JP2007238724A - Liquid state material, method for producing substrate plate having membrane, method for producing electro-optical device and method for producing electronic instrument - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid state material forming a highly fine-patterned membrane on a substrate plate simply and inexpensively by removing a solvent, a method for producing a substrate plate having a membrane forming the substrate plate equipped with the highly fine-patterned membrane by using such the liquid state material, and method for producing an electro-optical device and an electronic instrument by using such the method of production. <P>SOLUTION: This liquid state material is used for forming the membrane having a prescribed pattern on the substrate plate. Such the liquid state material is provided by dissolving a polymer without substantially having polarity in a solvent, and satisfying a relationship of A-B≥5° by taking a retreating contact angle of the solvent against the substrate plate as A° and the retreating contact angle of the obtained liquid state material against the substrate plate as B°. Here, the retreating contact angle means that in a state of loading a liquid droplet on the surface of the substrate plate and by increasing the inclined angle of the substrate plate gradually, at a time point that the liquid droplet begins to move relative to the substrate plate, it is the contact angle measured at the reverse side to the moving direction of the liquid droplet. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a liquid material, a method for manufacturing a substrate with a film, a method for manufacturing an electro-optical device, and a method for manufacturing an electronic apparatus.

Conventionally, as a method for manufacturing a substrate with a film, that is, a method for patterning a film on a substrate, a liquid material is supplied onto the substrate using a droplet discharge method, and the formed droplets are dried to obtain a desired A method of forming a dry film having a shape is known (for example, see Patent Document 1).
In this method, the concentration of the solid content (solute) dissolved in the liquid material and at least one of the drying speed of droplets formed by dropping the liquid material on the substrate are used as parameters, and the dry film is formed. Control the shape. According to this method, a dry film having a desired shape can be easily obtained without using a patterning method that frequently uses complicated processes such as photolithography.
However, it may be difficult to form a dry film with high dimensional accuracy depending on the combination of the constituent materials of the solute and the solvent constituting the liquid material and the constituent material of the substrate onto which the liquid material is dropped.

JP 2005-28275 A

  An object of the present invention is to provide a liquid material capable of easily and inexpensively forming a high-definition pattern film on a substrate by removing the solvent, and a substrate provided with a high-definition pattern film using the liquid material. An object of the present invention is to provide a method for manufacturing a substrate with a film that can be formed, a method for manufacturing an electro-optical device using the method, and a method for manufacturing an electronic apparatus.

Such an object is achieved by the present invention described below.
The liquid material of the present invention is a liquid material used to form a film having a predetermined pattern on a substrate,
The liquid material is obtained by dissolving a substantially non-polar polymer in a solvent, the receding contact angle of the solvent with respect to the substrate is A [°], and the receding contact angle of the liquid material with respect to the substrate is B. When [°], the relationship of AB ≧ 5 ° is satisfied.
Thereby, by removing the solvent, it is possible to obtain a liquid material capable of easily and inexpensively forming a high-definition pattern film on the substrate. In addition, the liquid material exhibiting such characteristics can more reliably suppress the contraction of the droplets, and can reliably form a film having a particularly high dimensional accuracy at a target position.
Here, the receding contact angle refers to a state in which the droplet starts to move relative to the substrate when the tilt angle of the substrate is gradually increased with the droplet placed on the surface of the substrate. This is the contact angle measured on the opposite side of the moving direction.

In the liquid material of the present invention, the dipole moment of the unit structure constituting the repeating unit of the polymer is preferably 1D (Debye unit) or less.
The dipole moment of the unit structure substantially controls the polarity of the polymer (solute). For this reason, if this dipole moment is a small value as in the above range, the polarity of the polymer becomes extremely small and the polymer becomes substantially nonpolar. Such a polymer has a particularly high affinity for a substrate having a strong liquid repellency with respect to the liquid material, and a liquid material that easily undergoes pinning can be obtained.

In the liquid material of the present invention, the static contact angle of the solvent with respect to the substrate is preferably 50 ° or more.
It can be said that a solvent having such a large static contact angle with respect to the substrate has a moderately low affinity for the substrate, that is, a relatively high liquid repellency. Therefore, when a liquid material containing such a solvent is supplied as a droplet on a substrate, it forms a droplet that is hard to spread more than necessary and can more reliably obtain a film having a desired shape and size. It becomes.

In the liquid material of the present invention, the second virial coefficient of the solvent with respect to the polymer is preferably 0 to 1.5 × 10 ⁻⁴ cm ³ · mol / g ² .
A solvent having a second virial coefficient for the polymer within the above range can dissolve the polymer, but its solubility is low. Therefore, although such a polymer and a solvent can exist as a solution (liquid material), since the solubility is low, the polymer is likely to be deposited from within the droplet, and the edge of the droplet with respect to the substrate is present. Easy to fix. Therefore, a liquid material containing such a solution and a polymer is very easily pinned, and a film having a particularly high dimensional accuracy can be reliably formed.

In the liquid material of the present invention, the solvent preferably contains an aprotic polar organic solvent as a main component.
An aprotic polar solvent is suitably used as a solvent contained in a liquid material because it dissolves various polymers stably over a long period of time.
In the liquid material of the present invention, the polymer is preferably composed mainly of polystyrene, and the solvent is preferably composed of γ-butyrolactone.
Thereby, the liquid material is particularly prone to pinning, and a film having high dimensional accuracy can be reliably formed.

The liquid material of the present invention preferably has a viscosity (normal temperature) of 0.5 to 20 cP.
A liquid material having such a viscosity is easily supplied as a fine droplet on the substrate by a droplet discharge method, for example, and the shape of the droplet is not easily deformed. For this reason, the dimensional accuracy of the film finally obtained can be improved. Furthermore, the liquid material can be reliably discharged from the discharge port of the droplet discharge device.

The liquid material of the present invention preferably has a surface tension of 20 to 40 mN / m.
By using a liquid material having such a surface tension, the surface of the droplet is more easily smoothed while preventing the droplet from becoming too spherical. For this reason, a film with small variation in thickness can be easily obtained.

The liquid material of the present invention is preferably used for a droplet discharge method.
In the droplet discharge method, since a liquid material can be supplied in a fine pattern, a separate patterning process is not required, and a film having a precise shape can be formed by a simple process. Therefore, it is possible to more effectively form a film with the liquid material of the present invention.

