KR101769099B1 - Preparation method of polymer thin layer, preparation method of polymer-inorganic complex thin layer, polymer thin layer, and polymer-inorganic complex thin layer - Google Patents

Abstract

The present invention relates to a polymer thin film which is produced by using a specific oxetane monomer and which has uniform physical properties and thickness over the entire region, but also has excellent mechanical properties and high heat resistance, a method for producing the same and a method for producing the same, Inorganic composite thin film having high mechanical strength, high mechanical strength and high heat resistance, high airtightness and low water permeability, and a method for manufacturing the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for producing a polymer thin film, a method for producing a polymer-inorganic composite thin film, a method for producing a polymer thin film and a polymer-inorganic composite thin film, COMPLEX THIN LAYER}

The present invention relates to a method for producing a polymer thin film, a method for producing a polymer-inorganic composite thin film, and a method for producing a polymer thin film and a polymer-inorganic composite thin film.

Chemical vapor deposition (CVD) of polymeric materials is a well - known liquid organic synthesis reaction applied to a gas phase reaction process. This process is a process in which a vaporized monomer is activated in a gas phase reactor to perform a polymer polymerization reaction, and a polymer thin film is formed on a substrate. Polymerization polymerization and thin film deposition are simultaneously performed in one process. Therefore, various kinds of polymer thin films have a great advantage that uniform thin films can be formed while maintaining various shapes of micro or nano size on the substrate surface.

In fact, the CVD process is one of the most important and widely used processes in the semiconductor device fabrication process, and has been widely used for deposition of inorganic materials, and the process itself is well developed. The CVD process has important advantages such as ultra-high-purity thin film formation and easy control of interfacial properties. Above all, much of the knowledge required to control the physical properties of thin films through the development experience of conventional CVD processes is well known. Therefore, if a well-developed CVD process is extended to a polymer material with various functions, it is expected that various difficulties that can not be solved through the conventional liquid process can be solved through the CVD process of the polymer thin film.

Initiated chemical vapor deposition (iCVD) using initiators has been widely used to solve the limitations of conventional deposition processes such as the use of volatile organic solvents or the application of high temperature process conditions. This iCVD process is a process in which a polymer thin film is deposited on the surface of a substrate by vaporizing an initiator and a monomer to cause a polymer reaction in a gas phase

Since the iCVD process can form a film with a uniform thickness from the surface of the substrate, the polymer thin film can be formed while maintaining the structure of the substrate with a complicated structure having a nanometer or micrometer size.

However, not only the monomer compounds known to be usable in the iCVD process are limited, but the polymer thin films formed from these monomers often have insufficient mechanical properties, heat resistance and chemical durability in many cases, There are certain limitations in applying the functionality required in the application.

The object of the present invention is to provide a method for producing a polymer thin film having high heat resistance with excellent mechanical properties while having uniform physical properties and thickness over the entire area.

The present invention also provides a method for producing a polymer-inorganic composite thin film having uniform physical properties and thickness over the entire region, high mechanical properties and high heat resistance, high airtightness and low water permeability.

Further, the present invention is to provide a polymer thin film having uniform physical properties and thickness over the entire region, and having excellent mechanical properties and high heat resistance.

The present invention also provides a polymer-inorganic composite thin film having uniform physical properties and thickness over the entire region, high mechanical properties and high heat resistance, high airtightness and low water permeability.

In this specification, thermal decomposition of a gaseous thermal initiator to form radicals; A step of reacting oxetane (Oxetane) substituted with at least one reactive functional group selected from the group consisting of a vinyl group and a (meth) acrylate group and the formed radical; And a step of depositing the polymer obtained in the polymer synthesis step on a substrate.

Also, in the present specification, a method of manufacturing a polymer thin film, And forming an inorganic thin film on the polymer thin film.

In the present specification, a polymer resin containing at least one repeating unit selected from the group consisting of a vinyl-based repeating unit and a (meth) acrylate-based repeating unit and having at least one oxetanyl group substituted on the surface thereof And a glass transition temperature of from 50 캜 to 150 캜.

In addition, the present invention provides a thin film transistor comprising: at least one thin film of the polymer deposition; And an inorganic thin film formed on at least one surface of the polymer deposited thin film.

Hereinafter, a method of preparing a polymer thin film, a method of producing a polymer-inorganic composite thin film, a polymer deposited thin film, and a polymer-inorganic composite thin film according to a specific embodiment of the present invention will be described in detail.

In the present specification, (meth) acrylate is meant to include both acrylate and methacrylate.

