JPH1020509A - Production of liquid crystal display element and liquid crystal display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To develop a resist film, to peel a residual resist and to process a metal thin film, semiconductor thin film or insulating thin film in complete dry processes. SOLUTION: A multilayered film 200 including a metal thin film, dielectric insulating film or semiconductor thin film or in which a part of these thin films is formed as a pattern is formed on a glass substrate 100. Further, a resist film 300 comprising a polymer material having urethane bonds and/or urea bonds is applied on the substrate 100 and irradiated with excimer laser beam through an exposure mask 400 having a specified opening pattern. The resist film 300 in the irradiated part is removed by abrasion development to obtain a resist film pattern. The exposed part through the resist film pattern is removed by etching, and then the residual resist film 300 is removed by abrasion development using excimer laser beam.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a liquid crystal display element in which various thin films constituting a liquid crystal display element are formed on a glass substrate and a predetermined thin film pattern is formed on the thin film by lithography using a resist film. The present invention relates to a method and a liquid crystal display device.

[0002]

2. Description of the Related Art A liquid crystal display device is frequently used as an image display device used for a monitor of a television receiver or a personal computer. This type of liquid crystal display device includes a simple matrix type in which a liquid crystal layer is sandwiched between two sets of electrodes arranged in a matrix and one pixel is formed at the intersection of the electrodes, and a switching element such as a thin film transistor (TFT) for each pixel. Are roughly divided into active types.

In particular, an active type liquid crystal display (TF)
T-LCDs) have become the mainstream of liquid crystal display devices because of their high operating speed and contrast and high resolution.

A thin film transistor type liquid crystal display device has a liquid crystal layer sandwiched between one glass substrate on which a thin film transistor as a selection element is formed and the other glass substrate on which a color filter is formed, and a driving IC is provided around the glass substrate. And a backlight as an illumination light source is installed on the lower surface.

[0005] A thin film pattern of a semiconductor or the like is formed on one of the above substrates by forming a thin film by sputtering, CVD, or the like, applying a resist thereon, and exposing, developing, etching, and stripping the resist. Lithographic processes have been used.

Similarly, a color filter film for the other substrate is formed by a series of photolithography processes.

Conventionally, in this type of color filter, a black matrix is first formed on a transparent substrate such as a glass plate, and then red, green, and blue filters are sequentially formed. These forming methods are so-called photolithography in which each material is made to have photosensitivity, these thin layers are formed, irradiated with ultraviolet rays through an exposure mask having openings of a predetermined pattern, and subjected to development processing. Is generally adopted.

A resist material or a photosensitive color filter material used in this type of photolithography process is classified into a positive type in which solubility in a developing solution is caused by exposure to light, and a negative type in which solubility is lost in the opposite direction. However, each of the resist film and the color filter film applied over the thin film to be processed is subjected to pattern formation by liquid development which is a wet process.

In the TFT thin film processing, a required thin film pattern is obtained by a wet or dry etching process using a resist film formed by development as a mask.

After completion of the etching process, the remaining resist film is removed by a stripping solution or dry etching.

The prior art relating to this type of liquid crystal display device is disclosed in, for example, JP-A-63-30.
No. 9921 and “12.5-inch active matrix color liquid crystal display employing a redundant configuration” (1986
Published by McGraw-Hill on December 15, 2000
December 15, 1986, pp. 193-210).

[0012]

The above-described conventional patterning of a resist film or a color filter film is formed by two processes of exposure and development. In the development process, a developer and a developing device are required, but the increase in the size of the substrate of the liquid crystal display device and a large increase in the production amount are accompanied by the use amount of the developing solution, the enlargement of the developing device, and the expansion of the clean space. This has led to an increase in the size of air conditioning equipment.

At the same time, the cost of waste liquid treatment of the developing solution,
Problems such as environmental impact also occur. The same occurs for the resist stripping process.

On the other hand, recently, using an excimer laser which is an ultraviolet pulse laser, the metal film, the dielectric insulating film, the resist for patterning the thin film of the semiconductor film, the black matrix and each filter material are not subjected to wet development processing. There has been proposed a method of processing.

This processing method utilizes the ablation phenomenon of excimer laser light, and has been conventionally mainly used in the field of micromachining.

On the other hand, when an ablation phenomenon of an excimer laser is applied to pattern processing of a thin film having a precision of a thin film transistor type liquid crystal display device, there are many problems in various points such as a device configuration, a precision, a processing area and a processing time. Is generated.

That is, in the processing for making holes or the like in the circuit board, the processing pattern is a circle having a diameter of at most about 30 μm and the center-to-center positional accuracy of about ± 2 μm is required. About 10 to 10 μm is acceptable. Further, the thickness of the insulating layer of the circuit board is 20 to 50 μm, and processing using ablation of a conventional excimer laser is a technique belonging to a category of a processing region different from processing at the accuracy of an LSI level.

Further, in the above-mentioned processing using the ablation phenomenon of the excimer laser, since the ratio of the area or volume of the processed portion to the entire configuration of the circuit board to be processed is extremely small, the utilization rate of the amount of exposure light is not controlled. It is an important matter to improve the image quality, and a unique illumination optical system is adopted according to the shape and thickness of the processing object, and the image formation is usually of a reduced type.

On the other hand, since a panel (glass substrate) of a TFT-LCD needs to form a fine repetitive pattern over a large area, the processing method utilizing the ablation phenomenon of the excimer laser as described above is applied as it is. It is not possible.

In the case where an excimer laser is simply used as an exposure light source of an exposure device as in the case of a VLSI, the light energy density of the excimer laser used is low. No major changes in the optics are required. However, in order to use the ablation phenomenon, a much higher energy density is required as compared with resist exposure of LSI or the like, so that the basic concept of an existing exposure machine can be used as an imaging system.
An optical system that takes measures against damage to optical components is required.

That is, in the ablation processing technology that requires TFT-LCD level accuracy, it is impossible to directly apply the optical system employed in the conventional exposure apparatus from the viewpoint of processing accuracy and energy density. There is a problem.

In addition, processing utilizing the ablation phenomenon of excimer laser light is, in principle, a thin film processing with higher precision than micromachining processing, for example, formation of a high-definition pattern such as a TFT substrate or a color filter substrate of a TFT liquid crystal display element. Level processing is possible.

There are several elemental technologies for realizing the processing of the high-definition pattern described above. One of them is to improve the processing resistance of an exposure mask exposed to excimer laser light.

For example, in consideration of application to the manufacture of a TFT substrate of a TFT liquid crystal display element, the pattern accuracy of an exposure mask needs to be at least 2 μm or less.

When considering ablation of a resist, an incident energy density of at least 100 mJ / cm ² is required. This depends on the imaging optical system, but the incident energy on the mask is at least 200 mJ / cm ^2.
This means that the exposure mask must have processing resistance to such high input energy in order to maintain processing accuracy.

Recently, the output of an excimer laser has been increasing more and more, and in order to improve the throughput, it is necessary to consider the incident energy to the exposure mask up to about 500 mJ / cm ² . The output area of the excimer laser light is smaller than that of a lamp for an ordinary exposure machine. If this is converted into slit-like illumination light that covers the entire width of the substrate, there is a problem that the aperture of the imaging lens becomes large, which makes it impractical.

However, since this excimer laser is so-called invisible light, a positioning mark is formed in advance on an exposure mask, and the projected image of the positioning mark on the processing substrate is used as a guide to apply the photomask to the processing substrate. There is a problem that the conventional method of performing alignment cannot be applied.

Therefore, an optical system for projecting a positioning mark of a photomask (exposure mask) using visible light is generally provided separately from an optical system for projecting a pattern of a photomask by an excimer laser. Was.

However, such a configuration cannot avoid the complication caused by providing a separate optical system.

Such a problem also applies to a laser processing apparatus which performs processing by selectively irradiating an excimer laser through an exposure mask.

As the above countermeasure, an exposure mask in which a dielectric film and a metal film are overlapped may be used. However, the metal film is easily damaged by strong ultraviolet laser light. A structural problem arises.

Further, when a dielectric film for reflecting ultraviolet light is formed, the dielectric film is often transparent to visible light, so that an ordinary optical system is required for alignment between the exposure mask and the substrate to be processed. There is a problem that it is difficult to use.

Further, debris, which is a processing product generated by ablation, may be used to clean the work after processing,
Alternatively, depending on the processing material, the reduction is achieved by processing in an inert atmosphere such as helium or processing in an oxygen atmosphere.

However, it is difficult to completely remove the debris generated by ablation in the above-mentioned conventional technology. In particular, it is difficult to remove debris that has re-adhered to the workpiece.

Further, the form of the debris may vary from gaseous to several μm depending on the type of material and the intensity of incident energy.
Various methods must be considered depending on the form of the debris that is distributed in a wide range of particles up to the size of the medium, and that also undergoes cleaning after processing.

In the processing in the helium atmosphere, the debris is dispersed far away because the jet velocity of the ablation plume (explosion cloud) is faster than that in the air, so that the debris is apparently reduced. appear. This is considered to be a result of the generated debris being oxidized into a gaseous state in an oxygen atmosphere.

Processing in an atmosphere of helium or oxygen described above has an effect only in processing of a relatively limited material, and is not effective in processing of any material.

Furthermore, an essential point to be considered is that as the oscillation frequency of the excimer laser is increased for high-speed processing, the plume generated by the preceding excimer laser pulse is still in the optical path of the excimer laser. However, since the ablation by the subsequent excimer laser is performed in a state where the excimer laser is present, there is a problem that the excimer laser for the subsequent ablation causes energy loss.

For this reason, it is more important to remove plumes generated by ablation at high speed than to simply remove debris.

In order to solve the above-mentioned problems of the prior art, a first object of the present invention is to use a new principle of developing a resist film, removing a residual resist, and processing a metal thin film, a semiconductor thin film or an insulating thin film. It is an object of the present invention to provide a method for manufacturing a liquid crystal display element which can reduce the manufacturing cost and solve environmental problems by performing a complete dry process. A second object of the present invention is to provide a liquid crystal display device manufactured by performing development of a resist film and stripping of a residual resist by a completely dry process using a new principle.

A third object of the present invention is to provide a method for manufacturing a liquid crystal display element which is highly accurate and avoids damage to an optical system due to excimer laser light.

A fourth object of the present invention is to provide a method and an apparatus for forming a resist pattern for manufacturing a large-sized liquid crystal display element substrate using a small-area exposure mask. A fifth object of the present invention is to provide an apparatus for manufacturing a liquid crystal display device having an excimer laser processing exposure mask formed of a high-precision dielectric multilayer film having increased processing resistance to excimer laser light. is there.

A sixth object of the present invention is to provide an apparatus for manufacturing a liquid crystal display device having an alignment device for aligning an exposure mask and a glass substrate with high accuracy with a simple structure.

A seventh object of the present invention is to provide an apparatus for manufacturing a liquid crystal display device having an apparatus for removing debris generated by ablation using excimer laser light.

In the following description, an ablation apparatus using an excimer laser is also referred to as a developing machine or an exposing machine.

[0046]

[Means for Solving the Problems]

[Configuration to Achieve the First Object] To achieve the first object, a metal film, a dielectric insulating film, a thin film of a semiconductor film, or a part of the thin film for forming a liquid crystal display element A resist film composed of a polymer material having urethane bonds and / or urea bonds is applied on a glass substrate on which a multilayer film formed in a pattern is formed, and excimer laser is applied through a mask having a predetermined opening pattern. A resist film pattern exposing the thin film corresponding to the opening pattern of the mask is formed by irradiating light and removing the resist film of the irradiated portion by an ablation phenomenon, and the thin film exposed by the resist film pattern is formed on the thin film. It is characterized by removing the residual resist film by ablation phenomenon by irradiating excimer laser light after removing by etching treatment. That.

Further, the polymer material constituting the resist film is a polymer compound produced by a polymerization reaction of a polyisocyanate with a polyol and / or a polyamine.

It should be noted that the above-mentioned polymer compound is represented by "-" in the structure.
A material having a partial structure of "Ar-NHCOO-" (Ar represents an aromatic hydrocarbon group having or not having a substituent) is used.

Further, the above-mentioned polymer compound is represented by “-” in the structure.
A material having a partial structure of "Ar-NHCONH-" (Ar represents an aromatic hydrocarbon group having or not having a substituent) is used.

Further, the polyisocyanate is characterized in that it is at least one of toluene diisocyanate, methylene bisphenyl isocyanate and naphthalenediisocyanate.

Further, the extinction coefficient of the resist film was set to 5 × 10 ^{4 with} respect to excimer laser light having a wavelength of 248 nm.
It is characterized by using a material of cm ^-1 or more.

Further, the polymer compound is characterized in that it is of a thermosetting type which forms a cyclic or network-like crosslinked structure by heating or drying.

Further, the resist film is formed with a wavelength of 248 n.
m, a material having an ablation speed of 0.04 μm / shot or more with respect to pulse light of an excimer laser having an energy density of 100 mJ / cm ² .

[Configuration for Achieving the Second Object] To achieve the second object, a metal film, a dielectric insulating film,
A thin film of a semiconductor film or a multilayer film of one or more of the above thin films obtained by processing by an ablation phenomenon of an excimer laser beam using a resist film composed of a polymer material having urethane bonds and / or urea bonds. A liquid crystal device is formed by sandwiching a liquid crystal layer between the glass substrate described above and the other glass substrate on which a black matrix and a plurality of color filters are formed.

In order to achieve the second object,
The black matrix of the glass substrate and / or the plurality of color filters are formed of a black matrix film and / or
Alternatively, the plurality of color filter films are irradiated with an excimer laser through a mask having a predetermined opening pattern, and the black matrix film and / or the plurality of color filter films at the irradiated portions are processed by an ablation phenomenon. I do.

[Operation of Configuration for Achieving First Object] Ablation Phenomenon of Excimer Laser Light (Photo
Decomposition Ablation: Photo Deconposit
The processing of polymer materials by ion ablation is based on the phenomenon (cleavage) in which polymer bonds are non-thermally cut by a short-pulse ultraviolet laser, and high-precision thin film processing can be performed. It has the feature of being able to.

By utilizing this ablation phenomenon, it is possible to form a pattern of a resist film only by an exposure process using an exposing machine using excimer laser light, and the conventional development process can be omitted completely.

Further, the resist remaining after the pattern processing can be removed by simple irradiation of excimer laser light, and a large-area resist peeling apparatus and a peeling liquid, which are indispensable in the prior art, become unnecessary.

A resist material suitable for processing utilizing the above-described ablation phenomenon naturally requires properties different from those of a conventional resist material. In other words, it is important that the excimer laser light is efficiently absorbed and the bonds between atoms are efficiently cleaved by the absorbed energy.

At present, there are four types of wavelengths of the main oscillation frequency of the excimer laser.
8 nm is practical, and the wavelength of 248 nm is particularly important for bond cleavage.
Excimer laser light is advantageous.

As a result of examining the cleavage of various polymer materials with an excimer laser beam having a wavelength of 248 nm, in order to perform ablation at a high rate, the absorption coefficient of the resist film needs to be 5 × 10 ⁴ cm ⁻¹ or more. It turned out to be.

In order to exhibit such strong absorption, a substituent having an aromatic ring (Ar: aromaticate) must be present in the resist material. The difference in the absorption intensity due to the difference in the bonding mode of the substituent is almost uniquely determined by the direct bonding mode to the aromatic ring. Regarding this point, for example, "Absorption Spectra in the Ultraviolet and visibl
e region "(Edited by L. Lang, Akademimi Kiado, Bud
It is clear from comparing the data of apest 1966).

The bond in which the energy absorbed in the aromatic ring is efficiently converted into a cleavage is based on the results of the previous studies.
An imide bond and a urethane bond. However, an imide-bonding material such as polyimide as a typical example has a structure in which a large number of aromatics are generally bonded, so that there are many residues (debris) generated by the ablation phenomenon.