The method for manufacturing a substrate with a film according to the present invention is a method for manufacturing a substrate with a film by forming a film on the substrate and manufacturing the substrate with a film,
A first step of forming a liquid film on the substrate by supplying a liquid material obtained by dissolving a substantially non-polar polymer in a solvent;
Removing the solvent from the liquid coating to obtain the film,
When the receding contact angle of the solvent with respect to the substrate is A [°] and the receding contact angle of the liquid material with respect to the substrate is B [°], the relation of AB ≧ 5 ° is established. It is characterized by using a satisfactory one.
This makes it possible to easily and inexpensively form a film-coated substrate having a high-definition pattern film on the substrate.

In the method for manufacturing a film-coated substrate according to the present invention, it is preferable to have a step of performing a liquid repellent treatment on at least one surface of the substrate prior to the first step.
As a result, the surface of the substrate that has been subjected to the liquid repellent treatment enhances the liquid repellency relative to the liquid material described later. As a result, it is possible to prevent the liquid material supplied on the substrate from spreading out more than necessary and deviating from the target shape and dimensions of the film. In addition, since variation in liquid repellency with respect to the liquid material on the substrate surface can be reduced, variation in the shape of the film on the substrate can also be suppressed.

The method for manufacturing an electro-optical device according to the present invention includes the method for manufacturing a film-coated substrate according to the present invention.
Thereby, an electro-optical device with high reliability can be manufactured.
The method for manufacturing an electronic apparatus according to the present invention includes the method for manufacturing the electro-optical device according to the present invention.
Thereby, a highly reliable electronic device can be manufactured.

Hereinafter, a liquid material, a method for manufacturing a substrate with a film, a method for manufacturing an electro-optical device, and a method for manufacturing an electronic device according to the present invention will be described in detail based on the preferred embodiments shown in the drawings.
First, prior to description of the manufacturing method of the liquid material of the present invention and the film-coated substrate of the present invention, the film-coated substrate manufactured by the manufacturing method will be described.
The method for manufacturing a substrate with a film according to the present invention forms a film with a high-definition pattern on the substrate, and can form a film that can be used for electrical wiring, an electrode, an insulating film, or the like on the substrate. Is. Hereinafter, an active matrix device will be described as an example of a film-coated substrate. An example in which a film on a substrate with a film is used as a gate insulating film of a thin film transistor included in the active matrix device will be described.

FIG. 1 is a block diagram showing a configuration of an active matrix device (substrate with a film) according to the present embodiment, and FIG. 2 is a diagram showing a configuration of a thin film transistor included in the active matrix device of the present embodiment (longitudinal sectional view and FIG. Is a plan view). In the following description, in FIG. 2B, the upper side is described as “upper” and the lower side is described as “lower”.
The active matrix device 100 shown in FIG. 1 includes a substrate 48, a plurality of data lines 101 and a plurality of scanning lines 102 that are provided on the substrate 48 and intersect each other, and the data lines 101 and the scanning lines 102. It has a thin film transistor 1 and a pixel electrode 103 provided near each intersection.

As shown in FIG. 2, in the present embodiment, the thin film transistor 1 is a top gate type thin film transistor, and a source electrode 72 and a drain electrode 73 provided separately from each other on the substrate 48, and a source electrode 72 and a drain. On the semiconductor layer 78 provided in contact with the electrode 73, the gate insulating film 79 provided so as to cover the source electrode 72, the drain electrode 73 and the semiconductor layer 78, and on the gate insulating film 79 corresponding to the semiconductor layer 78 And a gate electrode 80 provided.
In such a thin film transistor 1, the gate electrode 80 is connected to the scanning line 102, the source electrode 72 is connected to the data line 101, and the drain electrode 73 is connected to the pixel electrode (individual electrode) 103.

The pixel electrodes 103 are divided so as to be regularly arranged in a matrix, that is, vertically and horizontally.
Note that the thin film transistor 1 may be a bottom-gate thin film transistor.
Such an active matrix device 100 can be manufactured as follows, for example.

Hereinafter, as an example, a method for manufacturing the active matrix device 100 (a method for manufacturing a substrate with a film of the present invention) will be described. In the following, the method for manufacturing the thin film transistor 1 will be mainly described.
The manufacturing method of the thin film transistor 1 in this embodiment includes a step of forming a source electrode 72 and a drain electrode 73 on a substrate 48 (hereinafter referred to as a source electrode and drain electrode formation step), and a step of forming a semiconductor layer 78 (hereinafter referred to as a source electrode and drain electrode 73). A step of forming a gate insulating film 79 (hereinafter referred to as a gate insulating film forming step), and a step of forming a gate electrode 80 (hereinafter referred to as a gate electrode forming step).

Hereinafter, each process will be described in sequence with reference to FIG.
FIG. 3 is a view (cross-sectional view) for explaining a method for manufacturing the active matrix device 100 (substrate with a film) according to this embodiment. In the drawings used for the following description, the scale of each part is appropriately changed for convenience of description.

[A1] Source and Drain Electrode Formation Step First, as shown in FIG. 3A, the source electrode 72 and the drain electrode 73 are formed on the substrate 48.
Specifically, first, a substrate 48 is prepared.
Examples of the substrate 48 include a glass substrate, polyimide, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polymethyl methacrylate (PMMA), polycarbonate (PC), polyethersulfone (PES), and aromatic polyester (liquid crystal polymer). Or the like, a plastic substrate (resin substrate), a quartz substrate, a silicon substrate, a gallium arsenide substrate, or the like can be used. In the case where flexibility is given to the thin film transistor, a resin substrate is selected as the substrate 48.

Next, the surface of the substrate 48 on which the source electrode 72 and the drain electrode 73 are formed is subjected to a liquid repellent treatment. As a result, the surface of the substrate 48 that has been subjected to the liquid repellent treatment has a higher liquid repellency than the liquid material described later. As a result, it is possible to prevent the liquid material supplied onto the substrate 48 from spreading out more than necessary and deviating from the target shape and dimensions of the film.
In addition, variations in liquid repellency with respect to the liquid material on the surface of the substrate 48 can be reduced, so that variations in the shape of the film on the substrate 48 can also be suppressed.