According to an embodiment of the present invention, there is provided a method of manufacturing a semiconductor device, comprising: thermally decomposing a thermal initiator on a gaseous phase to form a radical; A step of reacting oxetane (Oxetane) substituted with at least one reactive functional group selected from the group consisting of a vinyl group and a (meth) acrylate group and the formed radical; And a step of depositing the polymer obtained in the polymer synthesis step on a substrate.

The present inventors have found that, when vapor-deposited oxetane substituted with at least one reactive functional group selected from the group consisting of a vinyl group and a (meth) acrylate group in the presence of a radical of a thermal initiator, And the thickness of the polymer thin film having excellent mechanical properties and high heat resistance can be obtained.

The polymer obtained from oxetane substituted with at least one reactive functional group selected from the group consisting of a vinyl group and a (meth) acrylate group has an oxetanyl group on its surface and is subjected to a post-heat treatment to perform a crosslinking reaction It can be said that the thermal stability of the oxetanyl group is higher than that of the monomer containing an epoxy group and the thermal stability can be controlled by preventing the reactive ring from being opened in the process of depositing the polymer thin film .

Accordingly, in the polymer thin film provided by the manufacturing method of one example of the present invention, the reactive ring in the monomer due to the surrounding environment during the vapor deposition process or after the deposition, that is, the opening of the oxetanyl group, Not only can it have good mechanical properties due to the crosslinking reaction through post-heat treatment, but also, due to the high reactivity due to the ring opening of the oxetanyl group, accompanied by the additional organic or inorganic layer deposition process Another organic thin film or an inorganic thin film can be firmly laminated on the surface thereof. The polymer vapor deposition layer is heated to a temperature higher than the glass transition temperature by the temperature applied to the substrate during the deposition of the organic or inorganic film deposited thereon to form a fusion layer or a composite layer having a thickness of several nanometers to several tens of nanometers So that the bonding force between the layers can be further increased.

Specifically, the polymer deposited thin film provided according to the method for producing a polymer thin film may have a glass transition temperature of 50 ° C to 150 ° C, or 70 ° C to 100 ° C. When the polymer vapor-deposited thin film is heat-treated at 100 ° C to 300 ° C, the glass transition temperature of the polymer vapor-deposited thin film may be increased by 30% to 80% before and after the heat treatment. The polymer vapor deposited thin film may have a glass transition temperature of 65 ° C to 270 ° C, 100 ° C to 200 ° C, or 90 ° C to 180 ° C after heat treatment at 100 ° C to 300 ° C.

In addition, in the polymer thin film obtained through the above-described method, besides the byproducts are not only generated, but also the surface of the polymer thin film formed has uniform physical properties, and the amount of reactive functional groups remaining unreacted is small, .

The specific kind and shape of the reactor in which the deposition proceeds are not particularly limited, and a deposition reactor or a deposition chamber known to be usable for a conventional chemical vapor deposition reaction may be used.

The polymer thin film produced may have a thickness of 10 nm to 1,000 nm.

On the other hand, the characteristics of the polymer thin film prepared according to the present invention appear to depend on the oxetanyl group contained in the surface. The oxetanyl group may have higher thermal stability than other organic functional groups such as an epoxy group, and thus oxetane substituted with at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group ) Is heated to 50 ° C or higher, or 80 ° C or higher, or the polymer thin film is heated or dried at 50 ° C or higher or 80 ° C or higher after the preparation, the ring of the oxetanyl group is not opened, Can maintain high reactivity.

Oxetane substituted with at least one reactive functional group selected from the group consisting of a vinyl group and a (meth) acrylate group means a vinyl group, a (meth) acrylate group, or an oxetane compound in which all of them are substituted with one or more do. For example, oxetane substituted with at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group may include a compound represented by the following formula (1).

[Chemical Formula 1]

Wherein R ₁ is - (CH ₂ ) _x H, x is an integer of 0 to 4, R ₂ is a functional group of the following formula (2)

(2)

또는

or

In Formula 2, y and z are each an integer of 1 to 10, R ₃ and R ₄ are each hydrogen or an alkyl group having 1 to 3 carbon atoms, and * indicates a bonding point.

On the other hand, in one example of the production method of the present invention, the gas phase decomposition agent is thermally decomposed to form a radical, and the radical is substituted by oxetane substituted with at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) (Oxetane), and the chain polymerization reaction proceeds to synthesize the polymer. The polymer thin film may be formed as the synthesized polymer is deposited on a predetermined substrate.

The thermal decomposition of the thermal initiator on the gaseous phase can be carried out without any limitation by a generally known method, but a metal filament which is heated and maintained at a high temperature may be used in order to proceed more efficient polymer polymerization.

