CN104040428B - Phase shifting mask and the corrosion-resisting pattern forming method for using the phase shifting mask - Google Patents

Phase shifting mask and the corrosion-resisting pattern forming method for using the phase shifting mask Download PDF

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Publication number
CN104040428B
CN104040428B CN201380004907.9A CN201380004907A CN104040428B CN 104040428 B CN104040428 B CN 104040428B CN 201380004907 A CN201380004907 A CN 201380004907A CN 104040428 B CN104040428 B CN 104040428B
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Prior art keywords
phase
mentioned
size
exposure
phase shift
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CN104040428A (en
Inventor
木下树
木下一树
飞田敦
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Dai Nippon Printing Co Ltd
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Dai Nippon Printing Co Ltd
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Priority to CN201811233403.5A priority Critical patent/CN109298592A/en
Priority to CN201811233402.0A priority patent/CN109298591A/en
Publication of CN104040428A publication Critical patent/CN104040428A/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F1/00—Originals for photomechanical production of textured or patterned surfaces, e.g., masks, photo-masks, reticles; Mask blanks or pellicles therefor; Containers specially adapted therefor; Preparation thereof
    • G03F1/26—Phase shift masks [PSM]; PSM blanks; Preparation thereof
    • G03F1/34—Phase-edge PSM, e.g. chromeless PSM; Preparation thereof

Abstract

The present invention provides one kind and existing image display device exposure device for making can be used, on the processed material such as transparent substrate, formed has the not up to phase shifting mask of the given corrosion-resisting pattern of the size of the resolution of exposure equipment limit and the corrosion-resisting pattern forming method using the phase shifting mask with high precision.The corrosion-resisting pattern formation of the not up to design size of the resolution of exposure equipment limit has with phase shifting mask：Transparent substrate assigns the phase shift portion of given phase difference to the light of the exposure from exposure device and is adjacent to the non-phase-shifted portion in phase shift portion, at least either in phase shift portion and non-phase-shifted portion is the size of the not up to resolution of exposure equipment limit, and the size in phase shift portion is different from the size in non-phase-shifted portion, the size comprising the area of the pattern including phase shift portion and non-phase-shifted portion on transparent substrate is the light shielding part without the not up to size of the resolution of exposure equipment limit at least in area of the pattern on one side for 300mm or more.

Description

Phase shifting mask and the corrosion-resisting pattern forming method for using the phase shifting mask
Technical field
The present invention relates to a kind of phase shifting masks for forming given corrosion-resisting pattern on being processed material and use should The corrosion-resisting pattern forming method of phase shifting mask.
Background technology
Liquid crystal display generally has following construction：It will be with the switch active element (film for driving pixel electrode Transistor (TFT, Thin Film Transistor)) TFT substrate, with comprising with given opening portion black matrix" and The colored filter substrate for being formed in the dyed layer on the opening portion is oppositely disposed, and around sealing, gap is enclosed therebetween and fills There is liquid crystal material.
In the liquid crystal display, TFT in TFT substrate etc. can be formed by operating as follows：Include this being formed with A bit on the film on the transparent substrate of the film of (gate electrode, source electrode, drain electrode etc.) constituent material, formation has The photoresist of given pattern is etched using patterned photoresist as mask.Colorized optical filtering chip base Black matrix" on plate etc. can also same way formed.
In addition, organic electroluminescent (EL, Electro Luminescence) display has following construction：In transparent base Cathode electrode, organic EL films, anode electrode are stacked gradually on plate, and are sealed by diaphragm seal etc. on them；Or tool There is following construction：Organic EL films, public electrode are stacked gradually on the tft substrate, and on them bys diaphragm seal etc. Sealing.
In these organic el displays, also in the same manner as liquid crystal display, cathode electrode, anode electrode, TFT etc. can lead to It crosses following operation and is formed：On the film on the transparent substrate for being formed with the film comprising these constituent materials, tool is formed Patterned photoresist is etched by the photoresist for having given pattern as mask.
During manufacturing the image display devices such as these liquid crystal displays, organic el display, as in transparent base The method that given corrosion-resisting pattern is formed on plate generally uses photoetching process, is using with comprising given pattern form The photomask (binary mask) of the light shielding part of crome metal etc. is exposed and develops to the photoresist.Moreover, having these The transparent substrate of electrode, TFT etc. are the transparent substrate using large area mostly to help to seek mass production and reduce cost (for example, transparent substrate of 330mm × 450mm or more) is bonded by multi-panel and produced, even if so as when in transparent substrate It is upper to form the exposure device used when given corrosion-resisting pattern, also it can unify usually using having or be divided into repeatedly to large area The large-scale exposure device of equimultiple projection exposure optical system that is exposed of transparent substrate.
By the size of corrosion-resisting pattern that photoetching process as described above is formed (for example, if the against corrosion of line and gap-like Pattern is then the width of the short side direction of line pattern or space pattern；That is line width) the resolution of exposure equipment limit is depended on, make For image display device exposure device for making, generally 3 μm or so are limited to using resolution pole.It is shown if existing image Device resolution ratio, if the patterning that can be then exposed device resolution limit or more just not will produce problem, but in recent years, Constantly it is expected pixel number is made to increase, the exploitation of image display device with higher resolution, in being less than existing image The patterned necessity of the size of display device exposure device for making resolution limit is constantly surging.
Under such present situation, attempted as follows：It will be in large scale integrated circuit (LSI, Large Scale ) etc. Integration in the manufacturing process of semiconductor devices for the patterned phase shifting mask in minimum size as figure As display device manufacturing process in photomask use.For example, proposing there is a kind of photomask, have on the transparent substrate saturating Light portion (light transmission rate of exposure is 100%) and semi light transmitting part (light transmission rate of exposure is 20~60%), transmittance section and semi-transparent At least one of work as the sized fraction (referring to patent document 1) with not up to 3 μm in light portion.
[prior art document]
[patent document]
[patent document 1] Japanese Patent Laid-Open 2009-42753 bulletins
Invention content
(problems to be solved by the invention)
However, using the photomask of above patent document 1, manufactured with exposure dress by using existing image display device It sets and is exposed and develops, although the size for being formed by corrosion-resisting pattern can be made to be not up to image display device manufacture exposure dress Resolution limit is set, but thinning in the presence of the thickness (height of line pattern) for being formed by corrosion-resisting pattern, it is patterned to make Photoresist is difficult to the problem of playing the effect as the etching mask in etching step thereafter.
In addition, the thickness by corrosion-resisting pattern is thinning, be formed by the side of sidewall portion of corrosion-resisting pattern angle (if line and The corrosion-resisting pattern of gap shape is then the setting angle of the line pattern side of sidewall portion in the vertical direction of real estate) it can become smaller.The angle becomes The unevenness of the thickness (aspect ratio) of corrosion-resisting pattern in the small face meaned on substrate becomes larger.As a result, in the presence of etching thereafter The problem of high-precision etching in step becomes difficult.
The light obtained by equimultiple projection exposure by using existing image display device exposure device for making is parallel The less light of light component, so the transmittance section of photomask through light to the underface detour of semi light transmitting part, to also expose to On the photoresist of the underface in the semi-permeable portion.It will produce problem as described above as a result,.
On the other hand, it is filled if the exposure for the reduced projection exposure optical system for having the semiconductor devices manufacture such as LSI It sets, then can be exposed by the more light of parallel light component, so by using the semiconductor device exposure device for making, Can inhibit through photomask (phase shifting mask) transmittance section underface detour from light to semi light transmitting part the case where.
However, since the exposure area of semiconductor device exposure device for making is minimum, if so in order to for image Corrosion-resisting pattern is formed on the substrate of the large area of display device and uses semiconductor device exposure device for making, then will produce figure The problem for the treatment of capacity manufactured as display device declines.
In view of this problem, the purpose of the present invention is to provide one kind, and existing image display device manufacture can be used to use Exposure device is formed with high precision on the processed material such as transparent substrate with the not up to resolution of exposure equipment limit The phase shifting mask of the given corrosion-resisting pattern of size and the corrosion-resisting pattern forming method for using the phase shifting mask.
(technical means to solve problem)
In order to solve the above problems, the present invention provides a kind of phase shifting mask, for passing through the exposure from exposure device Light is to which the corrosion-resisting pattern for the design size for being not up to the resolution of exposure equipment limit to be formed on processed material, feature It is have：Transparent substrate；Phase shift portion concavely or convexly, is set on above-mentioned transparent substrate, is filled to coming from above-mentioned exposure The light for the exposure set assigns given phase difference；And non-phase-shifted portion, it is adjacent to above-mentioned phase shift portion, above-mentioned phase shift portion and above-mentioned At least either in non-phase-shifted portion is the size of the not up to above-mentioned resolution of exposure equipment limit, and the ruler in above-mentioned phase shift portion It is very little different from the above-mentioned size in non-phase-shifted portion, any one smaller performance of size in above-mentioned phase shift portion and above-mentioned non-phase-shifted portion The function of exposing the photoresist on above-mentioned processed material, another one play the photoresist made on above-mentioned processed material The function of film exposure, the size for including the area of the pattern including above-mentioned phase shift portion and above-mentioned non-phase-shifted portion on above-mentioned transparent substrate It is that the ruler of the not up to above-mentioned resolution of exposure equipment limit is not arranged at least in above-mentioned area of the pattern by 300mm or more on one side to be Light shielding part (invention 1) that is very little, being constituted with photomask.