Therefore, as a practical ablation resist material having less debris, a polymer compound produced by a polymerization reaction using polyisocyanate as a starting material is most suitable. More specifically, polyisocyanate and polyol or polyamine are used. A polymer compound having one or both of a urethane bond and a urea bond formed by a polymerization reaction with is preferred.

In particular, it has a urethane bond, and the structure has "-
A polymer compound having a partial structure of "Ar-NHCOO-" (Ar represents an aromatic hydrocarbon group having or not having a substituent), or a polymer compound having a urea bond and having "-Ar
-NHCONH- "(Ar represents an aromatic hydrocarbon group having or not having a substituent) is preferably a polymer compound having a partial structure, and the polyisocyanate is selected from toluene diisocyanate, methylene bisphenyl isocyanate, and naphthalene diisocyanate. At least one of
Various types of polymer compounds are the most suitable resist materials for excimer laser beam ablation processing.

By using such a material, the absorption efficiency with respect to the excimer laser beam at or near the wavelength of 248 nm can be improved.

In the above structure, “—Ar—NHCOO
-"(Ar represents an aromatic hydrocarbon group with or without a substituent), a polymer compound having a partial structure, or a urea bond, and" -Ar-NHCONH
Examples of the polymer compound having a partial structure of "-" (Ar represents an aromatic hydrocarbon group having or not having a substituent) include the above-mentioned materials, a melamine resin, and the like.

In the above-described resist material for ablation processing of excimer laser light, a polymer compound having at least one urethane bond or urea bond forms a cyclic or network-like crosslinked structure by either heating or drying. It is necessary to be a thermosetting type in order to realize non-thermal ablation and a high-accuracy processing end face. These are, of course, spin-coated, roll-coated, and rod-coated on thin films such as metal films, dielectric insulating films, and conductive films formed on glass substrates as resist materials or multilayer films in which a part of them are patterned. It is necessary that a uniform coating film of 3 μm or less can be formed by a coating means such as that described above. For this purpose, it is necessary to adjust a molecular weight, a mixing amount of a solvent, a surfactant, a filler, and the like to satisfy required coating characteristics. is important.

Further, after heat polymerization as a resist material,
It is important that the underlying thin films have sufficient resistance to an etching atmosphere in wet etching or dry etching.

FIGS. 1 and 2 are process diagrams for explaining a method of manufacturing a liquid crystal display device according to the present invention using a resist material for ablation processing of excimer laser light having the above-described characteristics.

First, as shown in FIG. 1A, a glass on which a thin film of a metal film, a dielectric insulating film, a semiconductor film, or a multilayer film 200 in which a part of the thin film is formed in a pattern is formed. On the substrate 100, a uniform coating film of the resist film 300 having a thickness of 3 μm or less is formed by applying means such as spin spin coating, roll coating, and rod coating (b).

Glass substrate 1 coated with resist film 300
00 is irradiated with an excimer laser beam having a wavelength of, for example, 248 nm through an exposure mask 400 having a required opening pattern using a dielectric multilayer film as an opaque film (c).

At this time, the excimer laser light is obtained by converting the laser light from the excimer laser to the resist film 3 by an imaging lens.
Imaged at 00. The irradiation energy density is 50 m
J / cm ² or more and 300 mJ / cm ² or less.

As a result, as shown in (d), the resist pattern from which the resist corresponding to the opening pattern of the exposure mask 400 was removed was processed by the ablation phenomenon of the excimer laser light, and the metal film and the dielectric insulating material were removed. film,
The thin film of the semiconductor film or the multilayer film 200 in which a part of the thin film is formed in a pattern is exposed in a required pattern.

Next, as shown in FIG.
(D) The glass substrate is subjected to wet etching or dry etching to remove the exposed portions of the metal film, the dielectric insulating film, the thin film of the semiconductor film, or the multilayer film 200 in which a part of the thin film is formed in a pattern. Thus, a required pattern is formed.

After that, the remaining resist film is removed by an ablation process of irradiating the entire surface of the pattern forming surface with an excimer laser beam having a wavelength of 248 nm or 308 nm having an energy density of 150 mJ / cm ² or less (f). Metal film patterned into a pattern,
A glass substrate 100 on which a dielectric insulating film, a thin film of a semiconductor film, or a multilayer film 200 in which a part of the thin film is formed in a pattern is obtained (g).

As described above, except for the etching process, the lithographic apparatus requires only two excimer laser light irradiating apparatuses, ie, exposing and peeling. In particular, the resist peeling apparatus does not use a mask. An inexpensive excimer laser light irradiating device having an extremely simple configuration may be used, and the cost of the manufacturing apparatus can be greatly reduced.

[Operation of Configuration for Achieving the Second Object] For example, a metal film for forming a thin film transistor on a TFT substrate (switching element side substrate), which is one glass substrate in the case of a TFT-LCD, The processing of a body insulating film, a thin film of a semiconductor film, or a multilayer film composed of one or more of the thin films is performed by an ablation phenomenon of an excimer laser using a resist film composed of a polymer material having a urethane bond and / or a urea bond. Process.

By sandwiching a liquid crystal layer between the glass substrate and the other glass substrate on which a black matrix and a plurality of color filters are formed, a low-cost, high-quality liquid crystal display device that does not affect the environment is provided. Is obtained.

Further, the black matrix and / or the plurality of color filters of the other glass substrate have the black mask film and / or the plurality of color filter films made of a polymer material having a urethane bond and / or a urea bond. By using a material processed by the ablation phenomenon of an excimer laser using a resist film, a high-quality liquid crystal display device with lower cost and no influence on the environment can be obtained.

[Structure for Achieving the Third Object] In order to achieve the third object, the present invention is characterized by having the structure shown in FIG. 3 and described below.

FIG. 3 is a schematic diagram for explaining an example of the configuration of an exposure machine utilizing the ablation phenomenon of an excimer laser beam used for manufacturing a liquid crystal display device according to the present invention, where 1 is an excimer laser, 3, 5 are lenses, 4 is a split lens, 6
Is a condenser lens, 7 is an exposure mask, 8 is an imaging lens, 9 is an entrance pupil, 10 is a resist-coated glass substrate which is a workpiece, 11 is an XY table (11a is an XY mask table, 11b is X -Y substrate table).

In the figure, (1) an ultraviolet pulse laser is used as the excimer laser 1, and an output light beam (excimer laser light) from the excimer laser 1 is applied to an exposure mask 7 having a predetermined aperture pattern and an imaging lens 8. (A resist-coated glass substrate, hereinafter simply referred to as a "workpiece") 10 placed on the image forming surface through a mask and processed (developed) by a pattern ablation phenomenon corresponding to the opening pattern of the exposure mask 7 I do.

The output light beam of the excimer laser 1 is divided into a large number of light beams having a small area, each light beam is condensed, and the surface of the exposure mask 7 is uniformly irradiated using each converging point as an illumination light source. Also, an image of the illumination light source is formed on the entrance pupil 9 of the imaging lens 8, and the aperture pattern of the exposure mask 7 is applied to a limited area of the workpiece 10 placed on the imaging surface of the imaging lens 8. By forming a one-to-one image and scanning the limited area over the entire area of the workpiece 10, a pattern corresponding to the aperture pattern of the exposure mask 7 due to the ablation phenomenon is formed on the entire area of the workpiece 10.

(2) The output light beam of the excimer laser 1 is passed through the exposure mask 7 having a predetermined aperture pattern and the imaging lens 8 to the workpiece 10 placed on the imaging surface.
A liquid crystal display device using an ablation phenomenon of an excimer laser beam for developing and forming a pattern corresponding to an opening pattern of the exposure mask 7 on the workpiece 10 by an ablation phenomenon. A lens array 4 for dividing the output light beam into light beams having a small area and condensing the light beams; an illumination optical system 6 for uniformly irradiating the surface of the exposure mask 7 using the converging point of the lens array 4 as an illumination light source; An imaging lens 8 having an entrance pupil 9 for forming an image of the exposure mask 7 illuminated by the illumination optical system 6 on a limited area of the workpiece 10 in a one-to-one manner; XY tables 11a and 11b for moving the exposure mask 7 and the workpiece 10 in two directions parallel to the plane of the exposure mask 7 so as to scan the limited area. By scanning the entire object 10, characterized in that a configuration ablating development to form developing a pattern corresponding to the opening pattern of the exposure mask 7 by ablation phenomenon over the entire workpiece 10.

The XY tables 11a, 11b
Can be used to move one table 11a for exposing mask movement and the other table 11b for moving workpieces, and relatively move both directions in one direction (eg, X direction) and the other direction (eg, X direction) orthogonal to the one direction. (Y direction).

(3) The illumination optical system in the above (2) is to convert the output light beam of the excimer laser 1 into a parallel beam along the optical axis before splitting the output light beam into a small area light beam by the lens array 4. And the lens array 4 is composed of two sets of split lenses each consisting of an even number of lenses. Each of the two sets of lenses splits and converges the output light beam of the ultraviolet pulsed laser that is incident in parallel. The first lens and the second lens constitute an array, the focal point created by the first lens is located in the middle of the second lens, and the luminous flux diverging from the focal point corresponds to the corresponding lens of the second lens. The third lens is arranged so as to completely fit within the area, and converges each light beam emitted from the second lens to the same area in the vicinity of the surface of the exposure mask 7 after the first and second lenses. Install lens 5 The focusing surface of the third lens is made to completely coincide with the surface of the exposure mask 7 near the surface of the exposure mask 7 and at the same time, the image of the focal array by the split lens is formed on the entrance pupil 9 of the imaging lens 8. A fourth lens 6 is provided.

(4) When the illumination optical system in the above (3) is such that the cross section of the output light beam of the ultraviolet light pulse laser 1 is an XY coordinate plane, each independent parallel to the X axis and the Y axis. Each of the optical systems is constituted by a cylindrical lens having a coordinate axis formed by the X axis and the Y axis as a cylinder axis.

Further, (5) the X axis in the above (4),
The fourth lens 6 constituting each optical system on the Y axis is a single aspherical lens.

(6) The imaging lens 8 in the above (2) is characterized in that it is a telecentric symmetric lens configured such that a portion where the light beam is most narrowed in the lens is hollow.

(7) The exposure mask 7 in the above (2) is formed by patterning a dielectric multilayer film serving as a reflection film with respect to the wavelength of the output light beam of the excimer laser 1, and is provided on the image plane. It is characterized in that both the workpiece 10 and the exposure mask 7 are moved so as to be point-symmetric with respect to one point on the optical axis of the object 10 and the imaging lens 8.

(8) The illumination area on the exposure mask 7 in the above (7) is rectangular, and the length of the long side is a range satisfying the predetermined resolution and image distortion of the symmetric lens in the above (6). When the exposure mask 7 and the workpiece 10 are continuously moved in the short side direction and reach the ends of the workpiece 10 and the exposure mask 7, the exposure mask 7 and the workpiece 10 are moved in the longitudinal direction of the illumination area. Is moved, and then scanning for continuously moving in the short side direction is repeated to perform ablation processing on the entire area of the workpiece 10.

(9) The rising of the energy density distribution at the end of the long side of the rectangular illumination area on the exposure mask 7 in the above (8) is set to be 50 μm or less from the end of the short side. An illumination area adjusted by a rectangular aperture pattern by a knife edge or a rectangular aperture pattern of a dielectric multilayer film is provided above the exposure mask 7, and a short side of the rectangular aperture pattern is located at an intermediate position between the aperture patterns. It is characterized by doing.

(10) The output light beam of the excimer laser 1 in the above (2) is set in the horizontal direction, and the X-Y holding the exposure mask 7 and the workpiece 10 is set.
With the tables 11a and 11b in the horizontal direction, the illumination light is made incident on the surface of the exposure mask 7 by only one 45-degree reflection, and the above-described (6)
Is arranged.

(11) In the above (10), the fourth lens of the illumination optical system of the above (2) and (3) is
It is characterized in that it is arranged at the subsequent stage of the 5-degree reflection mirror and immediately before the exposure mask 7.

(12) In the above (10),
The light source unit composed of the ultraviolet pulse laser 1 and the ablation developing unit composed of the components excluding this light source are installed in rooms with different cleanliness separated by separating walls, and the light source unit composed of the ultraviolet pulse laser is installed. And a laser beam (excimer laser beam) emitted from the ablation developing section is introduced through a transmission window plate provided on the separation wall.

(13) Each part of the ablation developing section consisting of the light source section composed of the excimer laser 1 and the part excluding the light source in the above (12) is installed on a vibration-isolated floor.

(14) The deviation of the laser light beam emitted from the light source unit comprising the excimer laser 1 in the above (12) with respect to the optical system constituting the ablation developing unit is corrected by converting it into the inclination of the transmission window plate. It is characterized by the following.

As described above, the method and the apparatus having the above-described structures are particularly suitable for the light absorbing film (BM, so-called black matrix) and the three-color color filter of the color filter substrate constituting the color liquid crystal display panel such as a TFT. It is suitable for patterning of a color filter thin film at the time of formation and patterning of various thin films constituting a TFT substrate with a resist and a resist pattern.

[Effect of Configuration for Achieving the Third Object] This configuration utilizes an ablation phenomenon of excimer laser light, and particularly, a TFT component film and a color filter which constitute a color liquid crystal display panel such as a TFT. It performs high-definition pattern processing such as patterning of a resist thin film when forming a light absorbing film (MB, a so-called black matrix) of a substrate or a color filter of three colors, and resist patterning of each TFT layer.

As described above, the ablation phenomenon is as follows.
When ultraviolet excimer laser light (excimer laser light) having a high energy density is applied to a material, the material that is exposed to light is photolyzed (cleaved) and scattered.

Therefore, when the excimer laser beam is irradiated through the exposure mask having the opening pattern so as to form an image on the material, a pattern corresponding to the opening pattern of the exposure mask is formed on the material.

Decomposition of a substance upon irradiation with a laser beam having a wavelength longer than the wavelength of visible light is mainly caused by a thermal process. In the case of excimer laser beam, a chemical bond is directly broken particularly for many organic substances. Decomposes by a non-thermal process that breaks (cleaves).

The development of a resist film utilizing the ablation phenomenon (ablation development) is to form a pattern on a resist or the like by utilizing such non-thermal photolysis, and the exposure and development by conventional photolithography are performed. This is a processing method in which the two steps are completed only by the exposure step.

As is clear from the above description, the apparatus for performing ablation development is essentially an exposure machine, and the principle of the optical system that forms an exposure mask pattern on a resist film with required accuracy is based on the ablation development. The case of the machine does not change.

The basic conditions of the optical system of the exposure machine are that the light intensity distribution on the image plane is uniform and that the required precision of the image pattern is satisfied. Under this condition, the optical system of the exposure apparatus is divided into two parts, an illumination optical system and an imaging lens system. The former mainly determines uniform illumination, and the latter determines imaging performance.

[Structure for Achieving Fourth Object] A fourth object of the present invention is to form a resist pattern for manufacturing a large-sized liquid crystal display element substrate (glass substrate) using a small-area exposure mask. The method and the apparatus are achieved by the following configuration.

(1) An illumination optical system that uses an excimer laser having a wavelength of 248 nm or 308 nm as a light source and illuminates an exposure mask having a predetermined opening pattern made of a dielectric multilayer film in a slit shape, An XY table (XY mask table) that can be moved in the Y direction, a refraction-type symmetric imaging optical lens that projects an aperture pattern of an exposure mask 1: 1 onto a substrate constituting a liquid crystal display element, and the glass An XY table (XY substrate table) capable of holding the substrate and moving in the X and Y directions independently of the XY mask stage is used as an exposing machine. Move the Y substrate stage one-dimensionally in the same direction or the opposite direction, and ablate the excimer laser light to change the opening pattern of the exposure mask. A resist layer coated on the glass substrate 1: to form a 1.