The step of thermally decomposing the thermal initiator on the gaseous phase to form a radical may include contacting the gaseous thermal initiator with a metal filament heated to a temperature of 150 ° C to 500 ° C or 180 ° C to 300 ° C Step < / RTI >

The temperature of the filament is sufficiently high to pyrolyze the thermal initiator, but oxetane substituted with at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group is not decomposed at such a temperature Do not. Since the driving force used in the polymer polymerization reaction is only the high temperature of the filament and various kinds of monomer materials are not chemically damaged at the temperature of the filament, . ≪ / RTI >

The specific examples of the thermal initiator are not limited to a great extent. In order to apply the vapor deposition reaction, it is preferable to use an initiator that is liquid at room temperature or below the decomposition temperature and is able to vaporize easily when heated to room temperature or below the decomposition temperature while reducing the pressure to below normal pressure to form a flow.

Specific examples of such thermal initiators include peroxides, azo-based compounds, and mixtures of two or more thereof. Although specific examples of the peroxide and the azo compound are not limited, examples of the peroxide include di-tert-butyl peroxide, di-tert-amyl peroxide Azo compounds such as 2,2'-azobis (2-methyl-propane), and the like can be given as azo compounds.

The polymer synthesis step; And the step of depositing the polymer obtained in the polymer synthesis step on the substrate may be carried out under a pressure of 10 mTorr to 5,000 mTorr or 0.1 Torr to 1 Torr, respectively.

In the step of depositing the polymer obtained in the polymer synthesis step on the substrate, the substrate may be maintained at a temperature of -20 캜 to 100 캜, or 0 캜 to 60 캜.

On the other hand, the temperature in the reactor in which the deposition progresses depends on the temperature of the substrate, the temperature at which the step of thermally decomposing the thermal initiator on the gaseous phase to form the radical, the temperature of the polymer synthesis step, And may be about 20 ° C to 200 ° C.

The time for performing the step of depositing the synthesized polymer on the substrate, etc. may be determined according to the thickness and physical properties of the polymer thin film to be finally produced, and may be, for example, 10 seconds to 120 minutes, or 30 seconds to 60 minutes Lt; / RTI >

The method for producing a polymer thin film according to an embodiment of the present invention is characterized in that oxetane or a thermal initiator substituted with at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group is reacted at a temperature of 20 ° C to 200 ° C And further comprising the step of vaporizing.

The apparatus and method that can be used in the vaporizing step are not particularly limited, and examples thereof include a heating mantle, a heating band, a heating jacket, a heating box, a heating block (meth) acrylate group by using at least one of a direct heating device such as a heating block and an indirect heating device such as a water bath to remove oxetane or a thermal decomposition agent substituted with at least one reactive functional group selected from the group consisting of a vinyl group and a The contained vessel may be heated and depressurized to a process or sub-pressurized pressure through a vessel connecting the vessel to the deposition chamber or vacuum pump to vaporize the oxetane or thermal initiator, respectively, or simultaneously.

Meanwhile, the polymer synthesis step may include a step of reacting the gaseous phase of oxetane and the gaseous phase decomposition agent. Specifically, the polymer synthesis step may include a step of synthesizing the metal filament ; And a substrate disposed below the metal filament in a gravitational direction; and a gas containing oxetane gas in which at least one reactive functional group selected from the group consisting of vinyl group and (meth) acrylate group is substituted into the deposition reactor And injecting a thermal initiator on the gaseous phase.

A metal filament heated to a temperature of 150 ° C to 500 ° C; And a substrate disposed below the metal filament in a gravitational direction, wherein the gaseous phase of oxetane and the gaseous phase thermal initiator described above are injected into the deposition reactor including the substrate, Oxetane (Oxetane) in which at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group is substituted with a metal filament heated to a temperature of 150 to 500 ° C and thermally decomposed to form a radical, ) And the chain polymerization reaction proceeds to synthesize the polymer. The synthesized polymer may be deposited on the substrate spaced apart from the metal filament in the gravity direction to form the polymer thin film.

The step of synthesizing the polymer and the step of depositing the synthesized polymer on the substrate may be performed at the same time. That is, the step of reacting the monomer mixture with the formed radical to form the polymer may be performed on the substrate, and the step of depositing the polymer on the substrate at the time of forming the polymer may proceed.

The present invention is not limited to the specific types of the base material on which the synthesized polymer is deposited. For example, a silicon wafer, a glass substrate, a metal substrate, a polymer substrate, a battery separator, a cathode material or a cathode material of a battery, An electric element such as an LCD or an OLED, or other fine electric element.

In addition, the polymer thin film produced may have uniform surface characteristics, and the average surface roughness of the polymer thin film may be 15 nm or less or 0.1 nm to 15 nm.

