KR20120106086A - Chemically amplified positive-imageable organic insulator composition and method of forming organic insulator using thereof - Google Patents
Chemically amplified positive-imageable organic insulator composition and method of forming organic insulator using thereof Download PDFInfo
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- KR20120106086A KR20120106086A KR1020110023947A KR20110023947A KR20120106086A KR 20120106086 A KR20120106086 A KR 20120106086A KR 1020110023947 A KR1020110023947 A KR 1020110023947A KR 20110023947 A KR20110023947 A KR 20110023947A KR 20120106086 A KR20120106086 A KR 20120106086A
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0045—Photosensitive materials with organic non-macromolecular light-sensitive compounds not otherwise provided for, e.g. dissolution inhibitors
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/039—Macromolecular compounds which are photodegradable, e.g. positive electron resists
- G03F7/0392—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition
- G03F7/0397—Macromolecular compounds which are photodegradable, e.g. positive electron resists the macromolecular compound being present in a chemically amplified positive photoresist composition the macromolecular compound having an alicyclic moiety in a side chain
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/40—Treatment after imagewise removal, e.g. baking
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/027—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34
- H01L21/0271—Making masks on semiconductor bodies for further photolithographic processing not provided for in group H01L21/18 or H01L21/34 comprising organic layers
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/582—Recycling of unreacted starting or intermediate materials
Abstract
The present invention relates to a chemically amplified positive photosensitive organic insulating film composition and a method of forming an organic insulating film using the same. In the chemically amplified positive photosensitive organic insulating film composition including a binder resin, the binder resin has an acid decomposability of a ring structure. It comprises a unit (moiety) comprising a protecting group, characterized in that it comprises a polymer or copolymer comprising the unit.
According to the present invention, unlike the prior art, by configuring the ring-degradable acid-decomposable protecting group and the newly developed chemical structure in the form of a copolymer, not only the sensitivity is significantly increased, but also the film reduction of the unexposed portion at the time of development can be significantly reduced. It is possible to significantly reduce the generation of volatile vapor during exposure, to implement a high resolution of the display, there is an advantage that can maintain a high transmittance.
Description
The present invention relates to a chemically amplified positive photosensitive organic insulating film composition and a method of forming an organic insulating film using the same, and more particularly, in forming an organic insulating film such as a liquid crystal display device, not only significantly improves sensitivity compared to the prior art, The present invention relates to a chemically amplified positive photosensitive organic insulating film composition having excellent physical properties such as low volatility, transparent film color (non-yellowish / non-redish), high residual film ratio, and high resolution, and a method of forming an organic insulating film using the same.
In display devices such as thin film transistor (TFT) type liquid crystal displays, an inorganic protective film such as silicon nitride (SiOx or SiNx) is conventionally used as a protective film for protecting and isolating a thin film transistor (TFT) circuit. However, there is a problem that it is difficult to improve the aperture ratio due to the cost of vacuum deposition, the burden of delaying the process time, and the high dielectric constant value. Therefore, in order to overcome this problem, the demand for a low dielectric constant and coatable liquid organic insulating film is increasing. .
In addition, the organic insulating film applied at this time provides a photosensitive function to the insulating film itself, thereby enabling the formation of a fine pattern for providing interconnection passages between circuits without a separate process, and through this, a separate photo using a photoresist on a conventional inorganic insulating film. The process can be reduced, resulting in higher productivity and cost savings, leading to increased use.
The organic insulating film is a photosensitive resin, which is a polymer compound in which the solubility in a specific solvent is changed by chemical reaction by light and electron beams. Generally, the microprocessing of the circuit pattern is performed by the polarization of the polymer due to the photoreaction of the organic insulating film. By change or crosslinking reaction. In particular, the organic insulating film material utilizes a change characteristic of solubility in a developer such as an aqueous alkali solution after exposure.
The organic insulating film is classified into a positive type and a negative type according to the solubility of the sensitized part. In the positive photoresist, the exposed part is dissolved by the developer due to the polarity change, and in the negative type photoresist, the exposed part is not dissolved in the developer through the crosslinking reaction and the unexposed part is dissolved to form a pattern.
Among these, the positive type organic insulating film is advantageous in terms of working environment because there is no problem in the development of the developer, unlike the disadvantage of foreign matter generation when mixed with the alkaline developer in which the negative type organic insulating film is widely used in the existing mass production process. Since the swelling phenomenon of the portion not exposed to ultraviolet rays can be prevented, the resolution is improved. In addition, since the removal of the organic film after the formation of the organic film is easy, there is an advantage that the substrate recovery and reusability is greatly improved by removing the organic film during the generation of a defective panel during the process.
For this reason, the positive type organic insulating film composition has been actively applied to a composition in which an acrylic polymer resin and a quinonediazide-based photosensitive compound (PAC) used as a representative binder resin are mixed. In recent years, the insulating film has been widely applied, and various high brightness devices through high aperture ratio have been released.
Sensitivity is mentioned as an important characteristic among the characteristics calculated | required by the said organic insulating film. Since the improvement of the sensitivity enables a significant reduction in the production time in the industrial production of the display apparatus, in the present situation in which the demand for liquid crystal display devices and the like is remarkably increasing, the sensitivity is the most required for this kind of organic insulating film. It is recognized as one of the important characteristics.
However, the organic insulating film composition using acrylic photosensitive resins and PACs, which are conventionally used, have a low sensitivity due to their low transmittance to wavelengths of exposure to ultraviolet light. In many cases, the difference in solubility is not so large that it does not have sufficient resolution.
For example, Korean Patent Nos. 10-0867948 and 10-0737723, which use quinone diazide as an alkali soluble resin and a photosensitive compound (PAC), have a high content of quinone diazide (at least 5 wt% or more) and accordingly There is a problem that improvement of sensitivity (100 mJ /
In addition, US Patent No. 4139391 discloses a photosensitive resin organic insulating film composition prepared by using a copolymer of an acrylic acid compound and an acrylate compound as a binder resin and an acrylate compound as a polyfunctional monomer. In the non-exposure region, which must remain, the dissolution inhibiting ability is not high, so the difference in dissolution rate between the exposed portion and the non-exposed portion is not large enough so that the development characteristics are not good.
As described above, the conventional positive type organic insulating film not only satisfies the problem of sensitivity sufficiently, but also has a limitation in resolution to cope with miniaturization for higher integration.
Although it is possible to improve the sensitivity by minimizing the content of PAC in the polymer used to increase the transmittance to exposure light or to increase the development time, this method has limitations and also the solubility of the unexposed part, resulting in overall Residual film ratio fell, and this had the fault which causes a film bleeding and a pattern damage in a large display substrate.