  Examples of such liquid repellent treatment include a method of forming a self-assembled film (self-assembled monolayer: SAM (Self Assembled Monolayer)) having a liquid repellent functional group on the substrate 48. . A self-assembled film consists of a binding functional group capable of reacting with surface layer atoms of a substrate and other linear molecules, and is formed by orienting a highly oriented compound by the interaction of linear molecules. Film. Since this self-assembled film is formed by orienting single molecules, the film thickness is extremely thin, and the film is uniform at the molecular level. That is, since the same molecule is located on the surface of the film, uniform and excellent liquid repellency can be imparted to the surface of the film.

In this embodiment, a self-assembled film having a liquid repellent functional group such as an alkyl group or a fluoroalkyl group is formed on the substrate 48. Thereby, the liquid repellent process which can provide the above outstanding characteristics can be performed.
As the compound having a liquid repellent functional group, for example, when the substrate 48 is composed of a silicon substrate, alkyl silanes such as hexyltrimethoxysilane and octyltriethoxysilane, and fluoroalkylsilanes (silane coupling agents) Etc. can be used.

In addition, the liquid repellent treatment may be performed by, for example, forming a layer having liquid repellency on the surface of the substrate 48 or an atom having liquid repellency on the surface of the substrate 48 instead of the method of forming the self-assembled film as described above. It may be performed by a method of injecting (for example, fluorine atoms).
Note that the liquid repellent treatment may be performed on both surfaces of the substrate 48.
The liquid repellent treatment may be performed as necessary, and may be omitted when the substrate 48 itself has appropriate liquid repellency.

  Next, a conductive film is formed on the substrate 48. This includes, for example, chemical vapor deposition (CVD) such as plasma CVD, thermal CVD, and laser CVD, vacuum deposition, sputtering (low temperature sputtering), dry plating methods such as ion plating, electrolytic plating, immersion plating, and electroless plating. It can be formed by a wet plating method such as a thermal spraying method, a sol-gel method, a MOD method, or a metal foil bonding.

The constituent material of the conductive film (that is, the constituent material of the source electrode 72 or the drain electrode 73) is not particularly limited as long as it has conductivity. For example, Pd, Pt, Au, Ag, W, Ta, Mo , Al, Cr, Ti, Cu or conductive materials such as alloys containing these, conductive oxides such as ITO, FTO, ATO, SnO ₂ , carbon-based materials such as carbon black, carbon nanotubes, fullerene, polyacetylene, polypyrrole , Conductive polymer materials such as polythiophene such as PEDOT (poly-ethylenedioxythiophene), polyaniline, poly (p-phenylene), polyfluorene, polycarbazole, polysilane, or derivatives thereof. Alternatively, two or more kinds can be used in combination. The conductive polymer material is usually used in a state where it is doped with a polymer such as iron chloride, iodine, an inorganic acid, an organic acid, polystyrene sulfonic acid, and imparted with conductivity. Among these, as the constituent material of the conductive film, materials mainly composed of Ni, Cu, Co, Au, Pd, Ag, or alloys containing these are preferably used.

  On the conductive film, a resist material is applied and then cured to form a resist layer having a shape corresponding to the shape of the source electrode 72 and the drain electrode 73. Using this resist layer as a mask, unnecessary portions of the conductive film are removed. For removing the conductive film, for example, one or more of physical etching methods such as plasma etching, reactive ion etching, beam etching, and light-assisted etching, and chemical etching methods such as wet etching are used. Can be used in combination.

Then, the source electrode 72 and the drain electrode 73 are obtained by removing the resist layer.
For example, the source electrode 72 and the drain electrode 73 are formed by supplying a conductive material containing conductive particles onto the substrate 48 to form a liquid film, and then post-treating the liquid film as necessary (see FIG. For example, it can be formed by applying heat, infrared irradiation, application of ultrasonic waves, or the like.

Examples of the method for supplying the conductive material include spin coating, casting, micro gravure coating, gravure coating, bar coating, roll coating, wire bar coating, dip coating, and spray coating. , Screen printing method, flexographic printing method, offset printing method, ink jet method, microcontact printing method and the like, and one or more of them can be used in combination.
At this time, the data line 101 and the pixel electrode 103 are also formed.

[A2] Semiconductor Layer Formation Step Next, a semiconductor layer 78 is formed so as to fill a gap between the source electrode 72 and the drain electrode 73 as shown in FIG. In the semiconductor layer 78, a region between the source electrode 72 and the drain electrode 73 becomes a channel region.
The method for forming the semiconductor layer 78 is not particularly limited, and can be appropriately selected from the various methods described in the method for forming the source electrode 72 and the drain electrode 73 described above according to the constituent materials.
The constituent material of the semiconductor layer 78 is not particularly limited, and various organic semiconductor materials and various inorganic semiconductor materials can be used.

  Among these, examples of organic semiconductor materials include naphthalene, anthracene, tetracene, pentacene, hexacene, phthalocyanine, perylene, hydrazone, triphenylmethane, diphenylmethane, stilbene, arylvinyl, pyrazoline, triphenylamine, triarylamine, oligothiophene. , Low molecular organic semiconductor materials such as phthalocyanine or derivatives thereof, poly-N-vinylcarbazole, polyvinylpyrene, polyvinylanthracene, polythiophene, polyhexylthiophene, poly (p-phenylenevinylene), polytinylenevinylene, poly Arylamine, pyrene formaldehyde resin, ethylcarbazole formaldehyde resin, fluorene-bithiophene copolymer, fluorene-arylamine copolymer Alternatively, a high molecular organic semiconductor material (conjugated high molecular material) such as a derivative thereof can be used, and one or more of these can be used in combination. It is preferable to use a material mainly composed of a material (conjugated polymer material). The conjugated polymer material has a particularly high carrier mobility due to its unique electron cloud spread. Such a high-molecular organic semiconductor material can be formed by a simple method and can be relatively easily oriented.

  On the other hand, examples of the inorganic semiconductor material include silicon such as polycrystalline silicon and amorphous silicon, germanium, gallium arsenide, and the like, and one or more of these can be used in combination. In the case of forming the semiconductor layer 78 using a droplet discharge device, for example, liquid silicon containing cyclopentasilane is supplied to the gap between the source electrode 72 and the drain electrode 73 by the droplet discharge device, and this is used. The semiconductor layer 78 can be formed by drying and baking.

