KR101981408B1 - Coating material, pattern formation method, and electronic device and method for manufacturing same - Google Patents

Abstract

The coating material is for forming a pattern having the highest peak of the enemy within 20% from the center of the other enemy, and is composed of two kinds of solvents A and B, which are both solvents having a raw material and a solubility parameter SP value of 20.3 MPa ^1/2 or less , And the solvent A has a surface tension higher than that of the solvent B and a high vapor pressure and a solvent volume content of 20% or more and 50% or less. In the pattern forming method, the above-described pattern is formed by using the coating material. A manufacturing method of an electronic device is such that at least one layer of an electronic device is formed by a pattern formed by using the pattern forming method.

Description

TECHNICAL FIELD [0001] The present invention relates to a coating material, a pattern forming method, and a manufacturing method of the electronic device. [0002] COATING MATERIAL, PATTERN FORMATION METHOD, AND ELECTRONIC DEVICE AND METHOD FOR MANUFACTURING SAME [

The present invention relates to a coating material, a method of forming a pattern and a method of manufacturing an electronic device, and more particularly to a coating material in which a good cross-section pattern is obtained in an inkjet process in the field of printed electronics, A pattern forming method using a coating material as an ink jet ink, and a method of manufacturing an electronic device having a functional layer formed by a pattern formed by using the pattern forming method.

In recent years, various research institutes have been accelerating research and development to manufacture electronic devices and energy devices such as transistors by the remarkable resource saving and energy saving techniques such as liquid process. These technologies are collectively referred to as " printed electronics " and are highly anticipated as next-generation semiconductor manufacturing process technologies.

There is a phenomenon called " coffee stain " in the edge portion, that is, a phenomenon that the periphery or end of the wiring or the electrode rises when the inkjet is used as the process. These are not limited to electrodes, and it is not preferable in terms of reliability in electronic devices that such a shape is generated in a semiconductor material or an insulating material.

Generating factors of the coffee stain are generally said to be caused by the occurrence of Marangoni convection resulting from the concentration dependence of the surface tension. In the general solution, since the relationship between the relationship of the surface tension and the concentration is in a proportional relationship, the surface tension of the end portion of the droplet, which is likely to increase in concentration due to drying, increases. As a result, a gradient of the surface tension occurs in the droplet, and the liquid spreads as if the entire liquid is drawn to the end. As a result, a solute is concentrated at the end portion, and the edge becomes a patterned shape (see Patent Document 1).

Thus, in the wiring pattern disclosed in Patent Document 1, the conductive pattern is formed on the high-surface energy portion, which is changed from the low-surface energy portion by the application of energy to the wettability- The shape viewed from the plane is formed into a rectangular wiring shape having rounded end portions chamfered at corner portions.

Thus, in the technique disclosed in Patent Document 1, in the process of forming the wiring pattern, when a flow of ink applied from the center of the pattern having a slow evaporation rate to the periphery of the pattern having a high evaporation rate occurs and the ink is wet- The ink at the edge portion having a higher evaporation rate at the end portion of the rectangular wiring shape seen from the plane of the layer flows, particularly the edge portion with the sharp and right angle, flows. Particularly, the film thickness of the corner portion becomes thick, So that a peak (convex bump), so-called " bulge " is prevented from being formed.

Patent Document 1: JP-A-2008-066567

However, in the technique disclosed in Patent Document 1, since the end portion of the rectangular wiring shape viewed from the plane of the conductive pattern layer is formed into a round shape, the edge of the protruding edge at the sharp corners of the rectangular wiring- However, since the rectangular wiring pattern viewed from this plane has an edge even if it has a round shape, the edge rises even if it is at a low level, and there is a problem that the edge ridge itself can not be prevented.

Further, in the field of printed electronics, a solution used in a general coating process such as a spin coat or a slit coat often uses a solution composition in which the relationship between the surface tension and the concentration is proportional to each other. &Quot;, the rise of the edge portion becomes an inevitable problem.

In order to solve the above problems, there is a case where a surfactant or the like is added so as to reduce the relationship between the surface tension and the concentration dependency as much as possible. In such a case, there is a fear that the surfactant itself may affect the electrical properties In the field of printed electronics, it is not preferable to add an additive to a coating material because there is a problem.

In order to control such a rising shape of the edge, there is an example in which a coating process is devised to solve the problem. However, there is a problem in that it causes an increase and complication of the process inevitably, It is preferable not to give a process.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems and problems in the prior art, and it is an object of the present invention to provide a coating material which is used in the field of printed electronics and which can obtain a good cross- And a method of manufacturing an electronic device manufactured by a pattern formed by using the pattern forming method.

As a result of intensive studies, the inventors of the present invention have found that a solvent of a solution of a coating material is composed of two or more components, and the relationship between the surface tension and the concentration dependency upon drying of the droplets is in inverse proportion , It is possible to obtain a good cross-section pattern by suppressing the ridges of the edge portions, and thus the present invention has been completed.

That is, the coating material according to the first aspect of the present invention is a coating material for forming a pattern having the highest peak of the enemy within 20% from the center of the droplet ejection, and has a raw material and solubility parameter SP value of 20.3 Wherein the solvent A contains two kinds of solvents A and B which are both solvents having an MPa ^1/2 or less and the solvent A has a surface tension higher than that of the solvent B and a vapor pressure higher than that of the solvent B and a solvent volume content of 20% .

Here, it is preferable that the solvent A has a surface tension higher by 1.17 times or more and a vapor pressure of 1.57 times or more higher than that of the solvent B.