Recently, in order to solve the sensitivity problem of the positive organic insulating film including the PAC, the solubility in the developer by changing the polarity by removing the protecting group of the polymer binder through an acid catalyst reaction using an acid generated through exposed light. A chemically amplified positive organic insulating film was introduced. (Korean Registered Patent No.0964733)
However, here, the acid-decomposable acetal protecting group used in the polymer binder has a small boiling point due to the small size of the product decomposed during exposure, and has a high volatility to generate a large amount of vapor during exposure, thereby easily contaminating an expensive lens of the exposure machine. In addition, there is a significant disadvantage that the thickness of the film through volume shrinkage is relatively reduced due to the detachment and volatilization of the protecting group during exposure.
This problem is not only in the exposure area during the exposure process, but also in the remaining non-exposed part film, the protector is easily volatilized by heat when exposed to an environment of high temperature and high humidity between post processes, thereby preventing outgas problems in the device. And technical limitations that ultimately affect device operation.
Therefore, there is a demand for the development of a new organic insulating material that can solve this problem.
The present invention is to solve the above problems, unlike the prior art, by configuring the acid-decomposable protecting group of the ring structure and the newly developed chemical structure in the form of a copolymer, not only significantly increases the sensitivity, but also reduces the film of the unexposed portion during development It is an object of the present invention to provide a chemically amplified positive photosensitive organic insulating film composition which is significantly reduced in number and a method of forming an organic insulating film using the same.
In addition, the generation of volatile vapor during exposure can be significantly reduced, the exposure time is also significantly reduced, the process cost can be reduced, the high resolution of the display can be implemented, the chemically amplified positive photosensitive organic insulating film composition that can maintain a high transmittance And to provide a method for forming an organic insulating film using the same.
In addition, by using an acid-decomposable protecting group of a ring structure, unlike the conventional, it is bulky (bulky), thereby improving the dissolution inhibitory ability, thereby maintaining a higher residual film ratio in the non-exposure range bar, exposed portion and Vino An object of the present invention is to provide a chemically amplified positive photosensitive organic insulating film composition capable of realizing a high resolution pattern by increasing the dissolution rate difference between the optical parts and a method of forming an organic insulating film using the same.
In addition, by using an acid-decomposable protecting group having a cyclic structure, even when a small amount is added, the dissolution inhibiting effect is the same or superior, so that an economical chemically amplified positive photosensitive organic insulating film composition and a method of forming an organic insulating film using the same are provided. It aims to provide.
In the chemically amplified positive photosensitive organic insulating film composition according to the present invention for achieving the above object, in the chemically amplified positive photosensitive organic insulating film composition comprising a binder resin, the binder resin is an acid-degradable protecting group of a ring structure It comprises a unit (moiety) comprising a, characterized in that it comprises a polymer or copolymer comprising the unit.
In addition, the unit is characterized in that consisting of at least one of the formula 1-1 to 1-17.
<Formula 1-1> <Formula 1-2>
<Formula 1-3> <Formula 1-4>
<Formula 1-5> <Formula 1-6>
<Formula 1-7> <Formula 1-8>
<Formula 1-9> <Formula 1-10>
<Formula 1-11> <Formula 1-12>
<Formula 1-13> <Formula 1-14>
<Formula 1-15> <Formula 1-16>
<Formula 1-17>
In Formulas 1-1 to 1-17, R 1 is a chain aliphatic group, a cyclic aliphatic group, an aryl group, a chain ester group, a cyclic ester group, a chain ether group or a cyclic ether group, and R 1 * Is a hydrogen group or a chain alkyl group, R 2 is a chain alkyl group or a cyclic alkyl group, R 3 is a hydrogen group or a chain alkyl group, R 4 is a hydrogen group, a chain alkyl group or a cyclic alkyl group, R 5 Is a chain alken group or a cyclic alken group, R 6 is a hydrogen group, a chain alkyl group, a cyclic alkyl group or an aryl group.
X may be any of a chain aliphatic group, a cyclic aliphatic group, an aryl group, a chain ester group, a cyclic ester group, a chain ether group, or a cyclic ether group, and the same group as R 1 may be obtained. X is omitted if R 1 is followed by Y without X, and X is hydrogen when terminated with R 1 without X and Y.
In addition, Y is any one of a hydrogen group, a hydroxyl group, an epoxy group, an isocyanate group, an acryloyl group, an aryl group, a vinyl group, or an alkoxy group, and X 1 * and X 2 * are furan-based acid-decomposable protecting groups or pyrans. (pyran) is an acid-decomposable protecting group.
In addition, the unit is characterized in that at least one of the formula (2) or formula (3).
<
In
In addition, the polymer or the copolymer is characterized in that it further comprises at least one of the formulas (4) to (7).
<Formula 4> <Formula 5>
<Formula 6> <Formula 7>
In
The polymer or the copolymer is characterized in that it further comprises at least one of the formulas (8) to (10).
(8)
<Formula 9>
<
In Formulas 8 to 10, A and B are any one of a nitrogen group or an oxygen group, R 8 is any one of a hydrogen group, a hydroxyl group, an alkyl group or an epoxy group, n is a repeating unit of a monomer in the polymer, n≥1 to be.
In addition, the polymer or the copolymer is characterized in that any one of the following formula 11 to formula 12.
<Formula 11>
<Formula 12>
The average molecular weight of the binder resin is 2000 to 100000, the dispersion degree is characterized in that 1 to 10.
In addition, further comprising a dissolution inhibitor, the dissolution inhibitor is an alkali-soluble phenol compound or a fluorene-based compound containing at least one phenol group, an alkali-soluble compound containing at least one carboxylic acid group or at least one An acid-decomposable protecting group is included in at least one of the alkali-soluble compounds containing a benzoic acid group, and in the dissolution inhibitor, the acid-decomposable protecting group is any one of the acid-decomposable protecting groups represented by Chemical Formulas 1-1 to 1-17. It is characterized by that.
In addition, further comprising a photoacid generator, the photoacid generator is made of at least one of an onium salt compound, a halogen-containing compound, a sulfone compound, a sulfonic acid ester compound or a triazine-based compound, based on 100 parts by weight of the binder resin, It is characterized by including 0.1 to 10 parts by weight.
In addition, it characterized in that it further comprises a PhotoActiveCompound (PAC) comprising a quinonediazide group (quinonediazide), and further comprises an additive, the additive is a thermal crosslinking agent, thermal stabilizer, photocuring accelerator, surfactant, base quencher, halle It is characterized by consisting of at least one of a ration inhibitor, an adhesion aid, a light stabilizer or an antifoaming agent.
The thermal crosslinking agent is made of a compound containing at least one of urea resin, melamine resin, isocyanate group, epoxy group, oxetane group, acrylate group, vinyl group, aryl group, hydroxy group or mercapto group The heat stabilizer is characterized by consisting of at least one of a phenolic, lactone-based, amine-based, phosphorus-based or sulfur-based compound.