The average surface roughness of the polymer thin film per 100 nm in thickness may be 3 nm or less, or 0.1 to 3 nm. For example, the polymer thin film having a thickness of 200 nm has an average surface roughness of 6 nm or less.

As described above, the polymer thin film produced may have high mechanical surface properties and heat resistance when the crosslinking reaction proceeds through post-heat treatment. The post-heat treatment temperature may generally be 100 ° C to 300 ° C, and may be treated for 30 minutes to 24 hours. The higher the temperature, the shorter the heat treatment time. For example, the heat treatment at 250 ° C for 1 hour can provide a sufficient effect.

Specifically, the polymer thin film prepared using the weight of 500 g according to ASTM D3363 may have a pencil hardness of HB or higher, or HB to 4H.

The step of reacting oxetane (Oxetane) substituted with at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group and the formed radicals may include reacting the vinyl group and the (meth) (Oxetane) substituted with at least one reactive functional group selected from the group consisting of the above-mentioned reactive groups and a reactive compound containing at least two vinyl groups or (meth) acrylate functional groups together with the formed radicals.

The reactive compound containing two or more of the vinyl groups or (meth) acrylate functional groups can form a polymer thin film having higher mechanical properties, chemical resistance, heat resistance and surface flatness.

The reactive compound containing at least two of the vinyl groups or (meth) acrylate functional groups is preferably a compound having two or more vinyl groups or (meth) acrylate functional groups and having a vapor pressure of 1 mmHg to 100 mmHg at a temperature of 20 캜 to 200 캜 Compounds may be used. Specific examples of the reactive compound containing two or more of the vinyl groups or (meth) acrylate functional groups include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di Propylene glycol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, divinylbenzene and the like.

According to another embodiment of the present invention, there is provided a method of manufacturing a polymer thin film, comprising: preparing a polymer thin film by the method of manufacturing a polymer thin film according to an embodiment of the present invention; And forming an inorganic thin film on the polymer thin film.

In the polymer thin film provided by the manufacturing method of the present invention, reactivity can be maintained because the reactive ring in the monomer due to the vapor deposition process or the surrounding environment after the vapor deposition, that is, the opening of the oxetanyl group, It is possible not only to have excellent mechanical properties due to the crosslinking reaction through post-heat treatment but also to add another organic thin film or inorganic thin film to the surface due to the high reactivity due to the ring opening of the oxetanyl group have.

In addition, the polymer thin film may be heated to a temperature higher than the glass transition temperature by the temperature applied to the substrate during the deposition of the organic or inorganic film deposited thereon, so that the interface can form a fusion layer having a thickness of several nanometers to several tens of nanometers, Thereby further increasing the bonding force between them.

In addition, the polymer thin film has a relatively small degree of change in the degree of thermal decomposition or shape under high temperature conditions that can be applied in the process of forming the inorganic thin film, and thus the uniform thin film of the polymer- . ≪ / RTI >

Accordingly, the polymer-inorganic composite thin film obtained by the method of producing the polymer-inorganic composite thin film can have uniform physical properties and thickness over the whole area, but also have excellent mechanical properties and high heat resistance, high airtightness and low permeability. The polymer layer complements defects such as pinholes in the inorganic film to lower the permeability and complements the low flexibility of the inorganic film, thereby providing properties suitable for application to the moisture barrier layer of the flexible substrate material.

The process for producing the polymer thin film by the method for producing a polymer thin film according to one embodiment of the present invention includes all of the above-mentioned contents regarding the method for producing the polymer thin film of one example of the invention.

The step of forming an inorganic thin film on the polymer thin film may include forming a thin film of an inorganic thin film on the polymer thin film by using a material such as silicon oxide, Zirconium oxide, and zirconium nitride may be vapor-deposited on the substrate.

The vapor deposition can be performed by a plasma chemical vapor deposition (PECVD) method, an atomic layer deposition method, or a sputtering method.

The inorganic thin film may have a thickness of 10 nm to 1,000 nm.

The polymer-inorganic composite thin film to be manufactured may have a multi-layer structure including at least one of the inorganic thin film and the polymer thin film. In order to form the multi-layered structure, the method of producing the polymer-inorganic composite thin film may further include stacking one or more of the inorganic thin film and the polymer thin film. At this time, when the polymer thin film is deposited on the inorganic thin film, the inorganic thin film plays a role of the inorganic thin film in the method of manufacturing the polymer thin film according to one embodiment of the present invention.

According to another embodiment of the present invention, there is provided a resin composition comprising at least one repeating unit selected from the group consisting of a vinyl-based repeating unit and a (meth) acrylate-based repeating unit and having at least one oxetanyl group substituted on the surface thereof A polymeric thin film including a polymer resin and having a glass transition temperature of 50 캜 to 150 캜 can be provided.