[A3] Gate Insulating Film Formation Step Next, as shown in FIG. 3C, a gate insulating film 79 is formed on the substrate 48 so as to cover the source electrode 72, the semiconductor layer 78, and the drain electrode 73.
The gate insulating film 79 is supplied with a liquid material containing a solute and a solvent for dissolving the solute so as to cover the source electrode 72, the semiconductor layer 78, and the drain electrode 73, and then subjected to post-processing as necessary. Can be formed.
As such a liquid material, the liquid material of the present invention can be used.

First, prior to the description of the gate insulating film forming step, the liquid material of the present invention will be described below.
In the following, dissolution includes a state in which a solute is finely dispersed, and the solvent includes a dispersion medium (medium) in which the solute is finely dispersed.
Here, as a method of forming a film having a predetermined pattern such as the gate insulating film 79 on the substrate, a liquid material containing a polymer material (solute) and a solvent has been used by a droplet discharge method. There has been known a method of forming a dry film having a desired shape by supplying a liquid onto a substrate and drying the formed droplets.

  When a film is formed by such a method, the solute in the liquid material needs to be dissolved in the solvent. Therefore, as described above, the solute has a high solvent solubility compared to the low molecular weight material. A molecular material (polymer) is used. Further, since the polymer does not need to be crystallized unlike the low molecular weight material, it is easy to handle, and the film formed using the liquid material containing the polymer has an advantage that it is rich in flexibility.

However, the interaction between the polymer (solute) in the liquid material, the solvent, and the substrate has a complicated mechanism of action, so depending on the combination of the constituent materials of the polymer, the solvent, and the substrate, The formed droplets shrink before drying. Thereby, there existed a problem that the dimensional accuracy of the dry film obtained fell, or the dry film of the target shape was not obtained.
Against this background, a method for developing a liquid material capable of forming a film having a predetermined pattern by finding an optimum combination of constituent materials of a polymer, a solvent, and a substrate by actually conducting experiments in the past. Was common. For this reason, there has been a problem of longer development or higher costs.

By the way, in order to obtain a film having a desired shape from the liquid material supplied on the substrate, the liquid material supplied as droplets on the substrate is quickly fixed (pinned) to the substrate, and the liquid is supplied. It needs to be something that prevents the droplets from shrinking.
Therefore, the present inventor aims to obtain a liquid material that can be easily and inexpensively formed of a film (in this embodiment, the gate insulating film 79) that is made of a polymer and has a desired shape with high dimensional accuracy. As a result of intensive studies, a liquid material obtained by using a polymer having substantially no polarity and dissolving the polymer in a solvent, the receding contact angle of the solvent with respect to the substrate being A [°], and the obtained liquid Assuming that the receding contact angle of the material with respect to the substrate is B [°], it has been found that a material satisfying the relationship of AB ≧ 5 ° is effective as the liquid material described above, and the present invention has been completed. It was.

Here, the contact angle is generally classified into a static contact angle and a dynamic contact angle.
FIG. 4 is a diagram for explaining the static contact angle and the dynamic contact angle.
Among these, the static contact angle refers to the contact angle θ ₁ measured in a state where the droplet L is placed on the surface of the substrate S maintained horizontally as shown in FIG.
On the other hand, the dynamic contact angle is such that when the inclination angle of the substrate S is gradually increased with the droplet L placed on the surface of the substrate S as shown in FIG. The contact angle θ ₂ and the contact angle θ ₃ measured at the time of starting movement with respect to S. Also, of the dynamic contact angle refers to a contact angle theta ₂ which is measured in the forward direction of movement of the droplet L and advancing contact angle, the contact angle measured on the opposite side to the moving direction of the droplet L theta ₃ is called the receding contact angle.

Each such contact angle can be an index reflecting the degree of interaction between the droplet L and the substrate S.
Specifically, the static contact angle θ ₁ tends to increase when the interaction between the droplet L and the substrate S is small, that is, when the affinity is low.
On the other hand, if the interaction between the solute in the droplet L and the substrate S is large, the solute in the droplet L is easily fixed to the substrate S at the edge of the droplet L, and the edge is the substrate S. It will be in the state where it was pinned to. Thus, the phenomenon that the edge of the droplet L is pinned to the substrate S by the solute in the droplet L is also referred to as “pinning”.
When the inclination angle of the substrate S is gradually increased in such a pinned state, the receding contact angle θ ₃ tends to gradually decrease. Such pinning of the solute in the droplet L with respect to the substrate S is considered to be due to the high affinity between the solute in the droplet L and the substrate S. Therefore, the receding contact angle θ ₃ is determined by the solute and the substrate S. It can be an index that more significantly reflects the interaction with.

Therefore, as described above, when the receding contact angle B [°] of the liquid material to the substrate is smaller than the receding contact angle A [°] of the solvent to the substrate, the affinity of the solute to the substrate is higher than that of the solvent. That is, the shrinkage of the liquid material is suppressed. In this state, when the solvent is removed by post-treatment or the like, a film having a desired shape can be easily obtained from the remaining solute. It is also possible to prevent the entire droplet from moving on the substrate.
Thus, paying attention to the index of “retreat contact angle”, by selecting a solute and a solvent for the substrate on which the film is formed, a film having a high dimensional accuracy and having a desired shape can be obtained. A liquid material that can be formed at a position can be obtained.

  The difference AB between the receding contact angle A [°] of the solvent with respect to the substrate and the receding contact angle B [°] of the liquid material with respect to the substrate is 5 ° or more, but is 25 ° or more. Preferably, it is 30 ° or more. The liquid material exhibiting such characteristics can more reliably suppress the contraction of the droplets, and can reliably form a film having a particularly high dimensional accuracy at a target position.

  In addition, the solvent in the liquid material preferably has a static contact angle with respect to the substrate of 50 ° or more, more preferably 60 ° or more. It can be said that a solvent having such a large static contact angle with respect to the substrate has a moderately low affinity for the substrate, that is, a relatively high liquid repellency. Therefore, when a liquid material containing such a solvent is supplied as a droplet on a substrate, it forms a droplet that is hard to spread more than necessary and can more reliably obtain a film having a desired shape and size. It becomes.

Further, the solvent preferably has a second virial coefficient with respect to the polymer (solute) of about 0 to 1.5 × 10 ⁻⁴ cm ³ · mol / g ² , and is preferably 0 to 1.2 × 10 ^−4. More preferably, it is about cm ³ · mol / g ² . A solvent having a second virial coefficient for the polymer within the above range can dissolve the polymer, but its solubility is low. Therefore, although such a polymer and a solvent can exist as a solution (liquid material), since the solubility is low, the polymer is likely to be deposited from within the droplet, and the edge of the droplet with respect to the substrate is present. Easy to fix. Therefore, a liquid material containing such a solution and a polymer is very easily pinned, and a film having a particularly high dimensional accuracy can be reliably formed.