When the surface tension of the solvent A at 20 캜 is 27 mN / m or more, the vapor pressure is 1.1 kPa or more, the surface tension of the solvent B at 20 캜 is 23 mN / m or less and the vapor pressure is 0.7 kPa or less .

It is also preferable that the solvent A contains 35% or more and 50% or less of the solvent volume content.

It is also preferable that the raw material is composed of a silazane compound.

It is also preferable that the coating material is an inkjet coating material.

The pattern forming method according to the second aspect of the present invention is characterized by using the coating material according to the first aspect to form a pattern having the highest peak of the enemy within a range of 20% from the center of the other enemy .

Here, a pattern having the highest peak of another enemy within 20% from the center of another enemy is within 20% of the center of the other enemy, and the cross-sectional profile of the other enemy passing through the center of the other enemy, It is preferable that the pattern has a maximum value.

It is also preferable that the edge portions on both sides of the cross-sectional profile of the other enemy are rounded.

The method for manufacturing an electronic device according to the third aspect of the present invention is characterized in that at least one layer of the electronic device is manufactured by the pattern forming method according to the second aspect of the present invention.

Here, it is preferable that at least one layer of the electronic device is at least one of an insulating layer, a protective layer, and an interlayer insulating layer.

It is also preferable that the electronic device is a thin film transistor.

According to the present invention, in the field of printed electronics, by making the solvent of the solution more than two components and making the relationship between the surface tension and the concentration dependency upon the droplet drying in an inverse relationship, A pattern forming method using the coating material, and a method of manufacturing an electronic device manufactured by a pattern formed by using the pattern forming method can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a cross-sectional view schematically showing an example of a pattern of another enemy formed in a pattern forming method using a coating material according to the present invention. FIG.
2 is a schematic cross-sectional view of one embodiment of a transistor which is an embodiment of an electronic device manufactured by the method of the present invention.
3 (A), 3 (B) and 3 (C) are schematic diagrams each showing an inkjet special pattern image formed using the coating material of Example 1, a graph showing a cross-sectional profile on the special pattern, 1 is a photograph showing a spin coating film formed using the coating material of Example 1 in place of the drawing.
4 (A), 4 (B) and 4 (C) are schematic views showing an ink-jet pattern pattern formed using the coating material of Comparative Example 1, a graph showing a sectional profile on the pattern, 5 is a photograph showing a spin coating film formed by using a coating material.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a coating material, a pattern forming method, and a manufacturing method of an electronic device according to the present invention will be described in detail with reference to the accompanying drawings based on the preferred embodiments.

(Coating material)

The coating material of the present invention, the other intended to form a pattern having an enemy other peaks in the region of less than 20% from the center of the enemy, the raw material, and a solubility parameter SP value of not more than 20.3MPa ^1/2 dual chained two kinds of solvent A, and B, wherein the solvent A has a surface tension higher than that of the solvent B, a higher vapor pressure, and a solvent volume content of 20% or more and 50% or less.

The coating material according to the present invention is useful as a liquid coating material used for forming a predetermined pattern constituting the functional layer when laminating functional layers such as an electronic device such as a thin film transistor in the field of printed electronics, Particularly, it is preferable to be a coating material for inkjet.

In the present invention, the electronic device is not particularly limited as long as it is an electronic device to which the printed electronic technology is applied. For example, a thin film transistor, a solar battery, a RFID, a temperature monitor, a gas sensor, An infrared sensor, an organic EL light, a display device, and the like.

The functional film is not particularly limited as long as it is a functional film constituting at least one layer of an electronic device or the like, and examples thereof include an insulating layer, a protective layer, an interlayer insulating layer, a gas barrier layer and an optical thin film.

(Special pattern)

First, patterns of other enemies formed by the coating material according to the present invention will be described with reference to Fig.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a cross-sectional view schematically showing an example of a pattern shape of an enemy object formed by the pattern forming method of the present invention using the coating material of the present invention. Fig.

As shown in Fig. 1, the special character 10 formed in the present invention is formed by a convex pattern formed on the substrate 12, preferably by ink droplets formed on the substrate 12 by inkjet And has a convex pattern. The upper surface of the pattern of this tangs 10 is located at the center of the tangs 10 when taking the center 14 of the tangs 10 in a direction perpendicular to the bottom surface of the tangs 10, Having a maximum point within a region 20 within 20%

Specifically, the pattern of the differentiator 10 is a pattern that passes through the center 14 of the other 10 as shown in Fig. 1 and has a plane perpendicular to the bottom surface, that is, the surface of the substrate 12 It is preferable that the cross-sectional profile 18 is a convex-shaped pattern having the highest point in the region 20 within 20% from the center of the target 10.

In the present invention, the top surface of the pattern of the target object 10, for example, the end face profile 18 of the target object 10 has the maximum point within the region 20 within 20% from the center of the target object 10 Any portion of the edge 16 existing on both sides of the center 14 of the marble 10 may be angled or rounded, It is preferable to have a convex curved shape that is convex upward from the both edges 16 of the convex portion 10 toward the center 14 thereof. Of the center of gravity from the center 14 of the target 10 to the center 14 from the edge 16 of the target 10 existing on both sides of the center 14, It is most preferable to have a peak at the inner core 14 of the inner tube 20.

Here, the pattern of the counter electrode 10 is not particularly limited, but is preferably a pattern formed by an ink-jet method. Any pattern may be used as long as it is an ink-jet pattern. For example, A circular pattern formed by a plurality of ink droplets ejected from a plurality of inkjet nozzles, or a closed-loop pattern such as a circular or elliptical shape formed by a plurality of ink droplets ejected from a plurality of inkjet nozzles Or may be a linear pattern.