(Oxetane) substituted with at least one reactive functional group selected from the group consisting of a vinyl group and a (meth) acrylate group is subjected to a gas phase reaction in the presence of a radical of a thermal initiator as shown in an example of the production method of the above- When the obtained polymer is deposited, a polymer thin film or a polymer thin film having high mechanical strength and high heat resistance can be obtained while having uniform physical properties and thickness over the entire region.

The polymer obtained from oxetane substituted with at least one reactive functional group selected from the group consisting of a vinyl group and a (meth) acrylate group has an oxetanyl group on its surface and is subjected to a post-heat treatment to perform a crosslinking reaction But also the thermal stability of the oxetanyl group makes it possible to control the opening of the reactive ring in the process of depositing the polymer thin film and thus to have high thermal stability.

Accordingly, in the polymer thin film provided by the manufacturing method of one example of the present invention, the reactive ring in the monomer due to the surrounding environment during the vapor deposition process or after the deposition, that is, the opening of the oxetanyl group, Not only can it have good mechanical properties due to the crosslinking reaction through post-heat treatment, but also, due to the high reactivity due to the ring opening of the oxetanyl group, accompanied by the additional organic or inorganic layer deposition process Another organic thin film or an inorganic thin film can be firmly laminated on the surface thereof. In addition, the polymer vapor deposition layer may be heated to a temperature higher than the glass transition temperature by the temperature applied to the substrate during the deposition of the organic or inorganic film deposited thereon, so that the interface can form a fusion layer having a thickness of several nanometers to several tens of nanometers, The bonding force can be further increased.

Specifically, the polymer vapor-deposited thin film may have a glass transition temperature of 50 ° C to 150 ° C, or 70 ° C to 100 ° C. When the polymer vapor-deposited thin film is heat-treated at 100 ° C to 300 ° C, the glass transition temperature of the polymer vapor-deposited thin film may be increased by 30% to 80% before and after the heat treatment. The polymer vapor deposited thin film may have a glass transition temperature of 65 ° C to 270 ° C, 100 ° C to 200 ° C, or 90 ° C to 180 ° C after heat treatment at 100 ° C to 300 ° C.

In addition, since the extent to which the polymer vapor-deposited thin film is thermally decomposed or the degree of the shape change is relatively small even at a high temperature condition which can be applied in the process of forming an organic or inorganic layer on the surface thereof, It is possible to provide a uniform polymer composite thin film without any problems.

The polymer deposited thin film may have a thickness of 10 nm to 1,000 nm.

As described above, the polymer deposited thin film may include a polymer obtained from oxetane substituted with at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group. Specifically, the polymer resin may include at least one selected from the group consisting of repeating units of the following formula (3) and repeating units of the following formula (4).

(3)

 [Chemical Formula 4]

Wherein R ₁ is - (CH ₂ ) _x H, x is an integer of 0 to 4, y and z are each an integer of 1 to 10, R ₃ and R ₄ are Hydrogen or an alkyl group having 1 to 3 carbon atoms, and * denotes a bonding point.

The weight average molecular weight of the polymer resin may be determined by, for example, the amount of the generated binder and the amount of the monomer used in the polymer deposited thin film. For example, the polymer resin may have a weight average molecular weight of 5,000 to 500,000.

In the process of preparing the polymer deposited thin film, a mixture of ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethylene glycol divinyl ether, diethylene glycol divinyl ether, At least one compound selected from the group consisting of triethylene glycol divinyl ether and divinylbenzene may be further used to increase the crosslinking density or mechanical properties of the polymer vapor deposited thin film. Accordingly, the polymer vapor-deposited thin film may further include one or more repeating units derived from the above-described compounds.

According to another embodiment of the present invention, there is provided a polymer deposition thin film of at least one of the above-described embodiments of the present invention; And an inorganic thin film formed on at least one side of the polymer deposited thin film.

The polymeric vapor-deposited thin film can maintain its reactivity because the reactive ring in the monomer due to the surrounding environment, that is, the opening of the oxetanyl group, does not progress during the vapor deposition process or after the vapor deposition, and is excellent as a crosslinking reaction through post- Mechanical properties of the organic thin film or the inorganic thin film can be enhanced by the ring opening of the oxetanyl group due to the additional organic or inorganic layer deposition process, . In addition, the polymer vapor deposition layer may be heated to a temperature higher than the glass transition temperature by the temperature applied to the substrate during the deposition of the organic or inorganic film deposited thereon, so that the interface can form a fusion layer having a thickness of several nanometers to several tens of nanometers, The bonding force can be further increased.