  Such a solvent is a nonpolar solvent having substantially no polarity (a solvent composed of nonpolar molecules having no charge bias such as hydrogen molecules, nitrogen molecules, carbon dioxide, methane, etc., for example, toluene, cyclohexane, etc. However, polar polar solvents (solvents composed of polar molecules having a charge-like nature such as hydrogen chloride, water, and ammonia) are preferred. A polar solvent has a relatively low solubility in a polymer having substantially no polarity as described above, although it depends on its polarity. For this reason, as described above, a liquid material in which the polymer easily precipitates from the droplets and pinning easily occurs is obtained.

  Examples of the polar solvent include γ-butyrolactone, acetone, acetonitrile, N, N-dimethylformamide (DMF), dimethyl sulfoxide (DMSO), 1,3-dimethyl-2-imidazolidinone (DMI), N-methyl- Examples include aprotic polar solvents such as 2-pyrrolidone (NMP), protic polar solvents such as acetic acid, methanol, ethanol, 1-propanol, 2-propanol, butanol, ethylenediamine, diethylamine, and water. Polar solvents are preferred. An aprotic polar solvent is suitably used as a solvent contained in a liquid material because it dissolves various polymers stably over a long period of time.

The polymer in the liquid material becomes a constituent material of a film finally formed on the substrate, and has substantially no polarity as described above.
Such a polymer preferably has a dipole moment of a unit structure constituting the repeating unit of 1D (Debye unit) (3.4 × 10 ⁻³⁰ C · m) or less, and 0.8D (2 0.7 × 10 ⁻³⁰ C · m) or less is more preferable. The dipole moment of the unit structure substantially controls the polarity of the polymer (solute). For this reason, if this dipole moment is a small value as in the above range, the polarity of the polymer becomes extremely small and the polymer becomes substantially nonpolar. Such a polymer has a particularly high affinity for a substrate having a strong liquid repellency with respect to the liquid material, and a liquid material that easily undergoes pinning can be obtained.

Examples of such polymers include acrylic resins such as polystyrene, polyimide, polyamideimide, polyvinylphenylene, polycarbonate (PC), and polymethyl methacrylate (PMMA), fluorine resins such as polytetrafluoroethylene (PTFE), and polyvinyl. Insulating polymers such as phenolic resins such as phenol or novolac resins, and olefinic resins such as polyethylene, polypropylene, polyisobutylene and polybutene.
In addition, a liquid material obtained by dissolving a solute containing polystyrene as a main component in a solvent containing γ-butyrolactone as a main component is particularly susceptible to pinning. Therefore, such a liquid material can reliably form a film having high dimensional accuracy.

  Such a liquid material has a viscosity (normal temperature) of preferably about 0.5 to 20 cP, and more preferably about 1 to 10 cP. A liquid material having such a viscosity is easily supplied as a fine droplet on the substrate by a droplet discharge method, for example, and the shape of the droplet is not easily deformed. For this reason, the dimensional accuracy of the film finally obtained can be improved. Furthermore, the liquid material can be reliably discharged from the discharge port of the droplet discharge device.

Further, the surface tension of the liquid material is preferably about 20 to 40 mN / m, and more preferably about 25 to 35 mN / m. By using a liquid material having such a surface tension, the surface of the droplet is more easily smoothed while preventing the droplet from becoming too spherical. For this reason, a film with small variation in thickness can be easily obtained.
In addition, although the polymer content rate in a liquid material changes a little with the combination of a polymer and a solvent, it is preferable that it is about 0.01-5 wt%, and it is more preferable that it is about 0.05-1 wt%. Thereby, the liquid material can form a film having a sufficient thickness.
The liquid material as described above has high dimensional accuracy and can reliably form a film having a target shape at a target position.

Next, a method for forming the gate insulating film 79 using such a liquid material will be described in detail.
After preparing or preparing the liquid material, the liquid material is supplied onto the substrate 48 so as to cover the source electrode 72, the semiconductor layer 78, and the drain electrode 73 (first step).
Examples of the method for supplying the liquid material onto the substrate 48 include a coating method such as a spin coating method and a dip coating method, a printing method such as a droplet discharge method (inkjet method) and a screen printing method.
Among these, it is preferable to use a droplet discharge method as a supply method of the liquid material. The droplet discharge method is a method in which a liquid material can be supplied in a fine pattern, so that a separate patterning step is unnecessary, and a film having a precise shape can be formed by a simple process. Therefore, according to such a droplet discharge method, a film can be formed more effectively using the liquid material of the present invention.

Next, the liquid material supplied on the substrate 48 is allowed to stand, and the solvent is removed from the liquid material by natural drying (second step). Thereby, the solvent is volatilized and removed from the liquid material over time, and the insulating polymer remains. In this way, as shown in FIG. 3C, a gate insulating film 79 made of an insulating polymer can be formed on the substrate 48.
Instead of removing the solvent by natural drying, post-treatment for forcibly removing the solvent from the liquid material may be performed.
Examples of the post-treatment method for removing the solvent include a method of blowing a gas such as air or nitrogen gas, a method of reducing the ambient pressure, and a method of heat treatment.

Next, if necessary, the formed gate insulating film 79 is polished to reduce the film thickness, thereby obtaining a highly flat surface.
As a method of reducing the film thickness, for example, a CMP method (chemical mechanical polishing method) can be employed. Specific conditions include, for example, a soft polyurethane pad and an ammonia-based or amine-based alkali. A combination of a polishing agent (slurry) in which silica particles are dispersed in a solution, a pressure of 30000 Pa, a rotation speed of 50 revolutions / minute, and a polishing agent flow rate of 200 sccm can be employed.

[A4] Gate Electrode Formation Step Next, as shown in FIG. 3D, a gate electrode 80 is formed on the gate insulating film 79 corresponding to the region between the source electrode 72 and the drain electrode 73.
The gate electrode 80 is not particularly limited, and the same method as the method for forming the source electrode 72 and the drain electrode 73 described above can be used.
Further, as the constituent material of the gate electrode 80, the same material as the source electrode 72 and the drain electrode 73 can be used.