In addition, in the present invention, the transmitance of so-called " transparent " light for referring to 350~450nm of wavelength is 85% or more, Preferably 90% or more, it is further preferred that being 95% or more.In addition, in the present invention, so-called " so that photoresist is exposed " refers to not Keep the photoresist in the light path through light of phase shifting mask (phase shift portion or non-phase-shifted portion) photosensitive, and setting is not only wrapped The case where light does not expose to the photoresist in the light path positioned at this through light is included, also includes that will not enable the photoresist sense The illumination of the intensity (low-intensity) of the degree of light is incident upon the situation on the photoresist.
In foregoing invention (invention 1), the ratio between the size in above-mentioned phase shift portion and the size in above-mentioned non-phase-shifted portion preferably 1: 1.5~1: 5.6 or 1.5: 1~5.6: 1 (invention 2).
In foregoing invention (invention 1,2), the size in above-mentioned phase shift portion and the above-mentioned non-phase-shifted portion for being adjacent to the phase shift portion The aggregate value of size be preferably the above-mentioned resolution of exposure equipment limit or more (invention 3).
In foregoing invention (invention 1), the smaller dark areas of size in above-mentioned phase shift portion and above-mentioned non-phase-shifted portion In the range of size is 0.6 μm~2.75 μm, with regard to the larger-size area pellucida domain in above-mentioned phase shift portion and above-mentioned non-phase-shifted portion The ratio between the size of size and above-mentioned dark areas for, in the case where the size of above-mentioned dark areas is set as 1, above-mentioned area pellucida domain It is preferably dimensioned to be 1.5 or more (inventions 4).
In foregoing invention (invention 1~4), also there can be above-mentioned resolution of exposure equipment pole in above-mentioned area of the pattern More than limit size, the light shielding part (invention 5) that is constituted with photomask.
May be either that above-mentioned concave phase shift portion is disposed on above-mentioned transparent substrate in foregoing invention (invention 1~5) Etching portion (invention 6) or the phase shift portion of above-mentioned convex are to be constituted (invention with the light-transmissive film being set on above-mentioned transparent substrate 7)。
In addition, the present invention provides a kind of corrosion-resisting pattern forming method, it is will have the not up to resolution of exposure equipment limit The corrosion-resisting pattern of design size be formed in the method on processed material, it is characterised in that comprise the following steps：Use above-mentioned exposure Electro-optical device, by the phase shifting mask of foregoing invention (invention 1~7), exposure is set to the photoresist on above-mentioned processed material The step of；And by making exposed above-mentioned photoresist develop, to form given resist on above-mentioned processed material The step of corrosion figure case (invention 8).
(invention effect)
According to the present invention, it is possible to provide one kind can use existing image display device exposure device for making, transparent On the processed material such as substrate, the given pattern with the size for being not up to the resolution of exposure equipment limit is formed with high precision Phase shifting mask and the corrosion-resisting pattern forming method for using the phase shifting mask.
Description of the drawings
Fig. 1 is the partial cut end view drawing of the schematic configuration for the phase shifting mask for indicating the 1st embodiment of the present invention.
Fig. 2 is the chart of the luminous intensity through light for the phase shifting mask for indicating the 1st embodiment of the present invention.
Fig. 3 is the top partial view diagram of the schematic configuration for the phase shifting mask for indicating the 1st embodiment of the present invention.
(a) to (e) of Fig. 4 is the flow chart of the manufacturing step for the phase shifting mask for indicating the 1st embodiment of the present invention.
(a) to (c) of Fig. 5 is the pattern forming method for the phase shifting mask for indicating the 1st embodiment using the present invention Flow chart.
Fig. 6 is the top partial view diagram of the specific composition example for the phase shifting mask for indicating the 1st and the 2nd embodiment of the present invention.
Fig. 7 is the partial cut end view drawing of the schematic configuration for the phase shifting mask for indicating the 2nd embodiment of the present invention.
Fig. 8 is the chart of the luminous intensity through light for the phase shifting mask for indicating the 2nd embodiment of the present invention.
Fig. 9 is the top partial view diagram of the schematic configuration for the phase shifting mask for indicating the 2nd embodiment of the present invention.
(a) to (e) of Figure 10 is the manufacturing step (method 1) for the phase shifting mask for indicating the 2nd embodiment of the present invention Flow chart.
(a) to (f) of Figure 11 is the manufacturing step (method 2) for the phase shifting mask for indicating the 2nd embodiment of the present invention Flow chart.
(a) to (c) of Figure 12 is the pattern forming method for the phase shifting mask for indicating the 2nd embodiment using the present invention Flow chart.
Figure 13 is the figure illustrated to the dark areas of the phase shifting mask in test example 6 and area pellucida domain.
Figure 14 is the figure illustrated to the dark areas of the phase shifting mask in test example 7 and area pellucida domain.
Specific implementation mode
Hereinafter, being illustrated to phase shifting mask of the invention and using the corrosion-resisting pattern forming method of the phase shifting mask.
In addition, the phase shifting mask of the present invention has 2 forms.Hereinafter, being illustrated to each form.
1. the 1st form
The phase shifting mask of the 1st form of the present invention is for the light by the exposure from exposure device to be not up to The corrosion-resisting pattern of the design size of the resolution of exposure equipment limit is formed in the phase shifting mask on processed material, and feature exists In：Have：Transparent substrate；Phase shift portion concavely or convexly, is set on above-mentioned transparent substrate, to coming from above-mentioned exposure device The light of exposure assign given phase difference；And non-phase-shifted portion, it is adjacent to above-mentioned phase shift portion；Above-mentioned phase shift portion and above-mentioned non-phase At least either in shifting portion be not up to the above-mentioned resolution of exposure equipment limit size, and the size in above-mentioned phase shift portion with The size in above-mentioned non-phase-shifted portion is different；Any one smaller performance of size in above-mentioned phase shift portion and above-mentioned non-phase-shifted portion does not make The function of photoresist exposure on above-mentioned processed material, another one performance make the photoresist on above-mentioned processed material expose The function of light；The size of the area of the pattern comprising above-mentioned phase shift portion and above-mentioned non-phase-shifted portion on above-mentioned transparent substrate is to be on one side 300mm or more；At least in above-mentioned area of the pattern, be not arranged the size of the not up to above-mentioned resolution of exposure equipment limit, by The light shielding part that photomask is constituted.
Herein, so-called " phase shift portion assigns desired phase difference to the light of the exposure from exposure device " specifically Refer to " phase shift portion make through above-mentioned phase shift portion exposure light phase relative to through above-mentioned non-phase-shifted portion exposure light phase Bit reversal ".In addition, about " phase shift portion makes the phase of the light of the exposure through above-mentioned phase shift portion relative to through above-mentioned non-phase-shifted The case where phasing back of the light of the exposure in portion ", will illustrate in the item of following " 2. the 2nd forms ".
According to the 1st form, it is above-mentioned relation by making the size in phase shift portion and the size in non-phase-shifted portion, a kind of phase can be formed Mask is moved, existing image display device exposure device for making can be used, on the processed material such as transparent substrate, with high-precision Degree forms the given pattern with the not up to size of the resolution of exposure equipment limit.
In addition, in the phase shifting mask of the 1st form, with the above-mentioned existing phase shifting mask for including through portion and semi-permeable portion It compares, it can more good precision formation corrosion-resisting pattern.It will be said in the item of following " 2. the 2nd forms " about its reason It is bright.
The phase shifting mask of 1st form has 2 embodiments.Hereinafter, one side faces the phase of the 1st form with reference to attached drawing, one Each embodiment for moving mask illustrates.
<1st embodiment>
[phase shifting mask]
Fig. 1 is the partial cut end view drawing of the schematic configuration for the phase shifting mask for indicating the 1st embodiment, and Fig. 2 is to indicate the 1st The chart of the luminous intensity through light of the phase shifting mask of embodiment, Fig. 3 are the outlines for the phase shifting mask for indicating the 1st embodiment The top partial view diagram of composition.