Accordingly, the polymer-inorganic hybrid thin film can have uniform physical properties and thickness over the whole area, but also have excellent mechanical properties and high heat resistance, high airtightness and low water permeability.

In addition, the polymer vapor-deposited thin film has a relatively small degree of change in the degree of thermal decomposition or shape under high temperature conditions that can be applied in the process of forming the inorganic thin film, Thereby enabling provision of a thin film.

Wherein the inorganic thin film is made of a material selected from the group consisting of silicon oxide, silicon nitride, silicon oxynitride (SiON), aluminum oxide, aluminum nitride, titanium oxide, titanium nitride, tantalum oxide, tantalum nitride, hafnium oxide, hafnium nitride, zirconium oxide and zirconium nitride And the like.

The inorganic thin film may have a thickness of 10 nm to 1,000 nm.

The polymer-inorganic composite thin film may have a multi-layer structure including at least one of the inorganic thin film and the polymer thin film.

According to the present invention, there is provided a polymer thin film having uniform physical properties and thicknesses over the entire region, having excellent mechanical properties and high heat resistance, a method for producing the same, and a method for producing the polymer thin film having excellent mechanical properties and uniform physical properties A polymer-inorganic composite thin film having high heat resistance, high airtightness and low water permeability, and a method for manufacturing the same.

1 shows an atomic force microscope (AFM) image of the surface of the polymer thin film obtained in Example 1. Fig.
2 is an atomic force microscope (AFM) image of the surface of the polymer thin film obtained in Comparative Example 1. FIG.
FIG. 3 is a graph showing a change in thickness of the polymer-deposited thin film of Example 1 measured using ellipsometry (spectroscopic ellipsometry). FIG.
FIG. 4 is a graph showing a change in thickness of the polymer-deposited thin film of Example 2 measured using ellipsometry (spectroscopic ellipsometry). FIG.
5 is a transmission electron microscope (TEM) image of a cross section of the polymer-inorganic composite thin film obtained in Example 3. Fig.
6 is a transmission electron microscope (TEM) image of a cross section of the polymer-inorganic composite thin film obtained in Comparative Example 2. Fig.

The invention will be described in more detail in the following examples. However, the following examples are illustrative of the present invention, and the present invention is not limited by the following examples.

[ Example 1 : Production of polymer thin film]

The silicon wafer, which is a deposition substrate, was pre-cleaned with an oxygen plasma and placed inside a thermal-chemical vapor deposition reactor. In the vapor deposition reactor, the surface temperature of the substrate was maintained at 25 ° C, the process pressure was applied at 0.3 Torr, and the hot wire of nickel-chrome (8: 2) was heated to 300 ° C.

Then, a gaseous 3-ethyl 3-oxetanyl methyl methacrylate (CAS 37674-57-0) was injected into the vapor deposition reactor in an amount of 0.3 sccm using a vapor mass flow controller. In the course of injecting the 3-ethyl 3-oxetanyl methyl methacrylate, vaporized tert-butyl peroxide was injected in an amount of 1 sccm using a mass flow controller.

The deposition process was continued for 20 minutes to prepare a polymer thin film having a thickness of 300 nm.

[ Example 2 : Heat Treatment of Polymer Thin Films]

The polymer thin film prepared as in Example 1 was placed in a vacuum oven and heat-treated at 250 ° C for 1 hour.

[ Example 3 : Preparation of Polymer-inorganic Composite Thin Films]

(1) Production of polymer thin film

A polymer thin film having a thickness of 100 nm was prepared in the same manner as in Example 1, except that the above deposition process was carried out for 10 minutes.

(2) Preparation of polymer-inorganic hybrid thin films

Silicon nitride (SiN _x ) was deposited on the polymer thin film by plasma-enhanced chemical vapor deposition (PECVD) to produce a polymer-inorganic composite thin film. Specifically, 850 sccm of nitrogen (N ₂ ) gas, 300 sccm of nitrogen gas containing 5% of silane (SiH ₄ ) gas and 20 sccm of ammonia (NH ₃ ) gas were flowed for deposition of silicon nitride, For 2 minutes to obtain a thin film with a thickness of 100 nm. At this time, the obtained polymer thin film was allowed to stand for 2 minutes in a deposition chamber at 300 ° C prior to the deposition of silicon nitride and heat-treated.

[ Comparative Example 1 : Production of polymer thin film]

A 300 nm thick polymer thin film was prepared in the same manner as in Example 1, except that glycidyl methacrylate epoxy compound was used instead of 3-ethyl 3-oxetanyl methyl methacrylate (CAS 37674-57-0) oxetane compound.