(2) As the dielectric exposure mask for the liquid crystal display element in the above (1), the pattern of each layer of the pixel portion is divided into integer parts, and the pattern other than the pixels is also divided appropriately.
A mask pattern is formed by enclosing each unit in a non-transmissive portion in parallel with the scanning direction, and the XY mask table and the XY substrate table are set at the scan start position corresponding to each mask pattern. Then, the corresponding exposure mask area is scanned, and then the exposure mask is returned to the original position, and the substrate is moved to the next repetition position to perform a similar scan (step-scan), and thereafter, the same process is repeated. Thereby, the entire pattern of the liquid crystal display element is formed.

(3) A method of forming a resist pattern for forming a required thin film pattern on an insulating substrate constituting a liquid crystal display element is performed by forming a predetermined opening pattern with an area smaller than the area of the thin film pattern formation region of the liquid crystal display element. The ablation phenomenon caused by irradiating the exposing mask having a slit-like excimer laser light in a direction perpendicular to the relative movement direction with respect to the exposing mask while relatively moving the exposing mask in a plane parallel to the thin film pattern forming region. The resist applied thereon is patterned according to the opening pattern of the exposure mask.

(4) The exposure mask has an opening pattern obtained by dividing the resist pattern in the pixel region of the insulating substrate into a unit area of an integral number, and an opening pattern obtained by dividing the resist pattern other than the pixel region into appropriate unit regions. A pattern and a region surrounding each unit region with a non-transmissive portion parallel to the scanning direction.
A step of step-moving the Y mask table and the XY substrate table in a direction orthogonal to the length direction of the slit of the slit-shaped illumination light of the excimer laser light;
The whole surface of the resist on the substrate is patterned by scanning.

(5) A resist pattern forming apparatus for forming a plurality of thin films constituting a liquid crystal display element on a glass substrate and forming a resist pattern for patterning the thin film is formed by an excimer laser having a wavelength of 248 nm or 308 nm. A light source for irradiating light, an exposure mask composed of a dielectric multilayer film having a predetermined opening pattern, an illumination optical system for illuminating the exposure mask in a slit shape with excimer laser light, and excimer laser light holding the exposure mask X direction in a plane perpendicular to the optical axis and Y orthogonal to the X direction
XY mask table movable in the direction, a refraction-type symmetric imaging optical lens for projecting the opening pattern of the exposure mask 1: 1 onto the insulating substrate, and XY holding the insulating substrate.
At least an XY substrate table which is movable independently of the mask table in an X direction in a plane parallel to the XY mask stage and in a Y direction orthogonal to the X direction,
By scanning the XY mask table and the XY substrate table one-dimensionally in the same or opposite directions,
The opening pattern of the exposure mask is patterned 1: 1 on the resist layer applied on the glass substrate by the ablation action of the excimer laser light passing through the opening pattern of the exposure mask.

[Operation of Configuration for Achieving the Fourth Object] With the above configuration, pattern exposure of a resist on a large-sized glass substrate can be performed by utilizing the step-scan exposure means and the ablation phenomenon of excimer laser light. And development are integrated, and a high-speed and low-cost resist patterning process is realized.

[Structure for Achieving the Fifth Object] A fifth object of the present invention is to provide a high-precision dielectric multilayer which has increased processing resistance to excimer laser light provided in an apparatus for manufacturing a liquid crystal display element. An exposure mask for excimer laser processing made of a film is formed on a surface opposite to a light incident surface of a glass substrate transparent to ultraviolet light, such as a dielectric multilayer film having the following requirements (1) to (5). Is achieved by forming

(1) A first layer having an optical path length of １ ／ of the wavelength used on a glass substrate, and a first layer having an optical path length of 1/4 on this first layer.
A second layer having four wavelengths is overlaid. The refractive index of the first layer is higher than the refractive index of the second layer, and a quarter-wavelength optical path length having a refractive index higher than the refractive index of the substrate glass is formed on the dielectric multilayer film having the above configuration. It has a multilayer structure in which a third dielectric layer is formed.

In forming a dielectric pattern, after forming a resist pattern, the pattern is formed by ion milling, or a metal film is formed on the uppermost layer.
Only this metal film is etched to form a desired metal film pattern, and the dielectric layer is patterned by dry etching using this as an exposure mask.

(2) The dielectric layer is configured such that the energy density transmitted through the dielectric layer with respect to the wavelength used in the above structure is equal to or lower than the ablation threshold of the film to be processed on the substrate.

(3) The structure is such that the mask metal film for patterning the dielectric in (1) is left as it is as a constituent material of the exposure mask. At this time, the dielectric layer is configured to have a thickness such that the transmission energy density of the dielectric layer with respect to the excimer laser light is equal to or less than the damage threshold of the metal film.

(4) Cr is particularly used as the metal film in the above configuration.

(5) LiF, MgF ₂ , SiO ₂ , YF ₃ , La as low-refractive-index materials constituting the above-mentioned dielectric layer
Using F ₃ and ThF _4, and using Al as a high refractive index material
₂ O ₃ , MgO, ThO ₂ , Sc ₂ O ₃ , Y ₂ O ₃ , H
Use any combination of fO ₂ .

More specifically, a more detailed configuration will be described. An exposure mask is formed by forming a glass substrate transparent to ultraviolet light and a dielectric multilayer film pattern for selectively reflecting the wavelength of ultraviolet light on the glass substrate. And a dielectric mask is formed.

The exposure mask comprises a glass substrate transparent to ultraviolet light, and a film having an optical path length of １ ／ wavelength of the used ultraviolet light on a surface of the glass substrate opposite to the ultraviolet light incident side. A first dielectric layer having a thickness, and a second dielectric layer having an optical path length of 波長 wavelength and smaller than the refractive index of the first dielectric layer on the first dielectric layer. A dielectric multilayer film formed by repeatedly forming a combination of two-layer films formed by stacking layers, and a refractive index larger than the refractive index of the glass substrate on the uppermost layer of the dielectric multilayer film, and the optical path length of the ultraviolet light used is It has a third dielectric layer having a quarter wavelength.

Further, an apparatus for manufacturing a liquid crystal display element uses an excimer laser beam of 248 nm and 308 nm as ultraviolet light.
m, 351 nm, and the transmission energy density of the dielectric layer formed on the glass substrate at each of the above wavelengths is set to be equal to or less than the ablation threshold of the film to be processed.

Further, a metal film was formed on the third dielectric layer, and the transmission energy density of the dielectric layer at each wavelength of the excimer laser light was set to be equal to or less than the damage threshold of the metal film. It is characterized by the following.

The material of the metal film is Cr.

Further, the first dielectric material constituting the dielectric layer is made of Al ₂ O ₃ , MgO, ThO ₂ , Sc.
₂ O ₃ , Y ₂ O ₃ , or HfO ₂ , or a combination of two or more thereof, wherein the second dielectric material is LiF, Mg
_{F 2, SiO 2, YF 3} , LaF 3, characterized in that it is a one or two or more combinations of the ThF _4.

The method of forming an exposure mask is to form a first dielectric layer having a film thickness with an optical path length of １ ／ wavelength of the used ultraviolet light on a glass substrate transparent to ultraviolet light, First
The optical path length is also 1/4 wavelength and the first
After forming a dielectric multilayer film formed by forming a second dielectric layer smaller than the refractive index of the dielectric layer, the uppermost layer of the dielectric multilayer film has a refractive index larger than that of the glass substrate and A dielectric multilayer film forming step of forming a third dielectric layer whose optical path length is １ ／ wavelength of the used ultraviolet light, a metal film forming step of forming a metal film on the dielectric multilayer film, A metal film patterning step of forming an opening pattern as an exposure mask by photolithography, and a dielectric multilayer film patterning step of forming an opening pattern as an exposure mask on the dielectric multilayer film by etching using the opening pattern of the metal film as a mask It is characterized by including.

[Function of Configuration for Achieving the Fifth Object] The function of the dielectric multilayer film such as selective reflection is applied to filters, mirrors, antireflection films and the like. Born & E. Wolf, "Prim
chips of Optics "4th Edit
ion 1970pp51-70.

According to the above document, the reflecting mirror is formed by alternately superposing a high-refractive-index quarter-wave film and a low-refractive-index quarter-wave film to obtain a given reflectivity depending on the refractive index and the number of layers. Can be obtained.

In the present invention, the first definition is to irradiate an exposure mask with excimer laser light to form an opening pattern image of the exposure mask on a film substrate to be processed. Since it is almost perpendicular, the discussion will be made below only for normal incidence. In this case, as shown in Equation 96 on page 69 of the above-mentioned document, N
The reflectance R (2N) of the multilayer film having the two-layer structure is given by the following equation (1). R (2N) = _{{[1- (n e / n 1)} × (n 2 / n 3) 2N ] / _{[1 + n e / n 1)} × (n 2 / n 3) 2N ]} ² · (1) where n ₁ is the refractive index of the incident medium constituting the mask, n
_e is the refractive index of the refractive _index, n 2, n ₃ are respectively the refractive index of the high refractive index side dielectric constituting the multilayer dielectric layer and the low refractive index side dielectric of the exit medium.

As is apparent from the above equation (1), the reflectance increases as the number of dielectric layers increases and as the ratio of n ₂ / n ₃ increases.

On the other hand, in order to form a pattern with high definition, it is necessary to reduce the number of dielectric layers as much as possible. For this purpose, a large combination of n ₂ / n ₃ is selected, but the value of the refractive index of the usable dielectric material is 1.3.
It is almost limited to the range of ~ 2.3, and an arbitrary combination is not necessarily obtained.

Further, when applying Max to ablation, it is necessary to consider the resistance to excimer laser light, but some literatures, for example, F. Rainer et al,
As shown in Applied Optics Vol. 24, No. 4 (1985), p. 496 to p. 500, materials having high resistance tend to have a small refractive index.

According to the above literature, LiF, MgF ₂ , SiO ₂ , YF ₃ , and LaF are used as low-refractive-index materials having high durability.
₃ , ThF ₄ and Al ₂ O ₃ ,
MgO, ThO ₂ , Sc ₂ O ₃ , Y ₂ O ₃ , HfO _{2 and the} like can be mentioned, but the high-refractive-index material has lower resistance than the low-refractive-index material without exception.

Therefore, since the combinations of materials are further limited, it is necessary to consider a configuration of a multilayer film for improving the reflectivity even a little.

FIG. 4 is a schematic cross-sectional view illustrating an example of the basic structure of a dielectric multilayer film mask, and FIG. 5 is a schematic cross-sectional view illustrating another example of the basic structure of a dielectric multilayer film mask. 7
1 is a quartz glass substrate, 72 is a high refractive index dielectric layer, and 73 is a low refractive index dielectric layer.

[0137] incident medium in FIG. 4 is emitted medium quartz glass is air, the refractive index n ₁ of the incident medium is 1.0, is a 1.5 refractive index n _e of the exit medium, the refractive index ratio n _e /
n ₁ is 1.0 / 15 = 0.66.

In FIG. 5, the incident medium is air and the exit medium is quartz glass, and the refractive index n ₂ of the incident medium is 1,
Refractive index n _e of the emission medium is a 1.5, the refractive index ratio n _e
/ N ₂ is 1.5 / 1.0 = 1.5.

By comparing the dielectric multilayer masks shown in FIGS. 4 and 5 with each other, it is clear which of the masks is advantageous.
It is the difference between the value of the refractive index ratio n _e / n ₁ described above is clear from equation (1).

[0140] Figure 6 refractive index ratio corresponding to FIG 4 is n _e /
FIG. 5 is an explanatory diagram showing the relationship between n ₁ and the reflectance using the number of layers as a parameter.

FIG. 7 is an explanatory diagram of the relationship between the refractive index ratio _ne / n ₁ and the reflectance corresponding to FIG. 5 using the number of layers as a parameter. The number of layers varies from 1 to 10 layers from bottom to top.

Here, the substrate constituting the mask is quartz glass, and the refractive index at a wavelength of 248 nm is 1.5.

In the case of FIG. 7 in which light is incident from the air side, the refractive index ratio _ne / n ₁ is 1.5. On the other hand, in the case of FIG. 6 in which light is incident from the substrate side, it is 1 / 1.5. It is clear from the figure that the difference is practically negligible as. However, when the value of n ₂ / n ₃ is not so large and there are 10 layers or less, this difference is remarkable.

FIG. 8 is a schematic sectional view for explaining the basic structure of an excimer laser processing mask (exposure mask) according to the present invention. The uppermost layer of the multilayer dielectric layer shown in FIG. wherein the further addition of refractive index n ₁ is greater than n> n ₁ becomes 1/4 wavelength film of the incident medium constituting (additional high refractive index layer 4) (1) is changed as the following equation (2) Thus, the above problem is solved.

[0145] R (2N + 1) = _{{[1- (n 1 n e / n} 2) · (n 2 / n 3) 2N ] / _{[1+ (n 1 n e / n} 2) · (n 2 / n ₃ ) ^2N ]｝ ² (2) Since the additional high-refractive-index layer 74 is not necessarily required to have high laser resistance since it is at the final stage of transmitted light,
A material with a high refractive index can be selected.

FIG. 9 shows the relationship between the refractive index ratio n ₂ / n ₃ of the multilayer dielectric layer and the reflectance when Al ₂ O ₃ is used as an additional high refractive index layer except for the metal film 75 of FIG. FIG. 4 is an explanatory diagram of characteristics of FIG.

It can be seen from the figure that the addition of the high refractive index layer improves the characteristics as compared with FIG. 6 as well as FIG.

When the dielectric layer mask is actually used, it is difficult to use a conventional alignment optical system or the like because it is almost transparent to ordinary visible light. As a countermeasure, a metal film may be stacked, but the excimer laser resistance of the metal film is low.
0 mJ / cm ² or less of what is most to life of the mask, it is desirable to use at 10 mJ / cm ² following irradiation.

Therefore, only the arrangement shown in FIG. 8 is possible in order to use the metal film over the dielectric layer. When a metal film is actually superimposed on a dielectric layer, there are many advantages not only in ease of use as a mask but also in manufacturing the mask.

As a method of manufacturing a multilayer dielectric multilayer mask,
Although ion milling and dry etching are generally used, a point to be considered is to inspect and correct the resist pattern before milling or etching.

In particular, since it is difficult to correct the multilayer dielectric layer itself, a complete inspection and correction of the resist pattern is required.

At present, the technique of the Cr mask has been established in this aspect, and this technique can be applied to a multilayer dielectric layer mask. That is, a metal film is formed on a multilayer dielectric layer uniformly formed on a substrate, and after confirming no defect, a pattern is formed by a normal photolithography process.

After the pattern is inspected and corrected for defects to obtain a complete metal film pattern, this is used as a resist pattern to form a pattern of the dielectric layer by the above etching.

By setting the transmission energy density of the dielectric layer lower than the damage threshold of the metal film and leaving the metal film pattern, it is possible to perform the same treatment as a normal exposure or etching mask.

It is needless to say that a mask on which a metal film is stacked is suitable for ablation with a low energy density.

[Structure for Achieving the Sixth Object] A liquid crystal display device having an alignment device for aligning an exposure mask and a glass substrate with high accuracy by a simple structure which is a sixth object of the present invention. Is as follows.

(1) In a liquid crystal display device, a predetermined pattern is formed by irradiating an excimer laser beam through an exposure mask on a surface on which a resist film applied to a workpiece such as a glass substrate constituting a liquid crystal display element is exposed. A positioning mark is formed on a part of the exposure mask, and a substrate is provided which is compatible with the workpiece in position and emits fluorescence at the projection of the positioning mark of the exposure mask. The present invention is characterized in that the exposure mask and the workpiece are aligned based on the location.

