further description thereof will be omitted.

The present invention also provides a negative photoresist pattern forming method comprising the following steps.

(a) forming a photoresist film by applying the photoresist composition according to the present invention to a substrate material for producing a microelement;

(b) exposing the photoresist film to an exposure source;

(c) developing the exposed product to obtain a photoresist pattern.

In the process may further comprise the step of performing a soft bake process before the exposure of step (b), or a post-baking process after the exposure of step (b), the baking process is preferably performed at 40 to 95 ℃ . The reason for this process is to evaporate the solvent so that photopolymerization can occur well.

Meanwhile, the developing step (c) may be performed using a developer such as tetrahydrofurane, toluene, benzene, propylene glycol monomethyl ether acetate, ethanol, or the like. Can be.

In addition, the substrate may be Si, glass, etc., depending on the application, but may be any material as long as it is stable at the heat treatment temperature for transition to ceramic. The exposure process is preferably performed at an exposure energy of 1 to 100 mJ / cm ² using mainly UV (selection of wavelength 250 to 850 nm), E-beam, laser beam or ion beam as a light source.

     The mechanism of action of the inorganic polymer negative photoresist according to the present invention is that the modified polymer of Chemical Formula 1 undergoes a crosslinking reaction and becomes insoluble when subjected to ultraviolet light, so that it is present as a pattern or structure without being removed in a subsequent development process. On the other hand, since the crosslinking reaction does not occur in the case of non-exposed sites, the mask phase may be left as a negative image by being dissolved and removed in a subsequent development process.

In the exposing step, two-dimensional or three-dimensional photoresist pattern structures are formed by three-dimensionally limiting selective crosslinking of an exposure region causing photopolymerization by using a two-photon absorption method using a femto laser.

     The present invention also provides an inorganic pattern structure prepared by heat-treating a two-dimensional or three-dimensional photoresist pattern structure prepared according to the above-described manufacturing method under an inert gas atmosphere. The inert gas is nitrogen or argon, the heat treatment temperature is 600 to 1200 ℃.

Hereinafter, the present invention will be described in detail by examples. However, the examples are only to illustrate the invention and the present invention is not limited by the following examples.

Synthesis Example 1 Preparation of Photoresist Modified Polymer (1)

4 g of a compatible polysilazane having a vinyl group and a Si-H functional group (manufactured by KiON Co., USA) and 2 g of 2-isocyanatoethyl methacrylate (2-isocyanatoethyl methacrylate) were added to 14 g of toluene. After homogeneous mixing, the reaction was carried out at 50 ° C. for 24 hours. Subsequently, the material which did not react with the solvent under vacuum was removed to prepare a polyureasilazane including a vinyl acrylate unit of Formula 2 below.

¹ H-NMR (600 MHz, CDCl ₃ ) δ 8.16, 5.15 ppm (CO-N H ), 6.05 & 5.55 (C = C H ₂ ), 5.92-5.71 (Si-CH = CH ₂ ), 4.61-4.34 (Si H ), 4.21-4.10 (-CH ₂ -O), 3.84-3.39 (-C H ₂ -N), 1.85 (C H ₃ -CH), 0.83 (N- H ), 0.26-0.09 (Si-C H ₃ )

Scheme 1

Synthesis Example 2 Preparation of Photoresist Modified Polymer (2)

    After dissolving 3.15 g of trivinyl trimethyl cyclotrisilazane in 20 g of tetrahydrofuran and mixing 8.74 g of triethylamine, 6 g of cinnamoyl chloride was added dropwise to 5 g of tetrahydrofuran over 10 to 30 minutes. After the reaction temperature was reacted at 0 ° C. for 12 hours, a substance not reacted with the solvent was removed under vacuum to prepare a silazane composition including cinnamoyl units.

¹ H NMR (300 MHz, C ₆ D ₆ ) δ 6.31-7.68 (CH = CH), 5.73-6.17 (SiCH = CH ₂ ), 0.09-0.33 (Si-CH ₃ )

Scheme 2

Example 1 Preparation of Negative Photoresist Composition (1)

    5 g of polyureasilazane obtained in Synthesis Example 1 and 0.25 g of Igacure 500, an optical crosslinking initiator, were dissolved in 5 g of organic solvent toluene and filtered through a 0.2 μm filter to obtain a photoresist composition. Commercial photoinitiator Igacure 500 consists of a mixture of 50% by weight of 1-hydroxycyclohexyl-phenylketone and 50% by weight of benzophenone.

Example 2 Preparation of Negative Photoresist Composition (2)

    3 g of polycinnamoylsilazane obtained in Synthesis Example 2 and 0.15 g of Igacure 500 (Irgacure 500), a photocrosslinking initiator, were dissolved in 7 g of an organic solvent propylene glycol monomethyl ether acetate (PGMEA) and filtered through a 0.2 μm filter. A composition was obtained.

Example 3 Photoresist Pattern Formation

    The photoresist composition obtained in Example 1 was spin coated on a silicon wafer and then baked at 80 ° C. for 90 seconds. After baking, the UV light of 40 kW / cm 2 was exposed for 1 minute using a mask and an ultraviolet exposure apparatus, and then baked again at 80 ° C for 1 hour. After baking, a developing process was performed to obtain a 100 nm pattern (see FIG. 3).