[ Comparative Example 2 : Preparation of Polymer-inorganic Composite Thin Films]

(1) Production of polymer thin film

A polymer thin film having a thickness of 100 nm was prepared in the same manner as in Comparative Example 1, except that the deposition process was carried out for 10 minutes.

(2) Preparation of polymer-inorganic hybrid thin films

On the prepared polymer thin film, silicon nitride (SiN _x ) was deposited by a plasma chemical vapor deposition apparatus in the same manner as in Example 3 to prepare a polymer-inorganic composite thin film.

[ Experimental Example ]

Experimental Example  1: Surface roughness measurement

Scanning was performed on a 10 탆 x 10 탆 area in a tapping mode using an atomic force microscope (Large stage AFM (Veeco Co., Ltd. Dimension 3100)), and the average surface roughness Ra of the polymer deposited thin films obtained in the above Examples and Comparative Examples ) Were measured.

As shown in FIG. 1, it was confirmed that the polymer deposited films prepared in the examples had an average surface roughness value (Ra) of 2.13 nm in a region of 300 nm thickness and 10 μm × 10 μm region, and had a very flat surface shape .

On the other hand, as shown in FIG. 2, the thin film of Comparative Example 1 produced using the epoxy monomer had an average surface roughness (Ra) value of 4.69 nm for a 10 nm x 10 um region of a 300 nm thick deposited film, 1, which has a rough surface.

Experimental Example  2: Measurement of thermal properties

The temperature of the substrate was changed from 30 ° C. to 300 ° C. at a rate of 10 ° C. per minute using ellipsometric spectroscopy (spectroscopic ellipsometry), and the psi and delta values were measured according to the temperatures of the evaporation films obtained in Examples 1 and 2 . The thickness at each temperature was determined by fitting psi and delta values using a Cauchy film model.

As a result of the measurement, as shown in FIG. 3, the polymer vapor deposition layer of Example 1 exhibited a glass transition temperature of about 67 ° C, and it was confirmed that pyrolysis gradually occurred from 160 ° C.

Further, as shown in FIG. 4, it was confirmed that the polymer vapor deposited film of Example 2 subjected to the heat treatment showed a glass transition temperature of about 103 ° C and a thermal decomposition start temperature of 213 ° C. It can be considered that the progress of the crosslinking reaction by the opening of some oxetanyl groups affected the increase of the heat resistance.

Thus, as can be seen from the above results, since the polymer vapor deposition films prepared in Examples 1 and 2 have a glass transition temperature of 70 ° C to 100 ° C, in the course of depositing the inorganic films on the vapor deposition films, The interface between the newly formed inorganic film and the inorganic film can be strengthened and the effect of the crosslinking of the polymer film can be obtained at the same time due to the heat applied to the substrate during the process of depositing the inorganic film.

Experimental Example  3: Cross-section observation of polymer-inorganic composite thin film

The cross sections of the polymer-inorganic composite thin films obtained in Example 3 and Comparative Example 2 were observed using a transmission electron microscope (TITAN G2 80-200 ChemiSTEM). In order to prevent surface damage caused by the ion beam during the specimen preparation process, the specimens were exposed to a specimen at room temperature After forming carbon and Pt protection layer on the surface (SiNx layer), TEM flakes were fabricated.

As shown in FIGS. 5 and 6, the transmission electron microscope results showed that the thicknesses of the silicon nitride inorganic layers in both samples of Example 3 and Comparative Example 2 were about 105 to 107 nm, Was about 90 nm in Example 3, and about 60 nm in Comparative Example 2. This is because the polymer thin film of Comparative Example 2 (including the epoxy group) is superior to the polymer thin film (oxetanyl group-containing polymer deposition layer) of Example 3 in the heat treatment process of the polymer thin film in the deposition chamber at 300 ° C prior to the silicon nitride ) Is more susceptible to heat, leading to more loss of film.

Claims (25)

Pyrolyzing the gaseous thermal initiator to form a radical;
A step of reacting a gaseous phase of oxetane substituted with at least one reactive functional group selected from the group consisting of a vinyl group and a (meth) acrylate group and the formed radical; And
And depositing the polymer obtained in the polymer synthesis step on a substrate,
The polymer synthesis step; And the step of depositing the polymer obtained in the polymer synthesis step on the substrate is carried out under a pressure of 10 mTorr to 5,000 mTorr,
A glass transition temperature of 50 ° C to 150 ° C, a glass transition temperature of 30 ° C to 80% before and after the heat treatment at 100 ° C to 300 ° C,
A method for producing a thin polymer film having a thickness of 10 nm to 1,000 nm.
delete The method according to claim 1,
Wherein the step of thermally decomposing the thermal initiator on the gaseous phase to form a radical comprises contacting the gaseous thermal initiator with a metal filament heated to a temperature of from 150 ° C to 500 ° C.
The method according to claim 1,
Wherein the thermal initiator comprises at least one selected from the group consisting of a peroxide and an azo compound.
The method according to claim 1,
Oxetane substituted with at least one reactive functional group selected from the group consisting of a vinyl group and a (meth) acrylate group includes a compound represented by the following Formula 1:
[Chemical Formula 1]