(2) In an exposure apparatus using an excimer laser beam through a photomask on a surface of a workpiece on which a resist film is formed, an alignment mark is formed on the exposure mask, and the alignment mark of the exposure mask is formed. A holder that emits fluorescent light at the projection unit and holds the processing substrate;
Means for positioning the substrate to be processed with respect to the holder based on the fluorescent portion of the holder.

[Operation of Configuration for Achieving the Sixth Object] In a substrate compatible with the workpiece in the configuration of (1) above, an alignment mark of an exposure mask is projected by an excimer laser beam. Fluorescent.

Based on the fluorescent light, the alignment mark projected on the above-mentioned substrate which is arranged in a position corresponding to the workpiece can be visually recognized, and the alignment effect is completely equivalent to that of the conventional projection of visible light. Can be obtained.

Therefore, alignment of the exposure mask with respect to the workpiece can be achieved with a simple configuration.

According to the above configuration (2), the alignment mark of the exposure mask is projected on the holder for holding the workpiece, and fluorescence is emitted at the projected location.

Then, the workpiece held by the holder on which the alignment mark is projected can be positioned between the holder and the exposure mask based on the location of the fluorescent light emitted by the projection light.

[Structure for Achieving the Seventh Object] (1) Debris generated by ablation processing using excimer laser light forms a laminar flow in the excimer laser irradiation area (processing area), or (2) nozzle And (3) arranging one or more tubular nozzles at the irradiation site, or forming an explosion cloud with an annular suction nozzle surrounding an irradiation region (working region) of excimer laser light. By setting and using a position on the workpiece where the speed of the (bloom) is lower than the flow speed of the suction, the suction is removed.

The debris removing device by suction described in (3) is a bottom plate having an entrance window made of quartz or the like that transmits excimer laser light, and a bottom plate having an opening opposed to the entrance window and close to a processing region of a workpiece. An exhaust port connected to an exhaust system, and a nozzle structure formed between the exhaust port and a space between the entrance window and the bottom plate.

The debris removing device of the above (3) is provided with a vacuum suction device at a position facing an ablation processing portion for irradiating an excimer laser beam, and removes debris generated by the ablation by suction. I do.

Further, the above-mentioned vacuum suction device is provided with at least one tubular nozzle, and this tubular nozzle is installed at a position on the workpiece where the speed of the plume by ablation is lower than the flow rate of vacuum suction.

Further, the vacuum suction device is provided with an annular suction nozzle surrounding the ablation portion, and is installed at a position on the workpiece where the speed of the plume due to ablation is lower than the flow rate of vacuum suction.

The vacuum suction device has an entrance window made of a quartz material that transmits excimer laser light, and a bottom plate having an exit port which is wider than the area of the ablation portion of the workpiece by about 2 mm and faces the entrance window. An exhaust port connected to an exhaust system, and a nozzle-like structure in which a flow velocity at a portion deviating from an optical path of excimer laser light between the space between the entrance window and the bottom plate and the exhaust port is 25 m / s or more. The bottom plate is provided at an interval of about 1 mm or less from the workpiece.

[Function of Configuration for Achieving the Seventh Object] As described above, ablation by irradiation of excimer laser light is performed when ultraviolet excimer laser light having a high energy density is irradiated on a substance. It is defined as the phenomenon in which the material exposed to light is photolyzed and scattered. At this time, the photolysis (cleavage) is in an explosion state, and the debris scatters as an explosion cloud (bloom).

Therefore, utilizing this ablation phenomenon, for example, by using a certain pattern as a mask and illuminating it with excimer laser light to form an image on the surface of the workpiece, the shape according to the above mask pattern can be obtained. It will be formed on the surface of the surface work.

In the case of laser light having a wavelength of visible light or longer, the decomposition of a substance by irradiation with the laser light mainly occurs by a thermal process (thermal decomposition). However, when excimer laser light is used, particularly for many organic substances, At present, it is mainly used in the field of ultra-precision processing such as micromachining because it is decomposed by a non-thermal process of directly breaking chemical bonds.

Actually, the processing technique utilizing the ablation phenomenon of excimer laser light can be applied not only to the above-mentioned field of micromachining but also to a thin film forming process in the manufacture of TFTs and the like. Ablation development, which allows simultaneous exposure and development processes using conventional photolithography technology, by selecting a suitable resist material
Similarly, application to ablation peeling or the like is also considered.

The ablation phenomenon is understood as a kind of explosion phenomenon, as described above, because an excimer laser beam having a pulse width of 20 to 30 ns photodecomposes a substance at a high energy density.

FIG. 10 is an explanatory view of an ablation phenomenon schematically showing a shadow graph of an ablation phenomenon by a dye laser (pulse width: about 5 ns) which is delay-synchronized with a pulse of an excimer laser beam.
Is the conceptual shape of the behavior of debris generated by irradiation of excimer laser light, 16, 16 'are shock waves,
Reference numeral 17 denotes a workpiece.

The figure shows that novolak resin has a wavelength of 248 n.
m, an excimer laser beam having an energy density of 100 mJ / cm ² .

First, when the surface of the workpiece 17 is irradiated with the above-described excimer laser light, as shown in FIG. 17A, the lift 15a in the initial state in which debris is emitted from the area of the workpiece 17 irradiated with the excimer laser light. Occurs.

The shock wave 16 is formed by the released gas or debris composed of light fine particles.

The front speed of the shock wave 16 is 1.5 at a delay time of 0.2 to 0.4 μs or less.
Although the supersonic speed is about km / s, this is 1 μs in (b).
Later on, shockwave 1 at normal sound speed level
6 '.

A high pressure is applied to the inside of the wave front of the shock wave, whereby relatively heavy particles, which are the main components of the debris 15b, are suppressed.
Since about 10 μs elapses, the internal pressure suddenly decreases, so that the debris 15 c starts to rise, and as shown in FIG.
Mushroom cloud-shaped plume 15d called so-called plume after s position
Is observed.

This plume 15d is formed like 15e in (e) and 15f in (f) over time.

The rising speed and the height of the plume in the air are 20 m / s and about 3 mm, respectively, at a delay time of 100 μs under the above conditions. When the incident energy density is 300 mJ / cm ² , the rate of ablation is about three times, but the height and ascending speed of the plume are at most about 1.5 times.

The behavior of the above-mentioned ablation phenomenon slightly changes depending on the material to be processed, and there is such a change that a clear mushroom cloud-like plume is not observed. In particular, the quantitative value naturally depends on the material. Is 300mJ /
It is one measure of cm ² or less.

That is, by providing a vacuum suction device for suctioning and removing debris generated by the ablation at a position facing the ablation processing portion for irradiating the excimer laser beam, the debris adheres to the surface of the workpiece. Or reduce the energy of subsequent laser pulses.

[0185] In addition, debris is efficiently removed by providing at least one tubular nozzle and installing the above vacuum suction device at a position on the workpiece where the speed of the plume by ablation is lower than the flow speed of vacuum suction. can do.

Further, by providing an annular suction nozzle surrounding the ablation processing section, the vacuum suction device is installed at a position on the workpiece where the speed of the plume by ablation is lower than the flow rate of vacuum suction. Debris is more efficiently removed.

[0187] The above vacuum suction device is provided with a bottom plate having an entrance window made of quartz material transmitting the excimer laser beam and an exit port which is wider than the area of the ablation portion of the workpiece by at least 2 mm and faces the entrance window. And an exhaust port connected to the exhaust system, and a nozzle having a flow rate of 25 m / s or more at a portion deviating from the optical path of the excimer laser light between the exhaust port and the space between the entrance window and the bottom plate. The debris can be more efficiently removed by providing the structure and disposing the bottom plate at an interval of about 1 mm or less from the workpiece.

[0188]

Embodiments of the present invention will be described below in detail with reference to the embodiments shown in the drawings. FIG. 11 is a plan view illustrating a configuration in the vicinity of one pixel of an active matrix type color liquid crystal display device to which the present invention is applied.

As shown in FIG. 28, each pixel has two adjacent pixels.
Scanning signal lines (gate signal lines or horizontal signal lines) GL
(A gate line) and an adjacent video signal line (drain signal line or vertical signal line) DL (data line) in an intersecting region (in a region surrounded by four signal lines). I have.

Each pixel is a thin film transistor TFT (TFT).
1, TFT2), a transparent pixel electrode ITO1, and a storage capacitor Cadd (additional capacitor). The scanning signal lines GL extend in the left-right direction in the figure, and a plurality of scanning signal lines GL are arranged in the up-down direction. The video signal lines DL extend in the up-down direction, and a plurality of video signal lines DL are arranged in the left-right direction.

Note that SD1 is a source electrode, SD2 is a drain electrode, BM is a black matrix, and FIL is a color filter.

FIG. 12 is a sectional view taken along the line 3-3 in FIG. 11, and shows a thin film transistor T on the lower transparent glass substrate SUB1 side with respect to the liquid crystal layer LC.
An FT and a transparent pixel electrode ITO1 are formed, and a color filter FIL and a light shielding film, that is, a black matrix BM are formed on the upper transparent glass substrate SUB2 side.
This upper transparent glass substrate is generally called a color filter substrate.

A silicon oxide film SIO formed by dipping or the like is provided on both surfaces of the transparent glass substrates SUB1 and SUB2.

On the inner surface (the liquid crystal layer LC side) of the upper transparent glass substrate SUB2, a black matrix BM, a color filter FIL, a protective film PSV2, a common transparent pixel electrode ITO2 (COM), and an upper alignment film ORI2 are sequentially laminated. It is provided.

In a conventional method of manufacturing a color filter for a liquid crystal display element, a material having a developing function is exposed and developed, except for a portion where a black matrix BM is formed of a metal film of Cr or the like. When using no material, pattern formation is performed by means such as lift-off.

On the other hand, in the present invention, the patterning of each thin film of the lower transparent glass substrate SUB1 constituting the liquid crystal display element and the upper transparent glass substrate SUB2 on which the color filter FIL and the light-shielding film, that is, the black matrix BM are formed, is performed by the excimer patterning. A high-precision liquid crystal display device can be manufactured by forming by processing utilizing the ablation phenomenon of laser light.

FIG. 13, FIG. 14, and FIG. 15 are explanatory views of a forming process by patterning a thin film multilayer structure constituting a TFT on a lower transparent glass substrate. In each figure, the first
Photo, second photo,... Show an integrated exposure / development process according to the present invention in which a resist film is applied to cover the thin film to be processed, and this is irradiated with excimer laser light through an exposure mask. Also, the left side of each figure is a TFT part in FIG. 12, the right side is a terminal lead-out part, and the center is a description of the process.

Step A (FIG. 13) First, after a silicon oxide film SIO is formed on both surfaces of a lower transparent glass substrate SUB1 made of 7059 glass (trade name) by dipping, baking is performed at 500 ° C. for 60 minutes. A first conductive film g1 made of chromium having a film thickness of 1100 ° is formed on the lower transparent glass substrate SUB1 by sputtering, a resist is coated thereon, and a first photo process using excimer laser light is performed. A resist pattern is formed.

Next, the first conductive film g1 is selectively wet-etched with a ceric ammonium nitrate solution as an etchant. Thereby, the gate terminal GTM,
An anodized bus line SHg for connecting the drain terminal DTM and the gate terminal GTM, a bus line SHd for short-circuiting the drain terminal DTM, and an anodized pad (not shown) connected to the anodized bus line SHg are formed.

Step B (FIG. 13) Al-Pd, Al-Si, Al-S having a thickness of 2800 °
Second conductive film g2 made of i-Ti, Al-Si-Cu, or the like
Is formed by sputtering. Apply resist,
A second photo process using excimer laser light is performed to form a resist pattern.

Next, the second conductive film g2 is selectively etched with phosphoric acid, nitric acid and glacial acetic acid. Step C (FIG. 13) Then, a third photo step of the anodic oxidation mask AO is performed to form a resist pattern. Next, the substrate SUB1 was immersed in an anodic oxidation solution consisting of a solution in which 3% tartaric acid was adjusted to pH 6.25 ± 0.05 with ammonia and diluted 1: 9 with an ethylene glycol solution. It is adjusted to be 0.5 mA / cm ² (constant current formation).

Next, anodic oxidation is performed until the formation voltage 125 V necessary for obtaining Al ₂ O ₃ of a predetermined thickness is obtained. Thereafter, it is desirable to hold this state for several tens of minutes (constant voltage formation). This is important for obtaining a uniform Al ₂ O ₃ film. Thereby, the second conductive film g2
Is anodized to form an anodic oxide film AO having a thickness of 1800 ° on the scanning signal line GL, the gate electrode GT, and the electrode PL1.
F is formed.

Step D (FIG. 14) An ammonia gas, a silane gas, and a nitrogen gas are introduced into a plasma CVD apparatus to form a 2000-nm-thick Si nitride film, and a silane gas and a hydrogen gas are introduced into the plasma CVD apparatus. After forming an i-type amorphous Si film having a thickness of 2000 °, hydrogen gas and phosphine gas are introduced into a plasma CVD apparatus to form an N (+)-type amorphous Si film having a thickness of 300 °. .

Step E (FIG. 14) A resist is applied, and a fourth photo step using excimer laser light is performed to form a resist pattern. Next, an island of the i-type semiconductor layer AS is formed by selectively etching the N (+)-type amorphous Si film using SF ₆ and CCl ₄ as a dry etching gas.

Step F (FIG. 14) A resist is applied, and a fifth photo step using excimer laser light is performed to form a resist pattern. Next, the Si nitride film is selectively etched using SF ₆ as a dry etching gas.

Step G (FIG. 15) A first conductive film d1 made of an ITO film having a thickness of 1400 ° is sputtered, a resist is applied, and a sixth photo step using excimer laser light is executed to form a resist pattern. I do. Next, the first conductive film d1 is selectively etched using a mixed solution of hydrochloric acid and nitric acid as an etchant, thereby forming the gate terminal GTM, the uppermost layer of the drain terminal DTM, and the transparent pixel electrode ITO1.

Step H (FIG. 15) A second conductive film d2 made of Cr having a thickness of 600 .ANG. Is formed by sputtering, and a second conductive film d2 having a thickness of 4000 .ANG.
Pd, Al-Si, Al-Si-Ti, Al-Si-C
A third conductive film g3 made of u or the like is formed by sputtering. A resist is applied, and a seventh photo process using excimer laser light is performed to form a resist pattern.

The third conductive film g3 is etched using the same liquid as in step B, and the second conductive film d2 is etched using the same liquid as in step A, so that the video signal line DL and the source electrode SD1 are etched. Then, a drain electrode SD2 is formed. Next, CCl ₄ and SF ₆ are introduced into the dry etching apparatus to
The N (+) type semiconductor layer d0 between the source and the drain is selectively removed by etching the (+) type amorphous Si film.

Step I (FIG. 15) An ammonia gas, a silane gas, and a nitrogen gas are introduced into a plasma CVD apparatus to form a 1 μm-thick Si nitride film. A resist is applied, and an eighth photo process using excimer laser light is performed to form a resist pattern.
Next, the protective film PSV1 is formed by selectively etching the Si nitride film by a photolithography technique using SF ₆ as a dry etching gas.

As described above, wet etching is used for etching a metal film, and dry etching is used for etching a semiconductor film and an insulating film.

The resist film after each photo step is stripped by irradiating the entire surface with excimer laser light with reduced energy, and does not perform the conventional wet processing using a stripping material.

Similarly, the thin film processing of the substrate PSV2 on the color filter side is performed by applying a black mask material and a color filter material and performing a photo process using excimer laser light using an exposure mask.

As described above, according to the present invention, since no liquid is used for developing and stripping the resist, the process can be simplified and the effect on the environment can be eliminated, and each substrate of the liquid crystal display element can be manufactured at low cost. It can be manufactured by

Next, exposure using excimer laser light /
An embodiment of the developing device will be described.