As shown in Figure 1, the phase shifting mask 1A of the 1st embodiment has：Transparent substrate 2A, it is set on transparent substrate 2A The multiple phase shift portion 3A and multiple non-phase-shifted portion 4A being arranged in a manner of being adjacent to each phase shift portion 3A；And in manufacture liquid crystal During the image display devices such as showing device, organic EL display device, for by using having the device used for image display The light of exposure of large-scale exposure device of equimultiple projection exposure optical system will to be not up to the resolution of exposure equipment limit (excellent Be selected as not up to 3 μm, preferably 1.5 μm or more and not up to 3 μm, it is further preferred that be 1.5~2 μm) design size corrosion-resisting pattern It is formed on processed material.
It as transparent substrate 2A, is not particularly limited, such as can be used：Alkali-free glass, quartz glass, Pyrex (registrars Mark) the not flexible transparent hard material etc. such as glass, synthetic quartz plate.
The size of transparent substrate 2A can be by for using the phase shifting mask 1A images to be manufactured of the 1st embodiment aobvious The size of substrate (TFT substrate, colored filter substrate etc.) in showing device has manufacture for the image display device In equimultiple projection exposure optical system large-scale exposure device Exposure mode (unified Exposure mode or dividing exposure mode) Deng and suitably set, for example, may be set to 330mm × 450mm~1600mm × 1800mm or so.
In addition, the thickness of transparent substrate 2A is not particularly limited, but due to that it must will not be made to protect deviously in exposure Phase shifting mask 1A is held, so can be suitably set by the size of transparent substrate 2A, for example, can be in the range of 5mm~20mm It is set.
Phase shift portion 3A is set on transparent substrate 2A, is constituted as the etching portion for being etched into given depth d.And And the non-etching portion for being adjacent to multiple phase shift portion 3A becomes non-phase-shifted portion 4A.
In the phase shifting mask 1A of the 1st embodiment, the size X of phase shift portion 3A is different from the non-phase-shifted size Y of portion 4A.If Size X, Y of the two is identical, against corrosion to be formed even if then making the light exposure increase from exposure device that can not also solve picture Pattern.
In addition, in the 1st embodiment, it is at least any in the size Y of the size X of phase shift portion 3A and non-phase-shifted portion 4A Person is not up to the exposure device point for the equimultiple projection exposure optical system for having existing used image display device manufacture The resolution limit (is preferably not up to 3 μm, more preferably 1.5 μm or more and not up to 3 μm, it is further preferred that being 1.5~2 μm).It as a result, can shape At the corrosion-resisting pattern with the not up to design size of the resolution of exposure equipment limit.
Phase shift portion 3A in 1st embodiment has the size X of the size Y less than non-phase-shifted portion 4A.By being formed in this way Composition, make phase shift portion 3A in the 1st embodiment for will be to use the photoetching technique of existing binary mask etc. to be difficult to shape At fine corrosion-resisting pattern be formed at the processed material (substrate in the light path through the light (penetrate light) of phase shift portion 3A Deng) on, to play the effect for the light shielding part for being equivalent to existing binary mask etc..
The size X of phase shift portion 3A can the design size according to the corrosion-resisting pattern to be formed or the exposure from exposure device Amount etc. and suitably set, preferably not up to 3 μm, it is further preferred that be 1.0~2.5 μm.To assigning and penetrating through the light of phase shift portion 3A The phase difference of the light difference about 180 degree of non-phase-shifted portion 4A, so phase shift portion 3A through light be adjacent to the non-of phase shift portion 3A Phase shift portion 4A's interferes with each other through light.Moreover, by making the size X of phase shift portion 3A be not up to above-mentioned resolution of exposure equipment pole Limit and less than non-phase-shifted portion 4A size Y, can make phase shifting mask 1A through in light, expose to the transmission positioned at phase shift portion 3A The intensity of light (irradiation light) on photoresist in the light path of light drops to the degree that the photoresist will not be enabled photosensitive (with reference to Fig. 2).As a result, the corrosion-resisting pattern with the not up to size of the above-mentioned resolution of exposure equipment limit can be formed.
On the other hand, if the size X of phase shift portion 3A is the size of the above-mentioned resolution of exposure equipment limit or more, i.e. phase shift portion The size Y of the size X of 3A and non-phase-shifted portion 4A is the size of the above-mentioned resolution of exposure equipment limit or more, then phase shift portion 3A It is interfered by non-phase-shifted being effectively prevented from through the detour of light for portion 4A through light, to which directive can not be made to be located at phase shift The intensity of the irradiation light of photoresist in the light path through light of portion 3A, which drops to, will not enable the photoresist photosensitive Degree.As a result, can in the light path through light of phase shift portion 3A, formed it is not expected that corrosion-resisting pattern.
As long as that is, in the phase shifting mask 1A corrosion-resisting patterns to be formed using the 1st embodiment, be existing two The resist pattern that first mask (photomask with the light shielding part and opening portion that are made of crome metal etc.) is just formed according to light shielding part Case is (for example, be line pattern by the corrosion-resisting pattern of positive light anti-etching agent line to be formed and gap-like, logical Cross negative type photoresist and be intended in the case of being formed be space pattern) design size not up to used in image display dress It sets in the case of the resolution of exposure equipment limit, in the phase shifting mask 1A of the 1st embodiment, has that be used to form this against corrosion The phase shift portion 3A of pattern.On the other hand, if the design size of the corrosion-resisting pattern is the above-mentioned resolution of exposure equipment limit or more, In the phase shifting mask 1A of the 1st embodiment, have be used to form the corrosion-resisting pattern, by the photomask structure comprising crome metal etc. At light shielding part 5A.
In addition, the size Y for the non-phase-shifted portion 4A for being adjacent to phase shift portion 3A and being arranged is according to the corrosion-resisting pattern to be formed Design size and suitably set, then may be either that not up to above-mentioned exposure device is differentiated as long as the size X more than phase shift portion 3A It is more than the rate limit or resolution limit.
If specifically being illustrated to the size X of phase shift portion 3A and the relationship of the size Y of non-phase-shifted portion 4A, the ruler of the two The ratio between very little X, Y (X: Y) they are preferably 1: 1.5~1: 5.6, and more preferably 1: 1.8~1: 4, it is further preferred that being 1: 1.8~1: 3.By making phase shift The ratio between size X, Y of portion 3A and non-phase-shifted portion 4A is above range, and as that clearly, can make to be formed from following embodiments institute Corrosion-resisting pattern Sidewall angles θ (with reference to Fig. 5) it is good (Sidewall angles θ can be changed according to type of photoresist etc., Preferably 60~90 degree, it is further preferred that being 70~90 degree), and resist pattern strictly according to the facts in design size can be formed with lower light exposure Case.
In the 1st embodiment, the size X of an a phase shift portion 3A and non-phase-shifted portion 4A for being adjacent to phase shift portion 3A Total (X+Y) of size Y be preferably the above-mentioned resolution of exposure equipment limit or more.If total (X+Y) is not up to above-mentioned exposure Electro-optical device resolution limit, then have that the formation of the corrosion-resisting pattern with good Sidewall angles θ (with reference to Fig. 5) becomes difficult can Energy.
It is by phase shifting mask and the used resolution of exposure equipment limit as specific above-mentioned total (X+Y) And suitably determine, it is not particularly limited, but preferably 3 μm or more, more preferably 3.5 μm or more.
In addition, the upper limit value as above-mentioned total (X+Y), be suitably selected according to purposes of phase shifting mask etc., and It is not particularly limited.As the upper limit value of above-mentioned total (X+Y), for example, it is preferable to for 17.9 μm hereinafter, more preferably 4.5 μm or less.
In the 1st embodiment, above-mentioned total (X+Y) is it is further preferred that be 4 μm or so.
Its reason is：It is that can be carried out well desired for obtaining in above range by above-mentioned total (X+Y) The design in the phase shift portion and non-phase-shifted portion of corrosion-resisting pattern.
In addition, in the 1st embodiment, in the case where above-mentioned total (X+Y) is in above range, preferably by phase shift The ratio between the size Y of the size X of portion 3A and non-phase-shifted portion 4A (X: Y) is set as above-mentioned numberical range.Its reason is：It can make institute's shape At corrosion-resisting pattern Sidewall angles it is better, preferably formed in design size so as to lower light exposure strictly according to the facts Corrosion-resisting pattern.
If enumerating concrete example and being illustrated in more details, it is intended to being limited to 3 μm of exposure device using resolution pole It, can be by phase in the case that the design size of formation line pattern and space pattern is respectively 2 μm of line and the corrosion-resisting pattern of gap-like The size X of shifting portion 3A preferably sets in the range of 0.6~1.6 μm, in the range of being more preferably set in 0.8~1.4 μm, it is further preferred that setting In the range of 1~1.4 μm, the size Y preferred settings of non-phase-shifted portion 4A can be set in the range of 2.4~3.4 μm, more preferably In the range of 2.6~3.2 μm, it is further preferred that being set in the range of 2.6~3 μm.
As long as the etching depth d of phase shift portion 3A is set as that given phase difference (170 can be assigned through light to phase shift portion 3A The phase difference of~190 degree (about 180 degree)) degree, and can be according to the thickness of transparent substrate 2A, the wave of the light of exposure Refractive index of material that is long, constituting transparent substrate 2A etc. and suitably set.