The light stabilizer, characterized in that consisting of at least one of benzotriazole-based, triazine-based, benzophenone-based, hindered amino ether-based or hindered amine-based compound, wherein the adhesion aid, isocyanate group, amino group, urea group, alkyl group , An alkoxy silane compound comprising at least one of an epoxy group, an acrylate group, a vinyl group or a mercapto group.
The base quencher is a nitrogen-containing organic compound, characterized in that the nitrogen-containing organic compound is composed of at least one of a primary amine, a secondary amine, a tertiary amine or an amide compound.
Next, in the method of forming an organic insulating film using the chemically amplified positive photosensitive organic insulating film composition according to the present invention, the organic insulating film composition is formed on a substrate of a display device, a source / drain or silicon nitride layer formed on the substrate. Applying; Pre-bake the organic insulating film composition; Selectively exposing the organic insulating film composition and then developing the organic insulating film composition to form a pattern; And forming an insulating protective film by exposing the organic insulating film composition to full surface exposure and heat treatment (cure bake).
In the forming of the pattern, a post-bake process may be added between exposure and development.
According to the chemically amplified positive photosensitive organic insulating film composition of the present invention and a method of forming an organic insulating film using the same, unlike the conventional method, the sensitivity is significantly increased by forming an acid-decomposable protecting group having a ring structure and a newly developed chemical structure in the form of a copolymer. In addition to the increase, there is an advantage that can significantly reduce the film reduction of the unexposed portion during development.
In addition, the generation of volatile vapor during the exposure can be significantly reduced, the exposure time is also significantly reduced to reduce the process cost, high resolution of the display is possible, there is an advantage that can maintain a high transmittance.
In addition, by using an acid-decomposable protecting group of a ring structure, unlike the conventional, it is bulky (bulky), thereby improving the dissolution inhibitory ability, thereby maintaining a higher residual film ratio in the non-exposure range bar, exposed portion and Vino By increasing the difference in dissolution rate between the miner, there is an advantage that can realize high resolution pattern.
In addition, by using an acid-decomposable protecting group having a cyclic structure, even when a small amount is added, the dissolution inhibiting effect is equivalent to or superior to that of the conventional art, and there is an economic advantage.
1 is a cross-sectional view showing a unit cell device of a TFT-LCD having a high opening ratio to which the chemically amplified positive photosensitive organic insulating film composition of the present invention is applied.
FIG. 2A is a surface optical photo of an organic insulating film pattern having a resolution evaluation according to the composition of Example 2-1 of the present invention. FIG.
FIG. 2B is a surface optical photo of an organic insulating film pattern having a resolution evaluation according to the composition of Example 2-2 of the present invention
2C is a surface optical photo of an organic insulating film pattern having a resolution evaluation according to a composition of Comparative Example 1 of the present invention.
FIG. 2D is a surface optical photo of an organic insulating film pattern having a resolution evaluation according to a composition of Comparative Example 2 of the present invention
<Description of Drawing>
1: lower substrate
2: gate insulating film
3: gate electrode
4: semiconductor layer
5: source electrode
6: drain electrode
7: storage electrode
8: data line
9: organic insulating film
10: pixel electrode
Hereinafter, a preferred embodiment of the present invention will be described in detail with reference to the accompanying drawings with respect to a chemically amplified positive photosensitive organic insulating film composition and a method for forming an organic insulating film using the same according to the present invention. The invention can be better understood by the following examples, which are intended for the purpose of illustration of the invention and are not intended to limit the scope of protection defined by the appended claims.
First, the chemically amplified positive photosensitive organic insulating film composition includes a binder resin, wherein the binder resin comprises a moiety including an acid-decomposable protecting group of a ring structure, and includes a polymer or air containing the unit. It is characterized by including the coalescence.
Here, the unit means a minimum unit including a monomer and is defined as including any substance containing an acid-decomposable protecting group of a ring structure.
In addition, the unit is characterized in that made of at least one of the formulas (1-1) to 1-17 and at least one of the formulas (2) to (3). In addition, the copolymer is characterized in that it further comprises at least one of the
When the acid-decomposable protecting group having a ring structure represented by Chemical Formulas 1-1 to 1-17 is applied to the organic insulating film for a liquid crystal display device, the organic insulating film remains after the pattern formation to function as an insulating and protective film of the wiring.
Thus, as a result of applying the acid-decomposable protecting group of the ring structure represented by the formula (1-1 to 1-17) of the present invention to the organic insulating film, by controlling the solubility in the composition, sensitivity, which is a characteristic required in the organic insulating film, It was confirmed that the effect of improving the residual film ratio, volatile vapor, and resolution was very excellent.
In addition, it was confirmed that exhibits high transmittance characteristics in the visible light region of 400nm or more.
In addition, the crosslinked structure of
In the binder resin, when the copolymer further comprises the
It may be made of a polymerized form of any one of
In addition, the binder resin may be made of a polymerized form of any one of Formulas 8 to 12, or may be made by simply mixing the copolymers. However, when mixing each polymer, at least one acid-decomposable protecting group represented by the formula (1-1 to 1-17) must be included.
Here, the average molecular weight of the binder resin is preferably 2000 to 200000, more preferably 5000 to 30000. In addition, the dispersion degree of the binder resin is preferably 1 to 10, more preferably 1.1 to 5.0 is effective. If it is out of the range of the optimum average molecular weight and dispersion degree, there is a problem that the characteristics of the organic insulating film is significantly lowered or the economy is inferior.
In addition, it is preferable that the organic insulating film composition of the present invention further comprises a dissolution inhibitor, wherein the dissolution inhibitor is an alkali-soluble phenolic compound or a fluorene-based compound containing at least one phenol group, at least one carr It is preferable that an acid-decomposable protecting group is contained in at least one of an alkali-soluble compound containing an acidic group or an alkali-soluble compound containing at least one benzoic acid group. In the dissolution inhibitor, it is preferable that the acid-decomposable protecting group is any one of the acid-decomposable protecting groups represented by Chemical Formulas 1-1 to 1-17.
Such a dissolution inhibiting agent is effectively mixed with the binder resin, thereby improving sensitivity and facilitating pattern formation.
The molecular weight of the dissolution inhibitor is preferably 5000 or less in the case of a monomolecular structure, and 5000 to 30000 in the case of the polymer structure.
As mentioned above, the binder resin of the present invention can be generated in the residual organic pattern film during or after the exposure process by using a minimum amount of an acid-decomposable protecting group to exhibit sufficient dissolution inhibiting ability of the developer in the non-exposed part. The amount of volatile vapor present can be significantly reduced, and the exposure part is deprotected at a very high rate by the catalytic reaction by the action of acid triggered from the photo acid generator (PAG) in the exposure process, so that the solubility in the developer is drastically reduced. By increasing the dissolved contrast of the organic insulating film composition, there is an advantage in that a fine circuit pattern of high resolution can be formed even under a light source having a complex wavelength of i, g, and h-line.