FIG. 16 is a schematic diagram for explaining the outline of the optical system of an exposure machine used in the method of manufacturing a liquid crystal display device according to the present invention, wherein 1 is an excimer laser, 2 is an illumination optical system,
2 'is a reflection mirror, 11a is an XY mask table, 8
Denotes an imaging lens system, 11b denotes an XY substrate table, 7 denotes an exposure mask (however, a multilayer film surface is on the lower side), and 10 denotes a substrate.

The excimer laser 1 as an exposure light source oscillates a laser beam having a wavelength of 308 nm and an output of 800 mJ at a repetition frequency of 350 Hz. The illumination optical system 2 is a homogenizer optical system that shapes a beam profile so as to have a uniform intensity distribution within a given shape. The illumination optical system 2 uses an exposure mask 7 installed on an XY mask table 11a via a mirror 2 ′. Light up.

The exposure mask 7 is a dielectric multilayer film mask.
Illuminate in the form of a slit of mm × 90 mm.

The imaging lens system 8 is composed of a 1: 1 telecentric symmetric lens, having an aperture of 120 mmφ, NA = 0.
1, the aperture pattern image of the exposure mask 7 is projected onto the substrate 10 placed on the XY substrate table 6. Due to the configuration of the imaging lens system 8, the opening pattern of the exposure mask 7 and the image on the substrate 10 have a mirror image relationship.

The XY substrate table 11b has a maximum length of 900 m.
A substrate having a size of mx 700 mm can be mounted. Also, X-
Y mask table 11a is up to 650mm x 650mm
An exposure mask having a size (650 square) can be mounted.

In this embodiment, a pixel (pixel) pitch of 0.12 m is formed on a glass substrate having a size of 800 mm × 450 mm.
m, a TFT layer having a display portion of 1024 × (1920 × 3) pixels was formed. The display area is 368.64 mm
X 691.2 mm, or 31 inches (78.7 cm) diagonal.

FIG. 3 shows an embodiment of this exposure / development apparatus.

Since the area of the output light of the excimer laser is small, the irradiation light to the exposure mask is formed in a slit shape, and the exposure mask and the glass substrate are relatively moved to complete the entire display area. Most of the actual display surface is a repeated portion of a pixel, and a unit of division is divided by this unit.

FIG. 17 is an explanatory view of the principle of dividing a substrate pattern for a step-scan exposure mask in the method of manufacturing a liquid crystal display element according to the present invention, where 10 is a glass substrate, 10a is a pixel portion, 10b and 10c. Is the terminal, ~
Indicates a divided area.

Here, each divided area on the substrate side,
Have the same repeating pattern, and are composed of a pixel portion 10a and upper and lower terminal portions 10c and 10c '. Also,
The divided region includes a pattern 10b near the left terminal portion, and the divided region includes a pattern 10b ′ near the right terminal portion.

FIG. 18 is a plan view schematically illustrating an example of the configuration of an exposure mask used in the method of manufacturing a liquid crystal display device according to the present invention, and is a view as seen from the multilayer film side of the exposure mask.

In the figure, reference numeral 7 denotes an exposure mask, and in this embodiment, three types of opening patterns are formed. That is, the first opening pattern portion is a portion where the opening pattern 7a corresponding to the pixel portion 10a and the opening patterns 7c and 7c 'corresponding to the upper and lower terminal portions 10c and 10c' are combined. The same pattern is shifted three times in the Y-axis direction in accordance with the area, and the exposure is repeated three times.

The second opening pattern portion corresponds to the opening pattern 7b corresponding to the pattern 10b near the terminal portion, and the third opening pattern portion corresponds to the third opening pattern portion.
Of the opening pattern portion is a pattern 10b 'near the terminal portion.
Is formed on a quartz substrate.

Reference numeral 12a denotes an excimer laser beam irradiating the first opening pattern portion, 12b denotes an excimer laser beam irradiating the second opening pattern portion, and 12c denotes the third opening pattern. The excimer laser light irradiating the pattern portion is shown for each exposure area for easy understanding, but these excimer laser lights are fixed. Also, 7d, 7d 'as light-shielding portions SH,
7e and 7e 'are formed.

Light shielding pattern portion (SH portion) of exposure mask
Means that 1 / of the oxide films HfO ₂ and SiO ₂
A multilayer film made of four wavelength (λ / 4) films
The vertical reflectance at 08 nm is set to 70% or more. The opening pattern portion of the exposure mask through which the excimer laser beam passes is a portion excluding the multilayer film by dry etching.

In this example, in consideration of the shortening of the exposure step time and the connection accuracy of the repetitive pattern portion, the repetition of the scanning in the X direction is not performed, and therefore, a large-sized display portion substantially equal to the width of the display portion in the X direction on the substrate is taken. An exposure mask 7 was used.

However, when the display area becomes even larger, the opening patterns 7b and 7b 'of the terminal portions formed on the exposure mask 7 are divided into the X and X regions of the substrate shown in FIG.
The size of the aperture pattern 7a in the pixel portion is set to be a fraction of the integral size in the X direction and the Y direction with respect to the divided area 、, and the aperture patterns 7a, 7b, 7
It is also possible to form a resist pattern of a large substrate by forming five types of pattern portions b ′, 7c, and 7c ′, forming a boundary portion with a light-shielding SH portion, and shifting in the X and Y directions.

The excimer laser beams 12a, 12b and 12c for irradiating the exposure mask 7 are fixed in a long slit shape in a direction orthogonal to the relative movement direction (arrow X) between the exposure mask and the substrate. By moving the exposure mask and the substrate relative to each other, the entire surface of the substrate is scanned and the resist is patterned.

At this time, the pattern of the exposure mask 7 is mapped on the glass substrate 10 as a mirror image with respect to the Y axis by the imaging lens. Further, upon exposure, an exposure mask 7
The multilayer film surface on which the pattern is formed is arranged so that the pattern forming surface of the glass substrate 10 faces the multilayer film surface.

For this reason, when forming the resist pattern in the divided area shown in FIG. 17, after the exposure mask 7 is turned over with respect to the Y axis, the start portion B at the upper left of the exposure mask uses the stationary imaging lens as the origin. Is initially set to a position where a mirror image is formed on the upper left of the corresponding glass substrate 10 with respect to the Y axis.

The exposure mask 7 and the glass substrate 10 are scanned with respect to the stationary imaging lens in the X direction at the same speed v in opposite directions. Here, the speed v is as follows: v = df / n n: the number of shots in which the resist is ablated f: the repetition frequency of the laser (shots / second) d: the width of the slit (X direction, short width) (cm) v: Scan speed (cm / sec).

That is, the scan start position indicated by the start portion B at the upper left starts from a position outside the pattern, and X
The repetition of the scan in the direction is not performed, but the scan is performed up to the position C where the resist pattern formation of the divided area is completed in one scan.

There is a certain relationship between the scan speed (v) and the ablation rate, and it is necessary to scan at an optimum speed in consideration of the resist film thickness and material. As a result, the resist in all regions of the substrate is exposed to a predetermined pattern, and the pattern of the exposure mask is developed and removed by ablation of excimer laser light.

In the above description, the excimer laser beam is used only for removing the resist. However, a predetermined patterning can be performed on the thin film by removing the resist and simultaneously ablating the underlying thin film.

Next, an example of a method for manufacturing a liquid crystal display device according to the present invention will be described.

[Example 1] 270 mm long x 200 m wide
A TFT type liquid crystal display element was manufactured using a glass substrate having a thickness of 1.1 mm and a thickness of 1.1 mm. The TFT pattern is 640x
It is a so-called VGA of 480 pixels, and the pixel pitch is 0.33.
mm.

The three colors R, G, and B are vertical stripes, and thus the horizontal dot pitch is 0.11. The overall layout of the screen is as shown in FIG.
It consists of a screen area of 158.4 mm and a peripheral terminal area, and the entire pattern area, that is, the area of step-scan is about 225 mm x 185 mm.

As shown in FIG. 18, an exposure mask corresponding to a pixel region divided into three equal parts and divided into five parts each having a gate terminal side and a liquid crystal enclosing side as one region is formed from three types of opening patterns. Become. The horizontal width of the pixel area 7a is 70.4 mm
And includes 640 dots.

An excimer laser having a wavelength of 248 nm was used as a light source, and illumination light for an exposure mask was formed into a slit of 5 mm × 75 mm. The imaging lens is a telecentric symmetric lens. A. (Numerical aperture) is 0.2.

The energy density on the glass substrate surface is 100
mJ / cm ² . The scan distance is 185 mm, and five horizontal movements are performed.

As a material for the resist film, a polyurethane resin containing polyethylene glycol and tolylene diisocyanate (TDI) as main components was used. The ablation rate in this case is 100 mJ / cm ^{2 of} energy density.
Was 0.05 μm / shot. The resist film was exposed to the above-described excimer laser light, and a TFT substrate and a color filter substrate were formed, a liquid crystal layer was sealed, a driving IC was mounted, and a backlight was assembled, thereby completing a liquid crystal display device.

With the liquid crystal display device completed in this way, a high quality image display could be obtained.

Example 2 A resist film made of a polyurethane resin in which tolylene diisocyanate used in Example 1 was replaced by methylene bisphenyl isocyanate (MDI) was used. In this case, processing is performed at an energy density of 100 mJ / cm ² at an ablation rate of 0.04 μm / shot, and a TFT substrate and a color filter substrate are formed and a liquid crystal layer is sealed, and a driving IC is mounted and a backlight is incorporated. The liquid crystal display was completed.

With the liquid crystal display device completed in this way, a similar high-quality image display could be obtained.

Example 3 A material made of a polyurethane resin in which methylene bisphenyl isocyanate used in Example 2 was replaced with naphthalene diisocyanate (NDI) was used as a resist film. In this case, 100mJ /
Processing at an ablation rate of 0.045 μm / shot with an energy density of cm ² , fabrication of a TFT substrate and color filter substrate, encapsulation of a liquid crystal layer, mounting of a drive IC, and incorporation of a backlight to complete a liquid crystal display device did.

In the liquid crystal display device completed in this way, a high-quality image display was obtained in the same manner as in the above embodiment.

Example 4 A material comprising a polyurethane resin in which the polyethylene glycol of Example 1 was replaced with a polyester polyol was used as a resist film. In this case, an energy density of 100 mJ / cm ² is 0.05
Processing at an ablation rate of μm / shot, TF
A liquid crystal display device was completed by preparing a T substrate and a color filter substrate, enclosing a liquid crystal layer, mounting a drive IC, and incorporating a backlight.

In the liquid crystal display device completed in this way, high quality image display could be obtained as in the above embodiment.

Example 5 A polyurea resin containing diethylene glycol bis (3-aminopropyl ether) and tolylene diisocyanate as main components was used as a resist material. In this case, processing is performed at an energy density of 100 mJ / cm ² at an ablation rate of 0.04 μm / shot, and a TFT substrate and a color filter substrate are formed and a liquid crystal layer is sealed, and a driving IC is mounted and a backlight is incorporated. The liquid crystal display was completed.

In the liquid crystal display device completed in this way, a high quality image display was obtained as in the above embodiment.

Example 6 Similar results were obtained using methylene bisphenyl isocyanate in place of tolylene diisocyanate of Example 5.

Next, an exposure apparatus (ablation developing machine) used in the method of manufacturing a liquid crystal display device of the present invention described with reference to FIG. 3 will be described in detail.

FIG. 19 is a principle diagram for explaining division of excimer laser light by a lens array in an ablation developing machine used in the method of manufacturing a liquid crystal display element according to the present invention, wherein the excimer laser light is parallelized to a pair of lens arrays 4a and 4b. The light beam 3a of the excimer laser is made incident, the light beam area is divided, and the condensing part is formed by the lens array 4a,
4B, the optical components (lens arrays 4a, 4b) are prevented from being damaged.

FIG. 20 is an explanatory diagram of an illumination optical system of an ablation developing machine used in the method of manufacturing a liquid crystal display device according to the present invention. The lens array 4a, 4b is used to separate the light source described with reference to FIG. Each light beam of the excimer laser light incident from the lens array 4b by the lens 5a and the lens 6a performs uniform illumination on the surface of the exposure mask 7a, and
An image is formed on the entrance pupil 9a of the imaging lens.

Generally, the energy space distribution of the light beam of the excimer laser, that is, the beam profile of the light beam shows a distribution close to a Gaussian distribution.

FIG. 21 is a diagram for explaining the uniformization of the illumination light of the exposure mask of the ablation developing machine used in the method of manufacturing the liquid crystal display element of the present invention. As shown in FIG. When the laser beam is split so as to be symmetrical with respect to the optical axis of the laser beam and the split portion is almost straight, the condenser lens is symmetrically overlapped on the reticle surface as shown in FIG. it can.
That is, in the case of a beam profile symmetric with respect to the central axis, it is advantageous that the number of lens arrays in FIG. 19 is an even number and the optical axis passes through the center.

In general, the beam profile of the excimer laser beam is not square, and the area irradiated on the reticle is not always square. Therefore, the splitting lens shown in FIG. 19 is not a simple spherical lens. That is,
The shapes of the illumination lenses 4 to 6 shown in FIG. 20 are determined by the illumination shape on the reticle, the position of the entrance pupil of the imaging lens, and the distance between the laser light source and the exposure mask.

In particular, when the illumination light on the reticle surface is rectangular, the illumination optical system can be divided into independent orthogonal optical systems. In this case, the cost is reduced and the adjustment is simplified by using the cylindrical lens as the individual lens.

However, since the lens 6a shown in FIG. 20 is inevitably close to the surface of the exposure mask, it is more convenient to combine the two lenses separated by the orthogonal optical system into one as described above. There is also.

Further, when a wavelength of 248 nm or less is used, a substance produced by the interaction between ultraviolet light and an atmospheric substance may adhere to the lens surface and lower the transmittance. To avoid this, it is effective to house the illumination optical system in a container in a nitrogen atmosphere.

As described above, it is better to reduce the number of lenses as much as possible. This point should be determined from cost performance.

If the focusing of the excimer laser beam is prevented from hitting the optical parts, the structure of the imaging lens is limited. Methods that have been conventionally studied as one-to-one (1: 1) imaging lenses for excimer laser light include Offner and Wyne-Dyson.
Dyson), a telecentric symmetric lens, and the like. The former two have a complicated structure due to a combination of a reflection and a refraction system, but the aberration is easily controlled.

On the other hand, the symmetrical lens has a simple structure and the condensing surface is in the space, so that the constituent lens is not damaged. However, in the case of a symmetrical lens, an attempt to increase the aperture increases the cost, and a method for forming a large area pattern becomes a problem.

In the present invention, as a method of forming a large-area pattern, a workpiece such as a color filter substrate or the like is relatively moved and scanned by using a one-to-one exposure mask, a symmetric lens, and rectangular illumination. It is a method.

FIG. 22 is a schematic diagram for explaining the scanning method of the ablation developing machine used in the method of manufacturing a liquid crystal display device according to the present invention. The scanning may be performed by alternately changing the moving direction or by moving in the same direction. However, the former requires a shorter processing time.

An essential problem in such a scanning method is as follows.
This is an area where illumination light overlaps. It goes without saying that even if the overlap slightly shifts, if the length of the illumination area is long, it can be clearly recognized visually. The shift in the overlapping area can be considered to be caused by two factors: mechanical fluctuation in scanning and image distortion due to the optical system.

The former can be dealt with by using a high-precision XY table, but it is difficult to produce a lens having no aberration in the latter, so that other measures must be taken.

FIG. 23 is an explanatory view of an example of setting the position of an illumination area in scanning by an ablation developing machine used in the method of manufacturing a liquid crystal display element of the present invention. The end portion is set so as to be located exactly in the middle of the repeated pattern 7b.

As a result, the end of the incident light 7a overlaps with the repeated pattern 7b, so that even if the overlap is shifted, the processed pattern is not affected.