In the phase shifting mask 1A of the 1st embodiment, phase shift portion 3A and non-phase-shifted portion 4A are set on transparent substrate 2A In area of the pattern 6A (with reference to Fig. 3).Area of the pattern 6A be according to use the phase shifting mask 1A of the 1st embodiment in processed material The upper corrosion-resisting pattern to be formed and be set at least one region on transparent substrate 2A, no matter the exposure of above-mentioned exposure device How is mode, at least in the entire surface in an area of the pattern 6A, is exposed by irradiation light by 1 time.
As shown in figure 3, in the phase shifting mask 1A of the 1st embodiment, multiple pattern areas are set on transparent substrate 2A Domain 6A also can only be set there are one area of the pattern 6A.In addition, in figure 3, phase shift portion 3A, non-phase in omission area of the pattern 6A The diagram of shifting portion 4A and light shielding part 5A.
The size of area of the pattern 6A can be filled according to using the phase shifting mask 1A of the 1st embodiment images to be manufactured to show The Exposure mode of the size (picture dimension), used exposure device set or the area that can once expose etc. and suitably set, And it is set for substantially rectangular shape (or substantially square shape) region of 300mm or more as short side (one side).
In addition, in an area of the pattern 6A, it can both be formed with the structure being used to form in an image display device At pattern, can also be formed with the pattern being used to form for the composition in multiple images display device.
In addition, in the 1st embodiment, in area of the pattern 6A, other than phase shift portion 3A and non-phase-shifted portion 4A, also set It is equipped with the size more than above-mentioned resolution of exposure equipment limit, the light shielding part that includes the photomask being made of crome metal etc. 5A, but be not arranged with the not up to size of the above-mentioned resolution of exposure equipment limit, comprising the photomask being made of crome metal etc. Light shielding part.That is, the phase shifting mask 1A of the 1st embodiment is referred to as so-called chromeless phase shift mask.If in area of the pattern 6A The size of light shielding part 5A be not up to the resolution of exposure equipment limit, then be adjacent to the phase shift portion 3A or non-phase-shifted of light shielding part 5A Portion 4A's can be to the lower section detour of light shielding part 5A through light, and can not play shade function.
By using the phase shifting mask 1A of the 1st embodiment, can make by the light of the exposure from above-mentioned exposure device The Sidewall angles θ (with reference to Fig. 5) of the corrosion-resisting pattern of formation it is good (Sidewall angles θ can according to type of photoresist etc. and It changes, for example, it is preferable to be 60~90 degree, it is further preferred that being 70~90 degree).This situation means to reduce by by the 1st embodiment party The exposure of the phase shifting mask 1A of formula and the unevenness in the corrosion-resisting pattern forming face of the thickness (aspect ratio) of corrosion-resisting pattern that is formed.From And according to the phase shifting mask 1A of the 1st embodiment, even with the large-scale exposure device of existing device used for image display, The scale error that can be formed with the not up to size of the resolution of exposure equipment limit and in corrosion-resisting pattern forming face is smaller Corrosion-resisting pattern.
Any one that size is smaller in the phase shifting mask of the 1st embodiment, in phase shift portion and non-phase-shifted portion has not Make the function of the photoresist being processed on material exposure, another one that there is the work(for the photoresist exposure for making to be processed on material Energy.Therefore, in the phase shifting mask of the 1st embodiment, in order to obtain desired corrosion-resisting pattern, it is necessary to adjust phase shift portion and non- In phase shift portion in the size of the smaller dark areas of size and phase shift portion and non-phase-shifted portion larger-size area pellucida domain ruler It is very little.
In the phase shifting mask of the 1st embodiment, smaller dark of size in above-mentioned phase shift portion and above-mentioned non-phase-shifted portion In the range of the size in region is 0.6 μm~2.75 μm, with regard to larger-size in above-mentioned phase shift portion and above-mentioned non-phase-shifted portion It is above-mentioned in the case where the size of above-mentioned dark areas is set as 1 for the ratio between the size in area pellucida domain and the size of above-mentioned dark areas Area pellucida domain is preferably dimensioned to be 1.5 or more.
In addition, about dark areas and the details in area pellucida domain, it can be with the content phase illustrated in the item of following " 2. the 2nd forms " Together, so omitting explanation herein.
[manufacturing method of phase shifting mask]
It can be manufactured in the following manner with the phase shifting mask 1A constituted as described above.Fig. 4 is to indicate the 1st embodiment party of manufacture The flow chart of the step of phase shifting mask 1A of formula.
First, as shown in Fig. 4 (a), prepare the transparent substrate 2A of given size, there will be existing image display device With the size more than resolution of exposure equipment limit (for example, 3 μm), the light shielding part 5A that is made of the photomask comprising crome metal etc. It is formed in the area of the pattern 6A on transparent substrate 2A (with reference to Fig. 3).
Secondly, as shown in Fig. 4 (b), in a manner of covering transparent substrate 2A (area of the pattern 6A) and light shielding part 5A thereon, And resist layer 7A is formed, as shown in Fig. 4 (c), using laser describing device, electron beam drawing apparatus etc. to resist layer 7A It is drawn, and forms desired pattern.At this point, at least size X of phase shift portion 3A not up to via the 1st embodiment Phase shifting mask 1A exposure in the device used for image display resolution of exposure equipment limit that uses and less than non-phase-shifted portion 4A's The mode of size Y, preferably with the ratio between size X, Y of phase shift portion 3A and non-phase-shifted portion 4A be in given range (1: 1.5~1: 5.6) mode draws resist layer 7A.
Then, it as shown in Fig. 4 (d), using the resist layer 7A with given pattern as etching mask, and carries out transparent The etching process of substrate 2A.The etching process may be either using the wet etch process of the etching solutions such as hydrofluoric acid, or use The processing of the dry-etchings such as the reactive ion etching of fluorine-based gas etc..The phase in the etching portion comprising given depth d is formed as a result, Shifting portion 3A.
Finally, can be by the way that the removals of the resist layer 7A on transparent substrate 2A will be remained in as shown in Fig. 4 (e), and manufacture the The phase shifting mask 1A of 1 embodiment.
[corrosion-resisting pattern forming method]
Secondly, the method for using the phase shifting mask 1A of above first embodiment to form corrosion-resisting pattern is illustrated.Fig. 5 It is the flow chart for indicating the corrosion-resisting pattern forming method in the 1st embodiment.
First, prepare the phase shifting mask 1A of the 1st embodiment, so as to form the processed material of object as corrosion-resisting pattern Photoresist 12A (in the 1st embodiment be positive light anti-etching film) on (substrate) 11A be formed with phase shifting mask 1A The face of phase shift portion 3A etc. separate given interval and phase shifting mask 1A is arranged in the mode of opposite direction (with reference to Fig. 5 (a)).
The substrate 11A that object is formed as corrosion-resisting pattern can suitably be selected according to purposes etc., for example, if as liquid crystal The TFT substrate of display device, colored filter substrate, organic EL display device TFT substrate etc. substrate, then as should Glass substrate, plastic base, synthetic resin film etc. can be used in substrate 11A.
Secondly, the light from device used for image display exposure device (not shown) is covered via the phase shift of the 1st embodiment Mould 1A is exposed on the photoresist 12A on substrate 11A, makes photoresist 12A photosensitive (with reference to Fig. 5 (b)).At this point, The phase shift portion 3A's of the phase shifting mask 1A of 1st embodiment interferes with each other with non-phase-shifted portion 4A through light through light, thus penetrates The intensity of the irradiation light of photoresist 12A in the light path through light positioned at phase shift portion 3A, which drops to, will not enable the position The photosensitive degree of photoresist 12A intensity.Therefore, in the photoresist 12A on substrate 11A, positioned at phase shift portion Photoresist 12A in the light path through light of 3A is not photosensitive, the light being only located in the light path through light of non-phase-shifted portion 4A Cause etchant resist 12A photosensitive.
Then, using given developer solution, make the photoresist 12A developments through overexposure, be located to will only remove Corrosion-resisting pattern 13A obtained from photoresist 12A in the light path through light of non-phase-shifted portion 4A is formed on substrate 11A (with reference to Fig. 5 (c)).
According to the corrosion-resisting pattern forming method in above first embodiment, the phase shift of the phase shifting mask 1A of the 1st embodiment The size X of portion 3A is at least the not up to size of the resolution of exposure equipment limit and the size Y less than non-phase-shifted portion 4A, thus may be used The size for having and being not up to the resolution of exposure equipment limit corresponding with phase shift portion 3A is faithfully at least formed in design size Corrosion-resisting pattern.
In addition, according to the corrosion-resisting pattern forming method in the 1st embodiment, can be formed with good Sidewall angles θ (meetings Type according to photoresist etc. and change, preferably 60~90 degree, it is further preferred that be 70~90 degree) corrosion-resisting pattern 13A.From And can be in forming face the smaller corrosion-resisting pattern of scale error.