Through the steps described above, the field effect thin film transistor 1 in which the semiconductor layer 78, the gate insulating film 79, the gate electrode 80, and the like are stacked is obtained.
At this time, the scanning line 102 is formed. Thereby, the active matrix device 100 shown in FIG. 1 is obtained.
In this embodiment, the scanning line 102 is formed separately from the gate electrode 80, but the scanning line 102 may be formed by continuously forming the gate electrode 80 of the adjacent thin film transistor 1.

Note that when a conductive polymer is used as a constituent material of the source electrode 72, the drain electrode 73, the gate electrode 80, the scanning line 102, the data line 101, or the pixel electrode 103, these are the same as the method for forming the gate insulating film 79. It can also be formed by a method.
In this case, the conductive polymer can be appropriately selected and used, for example, from the materials listed as the conductive polymer material described above in consideration of electrical conductivity and the like.
In the case where the above-described polymer semiconductor material is used as a constituent material of the semiconductor layer 78, the semiconductor layer 78 can be formed by a method similar to the method for forming the gate insulating film 79.

<Electro-optical device>
Next, an electrophoretic display device will be described as an example of the electro-optical device of the present invention in which the active matrix device (substrate with a film) as described above is incorporated.
FIG. 5 is a longitudinal sectional view showing an embodiment of the electrophoretic display device.
An electrophoretic display device 200 illustrated in FIG. 5 includes an active matrix device 100 and an electrophoretic display unit 400 that is electrically connected to the active matrix device 100.

As shown in FIG. 5, the electrophoretic display unit 400 includes a microcapsule 402, a transparent electrode (common electrode) 403, and a transparent substrate 404 that are sequentially stacked on the active matrix device 100.
The microcapsule 402 is fixed between the pixel electrode 103 and the transparent electrode 403 by a binder material 405.
As described above, the pixel electrodes 103 are divided so as to be regularly arranged in a matrix, that is, vertically and horizontally.

In each capsule 402, an electrophoretic dispersion liquid 420 including a plurality of types of electrophoretic particles having different characteristics, and in this embodiment, two types of electrophoretic particles 421 and 422 having different charges and colors (hues) are encapsulated. Has been.
In such an electrophoretic display device 200, when a selection signal (selection voltage) is supplied to one or a plurality of scanning lines 102, a thin film transistor connected to the scanning line 102 to which the selection signal (selection voltage) is supplied. 1 is turned on.

Thereby, the data line 101 connected to the thin film transistor 1 and the pixel electrode 103 are substantially conducted. At this time, if desired data (voltage) is supplied to the data line 101, this data (voltage) is supplied to the pixel electrode 103.
As a result, an electric field is generated between the pixel electrode 103 and the transparent electrode 403, and the electrophoretic particles 421 and 422 are either one of the electrophoretic particles 421 and 422 depending on the direction and strength of the electric field and the characteristics of the electrophoretic particles 421 and 422. Electrophoresis towards the electrode.

On the other hand, when supply of the selection signal (selection voltage) to the scanning line 102 is stopped from this state, the thin film transistor 1 is turned off, and the data line 101 and the pixel electrode 103 connected to the thin film transistor 1 are in a non-conductive state. Become.
Therefore, by appropriately combining the supply and stop of the selection signal to the scanning line 102 or the supply and stop of the data to the data line 101, the display surface side (transparent substrate 404 side) of the electrophoretic display device 200 can be obtained. A desired image (information) can be displayed.

In particular, in the electrophoretic display device 200 of the present embodiment, it is possible to display a multi-tone image by making the colors of the electrophoretic particles 421 and 422 different.
In addition, since the electrophoretic display device 200 of the present embodiment includes the active matrix device 100, the thin film transistor 1 connected to the specific scanning line 102 can be selectively turned on and off, so that crosstalk This is unlikely to occur, and the circuit operation can be speeded up, so that a high-quality image (information) can be obtained.

In addition, since the electrophoretic display device 200 according to the present embodiment operates with a low driving voltage, power saving can be achieved.
The electro-optical device in which the active matrix device 100 including the thin film transistor 1 as described above is incorporated is not limited to the application to such an electrophoretic display device 200, and for example, a liquid crystal device, organic or inorganic The present invention can also be applied to a display device such as an EL device or a light emitting device.

  Such an electrophoretic display device (electro-optical device) includes, for example, a step of preparing an electrophoretic display sheet including a transparent substrate 404, a transparent electrode 403, a microcapsule 402, and a binder material 405, and a pixel on the electrophoretic display sheet. It can be manufactured by a manufacturing method (manufacturing method of the electro-optical device of the present invention) having a step of bonding the active matrix device 100 manufactured by the manufacturing method of the film-coated substrate of the present invention so that the electrodes 103 are in contact with each other. it can.

  Further, when the electro-optical device is a liquid crystal device, for example, the liquid crystal device includes a step of bonding the active matrix device 100 manufactured by the method for manufacturing a film-coated substrate of the present invention and a transparent substrate, and a bonding process. Further, it can be manufactured by a manufacturing method (a manufacturing method of the electro-optical device of the present invention) including a step of injecting a liquid crystal material between the active matrix device 100 and the transparent substrate.

<Electronic equipment>
Such an electrophoretic display device 200 can be incorporated into various electronic devices. Hereinafter, an electronic apparatus of the present invention including the electrophoretic display device 200 will be described.
<< Electronic Paper >>
First, an embodiment when the electronic apparatus of the present invention is applied to electronic paper will be described.

FIG. 6 is a perspective view showing an embodiment when the electronic apparatus of the present invention is applied to electronic paper.
An electronic paper 600 shown in this figure includes a main body 601 composed of a rewritable sheet having the same texture and flexibility as paper, and a display unit 602.
In such electronic paper 600, the display unit 602 includes the electrophoretic display device 200 as described above.

<< Display >>
Next, an embodiment when the electronic apparatus of the present invention is applied to a display will be described.
7A and 7B are diagrams showing an embodiment in which the electronic apparatus of the present invention is applied to a display. FIG. 7A is a cross-sectional view, and FIG. 7B is a plan view.
A display 800 shown in this figure includes a main body 801 and an electronic paper 600 that is detachably provided to the main body 801. The electronic paper 600 has the same configuration as described above, that is, the configuration shown in FIG.