In addition, by adding at least one of a photoacid generator, an additive, and an organic solvent to the binder resin, its performance can be maximized.
First, any photoacid generator may be used as long as it is capable of generating an acid when exposed to live radiation and does not degrade optical properties such as protective film formation and transmittance, but preferably at a wavelength of 250 nm to 400 nm. It is effective to use a material having an appropriate light absorption and capable of maintaining the excellent transmittance and transparent color of the organic insulating film in the visible light region of 400 nm or more.
Thus, in the present invention, it was confirmed that at the end of several experiments, it is most suitable that the photoacid generator consists of at least one of an onium salt compound, a halogen-containing compound, a sulfone compound, a sulfonic acid ester compound, or a triazine-based compound.
The onium compound is effective to use an iodonium salt, a forest sulfonium salt, a phosphonium salt, a diazonium salt, an ammonium salt or a pyridinium salt, and the halogen-containing compound is a haloalkyl group-containing hydrocarbon compound or a haloalkyl group-containing heterocyclic compound. It is effective to use.
In addition, it is effective to use β-ketosulfone, β-sulfonylsulfone or α-diazo compounds thereof as the sulfone compound, and the sulfonic acid ester compound is alkyl sulfonic acid ester, haloalkyl sulfonic acid ester, aryl sulfonic acid ester, imino sulfo. It is effective to use nate or amide sulfonate.
In addition, the content of the photoacid generator, it is preferable to include 0.1 to 10 parts by weight, more preferably 1 to 5 parts by weight with respect to 100 parts by weight of the binder resin. If it is less than 0.1 part by weight, it is difficult to realize sensitivity at a sufficient speed due to the limitation of the amount of acid generated during exposure, and if it exceeds 10 parts by weight, problems of decrease in permeability and discoloration of the coating film may occur.
Next, the additive is preferably made of at least one of a thermal crosslinking agent, a thermal stabilizer, a photocuring accelerator, a surfactant, a base quencher, an antihalation agent, an adhesion aid, an optical stabilizer or an antifoaming agent.
The thermal crosslinking agent is added to improve thermal resistance and mechanical properties (hardness and strength) of the coating film by smoothly generating a crosslinking reaction between the binder resin and the thermal crosslinking agent through a post-exposure heat treatment process when forming the organic insulating film. It is most effective in the present invention that the compound comprises at least one of urea, melamine resin, isocyanate group, epoxy group, oxetane group, acrylate group, vinyl group, aryl group, hydroxy group or mercapto group. .
In addition, the thermal stabilizer is used to suppress discoloration and decrease in permeability due to heat generated during the subsequent process or during the reliability conditions of the device, and at least one of a phenolic, lactone-based, amine-based, phosphorus-based or sulfur-based compound. It is most preferred in the present invention that it consists of one.
The light stabilizer is used to maximize the light resistance of the organic insulating film composition, and the type of light stabilizer having such characteristics is not particularly limited, but benzotriazole-based, triazine-based, benzophenone-based, hindered amino ether-based or Use of at least one of the hindered amine compounds is most effective in the present invention.
The photocuring accelerator may be any material capable of promoting acid generation during exposure, and the adhesion assistant may include at least one of a socyanate group, an epoxy group, an acrylate group, a vinyl group, or a mercapto group. It is preferable that it consists of an alkoxy silane compound.
The base quencher serves to control the diffusion of the generated acid, and it is preferable to use a nitrogen-containing organic compound which does not change the basicity, more preferably a primary amine, a secondary amine, a tertiary amine or an amide compound. It is most effective to consist of at least one of.
In addition, the surfactant (surfactant) is used to improve the coating properties and thickness uniformity by improving the wetting properties (wetting) of the substrate and the organic insulating film composition, the type is not particularly limited, but preferably polyoxy lauryl ether , Polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether or polyethylene glycol dilaurate and the like. It is preferable to use content of these surfactant at 3 weight part or less with respect to 100 weight part of positive type organic insulating film compositions of this invention.
In addition, generally used photocuring accelerators, antihalation agents (leveling agents), antifoaming agents, and the like can be used. If necessary, various other additives can be used to improve desired properties in addition to the additives listed above.
In addition, an organic solvent may be used for the organic insulating film composition, and the organic solvent may preferably be at least one of an alcohol, acetate, ether, glycol, ketone, or carbonate organic solvent. Preferably, the use of propylene glycol methyl ether acetate (PGMEA) is most effective because of excellent coating properties and excellent film thickness uniformity of the organic insulating film on a large glass substrate.
In addition, R 1, R 2, R 3, etc. defined in the above formulas are commonly applied in all formulas. That is, R 1, R 2, R 3, etc., according to the chemical formula, are not otherwise defined.
Next, in the method of forming an organic insulating film using the chemically amplified positive photosensitive organic insulating film composition of the present invention, the organic insulating film composition is coated on a substrate, a source / drain or silicon nitride layer formed on the substrate of the display device. (S10), pre-bake the organic insulating film composition (S20), selectively exposing and developing the organic insulating film composition to form a pattern (S30) and the organic insulating film composition on the entire surface. And forming an insulating protective film by exposure and heat treatment (cure bake) (S40).
As the substrate, glass or transparent plastic resins commonly used in flat panel displays (FPDs) such as liquid crystal displays (TFT-LCDs) and OLEDs are mainly used, but are not particularly limited according to the characteristics of the display apparatus used. For example, the organic insulating film is formed on an ITO metal film used as an anode in an OLED, on an EL layer of each RGB color, or on a metal film constituting a gate electrode on a substrate such as glass, thereby protecting and insulating. Can be used for purposes.
In the present invention, the method of coating the organic insulating film composition on the substrate or the like may include a coating method using a slit nozzle such as a spray coating method, a roll coating method, a discharge nozzle type coating method, a rotary coating method such as a central dropping spin method, There are an extrusion coating method and a bar coating method, and two or more coating methods can be combined and coated.
The applied film thickness varies depending on the coating method, the solid content concentration of the composition, the viscosity, and the like, but is usually applied so as to have a film thickness of 0.5 to 10 µm after drying. After the grilling step is performed, the solvent is volatilized by applying vacuum, infrared rays, or heat to obtain a non-flowable coating film after forming the coating film. Heating conditions vary depending on the type and composition of each component, but in the case of hot plate heating, it is heated to 60 to 130 ° C. for 30 to 300 seconds, and to 60 to 150 ° C. when using a hot oven. It is common to heat for 30 to 1,000 seconds. Next, the selective exposure process may be excimer laser, far ultraviolet, ultraviolet light, visible light, electron beam, X-ray or g-ray (wavelength 436nm), i-ray (wavelength 365nm), h-ray (wavelength 405nm) or mixed rays thereof. Is carried out while examining. The exposure may be performed by contact, porximity, projection exposure, or the like.