The cutting method of the cross section of the other enemies in the present invention can be applied to any pattern of other enemies, for example, in a closed-curve pattern, a linear pattern, that is, Any cross section may be used as long as it is cut in a plane perpendicular to the plane. That is, the profile of another enemy may be a profile in any cross section.

In addition, the cross-sectional profile in the present invention can be measured using a device of Wyko manufactured by Veeco, an optical interference type surface roughness meter. Can be detected by measuring the cross section obtained by the optical interference method of a white LED and a green LED (535 nm) light source.

(menstruum)

In the present invention, it is necessary that the coating material for forming the above-mentioned special pattern is composed of two types of solvent A and solvent B having different surface tension and vapor pressure.

The two kinds of solvents A and B are solvents having a solubility parameter (SP value) of not more than 20.3 MPa ^1/2 , preferably not less than 14.1 and not more than 20.3, both of which are easy to dissolve the raw material of the coating material.

Here, the SP value of the two solvents A and B is limited to 20.3 MPa < ^{1/2 >} or less because if the SP value exceeds 20.3 MPa < ^{1/2 &} gt ;, solubility decreases.

Examples of such solvents include aliphatic hydrocarbons such as pentane (14.3), hexane (14.9), heptane (15.1), octane (15.6) and dodecane (16.2), methylcyclohexane , Cyclohexane (16.8) and cyclopentane (17.8), cumene (16.8), propylbenzene (17.6), ethylbenzene (18.0), p-xylene (18.0), mesitylene (16.6), isopropyl (16.6) chloride, 1-chloropropane (17.4), chloroform (19.0), and the like, which are aromatic hydrocarbons such as benzene (18.0), toluene (14.1), diethyl ether (15.1), dibutyl ether (16.0), dipropyl ether (16.0), and ethylene glycol (14.0) such as chlorobenzene (20.3), MEK (9.3), cyclohexanone (20.3), diisobutyl ketone (16.0), methyl isobutyl ketone (17.2), and diethyl ketone 18.0), and the like And a mixed solvent of two or more of the foregoing solvents. In addition, the numbers in parentheses after the organic solvent name indicate the SP value (unit: MPa ^1/2 ).

The SP value of such an organic solvent can be measured by a method described in, for example, "Polymer Handbook", Fourth Edition, pages VII-675 to VII-711 (particularly, Formula]. Values of Table 1 (VII-683) and Table 7 to Table 8 (pages VII-688 to VII-711) of the literature can be adopted as the SP value of the organic solvent. The SP value in the case where the organic solvent is a mixed solvent of a plurality of solvents can be determined by a known method. For example, the SP value of the mixed solvent can be determined as the sum of the product of the SP value and the volume fraction of each solvent, assuming that pseudo-property is established.

In the present invention, the good solvent is a solvent which easily dissolves the starting material to be the solute, preferably a solvent which is mixed with the starting material in an unlimited manner over the entire range of the normal temperature. For example, A solvent whose difference in SP value is 10 MPa < ^{1/2 >} or less is preferable.

In the present invention, it is necessary to use two kinds of solvents A and B different in surface tension and vapor pressure from the above-mentioned good solvent having an SP value.

In the two kinds of solvents A and B, it is necessary that one of the solvents, for example, the solvent A, has a higher surface tension and a higher vapor pressure than the other solvent, for example, the solvent B. It is also preferable that the solvent A has a surface tension higher by 1.17 times or more and a vapor pressure of 1.57 times or more higher than the solvent B, more preferably a surface tension of 1.25 times or more and a vapor pressure of 1.8 times or more . It is also preferable that the solvent A has a surface tension of at least 27 mN / m at 20 ° C, a vapor pressure of 1.1 kPa or more, a surface tension of the solvent B at 20 ° C of 23 mN / m or less and a vapor pressure of 0.7 kPa or less More preferable.

The upper limit value of the ratio of the surface tension and the vapor pressure of the solvent A to the solvent B is not particularly limited, but is preferably, for example, 6 times or less and 10 times or less, respectively.

The upper limit of the surface tension and the vapor pressure of the solvent A at 20 캜 is not particularly limited, but is preferably 90 mN / m or less and 100 kPa or less, for example. The lower limit of the surface tension and the vapor pressure of the solvent B at 20 캜 is not particularly limited, but is preferably 15 mN / m or more and 0.1 kPa or more, for example.

In addition, in the present invention, it is necessary to add, to the solution, a solvent having a high surface tension and a high vapor pressure in addition to the main solvent, for example, solvent B, as a solvent for the solution of the coating material. The reason is as follows.

In the case where two or more components are used, the surface tension of the solution is a weighted average with the composition ratio thereof, and when all the solvents are dried at the same volatilization rate, And as a result, a concentration rise occurs at the edge portion, and the surface tension is increased, so that the relationship between the surface tension and the concentration dependency is proportional. As a result, it is considered that the edge portion of the other enemy rises and the coffee stain phenomenon can not be suppressed.

However, most of the volatilization rates of the respective solvents are different due to different vapor pressures.

Therefore, when the effect of the solvent A having a high surface tension and a high volatility is large in the drying process, the relationship of the concentration dependence of the surface tension becomes inversely proportional. That is, since drying of the other enemies is faster at the edge portion than at the center portion of the other enemy, the concentration of the solution in the solution of the edge portion is increased, but the solvent A having a high surface tension and high volatility has a low surface tension, Is evaporated faster than the lower solvent B, the ratio of the solvent A in the solvent of the edge portion is lowered, and the ratio of the solvent B having a lower surface tension and lower volatility is increased. As a result, in the edge portion, the surface tension of the solvent is lower than in the center portion. As a result, the surface tension becomes small at the droplet end portion where the concentration becomes high, and the surface tension becomes large at the droplet center portion. As a result, it is possible to suppress the rising of the edge portion and suppress the coffee stain phenomenon.