An exposure mask having a band pattern may be used instead of the knife edge.

In the geometrical optics, the blur at the end depends on the displacement of the object position and the depth of focus of the imaging lens. However, if the imaging lens is made telecentric, the size of the image does not change and only the end is blurred. This blur amount is given as bNAδ _a / (fa) to _a first approximation.
Here, a is the object point distance, b is the image point distance, f is the focal length, and NA is the lens lens distance. A. , Δa are deviation amounts from the exposure mask surface such as _a knife edge.

In the case of a 1: 1 lens, b / a = 1, so that the above equation becomes NAδ _a / f. For example, NA = 0.
If 1, δ _a = 10 mm and f = 200 mm, the blur amount is 5 μm.

Since the mechanical accuracy in setting the knife edge and the like can be on the order of μm, it is sufficiently possible to set the knife edge and the like on the pattern photosensitive member in the case of the pattern accuracy of the TFT level and the repetitive pattern shape. is there.

According to the above method, even if there is no superposition in the pattern area of the illumination area, if the aberration around the imaging lens is largely different, the linear pattern can be visually recognized. Therefore, it is important that aberrations at least in one direction at the lens diameter, particularly in the peripheral portion, have the same shape.

FIG. 24 shows the overall configuration of an ablation developing apparatus in which the excimer laser light source section and the developing optical system of the ablation developing machine used in the method of manufacturing a liquid crystal display device according to the present invention are separated by separate walls and installed in rooms having different cleanliness. FIG. 3 is a diagram illustrating a so-called through-south configuration in which a laser beam emitted from a light source unit 20 composed of an excimer laser (ultraviolet pulse laser) is introduced into an ablation developing unit 22 through a transmission window plate 24 provided on a separation wall 21. Ablation developing machine.

As shown in the figure, the light source section 20 and the developing section 22 including the exposure optical system are separated, and the laser beam emitted from the light source section 20 is introduced into the ablation developing section 22 through the transmission window plate 24.

At this time, in order to prevent the energy of the laser beam from decreasing, it is preferable that the reflection by the mirror is performed only once as shown in the figure.

In order to prevent vibration, the light source unit 20
And the developing unit 22 are installed on a vibration isolation table 23.

In addition to or in place of the above-mentioned anti-vibration table 23, the transmission window plate 24 is provided with a laser beam relative to the developing optical system including the illumination optical system 22a and the imaging optical system 22b. By tilting the laser light beam in accordance with the vibration, it is possible to correct the deviation of the laser beam caused by the vibration.

FIG. 25 is an explanatory view of a shift correcting method for moving the optical axis in parallel by inclining a transmission window plate through which a laser beam passes in an ablation developing machine used in the method of manufacturing a liquid crystal display element of the present invention. , Transmission window plate 24
Where D is the thickness, n is the refractive index, and θ is the inclination of the transmission window, the deviation d of the laser beam is Dθ (1-1 / n).
Becomes

Of the relative light beam shifts from the laser light source, the shift in the longitudinal direction of the illuminated area is essential. That is, only the shift component in this direction is displayed, and the above shift can be corrected by changing the inclination of the transmission window plate 24 by the servo mechanism.

According to the above description and each configuration of the present invention, a large-area and high-definition pattern processing using the ablation phenomenon of the ultraviolet pulse laser can be performed.

Hereinafter, examples of the ablation developing machine used in the method for manufacturing a liquid crystal display device of the present invention will be described more specifically.

[Embodiment 7] FIG. 26 is a schematic view of the configuration of an exposure optical system of an ablation developing machine for explaining a seventh embodiment of the present invention. I have.

In this embodiment, KrF (wavelength 2
An excimer laser having a repetition frequency of 250 Hz and an output energy density of 600 mJ / cm ² is used.

The exposure optical system has a lens system as shown in the figure, and the illumination lens system is an independent system in the X and Y directions in order to provide slit-shaped illumination light. The illumination optical system is as shown in FIG.
X and 4Y represent the lens 4 in the X direction and the lens 4 in the Y direction, respectively. Hereinafter, 4X ', 4Y', 5Y, 5Y, 6X, 6Y
The same applies to.

FIG. 27 is a schematic diagram for explaining an example of the arrangement in the X and Y directions of the cylindrical lenses used for dividing the light source in this embodiment.

In the figure, (a) shows the arrangement direction of the cylindrical lens in the X-axis direction, (b) shows the arrangement direction of the cylindrical lens in the Y direction, and (a) and (b) are arranged orthogonally. These lenses 4X and 4Y are bonded by an optical contact. To reduce energy loss, all lenses are AR coated to ensure a transmission of 99% or more.

With this illumination optical system, the maximum illumination area on the exposure mask surface is 80 mm × 2 mm. The distribution of the energy density within this area is ± 5% or less. The length of the slit of the illumination light is adjusted by the blade, and the rise of the energy distribution at the end is 20 μm.

The exposure mask is １ ／ of SiO ₂ and HfO ₂ .
A film obtained by patterning a λ film by RIE (reactive ion etching) is used. The size of the substrate of this exposure mask is 300 mm × 225 mm, and the thickness is 5 m.
m.

FIG. 28 shows a black matrix (BM) formed on a color filter side glass substrate of a liquid crystal display device as an example of an opening pattern of an exposure mask in this embodiment.
It is explanatory drawing of the example of a pattern and the arrangement | positioning relationship of the blade for slit illumination.

The pitch of the openings 7c of the opening pattern formed on the exposure mask 7 for developing the BM pattern is 0.33.
mm × 0.11 mm, the long side of the illumination area is 52.8 mm
And the end 12a of the blade 12 has an opening pattern 7c.
The blade position is adjusted so as to be within the minimum width in the longitudinal direction of the blade. The above minimum width is 72 μm, and adjustment of the blade position is easy.

As the BM forming material, a material in which carbon black is dispersed in a matrix mainly composed of a polyimide polymer is used. The ablation rate of this material is 3
0.1 μm / shot for an excimer laser light input of 00 mJ / cm ² . The coating thickness is 1.2
15sho per μm per site (per unit development area)
When excimer laser light of t is applied, the actual time of ablation is 19 seconds, and the time required for lateral site movement, alignment of the exposure mask, etc. is about 30 seconds plus 1 hour.
0.4 inch display color filter substrate B
M can be processed.

[Embodiment 8] FIG. 29 is a schematic view of a color filter patterning by ablation development for explaining an eighth embodiment of the present invention.

In this embodiment, the same apparatus configuration as that of the above embodiment is used, and the color filters R, G, and B in the form of vertical stripes are subjected to ablation development using the exposure mask shown in FIG. Things.

In the figure, reference numeral 13 denotes a color filter substrate of a liquid crystal panel; 14a, a color filter of a first color;
b is a second color filter resist layer.

In forming this color filter, the length of the illumination area slit set by the blade 12 was set to 70.4 mm.
And the end of the blade 12 is a light shielding portion 7a of the exposure mask 7.
Then, the incident light 7a from the excimer laser is irradiated and the first color filter 14a is ablated and developed.

Thereafter, the resist layer 14b for the second color filter is applied, and the exposure mask 7 is moved by the filter pitch to perform ablation development. Thereafter, the third color filter is similarly developed to form a liquid crystal panel color filter. Here, BM is omitted.

Thus, three color filters can be formed on the color filter substrate of the liquid crystal panel by the dry method.

[Embodiment 9] In this embodiment, a resist pattern for each layer of a TFT substrate is formed by using the ablation developing machine of Embodiment 7 and a urethane-based or urea-based ablation resist material, followed by etching. Then, a pattern of each layer is formed by peeling the resist by ablation development using excimer laser light.

Thus, a required TFT layer can be formed on the TFT substrate of the liquid crystal panel.

Next, an embodiment of ablation development by step-scan using an exposure mask according to the present invention will be described.

As described with reference to FIG. 18, although the size of the exposure mask is greatly reduced, the joint of the divided portions in the step-scan may affect the display performance. This is not essential, X-
This is a problem of the machine accuracy of the Y table. Particularly, in the case of manufacturing a liquid crystal display element, a slight shift is corrected by the light shielding portion. Therefore, it is important to accurately form the light-shielding portion.

FIG. 30 is an explanatory view of a preferable dividing line of an exposure mask of an ablation exposing machine used in the method of manufacturing a liquid crystal display device according to the present invention. FIG. 31 is an explanatory view of a dividing line to be avoided. (SH), 81 indicates an opening pattern, and 82 and 83 indicate division lines.

The dividing line of the exposure mask is shown in FIG.
As shown in FIG. 31 (b), if the position passes on the light shielding portion 80 between the adjacent opening patterns 81, (a) and (b) of FIG.
The shift at the time of exposure is less conspicuous than the position passing over the opening pattern 81 as shown in FIG.

Note that such a dividing method can be applied not only to lithography using the ablation phenomenon of an excimer laser, but also to ordinary photolithography using a high-pressure mercury lamp as a light source.

In this case, not only a 1: 1 refraction type symmetric lens but also a small mirror projection type can be used as the imaging lens, so that the cost of the exposure apparatus can be greatly reduced. In particular, since the XY mask table can be kept constant regardless of the size of the glass substrate, the apparatus cost can be further reduced.

The mechanical time loss due to the step-scan exposure can be covered by increasing the irradiation intensity and the speed of each table.

In the present invention, since the step operation requires more mechanical time, the single-wafer method is more advantageous than the multi-piece operation, and the size of the exposure mask and the X-Y substrate table is given a margin. It is better to use a dedicated machine that can handle a certain center size and the substrate size before and after this. However, the only part to be changed is the table, and the optical system is common.

Hereinafter, a method of forming a resist pattern will be described in more detail with reference to the drawings.

[Embodiment 10] FIG. 32 is a schematic diagram illustrating an example of division of a substrate for explaining an embodiment of a method for forming a resist pattern in a method of manufacturing a liquid crystal display device according to the present invention. Constituent glass substrate, 10
A is a pixel portion, 10B is a left and right terminal portion, and 10C is an upper and lower terminal portion.

[0316] The glass substrate in the figure is 450 m long (X direction).
m, horizontal (Y direction) 800mm substrate size, vertical 36
The pixel section 10A has a size of 8.64 mm and a width of 691.2 mm.

In the present embodiment, in order to perform the exposure of the step-scan method, the pixel portion of the glass substrate 10 is divided into eight equal portions in the vertical direction, and each of the divided pixel portions is shared.
1 and 10 (terminal portions) surrounded by circles in the figure are each one unit. The width of each unit is a size that can be covered by the slit of the excimer laser beam.

FIG. 33 is a plan view for explaining a specific example of the exposure mask used in this embodiment. The overall size is 420 mm in the vertical direction (X direction) and 280 in the horizontal direction (Y direction).
mm.

The size of the vertical (X-direction) opening pattern of the exposure mask 7 is the same as the size of the vertical (X-direction) in FIG. 32, and the vertical size of the pixel portion opening pattern 7a is 36.
The horizontal (Y direction) is 86.4 mm obtained by dividing the pixel portion into eight equal parts.

The horizontal size of the left and right terminal portion opening patterns 7b is 10 mm, and the vertical size is 368.64+.
(10 × 2) = 388.64 mm, the vertical size of the upper and lower terminal portion opening pattern 7c is 10 mm, and the horizontal size is 86.4 mm, which is the same as the pixel portion 7a.

The light-shielding portions 7d, 7d ', 7e and 7e' are provided between the pixel portion opening pattern and the left and right terminal portion opening patterns 7b and outside the left and right terminal portion opening patterns 7d to avoid damage by excimer laser light. Are formed.

[0322] In the figure, reference numeral 12a denotes a state of irradiation of a slit-like excimer laser beam, and both ends of the chromium film 7d,
7d '. Although the illustrated excimer laser beam is irradiating the pixel opening pattern 7a, the end portions of the excimer laser light are similarly shielded from the light-shielding SH portions 7d and 7d when the terminal opening pattern 7b is irradiated.
e.

The light-shielding portion 7e arranged outside the terminal portion opening pattern 7b is made wider by the exposure mask 7
This is to prevent the excimer laser beam deviating from the exposure mask from ablating the XY mask table and generating dust when the is mounted on the XY mask table.

FIGS. 34A and 34B are explanatory views of an excimer laser beam irradiation state of a resist on a glass substrate through an exposure mask. FIG. 34A is a perspective view of a main part, and FIG. 34B is a sectional view of a main part of the exposure mask. This shows a state where the pixel portion of the exposure mask 7 is being exposed.

In the same figure, 1a is an excimer laser beam, 71 is a quartz glass substrate, 7 'is a dielectric multilayer film, 7a
Is a pixel portion pattern, 7b is a terminal portion pattern, 70 is an opening pattern, 8 is an imaging lens, 12 is a resist film, 12a
Is a resist pattern.

The slit-shaped excimer laser beam 1a is
The exposure mask 7 and the resist film 12 on the glass substrate are indicated by an arrow v.
The image of the opening pattern 70 of the exposure mask 7 is irradiated on the resist film 12 through the imaging lens 8 with the relative movement in the direction, and the resist pattern 12a is formed by the ablation phenomenon.

At this time, the lower thin film can be removed by ablation simultaneously with the ablation of the resist film.

After a resist pattern is formed and a required etching process is performed, an unnecessary residual resist film can be removed by irradiating the entire surface with excimer laser light.

As described above, the exposure mask of the present embodiment may have an area which is one third of that of the conventional 1: 1 mask, and the manufacturing cost of the exposure mask is greatly reduced.

The ablation resist used here was irradiated 10 times at an energy density of 100 mJ / cm ² (1
0 shot / site) completes ablation.
The scan area is 400 mm, and the patterning of the entire substrate is completed by 10 scans as described above. Therefore, the scan time is 28.6 seconds, the stepping time for 10 steps is 10 seconds, and the takt time of about 45 seconds is added to the time required for transport, desorption, and alignment of the substrate and the exposure mask.
An inch-diagonal TFT substrate was completed.

[0331]. Next, an embodiment of a method for manufacturing an exposure mask according to the present invention will be described.

The exposure mask has three dielectric layers each consisting of a pair of a light refractive index layer and a low refractive index layer (that is, the total number of high refractive index and low refractive index film forming materials is six). HfO ₂ was used as an additional high refractive index layer, and the thickness of the metal film was 100 nm.
Of Cr.

At this time, the transmittance of the dielectric layer was about 10%, and Cr (crosium) showed sufficient resistance to the energy density of 400 mJ / cm ² incident on the mask surface.

[Embodiment 11] FIG. 35 shows a combination of a high-refractive-index layer material and a low-refractive-index layer material which is a material for an exposure mask of an excimer laser exposure machine used for manufacturing a liquid crystal display device according to the present invention, and 10% or less. FIG. 4 is an explanatory diagram of the minimum number of layers of transmittance.

In the present embodiment, in the configuration shown in FIG. 8, the combination of the high refractive index material and the low refractive index material shown in FIG. As a result, a mask having a transmittance of the dielectric layer portion of 10% or less could be obtained.

In this case, even with the mask from which the metal film layer has been removed, the threshold is 50 mJ / cm ² for the input of excimer laser light having an energy density of 400 mJ / cm ^2.
A highly accurate ablation pattern of the resist film ² was obtained.

FIG. 36 is a schematic process chart for explaining an example of a method for manufacturing an exposure mask of an excimer laser exposure machine used for manufacturing a liquid crystal display device according to the present invention.

In the figure, first, (a) a first dielectric layer having an optical path length of 膜厚 wavelength of the used ultraviolet light is formed on a quartz glass substrate 90 transparent to ultraviolet light. A dielectric multilayer film formed on the first dielectric layer by forming a second dielectric layer also having an optical path length of 1/4 wavelength and a refractive index smaller than the refractive index of the first dielectric layer. Is formed, a third dielectric layer having a refractive index larger than the refractive index of the glass substrate and having an optical path length of 波長 wavelength of the used ultraviolet light is formed on the uppermost layer of the dielectric multilayer film. A dielectric multilayer film 91 is formed, and a metal film 92 is formed on the dielectric multilayer film 91.