In the present invention, after performing the alkali development, the step of performing the entire surface exposure and annealing (annealing) of the organic insulating film composition. The thermal crosslinking agent is applied to the composition of the organic insulating film composition of the present invention for the high temperature firing. The heat treatment step is performed for 30 minutes to 2 hours under a temperature of 150 ℃ to 250 ℃ using a heating apparatus such as a hot plate or oven. After the heat treatment, a completely cross-cured pattern is obtained.
The organic insulating film thus formed is, as shown in the display device of FIG. 1, the semiconductor layer 40, the source 51 made of the
Hereinafter, in the chemically amplified positive photosensitive organic insulation film composition of the present invention, a specific embodiment of a method of polymerizing a binder resin will be described.
Polymerization Method of Binder Resin (Example 1)
Example 1-1
Binder resin represented by the following formula (13) was prepared in the following manner. In Formula 13, a is 0.25, b is 0.10, c is 0.20, d is 0.10, e is 0.15, f is 0.20.
<Formula 13>
35 mol% of 4-acetoxystyrene, 20 mol% of alpha-methylstyrene, 10 mol% of methylmethacrylate, 15 mol of dicyclopentanyl acrylate %, A monomer mixture consisting of 20 mol% glycidyl methacrylate and 45% by weight of an organic solvent, propylene glycol methyl ether acetate (PGMEA), are heated to 70 ° C. and purged with nitrogen purge. ) Mix thoroughly in the state.
At this time, 4% by weight of the
Thereafter, 0.1 wt% hydrochloric acid (hydrochloric acid) relative to the weight of the polymer is added and mixed, followed by stirring at 45 ° C for at least 4 hours. After the temperature was lowered to 25 ° C., 3,4-dihydro-2H-pyran was added in an amount of 0.72 times the number of moles of 4-acetoxy styrene contained in the polymer resin and stirred under a nitrogen atmosphere for at least 48 hours. Let's do it.
After the reaction was completed, the temperature was lowered to room temperature, sodium hydroxide was added to the same mole number as the hydrochloric acid used above, neutralized, and only the polymer resin portion was extracted with excess distilled water. Clean the polymer resin. The finally obtained polymer resin is left to dry at 40 ° C. for at least 24 hours in a vacuum drying oven.
Examples 1-2
Binder resin represented by the following formula (14) was prepared in the following manner. In Formula 14, a is 0.25, b is 0.10, c is 0.20, d is 0.10, d is 0.15, e is 0.20.
<Formula 14>
3, 3-diethyl-oxetane methacrylate and dicyclopentenyl acrylate (dicyclopentenyl acrylate) were respectively substituted for the glycidyl methacrylate and dicyclopentanyl acrylate used as monomers in the polymer resin polymerization. The polymerization was carried out in the same manner as in Example 1-1, except that ethenoxy-methyl-benzene was used instead of 3,4-dihydro-2H-pyran as the acid-decomposable protecting group.
Example 1-3
A binder resin represented by Formula 15 below was prepared in the following manner. In Formula 15, a is 0.20, b is 0.10, c is 0.20, d is 0.10, e is 0.25, f is 0.15.
≪ Formula 15 >
Hydroxypropyl acrylate was added in place of the methyl methacrylate used as a monomer during the polymerization of the polymer resin, and 2- (2-Vinyloxy-ethyl)-instead of 3,4-dihydro-2H-pyran as an acid-decomposable protecting group. Except that naphthalene was used in an amount of 0.68 times the number of moles of 4-acetoxy styrene used in the polymerization of the polymer resin, the other polymerization method was carried out in accordance with the case of Example 1-1.
Example 1-4
The binder resin represented by the following formula (16) was prepared in the following manner. In Formula 16, a is 0.30, b is 0.05, c is 0.20, d is 0.10, e is 0.20, f is 0.15.
<Formula 16>
Benzylmethacrylate was added in place of the glycidyl methacrylate used as a monomer during the polymerization of the polymer resin, and 1,4-cyclohexanemethanol instead of 3,4-dihydro-2H-pyran as an acid-decomposable protecting group. Except that vinyl ether was used in an amount of 0.86 times the number of moles of the 4-acetoxy styrene used in the polymerization of the polymer resin, the other polymerization method was carried out in accordance with the case of Example 1-1.
Examples 1-5
Binder resin represented by the following formula (17) was prepared in the following manner. In Formula 17, a is 0.25, b is 0.10, c is 0.20, d is 0.20, e is 0.25.
<Formula 17>
In place of 4-acetoxy styrene and methyl methacrylate used as monomers in the polymerization of the polymer resin, methacrylic acid and methyl acrylate are added and used, respectively. Except for using 3,4-dihydro-2H-pyran as the degradable protecting group in an amount of 1.2 times the number of moles compared to the number of moles of the methacrylic acid used in the polymerization of the polymer resin, the polymerization method is different from that in Example 1-1. Was performed.
Examples 1-6
Binder resin represented by the formula (18) below was prepared in the following manner. In Formula 18, a is 0.25, b is 0.10, c is 0.15, d is 0.25, e is 0.25.
≪ Formula 18 >
Carboxytetracyclododecyl methacrylate is used in place of 4-acetoxy styrene except for alpha methyl styrene used as a monomer in the polymerization of the polymer resin, and 3,4-dihydro-2H-pyran is used as the acid-decomposable protecting group. Except that the amount of carboxytetracyclododecyl methacrylate used in an amount of 0.72 times the number of moles of carboxytetracyclododecyl methacrylate was carried out in accordance with the case of Example 1-1.
Example 1-7
The binder resin represented by the formula (19) below was prepared in the following manner. In Formula 19, a is 0.15, b is 0.25, c is 0.15, d is 0.20, and e is 0.25.
(19)
Methacrylic acid is used in place of the methyl methacrylate used as a monomer in the polymer resin polymerization, and 3,4-dihydro-2H-pyran is used as the acid-decomposable protecting group in the polymerization of the polymer resin. Other polymerization methods were carried out in accordance with the case of Example 1-1, except that the amount was used in an amount of 1.2 times the number of moles of the styrene and the methacrylic sheet.
Examples 1-8
Binder resin represented by the formula (20) below was prepared in the following manner. In Formula 20, a is 0.20, b is 0.10, c is 0.20, d is 0.25, e is 0.25.
<Formula 20>
Except for the hydroxypropyl acrylate used as monomer in the polymer resin polymerization, 3,4-dihydro-2H-pyran as an acid-decomposable protecting group, instead of bisphenol A-diethoxy divinyl ether was used in the polymer resin polymerization. Other polymerization methods were carried out in accordance with the case of Example 1-5, except that the amount was used in an amount of 0.68 times the number of moles of acid.
Example 1-9
Binder resin represented by the formula (21) below was prepared in the following manner. In Formula 21, a is 0.20, b is 0.15, c is 0.15, d is 0.10, d is 0.20, and e is 0.20.