In addition, in the 1st embodiment, the Sidewall angles θ of corrosion-resisting pattern 13A comes the sides self-reference substrate 11A in corrosion-resisting pattern 10% position 13A of the height (thickness) of 13AdownWith 90% position 13A of the height (thickness) of corrosion-resisting pattern 13AupIt Between arbitrary many places (such as at 30), measure the corrosion-resisting pattern forming face of the side wall of corrosion-resisting pattern 13A relative to substrate 11A Angle is found out using least square method as average value.The angle of the side wall of corrosion-resisting pattern 13A can for example be based on scan-type Electron microscope (SEM, scanning electron microscope) image finds out any place of the side wall of corrosion-resisting pattern 13A Coordinate value, then calculated based on the coordinate value.
In this way, according to the corrosion-resisting pattern forming method in the 1st embodiment, the good resist patterns of Sidewall angles θ can be formed Case 13A, so the unevenness of the thickness (aspect ratio) for the corrosion-resisting pattern 13A being formed on substrate 11A is can inhibit, as a result, conduct Subsequent step, in the etching step for using corrosion-resisting pattern 13A as etching mask, can obtain can carry out high-precision Etching effect.
For example, as can be in order to the transparent electricity for including tin indium oxide (ITO, Indium Tin Oxides) will be used to form The corrosion-resisting pattern of pole is formed on glass substrate and an example of phase shifting mask for using, can enumerate with pattern as shown in FIG. 6 Phase shift portion 3A, non-phase-shifted portion 4A and the light shielding part 5A of composition are set to the phase shifting mask 1A in an area of the pattern 6A.
Using the large-scale exposure device for the equimultiple projection exposure optical system for having device used for image display, via Fig. 6 institutes The phase shifting mask 1A shown is exposed and develops to the positive light anti-etching film being set in the ito film on glass substrate, thus Corrosion-resisting pattern (line pattern) corresponding with phase shift portion 3A and corrosion-resisting pattern corresponding with light shielding part 5A can be formed in ito film.And And by implementing etching step to the glass substrate for being formed with the corrosion-resisting pattern, can tool be formed with high precision on the glass substrate There is the transparent electrode of the not up to size of the device used for image display large size resolution of exposure equipment limit.
In addition, the phase shifting mask 1A of the 1st embodiment also may be used other than forming the purposes of the transparent electrode comprising ITO Applied to must use have can the large-scale of equimultiple projection exposure optical system of device used for image display of large area exposure expose Electro-optical device is formed on the substrate of large area in the not up to purposes of the corrosion-resisting pattern of the size of the resolution of exposure equipment limit. As such purposes, such as can enumerate：Gate electrode, source electrode, drain electrode in the TFT substrate of liquid crystal display etc., The formation of contact hole etc.；Black matrix" on colored filter substrate will colour component and be laminated into multilayer and the stacking column that constitutes The formation etc. of (lamination spacer) etc..
It, can as the light of the exposure used in the corrosion-resisting pattern forming method using the phase shifting mask of the 1st embodiment With the phase used in the large-scale exposure device for the equimultiple projection exposure optical system for having general device used for image display Together, it is not particularly limited, preferably the mixed wavelengths light of g rays, h rays, i rays.Itself reason for this is that：By using mixed recharge Long light can increase the light exposure exposed on photoresist, can shorten the station time of the formation of corrosion-resisting pattern.In addition, its Reason for this is that：Mixed wavelengths illumination is incident upon on photoresist by the phase shifting mask via the 1st embodiment, and via upper The situation for stating the existing phase shifting mask with through portion and semi-permeable portion is compared, and can get with given thickness and spaced walls The corrosion-resisting pattern of angle.
<2nd embodiment>
[phase shifting mask]
On one side with reference to attached drawing, a phase shifting mask for facing the 2nd embodiment illustrates.
Fig. 7 is the partial cut end view drawing of the schematic configuration for the phase shifting mask for indicating the 2nd embodiment, and Fig. 8 is to indicate the 2nd The chart of the luminous intensity through light of the phase shifting mask of embodiment, Fig. 9 are the outlines for the phase shifting mask for indicating the 2nd embodiment The top partial view diagram of composition.
As shown in fig. 7, the phase shifting mask 1B of the 2nd embodiment has：Transparent substrate 2B, it is set on transparent substrate 2B The multiple phase shift portion 3B and multiple non-phase-shifted portion 4B being arranged in a manner of being adjacent to each phase shift portion 3B；And with the 1st embodiment Phase shifting mask 1A similarly, during manufacturing the image display devices such as liquid crystal display device, organic EL display device, is used In the light of the exposure of the large-scale exposure device by using the equimultiple projection exposure optical system for having the device used for image display To be not up to the resolution of exposure equipment limit (be preferably not up to 3 μm, more preferably 1.5 μm or more and not up to 3 μm, it is further preferred that Be 1.5~2 μm) the corrosion-resisting pattern of size be formed on processed material.
It as transparent substrate 2B, is not particularly limited, the transparent substrate with the phase shifting mask 1A of the 1st embodiment can be used The identical substrates of 2A.
Phase shift portion 3B is set on transparent substrate 2B, as the transparent of the given thickness t being formed on transparent substrate 2B Film and constitute.Moreover, being adjacent to the non-forming portion of hyaline membrane (exposed division of transparent substrate 2B) of multiple phase shift portion 3B becomes non-phase Shifting portion 4B.
The hyaline membrane for constituting phase shift portion 3B be by the transmitance of the light of wavelength 365nm be 80% or more, preferably 85% with Above, it is further preferred that the transparent material for 90% or more is constituted.As the transparent material, such as can enumerate：SiO, ITO, fluorine resin etc..
The size Y of the size X of phase shift portion 3B and non-phase-shifted portion 4B can be with the phase shifts of the phase shifting mask 1A of the 1st embodiment The identical modes of size Y of the size X of portion 3A and non-phase-shifted portion 4A are set.
As long as the thickness t of phase shift portion 3B be set as can to phase shift portion 3B through light assign given phase difference (170~ The phase difference of 190 degree (about 180 degree)) degree, and can according to the thickness of transparent substrate 2B, the light of exposure wavelength, It constitutes refractive index of material of transparent substrate 2B etc. and suitably sets.
If in the phase shifting mask 1B corrosion-resisting patterns to be formed using the 2nd embodiment, be existing binary The corrosion-resisting pattern that mask (photomask with the light shielding part and opening portion that are made of crome metal etc.) is just formed according to light shielding part (for example, being line pattern by the corrosion-resisting pattern of positive light anti-etching agent line to be formed and gap-like, passing through Negative type photoresist and be intended in the case of being formed be space pattern) design size not up to used in image display device In the case of with the resolution of exposure equipment limit, in the phase shifting mask 1B of the 2nd embodiment, including it is used to form the resist pattern The phase shift portion 3B of case.On the other hand, if the design size of the corrosion-resisting pattern is the above-mentioned resolution of exposure equipment limit or more, In the phase shifting mask 1B of 2nd embodiment, including it is used to form being made of the photomask comprising crome metal etc. for the corrosion-resisting pattern Light shielding part 5B.
In the phase shifting mask 1B of the 2nd embodiment, phase shift portion 3B and non-phase-shifted portion 4B are set on transparent substrate 2B In area of the pattern 6B (with reference to Fig. 9).Area of the pattern 6B according to use the phase shifting mask 1B of the 2nd embodiment on being processed material The corrosion-resisting pattern to be formed and be set at least one region on transparent substrate 2B, no matter the exposure side of above-mentioned exposure device Formula is how, at least in the entire surface in an area of the pattern 6B, irradiation light by single exposure.
As shown in figure 9, in the phase shifting mask 1B of the 2nd embodiment, multiple pattern areas are set on transparent substrate 2B Domain 6B also can only be set there are one area of the pattern 6B.In addition, in phase shifting mask 1B shown in Fig. 9, omit in area of the pattern 6B Phase shift portion 3B, non-phase-shifted portion 4B and light shielding part 5B diagram.
The size of area of the pattern 6B can be filled according to using the phase shifting mask 1B of the 2nd embodiment images to be manufactured to show Exposure mode or 1 area that can be exposed of the size (picture dimension), used exposure device set etc. and suitably set, and It is to be set for substantially rectangular shape (or substantially square shape) region of 300mm or more as short side (one side).
In addition, in an area of the pattern 6B, it can both be formed with the structure being used to form in an image display device At pattern, can also be formed with the pattern being used to form for the composition in multiple images display device.