  The main body 801 has an insertion port 805 into which the electronic paper 600 can be inserted on the side (right side in the drawing), and two pairs of conveying rollers 802a and 802b are provided inside. When the electronic paper 600 is inserted into the main body 801 through the insertion port 805, the electronic paper 600 is installed in the main body 801 in a state of being sandwiched between the pair of conveyance rollers 802a and 802b.

  Further, a rectangular hole 803 is formed on the display surface side of the main body 801 (the front side in the drawing (b) below), and a transparent glass plate 804 is fitted into the hole 803. Thereby, the electronic paper 600 installed in the main body 801 can be viewed from the outside of the main body 801. That is, in the display 800, the display surface is configured by visually recognizing the electronic paper 600 installed in the main body 801 on the transparent glass plate 804.

In addition, a terminal portion 806 is provided at the leading end portion (left side in the drawing) of the electronic paper 600, and the terminal portion with the electronic paper 600 installed on the main body portion 801 is provided inside the main body portion 801. A socket 807 to which 806 is connected is provided. A controller 808 and an operation unit 809 are electrically connected to the socket 807.
In such a display 800, the electronic paper 600 is detachably installed on the main body 801, and can be carried and used while being detached from the main body 801.
Further, in such a display 800, the electronic paper 600 is configured by the electrophoretic display device 200 as described above.

  Note that the electronic apparatus of the present invention is not limited to the application to the above, and for example, a television, a viewfinder type, a monitor direct view type video tape recorder, a car navigation device, a pager, an electronic notebook, a calculator, an electronic Examples include newspapers, word processors, personal computers, workstations, videophones, POS terminals, and devices equipped with touch panels. The electrophoretic display device 200 can be applied to the display units of these various electronic devices. is there.

Such an electronic apparatus is, for example, a manufacturing method (a method of manufacturing an electronic apparatus according to the present invention) including a step of manufacturing an electro-optical device, and a step of assembling the electro-optical device and components constituting the electronic device. ).
The liquid material, the method for manufacturing a substrate with a film, the method for manufacturing an electro-optical device, and the method for manufacturing an electronic device have been described above, but the present invention is not limited to these.
In the method for manufacturing a film-coated substrate, the method for manufacturing an electro-optical device, and the method for manufacturing an electronic device according to the present invention, one or two or more steps for arbitrary purposes may be added.

Next, specific examples of the present invention will be described.
1-1. Preparation of liquid material (Example A)
As shown below, the liquid material No. 1-4 were prepared respectively.

((Liquid material No. 1))
A liquid material was prepared by dispersing and dissolving polystyrene (weight average molecular weight: 200000) in γ-butyrolactone (solvent) at a ratio of 0.1 wt%.
In addition, the 2nd virial coefficient with respect to this polystyrene of (gamma) -butyrolactone is 1.07 * 10 < ^-4 > cm < ³ > * mol / g < ² >.
The dipole moment of the unit structure of polystyrene is 0.1D.

((Liquid material No. 2))
The liquid material No. was changed except that the solvent was changed to cyclohexane. In the same manner as in No. 1, a liquid material was prepared.
In addition, the 2nd virial coefficient with respect to this polystyrene of a cyclohexane is -1.90 * 10 < ^-4 > cm < ³ > * mol / g < ² >.

(Comparative Example A)
((Liquid material No. 3, 4))
The liquid material No. was changed except that the solvent was changed to the one shown in Table 1. In the same manner as in No. 1, a liquid material was prepared.
In addition, Table 2 shows the second virial coefficient of each solvent with respect to the polystyrene.

1-2. Evaluation of Liquid Material For each liquid material, a static contact angle and a receding contact angle with respect to the substrate were measured.
Moreover, the static contact angle and receding contact angle with respect to the substrate were also measured for the solvents in each liquid material.
As the substrate, a silicon substrate subjected to a liquid repellent treatment with octyltriethoxysilane (silane coupling agent) was used.
The measurement results are shown in Table 1.

As shown in Table 1, the liquid material No. 1 and 2 (Example A), it was confirmed that the receding contact angle of the liquid material with respect to the substrate was larger than the receding contact angle of the solvent. For this reason, the liquid material No. 1 and 2 can be said to easily cause pinning.
In particular, liquid material No. No. 1 has a very large difference in receding contact angle between the liquid material and the solvent of 40 ° or more, and the static contact angle of the solvent is 50 ° or more, so that pinning is particularly likely to occur. It became clear.

Furthermore, the liquid material No. In No. 1, since the solvent is an aprotic polar organic solvent and the second virial coefficient of the solvent with respect to the solute also matches the conditions that are likely to cause pinning, the above-described tendency is considered to be more prominent. It is done.
On the other hand, the liquid material No. In Examples 3 and 4 (Comparative Example A), the receding contact angle of the liquid material with respect to the substrate was almost equal to the receding contact angle of the solvent.

2-1. Production of evaluation substrate with film (Example B)
As shown below, sample no. 1-4 substrates with evaluation films were produced, respectively.
((Sample No. 1))
First, a silicon substrate was prepared, washed with water, and then dried.

Next, the silicon substrate was subjected to a liquid repellent treatment using octyltriethoxysilane (silane coupling agent).
Next, on the surface of the silicon substrate subjected to the liquid repellent treatment, the liquid material No. 1 was formed by an inkjet method. 1 was supplied as a droplet.
Subsequently, in this state, the liquid droplets were allowed to stand and naturally dried to obtain a dry film. Thereby, the board | substrate with a film | membrane for evaluation was obtained.
((Sample No. 2))
Liquid material No. Sample No. 2 was used except that No. 2 was used. In the same manner as in Example 1, a substrate with an evaluation film was produced.

(Comparative Example B)
((Sample No. 3, 4))
The liquid materials are designated as liquid material No. 3 and liquid material no. Except for changing to No. 4, the sample No. In the same manner as in Example 1, a substrate with an evaluation film was produced.

2-2. Evaluation of substrate with film for evaluation Each of the films of the evaluation-coated substrate was observed with an optical microscope.
The obtained film was evaluated according to the following criteria.
○: The film size was almost the same as that of the droplet (the outer diameter of the film was 95% or more of the outer diameter of the droplet)
Δ: The film size is slightly smaller than the droplet (the outer diameter of the film is 80% or more and less than 95% of the outer diameter of the droplet)
X: The film size is significantly smaller than the droplet (the outer diameter of the film is less than 80% of the outer diameter of the droplet)
The evaluation results are shown in Table 2.