≪ Formula 21 >
Except for the use of 1,4-cyclohexanedimethanol divinyl ether instead of 3,4-dihydro-2H-pyran as an acid-decomposable protecting group in an amount of 0.58 times the number of moles of 4-acetoxystyrene used in the polymer resin polymerization, The polymerization method was carried out in accordance with the case of Example 1-1.
Example 1-10
Polymer resins represented by Chemical Formulas 13 and 17 were prepared as described above, respectively, and a binder resin obtained by mixing each polymer resin in a weight ratio of 60:40 was prepared.
Example 1-11
A polymer resin represented by the following Chemical Formulas 22 and 23 was prepared as follows, and a binder resin was prepared by mixing the polymer resin represented by the following Chemical Formula 22 with the polymer resin represented by the following Chemical Formula 23 in a weight ratio of 60:40.
In Formula 22, a is 0.30, b is 0.25, c is 0.20, d is 0.25, and in Formula 23, a is 0.45 and b is 0.55.
<Formula 22>
The other polymerization method was carried out according to the case of Example 1-5, except for the hydroxypropyl acrylate used as a monomer in the polymer resin polymerization, the polymerization was carried out to terminate the reaction.
≪ Formula 23 >
After dissolving 50 g of polyhydroxystyrene (weight average molecular weight 12,000) resin in 150 g of PGMEA, 23.33 g of 0.45 times mole of the number of moles of hydroxystyrene in the polymer resin injected with 3,4-dihydro-2H-pyran. ) 0.4 g was dropped and reacted by stirring at 25 ° C. for 48 hours or more under a nitrogen atmosphere. After the reaction was completed, the temperature was lowered to room temperature, sodium hydroxide was added to the same mole number as the hydrochloric acid used above, neutralized, and only the polymer resin portion was extracted with excess distilled water. Clean the polymer resin. The finally obtained polymer resin is left to dry at 40 ° C. for at least 24 hours in a vacuum drying oven.
Example 1-12
The polymer resin represented by the formula (24) below and the acid decomposable dissolution inhibitor represented by the formula (25) are prepared as follows, and the polymerizable resin of formula (24) and the acid decomposable dissolution inhibitor represented by the formula (25) are mixed in a weight ratio of 75:25. Binder resin was prepared.
In Formula 24, a is 0.15, b is 0.25, c is 0.20, d is 0.20, and e is 0.20.
≪ EMI ID =
Except for the alpha methyl styrene used as a monomer in the polymer resin polymerization, 0.7 times the number of moles of 3,4-dihro-2H-pyran as the acid-decomposable protecting group compared to the total moles of 4-acetoxy styrene used in the polymerization. Aside from the reaction, the polymerization was carried out in the same manner as in Example 1-1.
≪ Formula 25 >
10 g of bisphenol fluorene was dissolved in 110 g of ethyl aceate, and then, as an acid-decomposable protecting group, 2.5 times the number of moles of ethenoxy-methyl-benzene was added to the total moles of bisphenol fluorene. . After neutralization and purification with aqueous sodium bicarbonate solution, the dissolution inhibitor protected with the acid-decomposable protecting group was extracted through petroleum ether.
Example 1-13
The polymer resin represented by the formula (26) below and the acid decomposable dissolution inhibitor represented by the formula (27) were prepared as follows, and the polymerizable resin of the formula (26) and the acid decomposable dissolution inhibitor represented by the formula (27) were mixed in a weight ratio of 70:30. Binder resin was prepared.
In Formula 26, a is 0.30, b is 0.25, c is 0.20, and d is 0.25.
(28)
Except for alphamethylstyrene, which was used as a monomer in the polymer resin polymerization, p-tert-butoxystyrene was added instead of 4-acetoxy styrene to hydrolyze p-tert-butoxystyrene using concentrated hydrochloric acid after polymerization. The polymerization was carried out in the same manner as in Example 1-1, except that the reaction was terminated by hydrolysis.
≪ Formula 27 >
10 g of α, α-Bis (4-hydroxyphenyl) -4- (4-hydroxy-α, α-dimethylbenzyl) -ethylbenzene was dissolved in 110 g of ethyl aceate and dissolved. Then, 1,4-cyclohexanedimethanol divinyl ether as an acid-decomposable protecting group was dissolved. Add 0.45 times and 0.3 times moles of cyclohexyl vinyl ether to the total moles of α, α-Bis (4-hydroxyphenyl) -4- (4-hydroxy-α, α-dimethylbenzyl) -ethylbenzene, and add 0.1 g of 12M HCl. It reacts at 24 degreeC or more. After neutralization and purification with aqueous sodium bicarbonate solution, the dissolution inhibitor protected with the acid-decomposable protecting group was extracted through a mixed solvent of methanol and distilled water.
Evaluation of Physical Properties of Organic Insulating Film by Organic Insulating Film Composition (Second Embodiment)
Next, a photoresist, an organic solvent, a crosslinking agent, and other additives are added together with the binder resin prepared by the polymerization method to prepare an organic insulating film composition, and the results of evaluating the properties of the organic insulating protective film formed therefrom are examined. Shall be.
The organic insulating film composition prepared in Examples 2-1 to 2-8 below was applied onto the substrate, spin-coated at a rotation speed of 500 to 1,500 rpm per minute, and then exposed on a hot plate, and then exposed to a temperature of 90 ° C. After drying for 90 seconds to form a coating film. The formed coating film formed the thickness of 1.0-5 micrometers according to the rotation speed.
Example 2-1
To 100 parts by weight of an organic solvent (PGMEA), 31.96 parts by weight of the binder resin polymerized in Example 1-1, 0.64 part by weight of the photo-acid generator N-hydroxynaphthalimide triflate, and triethylamine as a base triethylamine) 0.09 parts by weight, and 0.10 parts by weight of surfactant F-475 (Dainippon Ink & Chemicals) for the coating property is completely dissolved, and then rotated on a glass substrate at a rotational speed of 500 rpm to 1000 rpm for 90 seconds on a hot plate. After drying to form a coating film having a thickness of 3.5㎛ ~ 4.0㎛, after exposure by light quantity, developed in a 2.38wt% TMAH (tetramethylammonium hydroxide) developer for 80 seconds at 23 ℃ to 24 ℃ for 80 seconds thickness and 20㎛ L The exposure dose for the / S pattern was confirmed, and the minimum resolvable line width was confirmed.
Subsequently, after UV exposure on the organic film at an exposure dose of 500 mJ /
Example 2-2
As the binder resin, the experiment was performed in the same formulation and method as in Example 2-1, except that the binder resin of Chemical Formula 14 polymerized in Example 1-3 was used.
Example 2-3
Experiments were carried out in the same manner as in Example 2-1 except that the binder resin of Chemical Formula (16) polymerized in Example 1-5 was used as the binder resin.