In addition, in the 2nd embodiment, in area of the pattern 6B, other than phase shift portion 3B and non-phase-shifted portion 4B, also set It is equipped with the size more than above-mentioned resolution of exposure equipment limit, the light shielding part that is made of the photomask comprising crome metal etc. 5B, but be not arranged and constituted with the not up to size of the above-mentioned resolution of exposure equipment limit, by the photomask comprising crome metal etc. Light shielding part.That is, the phase shifting mask 1B of the 2nd embodiment is referred to as so-called chromeless phase shift mask.If in area of the pattern 6B The size of light shielding part 5B be not up to the resolution of exposure equipment limit, then be adjacent to the phase shift portion 3B or non-phase-shifted of light shielding part 5B Portion 4B's can be to the lower section detour of light shielding part 5B through light, and can not play shade function.
In addition, in the phase shifting mask 1B of the 2nd embodiment shown in Fig. 7, including the transparent material with composition phase shift portion 3B Expect that identical material, size can also be completely covered the mode of light shielding part 5B slightly larger than the hyaline membrane of the size of light shielding part 5B and set It sets (1 (f) referring to Fig.1).In this way, light shielding part 5B by transparent plastic mulching, is thus adjacent to the feelings of light shielding part 5B in non-phase-shifted portion 4B , can be by the light for being endowed given phase difference of the boundary portion through non-phase-shifted portion 4B and light shielding part 5B under condition, increasing should The contrast of the irradiation light of boundary portion, so the edge shape of the corrosion-resisting pattern formed according to light shielding part 5B can be made good.
By using the phase shifting mask 1B of the 2nd embodiment, can make by the light of the exposure from above-mentioned exposure device The Sidewall angles θ (referring to Fig.1 2) of the corrosion-resisting pattern of formation is good, and (Sidewall angles θ can become according to type of photoresist etc. It is dynamic, preferably 60~90 degree, it is further preferred that being 70~90 degree).This situation means that the phase shift by via the 2nd embodiment can be reduced The exposure of mask 1B and the unevenness in the corrosion-resisting pattern forming face of the thickness (aspect ratio) of corrosion-resisting pattern that is formed.To, according to The phase shifting mask 1B of 2nd embodiment can also form tool even with the large-scale exposure device of existing device used for image display There are the size of the not up to above-mentioned resolution of exposure equipment limit and the smaller resist pattern of scale error in corrosion-resisting pattern forming face Case.
[manufacturing method 1 of phase shifting mask]
It can be manufactured in the following manner with the phase shifting mask 1B constituted as described above.Figure 10 is to indicate that manufacture the 2nd is implemented The flow chart of an example of the step of phase shifting mask 1B of mode.
First, as shown in Figure 10 (a), prepare the transparent substrate 2B of given size, there will be existing image display dress It sets with the size more than resolution of exposure equipment limit (for example, 3 μm), the light shielding part that is made of the photomask comprising crome metal etc. 5B is formed in the area of the pattern 6B on transparent substrate 2B (with reference to Fig. 9).
Secondly, as shown in Figure 10 (b), to cover the side of transparent substrate 2B (area of the pattern 6B) and light shielding part 5B thereon Formula, and resist layer 7B is formed, as shown in Figure 10 (c), using laser describing device, electron beam drawing apparatus etc. to the resist Layer 7B is drawn, and forms desired pattern.At this point, not up to being implemented via the 2nd at least size X of phase shift portion 3B The device used for image display resolution of exposure equipment limit that is used in the exposure of the phase shifting mask 1B of mode and it is less than non-phase-shifted portion The mode of the size Y of 4B, preferably with the ratio between size X, Y of phase shift portion 3B and non-phase-shifted portion 4B be in given range (1: 1.5~ 1: 5.6) mode draws resist layer 7B.
Then, it as shown in Figure 10 (d), on the resist layer 7B with given pattern, is formed comprising composition phase shift portion The hyaline membrane 30B of the transparent material (ITO etc.) of 3B.At this point, the thickness for being formed by hyaline membrane 30B becomes the thickness of phase shift portion 3B T, can be to the hyaline membrane of the thickness of the degree for assigning given phase difference (about 180 degree) through light of phase shift portion 3B so being formed 30B。
It finally, can be by the way that resist layer 7B and the resist layer on transparent substrate 2B will be remained in as shown in Figure 10 (e) Hyaline membrane 30B removals on 7B, and manufacture the phase shifting mask 1B of the 2nd embodiment.
[manufacturing method 2 of phase shifting mask]
The phase shifting mask 1B of 2nd embodiment, can also following manner manufacture other than above-mentioned method shown in Fig. 10. Figure 11 is another flow chart the step of indicating the phase shifting mask 1B of the 2nd embodiment of manufacture.
First, as shown in Figure 11 (a), prepare the transparent substrate 2B of given size, there will be existing image display dress It sets with the size more than resolution of exposure equipment limit (for example, 3 μm), the light shielding part that is made of the photomask comprising crome metal etc. 5B is formed in the area of the pattern 6B on transparent substrate 2B (with reference to Fig. 9).
Secondly, as shown in Figure 11 (b), to cover the side of transparent substrate 2B (area of the pattern 6B) and light shielding part 5B thereon Formula, and form the hyaline membrane 30B for including the transparent material (ITO etc.) for constituting phase shift portion 3B.At this point, being formed on transparent substrate 2B The thickness of hyaline membrane 30B become the thickness t of phase shift portion 3B, so given phase can be assigned through light to phase shift portion 3B by being formed The hyaline membrane 30B of the thickness of the degree of potential difference (about 180 degree).
Then, as shown in Figure 11 (c), resist layer 7B is formed in a manner of covering hyaline membrane 30B, such as Figure 11 (d) institutes Show, resist layer 7B is drawn using laser describing device, electron beam drawing apparatus etc., and forms desired figure Case.At this point, being so as to be equivalent to the resist layer 7B of the position of phase shift portion 3B and the resist layer 7B remainings on light shielding part 5B Mode draws resist layer 7B.In addition, on light shielding part 5B, size is preferably made to be slightly larger than the size of light shielding part 5B Resist layer 7B remaining.
Then, as shown in Figure 11 (e), using the resist layer 7B with given pattern as etching mask, to hyaline membrane 30B is etched, and forms phase shift portion 3B.The etching process may be either using the wet etch process of the etching solutions such as hydrofluoric acid, Or it is handled using dry-etchings such as the reactive ion etchings of fluorine-based gas etc..
Finally, can be by the way that the removals of the resist layer 7B on hyaline membrane 30B will be remained in as shown in Figure 11 (f), and manufacture the The phase shifting mask 1B of 2 embodiments.
[corrosion-resisting pattern forming method]
Secondly, the method for using the phase shifting mask 1B of above-mentioned 2nd embodiment to form corrosion-resisting pattern is illustrated.Figure 12 It is the flow chart for indicating the corrosion-resisting pattern forming method in the 2nd embodiment.
First, prepare the phase shifting mask 1B of the 2nd embodiment, so as to form the processed material of object as corrosion-resisting pattern Photoresist 12B (in the 2nd embodiment be positive light anti-etching film) on (substrate) 11B be provided with phase shifting mask 1B The face of phase shift portion 3B etc. separate given interval and phase shifting mask 1B (2 (a) referring to Fig.1) is arranged in the mode of opposite direction.
The substrate 11B that object is formed as corrosion-resisting pattern can suitably be selected according to purposes etc., for example, if as liquid crystal The TFT substrate of display device, colored filter substrate, organic EL display device TFT substrate etc. substrate, then as should Glass substrate, plastic base, synthetic resin film etc. can be used in substrate 11B.
Secondly, the light from device used for image display exposure device (not shown) is covered via the phase shift of the 2nd embodiment Mould 1B is exposed on the photoresist 12B on substrate 11B, makes photoresist 12B photosensitive (2 (b) referring to Fig.1).At this point, The phase shift portion 3B's of the phase shifting mask 1B of 2nd embodiment interferes with each other with non-phase-shifted portion 4B through light through light, thus penetrates The intensity of the irradiation light of photoresist 12B in the light path through light positioned at phase shift portion 3B, which drops to, will not enable the position The photosensitive degree of photoresist 12B luminous intensity.Therefore, in the photoresist 12B on substrate 11B, it is located at phase shift Photoresist 12B in the light path through light of portion 3B is not photosensitive, is only located in the light path through light of non-phase-shifted portion 4B Photoresist 12B is photosensitive.
Then, using given developer solution, make the photoresist 12B developments through overexposure, be located to will only remove Corrosion-resisting pattern 13B obtained from photoresist 12B in the light path through light of non-phase-shifted portion 4B is formed on substrate 11B (2 (c) referring to Fig.1).
According to the corrosion-resisting pattern forming method in above-mentioned 2nd embodiment, the phase shift of the phase shifting mask 1B of the 2nd embodiment The size X of portion 3B is at least the not up to size of the resolution of exposure equipment limit and the size Y less than non-phase-shifted portion 4B, thus may be used The size for having and being not up to the resolution of exposure equipment limit corresponding with phase shift portion 3B is faithfully at least formed in design size Corrosion-resisting pattern.