In Formula 1,
Wherein R ₁ is - (CH ₂ ) _x H, x is an integer from 0 to 4,
Wherein R ₂ is for a functional group of Formula 2,
(2)

or

In Formula 2,
y and z are each an integer of 1 to 10,
R ₃ and R ₄ are each hydrogen or an alkyl group having 1 to 3 carbon atoms,
* Denotes the coupling point.
The method according to claim 1,
The step of reacting oxetane (Oxetane) substituted with at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group and the formed radical,
(Oxetane) substituted with at least one reactive functional group selected from the group consisting of a vinyl group and a (meth) acrylate group, and a reactive compound containing at least two vinyl groups or (meth) acrylate functional groups together with the formed radical And a step of reacting the polyimide precursor with the polyimide precursor.
The method according to claim 6,
The reactive compound containing two or more of the vinyl group or (meth) acrylate functional group may be at least one selected from the group consisting of ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di And at least one selected from the group consisting of divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, and divinylbenzene.
delete The method according to claim 1,
Wherein the substrate is maintained at a temperature of 0 캜 to 60 캜 in the step of depositing the polymer obtained in the polymer synthesis step on the substrate.
The method according to claim 1,
The method of claim 1, further comprising vaporizing oxetane or a thermal initiator substituted with at least one reactive functional group selected from the group consisting of the vinyl group and the (meth) acrylate group at a temperature of 20 ° C to 200 ° C. ≪ / RTI >
11. The method of claim 10,
In the polymer synthesis step,
A metal filament heated to a temperature of 150 캜 to 500 캜; And a substrate disposed below the metal filament in a gravitational direction; and a gas containing oxetane gas in which at least one reactive functional group selected from the group consisting of vinyl group and (meth) acrylate group is substituted into the deposition reactor And injecting a thermal initiator on said gaseous phase.
A process for producing a polymeric thin film according to claim 1, And
And forming an inorganic thin film on the polymer thin film.
13. The method of claim 12,
The step of forming an inorganic thin film on the polymer thin film may include forming a thin film of an inorganic thin film on the polymer thin film by using a material such as silicon oxide, Zirconium oxide, zirconium oxide, zirconium oxide, zirconium oxide, and zirconium nitride.
14. The method of claim 13,
Wherein the vapor deposition is performed by a plasma chemical vapor deposition (PECVD) method, an atomic layer deposition method, or a sputtering method.
13. The method of claim 12,
Wherein the inorganic thin film has a thickness of 10 nm to 1,000 nm.
13. The method of claim 12,
Wherein the inorganic thin film and the polymer thin film are stacked one on top of the other.
A polymer resin having at least one oxetanyl group substituted on the surface, the polymer resin comprising at least one repeating unit selected from the group consisting of a vinyl-based repeating unit and a (meth) acrylate-based repeating unit,
Having a glass transition temperature of from 50 DEG C to 150 DEG C,
The glass transition temperature is increased by 30% to 80% before and after the heat treatment at 100 占 폚 to 300 占 폚,
Having a thickness of 10 nm to 1,000 nm.
delete 18. The method of claim 17,
And having a glass transition temperature of 65 ° C to 270 ° C after heat treatment at 100 ° C to 300 ° C.
18. The method of claim 17,
And having a glass transition temperature of 100 ° C to 200 ° C after heat treatment at 100 ° C to 300 ° C.
delete 18. The method of claim 17,
Wherein the polymer resin comprises at least one selected from the group consisting of repeating units of the following formula (3) and repeating units of the following formula (4):
(3)

[Chemical Formula 4]

In Formula 3 or Formula 4,
Wherein R ₁ is - (CH ₂ ) _x H, x is an integer from 0 to 4,
y and z are each an integer of 1 to 10,
R ₃ and R ₄ are each hydrogen or an alkyl group having 1 to 3 carbon atoms,
* Denotes the coupling point.
18. The method of claim 17,
Wherein the polymer resin has a weight average molecular weight of 5,000 to 500,000.
18. The method of claim 17,
Ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether and di Vinylbenzene, and the like. The polymer-deposited thin film further includes at least one repeating unit derived from at least one compound selected from the group consisting of vinylbenzene and vinylbenzene.
At least one polymeric thin film of claim 17; And
And a thin inorganic film formed on at least one surface of the polymer deposited thin film.

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