Examples 2-4
The experiment was performed in the same formulation and method as in Example 2-1, except that the binder resin of Chemical Formula 18 polymerized according to Example 1-7 was used as the binder resin.
Example 2-5
The experiment was performed in the same formulation and method as in Example 2-1, except that the binder resin of Chemical Formula 19 polymerized according to Example 1-8 was used as the binder resin.
Examples 2-6
The experiment was carried out in the same formulation and method as in Example 2-1, except that the binder resin of Chemical Formula 20 polymerized in Example 1-9 was used as the binder resin.
Examples 2-7
Except for using a binder resin mixed with a copolymer of the formula 21-1 and the formula 21-2 and the dissolution inhibitor in 60:40 weight ratio as a binder resin in the above Example 1-11 The experiment was carried out in the same formulation and method as 2-1.
Examples 2-8
Except for using the binder resin mixed with a copolymer of the formula 22-1 and the formula 22-2 and the dissolution inhibitor in a 75: 25 weight ratio as a binder resin in the above Examples 1-12 The experiment was carried out in the same formulation and method as 2-1.
Comparative Example 1
Polymerized as shown in Chemical Formula 28 using ethoxyethoxystyrene (PES) monomer using ethylvinyl ether as an acid-decomposable protecting group of hydroxystyrene. The experiment was conducted by the same formulation and evaluation method as in Example 2-1, except that the copolymer was used as the binder resin. In Formula 28, a is 0.30, b is 0.10, c is 0.20, d is 0.10, e is 0.10, and f is 0.20.
(28)
Comparative Example 2
The experiment was carried out by the same evaluation method as in Example 2-1, except that an existing organic insulating film composition (JSR 411B) made of a PAC compound containing an alkali-soluble acrylic resin and a quinonediazide group was used as the binder resin. Was performed.
Measuring the appropriate exposure amount (Eop), the residual film rate after development, the residual film rate after cure bake, the heat shrinkage rate, the resolution, and the total light transmittance using the patterns formed by the above Examples and Comparative Examples It was.
1) Optimum exposure dose (Eop)
When the 20µm pattern is realized by optical microscopy after UV exposure and development process using a photomask with a pattern of 20 µm in width (CD). The exposure amount of was confirmed.
2) Residual percentage after development
The thickness of the coating organic film thickness before development and the thickness of the residual organic film after development were measured, and the residual film ratio after development was calculated using the following equation. Here, the residual film ratio after the development is derived by a formula of (thickness of the coating film after development) / (thickness of the coating film before development) × 100 (%).
3) Remaining percentage after cure bake
After the development, the residual organic film was left in an oven at an additional 220 ° C. for 1 hour to undergo a cure bake process, and the thickness of the residual organic film was measured. The residual film rate after cure bake was calculated using the following equation. Here, the residual film rate after the cure bake is derived by a formula of (thickness of the coating film after cure bake) / (thickness of the coating film before development) × 100 (%).
4) Thermal shrinkage (shrinkage%)
After the development, the thickness of the residual organic membrane and the thickness of the residual organic membrane after cure bake were measured, respectively, and the thermal shrinkage was calculated using the following equation. Here, the thermal contraction rate is derived by the formula (thickness of the coating after development-thickness of the coating after cure bake) / (thickness of the coating after development) x 100 (%).
5) resolution
Based on the 1: 1 line & space (L / S) pattern, the pattern width (CD) that can be finely formed without distortion or peel-off of the pattern was measured. The optical micrograph of the pattern is as shown in Figs. 2a to 2d.
6) Total light transmittance (%)
After performing the final cure bake process, the light transmittance at 450 nm was measured using a UV-Visible-Spectrometer and PDA UV-Vis Spectro (Scinco).
Table 1 below shows the optimum coating amount (Eop), the residual film ratio after development, the residual film ratio after cure bake, the heat shrinkage, the resolution, and the light transmittance of the thin film coated according to Examples 2-1 to 2-8 As shown in FIG.
Residual rate (%)
Residual Rate (%)
(%)
(Μm)
(%)
As shown in Table 1, the pattern according to the embodiment of the present invention has excellent sensitivity with an exposure dose in the range of 35 to 60 mJ /
In particular, compared to Comparative Example 1 (chemically amplified organic insulating film having an acid-decomposable protecting group having a chain structure), the residual film ratio after cure bake is maintained relatively high, which is caused by acid catalysis or high temperature (220 ° C.) heat treatment during exposure. The reason why the volume shrinkage is limited due to the low volatility of the fallen ring protecting groups is the reason that the heat shrinkage is low.
The volatile deprotecting group itself has lower volatility than the protecting group of the chain structure, and the deprotecting group of the cyclic structure has a relatively high dissolution inhibiting ability to the developer, while maintaining a low concentration of the acid-decomposable protecting group in the binder resin while maintaining sufficient pattern realization. Because it can be realized, it is possible to keep the concentration of by-products generated from the binder resin low.
In addition, the dissolution inhibiting ability of the non-exposed part is higher than the acid-degradable protecting group of the chain structure, so that the acid-degradable protecting group of the ring structure is more maximized, thereby maximizing the dissolution contrast between the exposed part and the non-exposed part. Enables implementation of.
Thus, by providing photosensitivity to the organic insulating film itself prepared by the composition, it can be seen that it is possible to reduce the process of using a separate photoresist in the conventional inorganic insulating layer, it is easier to form a fine pattern.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed exemplary embodiments. It is clear that the present invention can be suitably modified and applied in the same manner. Accordingly, the above description does not limit the scope of the invention as defined by the limitations of the following claims.
Claims (19)
The binder resin is a chemically amplified positive photosensitive organic insulating film composition, characterized in that it comprises a unit (moiety) containing an acid-decomposable protecting group of the ring structure
The binder resin is a chemically amplified positive photosensitive organic insulating film composition comprising a polymer or copolymer comprising the unit
The unit is a chemically amplified positive photosensitive organic insulating film composition, characterized in that made of at least one of the following formula (1-1 to 1-17)
<Formula 1-1><Formula1-2>
<Formula 1-3><Formula1-4>
<Formula 1-5><Formula1-6>
<Formula 1-7><Formula1-8>
<Formula 1-9><Formula1-10>
<Formula 1-11><Formula1-12>
<Formula 1-13><Formula1-14>
<Formula 1-15><Formula1-16>
<Formula 1-17>
In Formulas 1-1 to 1-17, R 1 is a chain aliphatic group, a cyclic aliphatic group, an aryl group, a chain ester group, a cyclic ester group, a chain ether group or a cyclic ether group, and R 1 * Is a hydrogen group or a chain alkyl group, R 2 is a chain alkyl group or a cyclic alkyl group, R 3 is a hydrogen group or a chain alkyl group, R 4 is a hydrogen group, a chain alkyl group or a cyclic alkyl group, R 5 Is a chain alken group or a cyclic alken group, R 6 is a hydrogen group, a chain alkyl group, a cyclic alkyl group or an aryl group.