In addition, according to the corrosion-resisting pattern forming method in the 2nd embodiment, can be formed with (the sides good Sidewall angles θ Wall angle, θ can change, preferably 60~90 degree according to type of photoresist etc., it is further preferred that be 70~90 degree) resist pattern Case 13B.To the smaller corrosion-resisting pattern 13B of scale error that can be in forming face.
In addition, in the 2nd embodiment, the Sidewall angles θ of corrosion-resisting pattern 13B comes the sides self-reference substrate 11B in corrosion-resisting pattern 10% position 13B of the height (thickness) of 13BdownWith 90% position 13B of the height (thickness) of corrosion-resisting pattern 13BupIt Between arbitrary many places (such as at 30), measure the corrosion-resisting pattern forming face of the side wall of corrosion-resisting pattern 13B relative to substrate 11B Angle is found out using least square method as average value.The angle of the side wall of corrosion-resisting pattern 13B, such as SEM can be based on and schemed As the coordinate value of any place for the side wall for finding out corrosion-resisting pattern 13B, then calculated based on the coordinate value.
In this way, according to the corrosion-resisting pattern forming method in the 2nd embodiment, the good resist patterns of Sidewall angles θ can be formed Case 13B, so the unevenness of the thickness (aspect ratio) for the corrosion-resisting pattern 13B being formed on substrate 11B is can inhibit, as a result, conduct Subsequent step, in the etching step for using corrosion-resisting pattern 13B as etching mask, can obtain can carry out high-precision Etching effect.
For example, as can be in order to the corrosion-resisting pattern for being used to form the transparent electrode comprising ITO be formed on glass substrate And an example of the phase shifting mask used, phase shift portion 3B, non-phase-shifted portion 4B and the screening constituted with pattern as shown in FIG. 6 can be enumerated Light portion 5B is set to the phase shifting mask 1B in an area of the pattern 6B.
Using the large-scale exposure device for the equimultiple projection exposure optical system for having device used for image display, via Fig. 6 institutes The phase shifting mask 1B shown is exposed and develops to the positive light anti-etching film being set in the ito film on glass substrate, thus Corrosion-resisting pattern (line pattern) corresponding with phase shift portion 3B and corrosion-resisting pattern corresponding with light shielding part 5B can be formed in ito film.And And by implementing etching step to the glass substrate for being formed with the corrosion-resisting pattern, can tool be formed with high precision on the glass substrate There is the transparent electrode of the not up to size of the device used for image display large size resolution of exposure equipment limit.
In addition, the phase shifting mask 1B of the 2nd embodiment also may be used other than forming the purposes of the transparent electrode comprising ITO Applied to must use have can the large-scale of equimultiple projection exposure optical system of device used for image display of large area exposure expose Electro-optical device and on the substrate of large area formed be not up to the resolution of exposure equipment limit size corrosion-resisting pattern purposes On.As such purposes, such as can enumerate：Gate electrode, source electrode, drain electrode electricity in the TFT substrate of liquid crystal display etc. The formation of pole, contact hole etc.；Black matrix" on colored filter substrate will colour component and be laminated into multilayer and the stacking that constitutes The formation etc. of column (lamination spacer) etc..
It, can as the light of the exposure used in the corrosion-resisting pattern forming method using the phase shifting mask of the 2nd embodiment It is identical as in the large-scale exposure device for the equimultiple projection exposure optical system for having general device used for image display, not It is particularly limited to, preferably the mixed wavelengths light of g rays, h rays, i rays.In addition, about reason, it can be with above-mentioned 1st embodiment party Content illustrated in the item of formula is identical, so omit explanation herein.
<The phase shifting mask of 1st form>
In above-mentioned 1st and the 2nd embodiment, the size X of phase shift portion 3A, 3B of phase shifting mask 1A, 1B are less than non-phase-shifted The size Y of portion 4A, 4B, phase shift portion 3A, 3B play the effect of the light shielding part as existing binary mask, but the present invention and unlimited Due to size Xs of the size Y of such form or non-phase-shifted portion 4A, 4B less than phase shift portion 3A, 3B, non-phase-shifted portion 4A, 4B hair Wave the effect of the light shielding part as existing binary mask.In this case, the size Y of at least non-phase-shifted portion 4A, 4B are not reach To the large-scale resolution of exposure equipment limit of the used equimultiple projection exposure optical system for having device used for image display The ratio between size X, Y of size, phase shift portion 3A, 3B and non-phase-shifted portion 4A, 4B is preferably 1.5: 1~5.6: 1, more preferably 1.8: 1~4 : 1, it is further preferred that being 1.8: 1~3: 1.Moreover, the size X for being adjacent to phase shift portion 3A, 3B of non-phase-shifted portion 4A, 4B is according to be intended to shape At corrosion-resisting pattern design size and suitably set, as long as more than non-phase-shifted portion 4A, 4B size Y, then may be either not reach To more than the above-mentioned resolution of exposure equipment limit or resolution limit.
In above-mentioned 1st and the 2nd embodiment, in area of the pattern 6A, 6B of phase shifting mask 1A, 1B, it is provided with by wrapping Photomask containing crome metal etc. and light shielding part 5A, the 5B constituted, but the present invention is not limited to such forms, by by shading The design size of the corrosion-resisting pattern of formation is not up to the used equimultiple projection exposure optical system for having device used for image display In the case of the large-scale resolution of exposure equipment limit of system, it is not necessary that light shielding part 5A, 5B are arranged in the area of the pattern 6A, 6B, and As long as being provided with phase shift portion 3A, 3B (non-phase-shifted portion 4A, 4B) in a manner of corresponding with this corrosion-resisting pattern.
The method of phase shifting mask 1A, 1B as the 1st and the 2nd embodiment of manufacture, list and are being formed with by comprising gold Belong to the example of the method for setting phase shift portion 3A, 3B on transparent substrate 2A, 2B of light shielding part 5A, 5B of the photomask composition of chromium etc., But other than such form, for example, it is also possible to after transparent substrate 2A, 2B form phase shift portion 3A, 3B, formed by including gold The mode for belonging to light shielding part 5A, 5B of the photomask composition of chromium etc. is set.
2. the 2nd form
The phase shifting mask of the 2nd form of the present invention has：Transparent substrate, the concavity being set on above-mentioned transparent substrate or convex The phase shift portion of shape and the non-phase-shifted portion for being adjacent to above-mentioned phase shift portion, it is characterised in that：Above-mentioned phase shift portion makes to penetrate above-mentioned phase shift Phasing back of the phase of the light of the exposure in portion relative to the light of the exposure through above-mentioned non-phase-shifted portion；By above-mentioned phase shift portion and on It states the size smaller in non-phase-shifted portion to use as dark areas, by the size in above-mentioned phase shift portion and above-mentioned non-phase-shifted portion The greater is used as area pellucida domain；In the range of the size of above-mentioned dark areas is 0.6 μm~2.75 μm, with regard to the ruler in above-mentioned area pellucida domain For the ratio between very little and above-mentioned dark areas size, in the case where the size of above-mentioned dark areas is set as 1, the ruler in above-mentioned area pellucida domain Very little is 1.5 or more；The size of above-mentioned phase shifting mask is 330mm × 450mm or more.
In the 2nd form, so-called " phase shift portion makes the phase of the light of the exposure through phase shift portion relative to through non-phase-shifted portion Exposure light phasing back " refer to so that the light (phase shift portion penetrates light) of exposure through phase shift portion is non-phase-shifted with transmission The phase difference of the light (non-phase-shifted portion penetrates light) of the exposure in portion becomes the phase that can make two degree offseted through light interference The mode of potential difference adjusts the phase in phase shift portion.More specifically, with the transmission light through light and non-phase-shifted portion in above-mentioned phase shift portion The mode that is in the range of 180 ° ± 10 ° of phase difference adjust the phase in phase shift portion.In the 2nd form, above-mentioned phase difference is more In the range of 180 ° ± 5 °, it is further preferred that being 180 °.
In addition, the light of the exposure used together in the phase shifting mask with the 2nd form is the mixing of g rays, h rays, i rays In the case of wavelength light, preferably with the phase through light through light and the i rays in non-phase-shifted portion of the i rays in above-mentioned phase shift portion Potential difference meets the mode of above-mentioned relation, adjustment phase shift portion.
The concrete example of phase shifting mask as the 2nd form can enumerate Fig. 1 illustrated in the item of above-mentioned " 1. the 1st form " And Fig. 7 etc..In the 2nd form, in phase shifting mask 1A shown in Fig. 1, using as the phase shift portion 3A in etching portion as dark areas It uses, non-phase-shifted portion 4A is used as area pellucida domain.In addition, in phase shifting mask 1B shown in Fig. 7, by what is be made of hyaline membrane Phase shift portion 3B is used as dark areas, and non-phase-shifted portion 4B is used as area pellucida domain.