(B) Photosensitive resist 93 on metal film 92
Is applied, and is irradiated with ultraviolet rays 95 through an exposure mask 94, and is developed.

(C) The metal film 92 is patterned by a photolithography process using the etching medium 96 with the resist 93 remaining after the development as a mask.

(D) After patterning the metal film 92, the remaining resist is removed to obtain a patterned metal film 92 layer.

(E) The dielectric multilayer film 91 is etched using the etching medium 97 by using the opening pattern of the patterned metal film 92 as a mask.

(F) By patterning the dielectric multilayer film 91 by the above etching to form an opening pattern, an excimer laser processing is performed on the quartz glass substrate 90 by the multilayer dielectric film 91 and the metal film 92 superposed thereon. To obtain an exposure mask.

The exposure mask according to the present invention, that is, the excimer laser processing mask is not limited to the above-mentioned method. For example, an opening pattern of a photosensitive resist is formed on a metal film, and the excimer mask is formed using this opening pattern as a mask. It is also possible to obtain an exposure mask by irradiating a laser to remove the metal film and the underlying multilayer dielectric layer by ablation.

In this type of exposure machine, it is required that the alignment between the exposure mask and the glass substrate to be processed be performed precisely.

An embodiment of a mechanism for aligning an exposure mask with respect to a glass substrate to be processed will be described below.

[Embodiment 12] FIG. 37 is a schematic diagram for explaining an embodiment of a mechanism for aligning an exposure mask and a glass substrate as a workpiece, wherein 1a is an excimer laser beam,
Is an exposure mask, 7A is an alignment mark, 8 is an imaging optical system (imaging lens), 30 is a fluorescent plate, 30A is a fluorescent light emitting portion, 31 is a video camera, 32 is an arithmetic unit, 33 is an exposure mask adjusting mechanism, 34 Is a focus / magnification adjusting mechanism, and 35 is a backlight lamp.

[0348] In the figure, an exposure mask 7, an image forming optical system 8, a fluorescent plate 30, and a video camera 31 are arranged on the optical path irradiated with the excimer laser beam 1a.

The excimer laser beam 1a has a wavelength of, for example, 248 nm and an energy density of 10 to 20 mJ.
/ Cm ² .

The exposure mask 2 is, as described above,
For example, an aperture pattern is formed on a laminate in which nine layers each of HfO ₂ and SiO ₂ are alternately laminated with a thickness of １ ／ wavelength on a quartz substrate surface having a size of 330 mm × 250 mm and a thickness of 5 mm. The reflectance from the exposure mask 7 is 98% or more, and the S / N with the transmitted energy is 40%.
That is all.

The exposure mask 7 has an alignment mark 7A formed thereon. This alignment mark 7
A has, for example, a line width of 20 microns or less (preferably,
(5 microns) cross pattern. It is needless to say that the alignment mark 7A is not limited to a cross pattern, but may be another pattern such as a square shape.

FIG. 38 is a partial cross-sectional view illustrating the structure of the fluorescent plate. The fluorescent plate 30 is a substrate that generates fluorescence upon irradiation with excimer laser light, and as shown in the figure, for example, has a size of 270 mm × 200 mm and a thickness of 1.1 mm.
Fluorescent paint film 30b is about 500n on quartz glass 30a.
A film formed with a film thickness of m is used.

By the irradiation of the excimer laser beam 1a, the alignment mark 7A of the exposure mask 7 is imaged on the fluorescent plate 30 via the 1: 1 image forming optical system 8, and the fluorescent paint film 30b at the image forming position is formed. Fluorescent.

In this case, when a material having a high absorption coefficient with respect to the excimer laser beam 1A is used as the material of the fluorescent plate 30, the same effect can be obtained without necessarily requiring the above-mentioned fluorescent paint film.

The video camera 31 is fixed at a predetermined reference position, and the alignment mark 7A of the exposure mask 7
Is imaged from the back surface of the fluorescent plate 30.

[0356] The image data (image data) of the video camera 31 is input to the arithmetic unit 32. The arithmetic unit 32 calculates the position of the projected image 30A by comparison with the reference position to detect the amount of deviation of the projected image. The detected positional deviation data is given to the exposure mask adjusting mechanism 33, and the exposure mask adjusting mechanism 33 adjusts the position of the exposure mask 7 so that the positional deviation becomes zero.
That is, the position is adjusted so as to be a regular position.

[0357] The calculation of the positional deviation amount is performed, for example, in the following manner.
The arithmetic unit 32 is provided with a memory for storing information relating to the position coordinates of the projection image 30A of the alignment mark, and the difference is calculated between the position coordinate data and the image data of the video camera.

In this configuration example, the arithmetic unit 32 also calculates data on the focus state and size difference of the projected image 30A, and gives the result to the focus / magnification adjusting mechanism 34 to adjust the focus of the imaging lens 8. And a magnification adjustment. The reason why the focus and magnification need to be adjusted is that it becomes important to adjust the wavelength used at the time of ablation of the resist film by the excimer laser light, the focal position of the optical system, the magnification, and the like.

On the other hand, a glass substrate (not shown) for a liquid crystal display element having the same size and the same shape as the fluorescent plate 30 in the manufacturing process is prepared.
It is compatible with and is set at exactly the same position.

A glass substrate for a liquid crystal display element is, for example,
A metal vapor-deposited film is formed on the entire area of one of the surfaces, and a resist film is formed on the entire area covering the metal-deposited film.

At the stage when the glass substrate for the liquid crystal display element is interchangeable with the fluorescent plate 30, the glass substrate is aligned with the exposure mask 7 at a correct position, and then subjected to pattern exposure using the exposure mask 7. You.

As a result, the resist film on the glass substrate for the liquid crystal display element is patterned without performing the so-called conventional wet (wet) developing treatment, and is used for selective etching of the metal deposition film disposed thereunder. Used as a mask.

In the figure, a back illumination lamp 35 for irradiating the glass substrate (or the fluorescent plate 30) for the liquid crystal display element with light from the back is arranged. When a material formed in the second layer is processed in the production of a glass substrate for a liquid crystal display element, an alignment mark is formed on the material, and the back illumination lamp 35 is used as a means for detecting the alignment mark. The alignment mark can be detected by the video camera 31 by irradiating light having the same wavelength as that of the fluorescent light of the projected image 30A.

According to such a configuration, when the alignment mark 7A of the exposure mask 7 is projected by the excimer laser beam 1a on the fluorescent plate 30 compatible with the glass substrate for the liquid crystal display element during the manufacturing process, the projection location The alignment marks which generate fluorescence and are visible on the fluorescent plate 30 which is disposed in position corresponding to the glass substrate for the liquid crystal display element can perform exactly the same function as the projection obtained by visible light. it can.

According to this embodiment, the alignment of the exposure mask 7 with respect to the glass substrate for the liquid crystal display element can be achieved with a simple structure.

[Embodiment 13] FIG. 39 is a schematic diagram for explaining another embodiment of a mechanism for aligning an exposure mask with a glass substrate as a workpiece, wherein 7B and 7C are exposure masks 7A and 7B.
, 8a and 8b are mark-forming imaging lenses, 10B and 10C are alignment marks formed on a glass substrate 10 for a liquid crystal display element, and 30B and 30C.
Denotes a fluorescent plate, 31B and 31C denote video cameras for capturing fluorescence by projection of the alignment marks 7B and 7C formed on the fluorescent plates 30B and 30C, and 31D and 31E denote glass substrates 1.
A video camera for imaging the 0 alignment marks 10B and 10C; 36, a position adjusting mechanism for the glass substrate 10;
a and 40b are prisms, 40c and 40d are mirrors, 41
Is a glass substrate holder.

In this embodiment, the excimer laser beam 1a includes a plurality of prisms (two in FIG.
0b and mirrors 40 arranged corresponding to each prism
Irradiate the alignment marks 7B, 7C separated on the exposure mask 7 through the c, 40d.

Each of the alignment marks 7B and 7C is formed by a fluorescent light generating plate provided on a glass substrate holder 41 for holding a glass substrate 10 for a liquid crystal display element in a manufacturing process via mark dedicated imaging lenses 8a and 8b. An image is formed on 30B and 30C to generate fluorescent light. Fluorescence generating plate 30B, 30C
Has a configuration similar to that of FIG. 38 described in the above embodiment,
A fluorescent paint film having a thickness of about 500 nm is formed on the surface.

The light emission images from the fluorescent light generating plates 30B and 30C are detected by the mark detecting video cameras 31B and 31C installed on their rear surfaces.

On the other hand, a part of the glass substrate 10 held by the glass substrate holder 41 has alignment marks 10B, 1
0C, the alignment marks 10B, 1
0C is detected by the video cameras 31D and 31E arranged on the back of the glass substrate 10.

The alignment marks 10B, 1 detected by the video cameras 31D, 31E, respectively.
From the positional relationship (separation distance) of 0C, the glass substrate holder 4
It is determined whether or not the position of the glass substrate 10 with respect to the glass substrate 1 is accurate. If the position is not accurate, the shift amount is calculated, and the position adjustment of the glass substrate 10 with respect to the glass substrate holder 41 is performed based on the calculated value. It is configured to be performed by the adjusting mechanism 36.

After such position adjustment is performed, the resist film formed on the glass substrate for the liquid crystal display element is patterned by the excimer laser beam 1a through the exposure mask 7 and the imaging lens 8.

In the above configuration, a configuration is also provided in which the focus of the imaging lens and the magnification are adjusted as in the above embodiment.

The apparatus for aligning the exposure mask and the glass substrate described above is not limited to the patterning of the resist film, but can be similarly applied to an ablation machine for a thin film constituting a lower TFT after this patterning.

Next, an embodiment of an apparatus for removing debris in the processing of a resist film and various thin films utilizing the ablation phenomenon of excimer laser light will be described.

In the patterning of a resist film using the ablation phenomenon of excimer laser light and the processing of various thin films constituting a TFT, debris is generated with the ablation.

Conventionally, in the case where ablation processing using this excimer laser beam is applied to the field of micromachining, debris, which is a processing product generated by ablation, is used to clean the workpiece after processing, or to add Accordingly, the reduction is achieved by processing in an inert atmosphere such as helium or processing in an oxygen atmosphere.

However, in such a conventional removal technique,
It is difficult to completely remove debris generated by ablation. In particular, it is difficult to remove debris that has re-adhered to the workpiece.

Further, the form of debris can be changed from gaseous to several μm depending on the type of material and the intensity of incident energy.
Various methods must be considered depending on the form of the debris that is distributed in a wide range of particles up to the size of the medium, and that also undergoes cleaning after processing.

In the processing in a helium atmosphere, the debris is dispersed far away since the jet velocity of the ablation plume (explosive cloud) is faster than that in air, so that debris is apparently reduced. appear. This is considered to be a result of the generated debris being oxidized into a gaseous state in an oxygen atmosphere.

The processing in the atmosphere of helium or oxygen described above has an effect only in the processing of a relatively limited material, and is not effective in the processing of any material.

Further, the essential point to be considered is that when the oscillation frequency of the excimer laser is increased for high-speed processing, the plume generated by the preceding excimer laser pulse still remains in the optical path of the excimer laser. Since ablation by the subsequent excimer laser is performed in the existing state, there is a problem that the excimer laser for the subsequent ablation causes energy loss.

For this reason, it is more important to remove plumes generated by ablation at high speed than to simply remove debris.

Hereinafter, an embodiment of the ablation debris removing apparatus according to the present invention will be described in detail.

[Embodiment 14] FIG. 40 is a schematic view for explaining the structure of an embodiment of an ablation debris removing apparatus in the manufacture of a liquid crystal display device according to the present invention, wherein 50 is a suction nozzle, and 51 is a vacuum pump (not shown). , A suction buffer space 52, and a glass substrate 10 as a workpiece.

This embodiment has a configuration having a single suction nozzle 50, which is installed at a position close to the processing area of the workpiece 10 and at which the plume rise speed is sufficiently low, as indicated by arrows. Suction of debris A is performed as described above.

The shape of the opening of the suction nozzle is cylindrical, elliptical,
The shape may be a rectangular shape, a slit shape, or the like depending on the material of the workpiece, the configuration of the excimer laser light processing device, the energy used, and the like.

According to this embodiment, it is possible to provide an excimer laser processing apparatus in which the debris does not adhere to the surface of the workpiece and does not reduce the energy of the subsequent laser pulse.

[0389] The efficiency of suction can be improved by arranging a plurality of components having this configuration around the processing area.

[Embodiment 15] FIG. 41 is a schematic diagram for explaining the structure of another embodiment of an ablation debris removing apparatus in the manufacture of a liquid crystal display device according to the present invention.
The same reference numeral as 0 corresponds to the same function part.

In this embodiment, the suction nozzle 50 is formed in a slit-like annular shape which is opened so as to surround the work area of the workpiece. It is desirable that the respective suction buffer spaces 3a be communicated with each other, and the exhaust unit 2 may be provided at one place.

According to this embodiment, it is possible to provide an excimer laser processing apparatus in which the debris removing effect is improved and the debris does not adhere to the surface of the workpiece or reduce the energy of the subsequent laser pulse.

[Embodiment 16] FIG. 42 is a schematic view for explaining the construction of still another embodiment of the ablation debris removing apparatus in the production of a liquid crystal display device according to the present invention, wherein 53a and 53b constitute suction containers. Side walls, 54 are entrance windows for excimer laser light, 55 is a bottom plate constituting a suction container, 55a is an opening for irradiating laser light, and the same reference numerals as in FIG. 40 correspond to the same functional parts.

FIG. 39 shows that debris suction can be performed more efficiently.
In addition, in order to completely remove the plume, the suction region has a suction container structure which substantially surrounds the suction region.

That is, in this embodiment, the bottom plate 55 and the side walls 53a, 53 having the entrance window 54 for the excimer laser light and the opening for irradiating the glass substrate 10 with the laser light.
b constitutes a suction container. The suction buffer space 52 is in communication, and the exhaust unit 51 may be provided at one place.

The opening 55a of the bottom plate 55 is desirably as small as possible. However, since it is necessary not to hinder the movement of the shock wave front during ablation, the opening 55a which is approximately 2 mm wider from each edge of the processing area of the glass substrate 10 is required. It is preferable that The side walls 53a and 53b are also shaped so as not to hinder the irradiation of the laser beam.

It is important that the entrance window 54 is formed of a material that transmits excimer laser light, for example, a quartz plate, and that its installation height is set to be higher than the reach of the shock wave front.

Further, the bottom plate 55 is brought as close as possible to the glass substrate 10 on which the ablation processing is to be performed.
In addition, by increasing the entire area, the efficiency of suction can be further improved.

It is considered that this is because the pressure in the suction container decreases and the speed of the shock wave front increases. However, in the suction, it is necessary to consider a flow velocity and a streamline that do not cause local fluctuation of the refractive index due to gas disturbance in the optical path of the excimer laser light.

[Embodiment 17] FIG. 43 is a schematic diagram for explaining the construction of still another embodiment of the ablation debris removing apparatus in the manufacture of the liquid crystal display device according to the present invention, which is for mounting on an ablation processing apparatus. A specific structure is shown, the suction buffer space 52 communicates with the exhaust unit 51, and 56 is a suction container. Note that the same reference numerals as those in FIG. 42 correspond to the same functional portions.

In the figure, the height of the suction container 56 is 65
mm, and the bottom plate 55 of the suction container is placed on the surface of the workpiece with a gap of 1 mm.

The excimer laser beam enters from the entrance window 54 and is applied to the glass substrate through the opening 55a of the bottom plate 55.