As a result, in the pattern formed using the coating solution of the present invention, as shown in Fig. 1, the highest peak of the enemy is within 20% from the center of the other enemy, and the coffee stain phenomenon can be suppressed.

The reason why the ratio of the surface tension and the vapor pressure of the solvent A to the solvent B, the value of the surface tension and the vapor pressure of the solvent A, and the value of the surface tension and the vapor pressure of the solvent B are limited to the above- This is because the relationship between the concentration dependency of the surface tension of the solution in the other region is preferable in order to make the relationship in an inverse proportion to the rise of the edge portion in an appropriate manner.

In the present invention, when two kinds of solvents A and B are used as the solvent of the solution of the coating material, it is preferable that the solvent A having a high surface tension and a high vapor pressure has a solvent volume content of not less than 20% By weight or less.

The reason is that when the solvent volume content of the solvent A having a high surface tension and a high vapor pressure is within the range of 20% to 50%, as shown in FIG. 1, It is possible to form a pattern of the target 10 having a pattern shape defined by the present invention and having the highest point in the region of the area of the substrate 10 and suppressing the coffee stain phenomenon. However, when less than 20% or more than 50% It is not possible to form a special pattern having a pattern shape defined in the present invention.

Further, in the present invention, it is preferable that the solvent volume content of the solvent A having a high surface tension and a high vapor pressure is contained in an amount of 35% or more and 50% or less. In this case, not only the highest point in the region within 20% from the center 14 of the differentiator 10 but also the rounded portion of the edge 16 can form a convex-shaped special pattern.

(Raw material)

The raw material of the coating material according to the present invention is not particularly limited as long as it can form a special pattern, but it is preferable to form a predetermined special pattern constituting a functional layer such as an electronic device such as a thin film transistor, Examples thereof include a silazane compound, polystyrene, polycarbonate, polyethylene, and the like.

(Silazane compound)

The silazane compound is a compound having a bond of silicon and nitrogen (-SiN-) in the structure thereof, and is a silicon oxide film (hereinafter also referred to as SiO ₂ film) which is a functional film such as an insulating layer, a protective layer, (Hereinafter also referred to as a SiON film) or a silicon nitride film (hereinafter also referred to as a SiN film).

Such SiO ₂ film, SiON film and SiN film can be suitably used for various purposes. For example, a gate insulating film of a transistor, an interlayer insulating film, a gas barrier film, and an optical thin film can be given.

The silazane compound may be a low-molecular compound or a polymer compound (a polymer having a predetermined repeating unit). Examples of low molecular weight silazane compounds include hexamethyldisilazane, hexaphenyldisilazane, dimethylaminotrimethylsilazane, trisilazane, cyclotrisilazane, 1,1,3,3,5,5,5-hexa Methyl cyclotrisilazane, and the like.

The kind of the high-molecular-weight silazane compound (polysilazane compound) is not particularly limited. For example, a compound having a main skeleton composed of units represented by the following general formula (1) described in JP-A- Compound.

[Chemical Formula 1]

In the above general formulas, R ¹ , R ² and R ³ each independently represent a hydrogen atom, an alkyl group, an alkenyl group, a cycloalkyl group, an aryl group, an alkylsilyl group, an alkylamino group or an alkoxy group.

As the polysilazane, it is preferable that the polysilazane is a perhydro polysilazane (hereinafter also referred to as " PHPS ") in which all of R ¹ , R ² , and R ³ are hydrogen atoms.

Perhydro polysilazane is presumed to have a linear structure, a ring structure centered on a 6-membered ring and an 8-membered ring. The molecular weight is a number average molecular weight (Mn) of about 600 to 2000 (in terms of polystyrene), and may be a liquid or a solid substance (depending on the molecular weight). The perhydropolysilazane may be a commercially available product. Examples of commercially available products include Aquamica NN120, NN120-20, NN110, NAX120, NAX120-20, NAX110, NL120A, NL120-20, NL110A, NL150A, NP110, NP140 AZ Electronic Materials Co., Ltd.) and the like.

As another example of the polysilazane, a polysilazane having a silicon alkoxide additionally obtained by reacting a polysilazane represented by the above formula with a silicon alkoxide (for example, JP-A-5-238827) and glycidol (For example, JP-A-6-122852), an alcohol-added polysilazane obtained by reacting an alcohol (for example, JP-A-6-240208) (Japanese Unexamined Patent Publication (Kokai) No. 6-299118), an acetylacetonate complex addition product obtained by reacting an acetylacetonate complex containing a metal and a metal carboxylate added polysilane obtained by reacting a metal carboxylate (For example, Japanese Unexamined Patent Application Publication No. 6-306329), a metal fine particle-added polysilazane obtained by adding metal fine particles (for example, Japanese Unexamined Patent Application Publication No. 7-196986).

The molecular weight of the polysilazane compound is not particularly limited. For example, the average molecular weight in terms of polystyrene is preferably in the range of 1,000 to 20,000, more preferably 1,000 to 10,000. These polysilazane compounds may be used in combination of two or more.