Example 4 Photoresist Pattern and Structure Formation by Two-Photon Absorption Method

0.5 g of the photoresist composition obtained in Example 1 and two-photon absorption dye TP-Flu-TP2 (2,7-dibromo-9,9-diethylhexyl-9H-fluorene and diphenyl (4-vinyl phenyl) amine by Heck reaction Synthesis) 1 wt% is uniformly mixed with 1 g of tetrahydrofuran, an organic solvent, and the solvent is removed by vacuum volatilization. Then, one drop of the photoresist mixed composition (<2cc) was dropped on the transparent quartz glass (200 nm or less in thickness), and then subjected to exposure crosslinking using a femto laser exposure apparatus (variable range 750 to 850 nm). At this time, an exposure region (voxel of at least 100 nm) that absorbs two photons of long wavelength and causes photopolymerization can be selectively controlled in a three-dimensional space. Accordingly, by continuously crosslinking the exposure area in two or three dimensions, it is possible to manufacture a two-dimensional or three-dimensional structure having nano-scale precision. Subsequently, through a developing process using ethanol, a three-dimensional nanoporous hexahedron having a width of 140 and 230 nm, and the linear patterns were stacked one by one, and having a lower side of 9 μm and a height of 7 μm. In addition, it is possible to obtain the same result by using the platinum catalyst of cyclopentadienyl trimethyl platinum, methyl (η ⁵ -cyclopentadienylmethyl trimethylplatinium) instead of two-photon absorbing dye. (See Fig. 4)

Example 5 Ceramic Pattern Formation

The inorganic polymer photoresist pattern obtained in Example 3 was heat-treated to 800 ° C. under a nitrogen stream to obtain 140 nm and 230 nm linear patterns, respectively. On the other hand, the three-dimensional nanoporous inorganic polymer hexahedron having a lower side of 9 μm and a height of 7 μm obtained in Example 4 was transformed into a ceramic pyramid by shrinkage during heat treatment up to 800 ° C. under a nitrogen stream. In particular, it is well known that the shrinkage phenomenon increases as the distance from the contact surface with the substrate increases (see FIGS. 3 and 4).

As described above, by using a negative photoresist composition including an inorganic polymer that causes a crosslinking reaction during exposure, it is possible to form a ceramic fine pattern having excellent high temperature stability, friction, and wear characteristics.

Claims (14)

A photopolymerizable negative photoresist modified polymer produced by reacting a polymer comprising a polymerizing repeating unit represented by the following Chemical Formula 1 with a compound of the following Chemical Formula 2. [Formula 1]

or

Wherein R _a , R _b and R _c are independently selected from H, OR _d , NHR _d , vinyl or a C ₁ to C ₁₀ straight or branched lower alkyl group, and R _d is H or C ₁ to C _A linear or branched lower alkyl group of 10, n, m and k are integers from 1 to 200, and the polymer polymer composed of repeating units of the above formula also includes an inorganic polymer having a primary amine group at the chain end.) [Formula 2] (A) an acryl compound;

Wherein R is hydrogen or saturated hydrocarbon of C ₁ to C ₃ , R ′ is absent or C ₁ to C ₂₀ saturated hydrocarbon, Y is hydroxy (OH), isocyanate (CNO), vinyl (vinyl) , Or halogen.) (B) epoxy compounds;

(Wherein R 'is absent or is C ₁ to C ₂₀ saturated hydrocarbon, Y is hydroxy (OH), isocyanate (CNO), vinyl, halogen). (C) vinyl compounds; or (D) Cinnamoyl compounds.

(Wherein R 'is absent or is C ₁ to C ₂₀ saturated hydrocarbon, Y is hydroxy (OH), isocyanate (CNO), vinyl, halogen). The method of claim 1, The photopolymerizable negative photoresist modified polymer is an acrylated siloxane polymer, an acrylated silazane polymer, a urethane acrylated siloxane polymer, a urethane acrylated silazane polymer, a cinnamoyl siloxane polymer, a cinnamoyl silazane polymer, an epoxy siloxane. A photopolymerizable negative photoresist modified polymer, characterized in that it is any polymer selected from polymers, epoxy silazane polymers, vinyl siloxane polymers or vinyl silazane polymers. A photopolymerizable negative photoresist composition comprising the photopolymerizable negative photoresist modifier of claim 1, an organic solvent and a photoinitiator. The method of claim 3, wherein The organic solvent is at least one component selected from tetrahydrofurane, toluene, benzene or propylene glycol monomethyl ether acetate, and the organic solvent is used at 80 wt% or less with respect to the polymer. Photopolymerizable negative photoresist composition, characterized in that. The method of claim 3, wherein The photoresist composition is a photopolymerizable negative photoresist composition, characterized in that it further comprises a noble metal catalyst, or two-photon absorption dye selected from platinum or rhodium catalyst. The method of claim 5, The noble metal catalyst is cyclopentadienylmethyl trimethyl platinum (η ⁵ -cyclopentadienylmethyl trimethylplatinium) photopolymerizable negative photoresist composition. (a) applying a photoresist composition of any one of claims 3 to 6 to a substrate to form a photoresist film; (b) exposing the photoresist film to an exposure source; And (c) developing the resultant to obtain a photoresist pattern; Photoresist pattern forming method comprising a. The method of claim 7, wherein A method of forming a photoresist pattern further comprising the step of performing a soft bake process before exposure of step (b) or a post bake process after exposure of step (b). The method of claim 7, wherein And the exposure source is selected from UV, E-beam or laser beam. The method of claim 7, wherein A method for forming a two-dimensional or three-dimensional photoresist pattern by three-dimensionally limiting selective crosslinking of an exposure region causing photopolymerization. A method of manufacturing an inorganic pattern structure by heat-treating a photoresist pattern prepared by any one of claims 7 to 10. The method of claim 11, The heat treatment is a method for producing an inorganic pattern structure, characterized in that carried out at 600 ℃ to 1200 ℃ under a stream of nitrogen. An inorganic fine pattern structure formed by the manufacturing method of claim 11. Functional ceramic pattern element using the inorganic fine pattern structure of claim 13.

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