The debris A generated by the ablation reaches the exhaust part 51 from the suction buffer space 52 through the suction nozzle 50 as shown by the arrow, and is exhausted by a vacuum pump (not shown).

As a result of performing ablation processing of the novolak resin by the ablation processing apparatus using the ablation debris removing apparatus having this configuration, the laser oscillation frequency of 2 kHz was about 1.5 times that of the case without the suction container. Ablation rate was obtained. Furthermore, debris could be completely removed except for a small portion at the edge of the laser irradiation part.

With this configuration, it can be easily installed in the processing section of the ablation processing apparatus.
High quality processing can be performed by removing the generated debris.

FIG. 44 is an explanatory diagram of a configuration example in which the ablation debris removing device shown in FIG. 43 is mounted on an ablation processing machine and is applied to processing of a color filter substrate constituting a liquid crystal display element, where 1 is an excimer laser. , 1
a is an excimer laser beam, 1a 'is an irradiation laser beam, 7
Denotes an exposure mask (dielectric mask), 10 ′ denotes a color filter substrate which is a workpiece, and 11 denotes a color filter substrate.
XY table of 0 ', 60 is a color filter layer, 60
a is an unnecessary convex portion formed on the color filter layer, 61 is a uniform illumination optical system, 62 is an imaging optical system (lens), 63
Is a debris removal device.

In the figure, an excimer laser 1 oscillates a laser beam 1a having a wavelength of 248 nm, and is provided with a projection 6 on the surface of a color filter layer 60 of a color filter substrate 10 ′ by a uniform illumination optical system 61 including an integrator.
Illumination of a 2 × 50 mm ² slit-shaped mask pattern is performed on the exposure mask 7 having an opening formed to cover the removal region 0a.

The mask pattern is imaged on the surface of the color filter layer 60 by the 1: 1 image forming lens 62. The working distance of the imaging lens 62 is 70 mm, during which the ablation debris removing device 131 m incorporated in a suction container having a height of 65 mm as shown in cross section in FIG.
m.

For suction of debris, a dry vacuum pump or a vacuum suction device having an exhaust capacity of 300 liter / second is used. Excimer laser beam incident energy density 300m
J / cm ² .

[0410] With the ablation processing apparatus configured as described above, unnecessary projections 7a formed on the color filter layer of the color filter substrate are removed and flattened, and debris generated by the processing remains on the color filter layer. Thus, a high quality color filter substrate could be obtained.

FIG. 45 is an exploded perspective view for explaining a structural example of a TFT type liquid crystal display device manufactured according to the present invention.

[0412] In the same figure, MDL denotes a liquid crystal display device, S
HD is an upper frame metal shield case, WD
Is a display window for defining an effective screen of the liquid crystal display device, PNL is a liquid crystal display element, SCP is a diffusion plate, PCB1 is a drain side circuit board, PCB2 is a gate side circuit board, PCB3 is an interface circuit board, PRS is a prism sheet, S
PS is a diffusion sheet, GLB is a light guide, RFS is a reflection sheet, BL is a backlight, LP is a cold cathode fluorescent lamp constituting a lamp of the backlight BL, LS is a reflection sheet, and GC
Is a rubber bush, LPC is a lamp cable, MCA is a lower case having an opening MO for installing the light guide GLB, J
N1,2,3 are joiners for connecting circuit boards, TCP
1, 2 are tape carrier packages, INS 1, 2, 3
Is an insulating sheet, GC is a rubber cushion, BAT is a double-sided adhesive tape, and ILS is a light shielding spacer.

[0413] The components described above are laminated between the metal shield case SHD and the lower case MCA, and are sandwiched and fixed to form the liquid crystal display device MDL.

[0414] A diffusion plate SCP is stacked on the liquid crystal display element PNL, and various circuit boards are mounted around the diffusion plate SCP to drive for image display.

[0415] Further, on the back surface of the liquid crystal display element PNL, a backlight BL formed by laminating various optical sheets on a light guide GLB is installed, and a display window WD is provided by illuminating an image formed on the liquid crystal display element PNL. To be displayed.

[0416] The TFT type liquid crystal display device assembled by using the present invention can be used for various display devices having greatly reduced processing steps, capable of forming a high-precision thin film pattern, and having high image quality display performance. Applicable to

The processing method using the ablation phenomenon of excimer laser light according to the present invention is not limited to patterning of a resist film of a liquid crystal display element, various thin films constituting a TFT substrate or a color filter substrate, and the same patterning is performed. It can be applied to the patterning of various accompanying thin films.

[0418]

As described above, according to the present invention,
A resist film is formed from a high ablation rate and low debris polymer material, and the resist film is developed and the remaining resist film is removed by lithography using the ablation phenomenon of excimer laser light. Since patterning can be realized without using a wet process, the influence on the environment can be eliminated by waste liquid of the developer, the release agent, and other processing agents. Further, the process of forming the thin film pattern itself is simplified, and the process time can be greatly reduced, thereby reducing the manufacturing cost of the liquid crystal element.

Further, damage to the optical system due to high energy excimer laser light is prevented, and various thin films can be patterned with high accuracy on a large-area glass substrate, and the mass production effect is large.

Furthermore, the exposure mask according to the present invention has high durability against high-energy excimer laser light, and avoids the displacement of the pattern boundary with respect to a large-area glass substrate in the step-scan method, thereby achieving high precision. A patterning process is possible.

[0421] The alignment between the exposure mask and the glass substrate to be processed can be realized with high accuracy with a simple configuration, and debris generated by ablation can be removed in real time. Therefore, the quality of the manufactured liquid crystal display device can be improved.

[Brief description of the drawings]

FIG. 1 is a process diagram illustrating a method for manufacturing a liquid crystal display element according to the present invention using a resist material for ablation processing of excimer laser light.

FIG. 2 is a process diagram illustrating a method for manufacturing a liquid crystal display device according to the present invention using a resist material for ablation processing of excimer laser light.

FIG. 3 is a schematic diagram for explaining an example of the configuration of an exposing machine utilizing an ablation phenomenon of an excimer laser used for manufacturing a liquid crystal display device according to the present invention.

FIG. 4 is a schematic sectional view illustrating an example of a basic configuration of a dielectric multilayer film mask.

FIG. 5 is a schematic cross-sectional view illustrating another example of the basic configuration of the dielectric multilayer film mask.

6 is an explanatory view as a parameter the number of layers the relation of the refractive index ratio corresponding to FIG. 4 and n _e / n ₁ and reflectance.

7 is an explanatory view as a parameter the number of layers the relation of the refractive index ratio corresponding to FIG. 5 and n _e / n ₁ and reflectance.

FIG. 8 is a schematic cross-sectional view illustrating a basic structure of an excimer laser processing mask (exposure mask) constituted by a dielectric multilayer film mask according to the present invention.

FIG. 9 shows the refractive index ratio n of the multilayer dielectric layer when Al ₂ O ₃ is used as an additional high refractive index layer except for the metal film layer of FIG.
FIG. 4 is a characteristic explanatory diagram of the relationship between ₂ / n ₃ and reflectance.

FIG. 10 is an explanatory view of an ablation phenomenon schematically showing a shadow graph of an ablation phenomenon by a dye laser (pulse width: about 5 ns) which is delay-synchronized with a pulse of an excimer laser beam.

FIG. 11 is a plan view illustrating a configuration near one pixel of an active matrix type color liquid crystal display device to which the present invention is applied.

FIG. 12 is a cross-sectional view of a main part, taken along line 3-3 in FIG. 11;

FIG. 13 is an explanatory diagram of a forming process by patterning a thin-film multilayer structure constituting a TFT on a lower transparent glass substrate.

FIG. 14 is an explanatory diagram of a forming process by patterning a thin film multilayer structure constituting a TFT on a lower transparent glass substrate.

FIG. 15 is an explanatory diagram of a forming step by patterning a thin-film multilayer structure constituting a TFT on a lower transparent glass substrate.

FIG. 16 is a schematic diagram illustrating an outline of an optical system of an exposure / development apparatus used in a method of manufacturing a liquid crystal display device according to the present invention.

FIG. 17 is an explanatory view of a principle of dividing a substrate pattern for an exposure mask for step-scan in a method for manufacturing a liquid crystal display element of the present invention.

FIG. 18 is a plan view schematically illustrating a configuration example of an exposure mask used in the method for manufacturing a liquid crystal display element according to the present invention.

FIG. 19 is a principle diagram illustrating division of excimer laser light by a lens array in an ablation developing machine used in the method for manufacturing a liquid crystal display element of the present invention.

FIG. 20 is an explanatory diagram of an illumination optical system of an ablation developing machine used in the method for manufacturing a liquid crystal display element of the present invention.

FIG. 21 is an explanatory diagram of uniforming illumination light of an exposure mask of an ablation developing machine used in a method of manufacturing a liquid crystal display element of the present invention.

FIG. 22 is a schematic diagram illustrating a scanning method of an ablation developing machine used in the method for manufacturing a liquid crystal display device of the present invention.

FIG. 23 is an explanatory diagram of an example of setting the position of an illumination area in scanning by an ablation developing machine used in the method for manufacturing a liquid crystal display element of the present invention.

FIG. 24 is a diagram illustrating an overall configuration of an ablation developing apparatus in which excimer laser light source units and a developing optical system of an ablation developing machine used in a method of manufacturing a liquid crystal display device of the present invention are separated from each other by separate walls and installed in rooms having different cleanliness. FIG.

FIG. 25 is an explanatory diagram of a shift correction method for tilting a transmission window plate through which a laser light beam passes in an ablation developing machine used in a method of manufacturing a liquid crystal display element of the present invention to translate an optical axis in parallel.

FIG. 26 is a schematic diagram of a configuration of an exposure optical system of an ablation developing machine for explaining a seventh embodiment of the present invention.

FIG. 27 is a schematic diagram illustrating an example of an arrangement of cylindrical lenses used for dividing a light source in an X direction and a Y direction in a seventh embodiment of the present invention.

FIG. 28 shows a black matrix (BM) formed on a color filter side glass substrate of a liquid crystal display device as an example of an opening pattern of an exposure mask in a seventh embodiment of the present invention.
It is explanatory drawing of the example of a pattern and the arrangement | positioning relationship of the blade for slit illumination.

FIG. 29 is a schematic diagram of patterning by ablation development of a color filter for explaining an eighth embodiment of the present invention.

FIG. 30 is an explanatory view of a preferable division line of an exposure mask of an ablation exposure machine used in a method of manufacturing a liquid crystal display device according to the present invention.

FIG. 31 is an explanatory diagram of a dividing line to be avoided.

FIG. 32 is a schematic view for explaining an example of division of a substrate for explaining an embodiment of a method for forming a resist pattern in a method for manufacturing a liquid crystal display element according to the present invention.

FIG. 33 is a plan view illustrating a specific example of an exposure mask used in the present example.

FIG. 34 is an explanatory diagram of an irradiation state of excimer laser light on a resist on a substrate via an exposure mask.

FIG. 35 shows a combination of a high-refractive-index layer material and a low-refractive-index layer material, which are materials for an exposure mask of an excimer laser exposure machine used for manufacturing a liquid crystal display device according to the present invention, and a minimum number of layers having a transmittance of 10% or less. FIG.

FIG. 36 is a schematic process chart illustrating an example of a method for manufacturing an exposure mask of an excimer laser exposure machine used for manufacturing a liquid crystal display device according to the present invention.

FIG. 37 is a schematic diagram illustrating an embodiment of a positioning mechanism for aligning an exposure mask with a glass substrate as a workpiece.

FIG. 38 is a partial cross-sectional view illustrating a configuration of a fluorescent plate.

FIG. 39 is a schematic diagram for explaining another embodiment of a positioning mechanism for aligning an exposure mask with a glass substrate as a workpiece.

FIG. 40 is a schematic diagram illustrating the configuration of an embodiment of an ablation debris removing apparatus in the manufacture of a liquid crystal display device according to the present invention.

FIG. 41 is a schematic view illustrating the configuration of another embodiment of the ablation debris removing apparatus in the manufacture of a liquid crystal display device according to the present invention.

FIG. 42 is a schematic view illustrating the configuration of still another embodiment of the ablation debris removing apparatus in the manufacture of a liquid crystal display device according to the present invention.

FIG. 43 is a schematic diagram illustrating the configuration of still another embodiment of the ablation debris removing apparatus in the manufacture of a liquid crystal display device according to the present invention.

44 is an explanatory diagram of a configuration example in which the ablation debris removal device shown in FIG. 43 is mounted on an ablation processing machine and applied to processing of a color filter substrate forming a liquid crystal display element.

FIG. 45 is an exploded perspective view illustrating a structural example of a TFT type liquid crystal display device manufactured according to the present invention.

[Explanation of symbols]

REFERENCE SIGNS LIST 1 excimer laser 3, 5 lens 4 split lens 6 condenser lens 7 exposure mask 8 imaging lens 9 entrance pupil 10 resist coated glass substrate as workpiece 11 XY table (11a is XY mask table, 11b is X -Y substrate table).

Continued on the front page (51) Int.Cl. ⁶ Identification code Agency reference number FI Technical indication location G03F 7/039 501 G03F 7/039 501 (72) Inventor Nobuaki Hayashi 3300 Hayano, Mobara-shi, Chiba Hitachi, Ltd. Electronic Device Division (72) Inventor Yoshifumi Tomita 3300 Hayano, Mobara-shi, Chiba Hitachi, Ltd.Electronic Device Division

Claims (8)

[Claims] An urethane film is formed on a glass substrate on which a thin film of a metal film, a dielectric insulating film, or a semiconductor film for forming a liquid crystal display element or a multilayer film in which a part of the thin film is formed in a pattern is formed. Applying a resist film composed of a polymer material having a bond and / or a urea bond, and irradiating an excimer laser through a mask having a predetermined opening pattern to remove the irradiated portion of the resist film by an ablation phenomenon; After forming a resist film pattern exposing the thin film corresponding to the opening pattern of the mask, removing the thin film exposed by the resist film pattern by performing an etching process, irradiating an excimer laser to remove the residual resist film. A method for manufacturing a liquid crystal display element, wherein the liquid crystal display element is removed by an ablation phenomenon. 2. A method for manufacturing a liquid crystal display device according to claim 1, wherein the extinction coefficient of the resist film is 5 × 10 ⁴ cm ⁻¹ or more for excimer laser light having a wavelength of 248 nm or 308 nm. . 3. The method according to claim 1, wherein the polymer compound is
A method for manufacturing a liquid crystal display element, which is a thermosetting type in which a cyclic or network-like crosslinked structure is formed by either heating or drying. 4. The method of claim 1, wherein the resist film is, for the wavelength 248 nm, the energy density of 100 mJ / cm ² of excimer laser light pulse, 0.04 .mu.m / s
A method for manufacturing a liquid crystal display device, wherein the method has an ablation speed not less than hot. 5. A liquid crystal display device according to claim 1, wherein the polymer material constituting the resist film is a polymer compound produced by a polymerization reaction between polyisocyanate and polyol and / or polyamine. Production method. 6. The method according to claim 5, wherein the polyisocyanate is at least one of toluene diisocyanate, methylenebisphenyl isocyanate, and naphthalenediisocyanate. 7. A thin film of a metal film, a dielectric insulating film, a semiconductor film,
A glass substrate obtained by processing a multilayer film composed of one or more of the thin films by an ablation phenomenon of an excimer laser using a resist film composed of a polymer material having a urethane bond and / or a urea bond; A liquid crystal display device comprising a liquid crystal layer sandwiched between another matrix substrate on which a matrix and a plurality of color filters are formed. 8. The method according to claim 7, wherein the black matrix and / or the plurality of color filters of the glass substrate are formed by excimer laser through a mask having a predetermined opening pattern. A liquid crystal display device which is obtained by irradiating and processing a black matrix film and / or a plurality of color filter films in an irradiated portion by an ablation phenomenon.