The mass ratio of the silazane compound and the solvent (solvent A and solvent B) (mass of the silazane compound / mass of the solvent (solvent A and solvent B)) in the coating material of the present invention is not particularly limited, The optimum mass ratio is appropriately selected according to the thickness of the coating film (coating film), and is preferably 0.01 to 0.50, more preferably 0.05 to 0.20, from the standpoint of other suitability.

The coating material of the present invention may contain other additive components as required. Examples of such components include a viscosity adjusting agent and a crosslinking accelerator.

The coating material of the present invention is basically composed as described above.

(Pattern forming method)

The pattern forming method of the present invention is a method of forming a pattern having the highest peak of the enemy within the region 20 within 20% from the center of the target 10 as shown in Fig. 1 by using the coating material of the present invention described above Method.

In the pattern forming method of the present invention, since the solvent A is a good solvent for the raw material, and both the solvent A having a high surface tension and the vapor pressure and the low solvent B are both used, , It is possible to form a pattern having the highest peak of another enemy within the region 20 within 20% from the center of the target 10 as shown in Fig.

The other method of applying the coating material of the present invention is not particularly limited. However, by using the inkjet method, for example, a droplet of the coating material of the present invention is discharged onto the substrate 12 from an inkjet nozzle to form a special spot 10 If it can, it can be any method.

As described above, in the present invention, the pattern of the target object 10 can be ejected from one or more inkjet nozzles as long as it is a pattern having the highest point of other enemies within the region 20 within 20% from the center of the target object 10 Like shape such as a circular shape or an elliptical shape formed by at least one ink droplet formed thereon, or may be a linear pattern.

In the present invention, when a droplet of the coating material of the present invention is discharged from the inkjet nozzle to form a pattern of the target 10 on the substrate 12, a plurality of inkjet nozzles The loaded carriage may be moved, the substrate 12 may be intermittently transported and the carriage may be moved, or the carriage may be fixed and the substrate 12 may be transported.

The shape, structure and size of the substrate on which the coating material of the present invention is applied and on which other patterns are formed are not particularly limited and can be appropriately selected according to the purpose. The substrate may have a single-layer structure or a stacked-layer structure.

The material of the substrate is not particularly limited. For example, inorganic materials such as glass, alumina, and YSZ (yttrium stabilized zirconium), resin materials, and composite materials thereof can be used. Among them, a resin substrate and a composite material thereof are preferable in that they are lightweight and have flexibility.

The thickness of the pattern of the resist pattern 10 after the pattern formation can be appropriately adjusted so as to be suitable for the post-treatment performed on the pattern of the resist pattern 10 formed on the substrate 12, for example, in the ultraviolet ray irradiation and / It is preferable to be thin so as to be capable of being converted (telephoned). Due to this, the thickness of the special pattern is preferably 1.0 占 퐉 or less, more preferably 0.5 占 퐉 or less. On the other hand, although there is no lower limit to the thickness of the special pattern, from the viewpoint of the film formability, 0.05 m or more is preferable, and 0.1 m or more is more preferable.

When a flexible substrate is used as the substrate and a coating material containing a silazane compound is used as the coating material of the present invention, the SiO ₂ film, the SiON film, and the SiN film A special pattern of the coating material of the present invention may be formed on both sides of the substrate in order to suppress warpage of the substrate due to volumetric shrinkage that occurs when making a telephone call.

The pattern forming method of the present invention is basically configured as described above.

(Manufacturing Method of Electronic Device)

The method of manufacturing an electronic device of the present invention is a method of manufacturing at least one layer constituting an electronic device as a functional film by using a special pattern formed by the above-described pattern forming method of the present invention.

Hereinafter, as a typical example of a thin film transistor as an electronic device, a gate insulating film of a thin film transistor as a functional film is taken as a representative example, and a SiON film formed by the coating material of the present invention using a silane- However, it goes without saying that the present invention is not limited to this.

2 is a schematic cross-sectional view of one embodiment of a thin film transistor which is one embodiment of the electronic device of the present invention.

2, the thin film transistor 50 includes a substrate 52, a gate electrode 54 disposed on the substrate 52, a gate insulating film 56 disposed on the gate electrode 54, An oxide semiconductor layer 58 disposed on the insulating film 56 and a source electrode 60 and a drain electrode 62 disposed on the oxide semiconductor layer 58.

The gate insulating film 56 is formed by using the coating material of the present invention containing two kinds of solvents having a silazane compound as a raw material and being a good solvent for the raw material and having a different surface tension and a different vapor pressure, Formed by a SiON film having a tantalum pattern formed by a forming method.

The thin film transistor 50 is a bottom gate type thin film transistor. Hereinafter, only the bottom gate type thin film transistor will be described in detail, but the SiON film according to the present invention method may be applied to the gate insulating film of the top gate type thin film transistor. The gate insulating film 56 is disposed adjacent to the oxide semiconductor layer 58. When the SiON film is used, the interface characteristics with the oxide semiconductor layer 58 are further improved and the performance as a thin film transistor is further improved.

In the case of using the SiON film subjected to the oxidation process, it is preferable that the surface subjected to the oxidation process is disposed on the oxide semiconductor layer 58 side.

Although the oxide thin film transistor using the oxide semiconductor layer is described in detail in Fig. 2, the SiON film according to the present invention method is also suitable as a gate insulating film of an organic thin film transistor using an organic semiconductor layer containing an organic semiconductor material Can be used.

In manufacturing the thin film transistor 50 as an electronic device according to the method of the present invention, as shown in Fig. 1, first, an electrode material is vacuum deposited or sputtered on a substrate 52 by a known method The gate electrode 54 is formed.