As shown in Table 2, in the substrate with an evaluation film of each Example B, a film having an outer diameter of 80% or more of the droplets was obtained, and a film with sufficient dimensional accuracy was obtained. In particular, sample no. This tendency was more prominent with the substrate No. 1.
On the other hand, in each of the substrates with evaluation films of Comparative Examples B, a film having an outer diameter contracted to less than 80% of the droplets was observed.

3-1. Production of active matrix device (Example C1)
<1> First, a silicon substrate was prepared, washed with water, and then dried. Subsequently, a source electrode and a drain electrode were formed by a photolithography method.
<2> Next, the silicon substrate was subjected to a liquid repellent treatment using octyltriethoxysilane (silane coupling agent) on the silicon substrate.
<3> Next, pentacene was formed by vacuum deposition so as to fill the gap between the source electrode and the drain electrode, thereby forming a semiconductor layer.

<4> Next, in order to cover the source electrode, the drain electrode and the semiconductor layer, the liquid material No. 1 was supplied to form a liquid film.
<5> Next, the solvent was volatilized and removed from the liquid film by natural drying to form a gate insulating film.
<6> Next, scanning lines, data lines, pixel electrodes, and the like were formed to obtain an active matrix device.
(Example C2)
In the step <4>, the liquid material No. An active matrix device was obtained in the same manner as in Example C1 except that 2.

(Comparative Example C1)
In the step <4>, the liquid material No. An active matrix device was obtained in the same manner as in Example C1 except that 3 was used.
(Comparative Example C2)
In the step <4>, the liquid material No. An active matrix device was obtained in the same manner as in Example C1 except that 4 was used.

3-2. Evaluation of Active Matrix Device The characteristics of each thin film transistor formed in the active matrix device of each example and each comparative example were evaluated.
As a result, each thin film transistor obtained in each example functioned as a transistor.
On the other hand, the thin film transistor obtained in each comparative example did not function because the insulating property of the gate insulating film was insufficient. Moreover, when the longitudinal section of the thin film transistor obtained in each comparative example was observed with an electron microscope, a thin portion of the gate insulating film was observed, and in addition, a portion where the gate electrode and the semiconductor layer were short-circuited was also observed. It was.

It is a block diagram which shows the structure of the active matrix apparatus (substrate | substrate with a film | membrane) concerning this embodiment. It is a figure (a longitudinal cross-sectional view and a top view) which shows the structure of the thin-film transistor with which the active matrix apparatus of this embodiment is provided. It is a figure (sectional drawing) for demonstrating the manufacturing method of the active matrix apparatus of this embodiment. It is a figure for demonstrating a static contact angle and a dynamic contact angle. It is a longitudinal cross-sectional view which shows embodiment of an electrophoretic display apparatus. It is a perspective view which shows embodiment at the time of applying the electronic device of this invention to electronic paper. It is a figure which shows embodiment at the time of applying the electronic device of this invention to a display.

Explanation of symbols

  DESCRIPTION OF SYMBOLS 1 ... Thin film transistor 48 ... Substrate 72 ... Source electrode 73 ... Drain electrode 78 ... Semiconductor layer 79 ... Gate insulating film 80 ... Gate electrode 100 ... Active matrix device (substrate with film) 101 ... Data line DESCRIPTION OF SYMBOLS 102 ... Scanning line 103 ... Pixel electrode 200 ... Electrophoretic display device (electro-optical device) 400 ... Electrophoretic display unit 402 ... Microcapsule 420 ... Electrophoretic dispersion liquid 421, 422 ... Electrophoretic particle 403 ... Transparent electrode 404 ... Transparent substrate 405 ... Binder material 600 ... Electronic paper 601 ... Main body 602 ... Display unit 800 ... Display 801 ... Main body 802a, 802b ... Conveying roller pair 803 ... Hole 804 …… Transparent glass plate 805 …… Insertion slot 806 …… Terminal 8 07 …… Socket 808 …… Controller 809 …… Operation part L …… Droplet S …… Board

Claims (13)

A liquid material used to form a film with a predetermined pattern on a substrate,
The liquid material is obtained by dissolving a substantially non-polar polymer in a solvent, the receding contact angle of the solvent with respect to the substrate is A [°], and the receding contact angle of the liquid material with respect to the substrate is B. A liquid material characterized by satisfying a relationship of A−B ≧ 5 ° when [°].   The liquid material according to claim 1, wherein a dipole moment of a unit structure constituting the repeating unit of the polymer is 1D (Debye unit) or less.   The liquid material according to claim 1, wherein a static contact angle of the solvent with respect to the substrate is 50 ° or more. 4. The liquid material according to claim 1, wherein a second virial coefficient of the solvent with respect to the polymer is 0 to 1.5 × 10 ⁻⁴ cm ³ · mol / g ² .   The liquid material according to claim 1, wherein the solvent is mainly composed of an aprotic polar organic solvent.   The liquid material according to claim 1, wherein the polymer has polystyrene as a main component, and the solvent has γ-butyrolactone as a main component.   The liquid material according to any one of claims 1 to 6, wherein the liquid material has a viscosity (normal temperature) of 0.5 to 20 cP.   The liquid material according to any one of claims 1 to 7, wherein the liquid material has a surface tension of 20 to 40 mN / m.   The liquid material according to claim 1, wherein the liquid material is used for a droplet discharge method. A method for manufacturing a substrate with a film, which forms a film on a substrate to manufacture a substrate with a film,
A first step of forming a liquid film on the substrate by supplying a liquid material obtained by dissolving a substantially non-polar polymer in a solvent;
Removing the solvent from the liquid coating to obtain the film,
When the receding contact angle of the solvent with respect to the substrate is A [°] and the receding contact angle of the liquid material with respect to the substrate is B [°], the relation of AB ≧ 5 ° is established. A method for producing a substrate with a film, characterized by using a satisfactory one.   The manufacturing method of the board | substrate with a film | membrane of Claim 10 which has the process of performing a liquid-repellent process on the at least one surface of the said board | substrate prior to a said 1st process.   12. A method for manufacturing an electro-optical device, comprising the method for manufacturing a film-coated substrate according to claim 10. An electronic apparatus manufacturing method comprising the electro-optical device manufacturing method according to claim 12.

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