X may be any of a chain aliphatic group, a cyclic aliphatic group, an aryl group, a chain ester group, a cyclic ester group, a chain ether group, or a cyclic ether group, and the same group as R 1 may be obtained. X is omitted if R 1 is followed by Y without X, and X is hydrogen when terminated with R 1 without X and Y.
In addition, Y is any one of a hydrogen group, a hydroxyl group, an epoxy group, an isocyanate group, an acryloyl group, an aryl group, a vinyl group, or an alkoxy group, and X 1 * and X 2 * are furan-based acid-decomposable protecting groups or pyrans. (pyran) is an acid-decomposable protecting group.
Chemically amplified positive photosensitive organic insulating film composition, characterized in that the unit consists of at least one of the following formula (2) or (3)
<Formula 2><Formula3>
In Chemical Formulas 2 and 3, G is the unit.
The polymer or copolymer may include at least one of Chemical Formulas 4 to 7 below.
<Formula 4><Formula5>
<Formula 6><Formula7>
In Formulas 4 to 7, R 7 is a hydrogen group, a chain alkyl group, a cyclic alkyl group, a carbonyl group, an aromatic group including at least one benzene ring, a chain olefin group, a cyclic olefin group, a chain ester group, a cyclic group Any of ester group, chain ether group, cyclic ether group or alkoxy, Z is hydrogen group, hydroxyl group, chain alkyl group, cyclic alkyl group, alkoxy group, acetoxy group, t-butoxy group or t-butoxy Any one of a carbonyl group, P is either a carbonyloxy group (-COO-), a methyl group (-CH 2- ), a methyloxy group (-CH 2 O-) or an oxygen group (-O-), m Is a repeating unit of monomer in the polymer, where m ≧ 0.
The polymer or copolymer is any one of the following Chemical Formulas 8 to 10: chemically amplified positive photosensitive organic insulating film composition
(8)
≪ Formula 9 >
<Formula 10>
In Formulas 8 to 10, A and B are any one of a nitrogen group or an oxygen group, R 8 is any one of a hydrogen group, a hydroxyl group, an alkyl group or an epoxy group, n is a repeating unit of a monomer in the polymer, n≥1 to be.
The polymer or copolymer is any one of the following Chemical Formulas 11 to 12 chemically amplified positive photosensitive organic insulating film composition
<Formula 11>
<Formula 12>
The average molecular weight of the binder resin is 2000 to 200000, the dispersity is 1 to 10, the chemically amplified positive photosensitive organic insulating film composition
Further comprising a dissolution inhibitor, wherein the dissolution inhibitor is an alkali-soluble phenol compound or a fluorene-based compound containing at least one phenol group, an alkali-soluble compound containing at least one carboxylic acid group or at least one benzoic acid group A chemically amplified positive photosensitive organic insulating film composition, characterized in that an acid-decomposable protecting group is included in at least one of alkali-soluble compounds including
In the dissolution inhibitor, the acid-decomposable protecting group is any one of the acid-decomposable protecting groups represented by Chemical Formulas 1-1 to 1-17.
Further comprising a photoacid generator, wherein the photoacid generator is made of at least one of an onium salt compound, a halogen-containing compound, a sulfone compound, a sulfonic acid ester compound or a triazine-based compound, based on 100 parts by weight of the binder resin, from 0.1 to A chemically amplified positive photosensitive organic insulating film composition comprising 10 parts by weight
A chemically amplified positive photosensitive organic insulating film composition further comprising a PhotoActiveCompound (PAC) comprising a quinonediazide group.
Further comprising an additive, wherein the additive is a chemically amplified positive photosensitive type, characterized in that made of at least one of a thermal crosslinking agent, a thermal stabilizer, a photocuring accelerator, a surfactant, a base quencher, an antihalation agent, an adhesive aid, a light stabilizer or an antifoaming agent. Organic insulating film composition
The thermal crosslinking agent is made of a compound containing at least one of urea resin, melamine resin, isocyanate group, epoxy group, oxetane group, acrylate group, vinyl group, aryl group, hydroxy group or mercapto group Chemically amplified positive photosensitive organic insulating film composition
The thermal stabilizer is a chemically amplified positive photosensitive organic insulating film composition, characterized in that consisting of at least one of a phenolic, lactone-based, amine-based, phosphorous or sulfur-based compound
The optical stabilizer is a chemically amplified positive photosensitive organic insulating film composition, characterized in that consisting of at least one of benzotriazole-based, triazine-based, benzophenone-based, hindered amino ether type or hindered amine compound
The adhesion aid is a chemically amplified positive photosensitive organic insulating film composition, characterized in that the alkoxy silane compound comprising at least one of isocyanate group, amino group, urea group, alkyl group, epoxy group, acrylate group, vinyl group or mercapto group.
The base quencher is a nitrogen-containing organic compound, wherein the nitrogen-containing organic compound is at least one of a primary amine, a secondary amine, a tertiary amine or an amide compound.
Applying the organic insulating film composition on a substrate of a display device and on a source / drain or silicon nitride layer formed on the substrate;
Pre-bake the organic insulating film composition;
Selectively exposing the organic insulating film composition and then developing the organic insulating film composition to form a pattern;
Forming an insulating protective film by subjecting the organic insulating film composition to total surface exposure and cure bake; and forming an insulating protective film.
Priority Applications (5)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
KR1020110023947A KR101406382B1 (en) | 2011-03-17 | 2011-03-17 | Chemically amplified positive-imageable organic insulator composition and method of forming organic insulator using thereof |
TW101108662A TW201245859A (en) | 2011-03-17 | 2012-03-14 | Chemically amplified positive-imageable organic insulator composition and method of forming organic insulator using thereof |
CN2012800123299A CN103477284A (en) | 2011-03-17 | 2012-03-16 | Chemically amplified positive photosensitive composition for an organic insulation film, and method for forming an organic insulation film using same |
PCT/KR2012/001936 WO2012125009A2 (en) | 2011-03-17 | 2012-03-16 | Chemically amplified positive photosensitive composition for an organic insulation film, and method for forming an organic insulation film using same |
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2011
- 2011-03-17 KR KR1020110023947A patent/KR101406382B1/en active IP Right Grant
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2012
- 2012-03-14 TW TW101108662A patent/TW201245859A/en unknown
- 2012-03-16 JP JP2013558794A patent/JP2014514602A/en active Pending
- 2012-03-16 CN CN2012800123299A patent/CN103477284A/en active Pending
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Also Published As
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CN103477284A (en) | 2013-12-25 |
TW201245859A (en) | 2012-11-16 |
JP2014514602A (en) | 2014-06-19 |
WO2012125009A3 (en) | 2012-12-27 |
KR101406382B1 (en) | 2014-06-13 |
WO2012125009A2 (en) | 2012-09-20 |
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