Next, a special pattern without edge ridges is formed on the formed gate electrode 54 by the pattern forming method of the present invention by using the coating material of the present invention, and then a telephone process is performed to form the SiON film on the gate insulating film 56).

Thereafter, an oxide semiconductor layer 58 is formed on the gate insulating film 56 by a known method and patterned and separated on the oxide semiconductor layer 58 formed in the same manner as the gate electrode 54 The source electrode 60 and the drain electrode 62 are formed.

Thus, the thin film transistor 50 can be manufactured by the method of the present invention.

Hereinafter, the substrate, the gate electrode, the gate insulating film, the oxide semiconductor layer, the source electrode, and the drain electrode will be described in detail.

<Substrate>

The substrate serves to support a gate electrode, a source electrode, a drain electrode, and the like, which will be described later. The type of the substrate is not particularly limited, and the above-described substrate and the like are also exemplified.

<Gate electrode>

Examples of the material of the gate electrode include metals such as gold (Au), silver, aluminum, copper, chromium, nickel, cobalt, titanium, platinum, magnesium, calcium, barium and sodium; Conductive oxides such as In ₂ O ₃ , SnO ₂ and ITO; Conductive polymers such as polyaniline, polypyrrole, polythiophene, polyacetylene, and polydiacetylene; Semiconductors such as silicon, germanium, and gallium arsenide; Carbon materials such as fullerene, carbon nanotube, and graphite. Among them, a metal is preferable, and silver and aluminum are more preferable.

The thickness of the gate electrode is not particularly limited, but is preferably 10 nm or more and 1000 nm or less, more preferably 50 nm or more and 500 nm or less.

The method for forming the gate electrode is not particularly limited, and examples thereof include a method of vacuum depositing or sputtering an electrode material on a substrate, a method of applying or printing a composition for forming an electrode, and the like. When the electrode is patterned, the patterning may be performed by, for example, a photolithography method; Printing methods such as inkjet printing, screen printing, offset printing, and relief printing; And a mask deposition method.

&Lt; Gate insulating film &

The gate insulating film is formed of the above-described SiO ₂ film, SiON film, and SiN film.

Here, when the insulating film is formed, the coating material of the present invention containing two kinds of solvents, which are silazane compounds as raw materials and are both good solvents for the raw materials and whose surface tension and vapor pressure are different from each other, After the formation of a special pattern free of edge ridges by the pattern formation method, the formed special pattern is subjected to the telephotographic treatment with respect to the special pattern without drying or drying.

(Telephone process) in which ultraviolet rays are irradiated and / or a special pattern is heated (heat treatment is performed) is performed in a non-oxidizing atmosphere. By carrying out such a treatment, a call from the silazane compound to the desired SiON film and SiN film proceeds. In this manner, the SiON film and the SiN film having the pattern shape without edge ridges can be formed as the gate insulating film.

(Telephone process) in which an ultraviolet ray is irradiated and / or a special pattern is heated (a heating process is performed) is performed in an oxidizing atmosphere. By carrying out such a treatment, the dialysis from the silazane compound to the desired SiO ₂ film proceeds. Thus, an SiO ₂ film having a pattern shape without edge ridges can be formed as a gate insulating film.

The film thickness of the gate insulating film is not particularly limited, but is preferably 70 to 1000 nm.

In addition, although FIG. 2 shows an embodiment in which the gate insulating film is a SiON film, the present invention is not limited to this embodiment. For example, by using the coating material of the present invention, It may be a laminated insulating film in which a SiON film and another gate insulating film are laminated. In this case, it is preferable that the portion in contact with the oxide semiconductor layer is the SiON film of the present invention.

Examples of the other gate insulating film include a polymer insulating film containing a polymer as an insulating material. Examples of the polymer include at least one polymer selected from the group consisting of a vinyl polymer, a styrene polymer, an acrylic polymer, an epoxy polymer, an ester polymer, a phenol polymer, an imide polymer, and a polymer composed of a cycloalkene. And the like.

More specifically, examples of the polymer insulating film include films of polyethylene (PE), polypropylene (PP), polytetrafluoroethylene (PTFE), polyvinyl chloride (PVC), polyvinyl alcohol (PVA), polyvinyl phenol (PS), polyacrylate, polymethyl methacrylate (PMMA), polyacrylonitrile (PAN), polycarbonate (PC), polytetrafluoroethylene (PET), parylene, poly A polymer insulating film containing at least one polymer selected from the group consisting of phenylene sulfide (PPS), polyimide (PI), polybenzocyclobutene (BCB), polycyclopentene (CyPe), and polysilsesquioxane .

<Oxide Semiconductor Layer>

The oxide semiconductor layer functions as an active layer and is made of an oxide of one or more kinds of, for example, indium (In), gallium (Ga), tin (Sn) and zinc (Zn) Examples of such oxides include indium gallium gallium oxide (IGZO, InGaZnO). In addition to indium gallium indium oxide, it is possible to use indium zinc oxide, In-Sn-Zn-O alloy, In-Sn-Zn-O alloy, In-Zn-O alloy, In-Sn-O alloy, Zn- .

Although the thickness of the oxide semiconductor layer is not particularly limited, it is preferably 5 to 300 nm.

The method of forming the oxide semiconductor layer is not particularly limited, and a known method can be employed. For example, a spin coat, an ink jet, a dispenser, a screen printing, a relief printing, or a concave printing can be used. A vapor phase method such as a sputtering method or a vapor deposition method may be employed.

<Source Electrode, Drain Electrode>

Specific examples of the material of the source electrode and the drain electrode are the same as those of the above-described gate electrode.

The method for forming the source electrode and the drain electrode is not particularly limited. For example, a method of vacuum depositing or sputtering an electrode material on a substrate having a gate electrode, a gate insulating film and an oxide semiconductor layer formed thereon, And a method of printing. A specific example of the patterning method is the same as the above-mentioned gate electrode.

The channel length of the source electrode and the drain electrode is not particularly limited, but is preferably 0.01 to 1000 mu m.

The channel width of the source electrode and the drain electrode is not particularly limited, but is preferably 0.01 to 5000 mu m.

The method of manufacturing an electronic device of the present invention is basically configured as described above.

Example

Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto.

(Example I)

First, a polysilazane solution (120 series: dibutyl ether solvent and 110 series: xylene solvent) manufactured by AZ-EM was used as a raw material, and various solvents were mixed with solvent A and solvent B at a volume ratio of 1: 1 , The mixed solutions of Examples 1 and 2 and Comparative Examples 1 to 8 were obtained. Table 1 shows the mixed solutions of Examples 1 to 2 and Comparative Examples 1 to 8. The values of the vapor pressure and the surface tension shown in Table 1 are values at 20 占 폚.

[Table 1]

Wettability was confirmed by spin-coating the obtained mixed solutions of Examples 1 and 2 and Comparative Examples 1 to 8 on a silicon substrate.

A and A were applied uniformly, and B was evaluated when there was unevenness on the coated surface. The results are shown in Table 1.

As is apparent from the results shown in Table 1, in Examples 1 and 2 in which solvent A was toluene and chlorobenzene, solvent A and solvent B had a surface tension ratio of 1.17 or more, and a vapor pressure ratio was 1.57 or more when solvent B was dibutyl ether, As shown in Fig. 3 (C), it was confirmed that the spin coat film was in poor B evaluation.

On the other hand, in Comparative Examples 1 to 4 and 7 to 8 using Solvent A having a surface tension ratio of Solvent A and Solvent B of less than 1.17 when solvent B was dibutyl ether or xylene and the vapor pressure ratio of Solvent A and Solvent B was less than 1.57 It was confirmed that the spin coat films were evaluated as good A in Comparative Examples 1 and 5 to 6 using Solvent A and therefore in Comparative Examples 1 to 8 as shown in Fig.

The mixed solution of Examples 1 and 2 and Comparative Examples 1 to 8 was discharged using an inkjet apparatus DMP2830 manufactured by FUJIFILM DIMATIX, and the pattern shape of the discharged foreign object, that is, the cross-sectional profile was confirmed. Also, the cross-sectional profile was confirmed by measuring the optical interference phase with Wyko manufactured by Veeco.

A when the maximum value is taken in the region within 20% from the central portion of the special pattern, and B when the maximum value is taken in the region other than 20% from the central portion. The results are shown in Table 1.

As apparent from the results shown in Table 1, in Examples 1 and 2 in which the film was not formed well in the spin coat, as shown in Figs. 3 (A) and 3 (B) , It was confirmed that a cross-sectional profile having a convex shape with a good A evaluation from the edge to the center was obtained with the maximum value in the region of 20% from the center.

On the other hand, as shown in Figs. 4 (A) and 4 (B), in Comparative Examples 1 to 8 in which the spin-coat film was satisfactory, there was a problem that there was a ridge due to the occurrence of a coffee stain phenomenon on the formed ink- It is confirmed that the cross-sectional profile of the B evaluation with the B evaluation is obtained.

From the results in Table 1, it was confirmed that the solution composition without wetting diffusion of Examples 1 and 2 is suitable for inkjet pattern formation having a good cross-sectional profile.

(Example II)

Next, the wettability of the spin-coated film and the pattern shape on the ink-jet pattern, particularly the pattern shape on the ink-jet pattern, in particular, by changing the volume ratio of the toluene solvent A and the dibutyl ether solvent B in the combination of the raw material of Example 1, the solvent A and the solvent B And the change of the edge shape was confirmed.

The wettability of the spin coat film was evaluated in the same manner as in Example I.

The pattern shape on the ink-jet pattern is AA when the maximum value in the cross-sectional profile is in the center portion (in the region of 20% from the center) of the special pattern, the edge portion is rounded, A was evaluated when the edge portion was observed, and B when the edge portion was present at the edge portion of the other pattern. Also, the cross-sectional profile was confirmed by measuring the optical interference phase with Wyko manufactured by Veeco.

The results are shown in Table 2.

[Table 2]

As is clear from the results shown in Table 2, in Examples 11 to 17 in which the volumetric content of toluene as the solvent A was in the range of 20% or more and 50% or less, a good spin coat film free from unevenness was not formed, , It was confirmed that the pattern shape is the A or AA evaluation capable of suppressing the coffee stain phenomenon by taking the maximum value of the profile at the central portion (within 20% region from the center) of the special pattern.

On the other hand, in Comparative Examples 11 and 12, in which the volume ratio of toluene as the solvent A was more than 50%, and Comparative Examples 12 to 15, which were less than 20%, a good spin coat film having no unevenness could be formed and evaluation A was obtained. It was confirmed that the maximum value of the profile can not be taken in the center portion (within the range of 20% from the center), and the evaluation is the B evaluation in which the coffee stain phenomenon is not suppressed.

Particularly, in Examples 11 to 14 in which the volumetric content of toluene as the solvent A is in the range of 35% or more to 50% or less, the pattern shape is the center portion (in the region of 20% from the center) The maximum value of the profile is taken and the edge portion is also rounded to confirm that it is an AA evaluation that can obtain a good shape.

(Example III)

Next, a mixed solution of Examples 21 to 22 and Comparative Examples 21 to 22 was prepared by mixing various solvents at a volume ratio of 1: 1 using various solvents as Solvent A and Solvent B, using Wako Junyaku Polystyrene (Mw = 300) &Lt; / RTI &gt; The mixed solutions of these Examples 21 to 22 and Comparative Examples 21 to 22 are shown in Table 3. The values of the vapor pressure and the surface tension shown in Table 3 are values at 20 占 폚.

[Table 3]

The wettability was confirmed by spin-coating the obtained mixed solutions of Examples 21 to 22 and Comparative Examples 21 to 22 on a silicon substrate.

The wettability of the spin coat film was evaluated in the same manner as in Example I. The results are shown in Table 3.

As apparent from the results shown in Table 3, in Examples 21 and 22 in which solvent A was toluene and chlorobenzene, solvent A and solvent B had a surface tension ratio of 1.17 or more, and a vapor pressure ratio was 1.57 or more when solvent B was dibutyl ether, , It was confirmed that the spin coat film was in an unsatisfactory B evaluation.

On the other hand, Comparative Examples 21 to 22 using Solvent B having a surface tension ratio of Solvent A and Solvent B of less than 1.17 when solvent A was toluene, Comparative Example 21 using Solvent B having a vapor pressure ratio of Solvent A and Solvent B of less than 1.57, , And in Comparative Examples 21 to 22, it was confirmed that the spin coat film was a good A evaluation.

In the same manner as in Example I, the mixed solution of Examples 21 to 22 and Comparative Examples 21 to 22 was ejected using an ink jet apparatus DMP2830 manufactured by FUJIFILM DIMATIX, and the pattern shape of the ejected droplet, that is, the cross-sectional profile was confirmed. Also, the cross-sectional profile was confirmed by measuring the optical interference phase with Wyko manufactured by Veeco.

Evaluation of the pattern shape (cross-sectional profile) of the other enemy was performed in the same manner as in Example I. The results are shown in Table 3.

As apparent from the results shown in Table 3, in Examples 21 to 22 in which the film was not formed satisfactorily in the spin-coat, in Examples 21 to 22, in the inkjet pattern formed, , It was confirmed that a cross-sectional profile of a smooth convex shape and good A evaluation from the edge toward the center was obtained.

On the other hand, it was confirmed that, in Comparative Examples 21 to 22 in which the spin-coat film was satisfactory, a cross-sectional profile of B evaluation was obtained, which had a problem that there was a ridge due to the occurrence of a coffee stain phenomenon on the formed inkjet pattern.

From the results in Table 3, it was confirmed that the solution composition without wetting diffusion of Examples 21 and 22 is suitable for inkjet pattern formation with a good cross-sectional profile.

From the above results, the effect of the present invention is clear.

10 Exclusive
12 substrate
14 Center
16 edges
18 Section Profile
20 Area within 20% from the center
50 thin film transistor
52 substrate
54 gate electrode
56 gate insulating film
58 oxide semiconductor layer
60 source electrode
62 drain electrode

Claims (12)

As a coating material for an ink jet for forming a pattern having the highest peak of an enemy within a range of 20% from the center of the other enemy,
And two kinds of solvents A and B, which are both solvents having a solubility parameter SP value of 20.3 MPa ^1/2 or less,
The solvent A has a surface tension higher than that of the solvent B by 1.17 times or more, a vapor pressure of 1.57 times or more higher than that of the solvent B, and a solvent volume content of 35% to 50%
The surface tension of Solvent A at 20 占 폚 is 27 mN / m or more, the vapor pressure is 1.1 kPa or more, the surface tension of Solvent B at 20 占 폚 is 23 mN / m or less and the vapor pressure is 0.7 kPa or less Lt;
Wherein the raw material is composed of polysilazane, the solvent A is toluene, and the solvent B is dibutyl ether. As a coating material for an ink jet for forming a pattern having the highest peak of an enemy within a range of 20% from the center of the other enemy,
And two kinds of solvents A and B, which are both solvents having a solubility parameter SP value of 20.3 MPa ^1/2 or less,
The solvent A has a surface tension higher than that of the solvent B by 1.17 times or more, a vapor pressure of 1.57 times or more higher than that of the solvent B, and a solvent content of 50%
The surface tension of Solvent A at 20 占 폚 is 27 mN / m or more, the vapor pressure is 1.1 kPa or more, the surface tension of Solvent B at 20 占 폚 is 23 mN / m or less and the vapor pressure is 0.7 kPa or less Lt;
Wherein the raw material is composed of polysilazane, the solvent A is chlorobenzene, and the solvent B is dibutyl ether. A method for forming an ink-jet pattern, comprising: forming an ink-jet coating material according to claim 1 or 2, wherein a pattern having the highest peak is formed within a range of 20% from the center of the other object. The method of claim 3,
The pattern with the highest peak of the enemy within 20% from the center of the other enemy is within 20% of the center of the other enemy and has the maximum value of the cross-sectional profile of the other enemy passing through the center of the other enemy, Wherein the pattern is an inkjet pattern. The method of claim 4,
Wherein the edge portions on both sides of the cross-sectional profile of the other enemies are rounded. A method of manufacturing an electronic device,
Wherein at least one layer of the electronic device is manufactured by the ink jet pattern forming method according to claim 3. The method of claim 6,
Wherein at least one layer of the electronic device is at least one of an insulating layer, a protective layer, and an interlayer insulating layer. The method of claim 6,
Wherein the electronic device is a thin film transistor. delete delete delete delete

Images