According to the 2nd form, the size of above-mentioned dark areas and the size in area pellucida domain have above-mentioned size, thus can be used existing Image display device exposure device for making, on the processed material of transparent substrate etc., with high precision formed have not up to The given pattern of the size of the resolution of exposure equipment limit.
In addition, in the phase shifting mask of the 2nd form, can with it is above-mentioned include through it is existing including portion and semi-permeable portion Compare more good precision of phase shifting mask forms corrosion-resisting pattern.Though hereinafter, not being illustrated but can push away as follows about its reason It surveys.
Herein, as described above, there is through portion by what is used in the manufacturing process of the semiconductor devices such as existing LSI And the phase shifting mask in semi-permeable portion is applied in the photomask in the manufacturing process of image display device, and pass through existing image In the case that display device exposure device for making is exposed and develops, although the size of the corrosion-resisting pattern of gained can be made not reach To resolution limit, but it can become smaller due to the thickness of corrosion-resisting pattern or the side of sidewall portion of corrosion-resisting pattern becomes smaller, and there are corrosion-resisting patterns Not the problem of not playing the function as etching mask or the problem of can not be etched with high precision.It is such about leading to the problem of The reasons why, it can speculate as follows.
That is, photomask (6 inches of ratios of the photomask of image display device manufacture and common use in semiconductor manufacturing apparatus Example photomask) it compares, size is larger.In addition, with the enlargement of image display device in recent years, device used for image display Photomask it is further enlargement also constantly promote.As the size difference of the two, specifically, relative to 6 inches of ratios Cornerwise length of photomask is 215mm, and the photomask of device used for image display is 495mm~1856mm or so.Therefore, The photomask of device used for image display has relative to 6 inches of ratio photomasks is expressed as 2.3 times~8.6 times with the ratio between diagonal line Size, in turn, have with draw the manufacturing costs such as time, review time direct correlation area ratio be expressed as 4.4 times~ 72 times of area.
Therefore, in the equimultiple projection exposure using existing image display device exposure device for making, in order to use The photomask of above-mentioned device used for image display is exposed with the short period may require that big light quantity, so the light as exposure, example Such as, it is preferable to use g rays, the mixed wavelengths light of h rays, i rays.Specifically, for being 300mm or more with one side Area of the pattern photomask or photomask size be 330mm × 450mm or more photomask, in manufacturing condition, Preferably use the mixed wavelengths light of g, h, i ray.
On the other hand, in the manufacturing process of semiconductor device, in order to improve exposure resolution ratio, as the light of exposure, example Such as, it is preferred to use the single wavelength light of the short wavelength sides such as i rays, KrF rays (248nm), ArF rays (193nm), i.e., it is parallel The more light of light component.Therefore, the phase shifting mask used in the manufacturing process of semiconductor is generally for through portion and semi-permeable Portion, the adjustment phase place on the basis of the single wavelength light of short wavelength side.
Thus speculate：It is adjusted by light (the single wavelength light of short wavelength side) more relative to parallel component as described above Phase shifting mask in the manufacturing process of the semiconductor device of through portion and the phase in semi-permeable portion is applied to using above-mentioned parallel In the case of photomask in the manufacturing process of the image display device of the less light of light component (mixed wavelengths light), above-mentioned phase shift The through portion of mask is easy to the underface detour to semi-permeable portion through light, to not offset the transmission light in semi-permeable portion thoroughly Ground irradiates the light of the exposure for the degree for keeping above-mentioned photoresist photosensitive on photoresist corresponding with semi-permeable portion.Its As a result, thus it is speculated that：The thickness of the corrosion-resisting pattern of gained becomes smaller or the side of sidewall portion of corrosion-resisting pattern becomes smaller.
On the other hand, the phase shifting mask of the 2nd form is by the different phase shift portion of the size of dark areas and area pellucida domain and non-phase Shifting portion is constituted, so two regions have the transmitance of the light of same exposure, and the phasing back through light in each region.By This speculates：It is incident upon above-mentioned mixed wavelengths light as the illumination of exposure on photoresist in the phase shifting mask via the 2nd form In the case of, it can make to penetrate light more than existing semi-permeable portion through light in dark areas, so can fully offset to dark The area pellucida domain of region detour penetrates light (detour light), makes to can inhibit to irradiate on photoresist corresponding with dark areas The situation of the light of the exposure of the photosensitive degree of above-mentioned photoresist.
Hereinafter, being illustrated to the details of the phase shifting mask of the 2nd form.
[phase shifting mask]
The phase shifting mask of 2nd form is using the size smaller in above-mentioned phase shift portion and above-mentioned non-phase-shifted portion as dark areas It uses, size the greater in above-mentioned phase shift portion and above-mentioned non-phase-shifted portion is used as area pellucida domain.In addition, its feature exists In：The size of dark areas has specified value with the size in area pellucida domain.
In addition, making resist pattern exposing the photoresist on processed material using the phase shifting mask of the 2nd form In the case of case, dark areas is and (is not made photic by the region of the corresponding phase shifting mask in photosensitive region in photoresist The region of etchant resist exposure), area pellucida domain is (to make light by the region of the corresponding phase shifting mask in photosensitive region with photoresist Cause the region of etchant resist exposure).
The phase shifting mask of 2nd form is characterized in that：In the range of the size of above-mentioned dark areas is 0.6 μm~2.75 μm. Above-mentioned dark areas is usually the size of the not up to resolution of exposure equipment limit.
As the size of specific dark areas, according to the purposes etc. of the pattern form of dark areas, the phase shifting mask of the 2nd form And suitably select, it is not particularly limited, in the range of more preferably 0.8 μm~2.5 μm, it is further preferred that for 1.0 μm~2.0 μm of range It is interior.
More specifically, excellent as the size (line width) of dark areas in the case where the pattern form of dark areas is linear It is selected as 0.6 μm or more, more preferably 0.8 μm or more, it is further preferred that being 1.0 μm or more.In addition, the size (line width) as dark areas, excellent Be selected as 2.05 μm hereinafter, more preferably 2.0 μm hereinafter, it is further preferred that be 1.9 μm or less.
In addition, the pattern form of dark areas be square shape in the case of, as dark areas size (square it is short The width of edge direction), preferably 1.3 μm or more, more preferably 1.4 μm or more, it is further preferred that being 1.6 μm or more.In addition, as dark areas Size (width of the short side direction of square), preferably 2.75 μm hereinafter, more preferably 2.5 μm hereinafter, it is further preferred that for 2.3 μm with Under.
Its reason is：In the case where the size of dark areas is discontented with above-mentioned value, exist anti-through phase through dark areas The light turned can offset from area pellucida domain detour and the light quantity of light that arrives because that can not obtain therefore can not obtain good corrosion-resisting pattern shape Possibility.
In addition, its reason is：In the case where the size of dark areas is more than above-mentioned value, in the phase shift using the 2nd form For mask come in the case of exposing photoresist, the quantitative change through light of dark areas is more, making through light for dark areas is photic anti- Film exposure is lost, so there is a possibility that the central portion of corrosion-resisting pattern corresponding with dark areas is exposed.
In addition, in the phase shifting mask of the 2nd form, it is characterised in that：Size with regard to above-mentioned area pellucida domain and above-mentioned dark areas The ratio between size for, in the case where the size of above-mentioned dark areas is set as 1, the size in above-mentioned area pellucida domain is 1.5 or more.
As the size in above-mentioned area pellucida domain, as long as with the ratio between the size of dark areas more than above-mentioned value, to may be either not Reach the size of the size or resolution limit of resolution limit or more.About the size in specific area pellucida domain, can make The ratio between itself and the size of dark areas are the mode of above-mentioned value or more, are suitably determined according to various pattern forms.
The phase shifting mask of 2nd form is characterized in that：Its size is 330mm × 450mm or more.By making phase shifting mask Size is above-mentioned value or more, can manufacture the image display device of the composition with fine.
In addition, the size as the 2nd phase shifting mask, can suitably select according to its purposes etc., for example, may be set to 330mm × 450mm~1600mm × 1800mm or so.
The transparent substrate of phase shifting mask about the 2nd form, phase shift portion, non-phase-shifted portion and other compositions, can with it is above-mentioned Content illustrated in the item of " 1. the 1st form " is identical, so omit explanation herein.
In addition, in the phase shifting mask of the 2nd form, it also may include the ruler with the not up to resolution of exposure equipment limit Light shielding part that is very little, being made of the photomask of crome metal etc..As such light shielding part, for example, can be used as in phase shifting mask pair The amendment that the mask pattern being made of the light shielding part more than area pellucida domain, dark areas and resolution of exposure equipment limit is modified Pattern and be preferably used.
About the size and pattern form etc. for correcting pattern, can be filled according to the purposes and exposure of the phase shifting mask of the 2nd form It sets etc. and suitably selects.
[manufacturing method of phase shifting mask]
The manufacturing method of phase shifting mask about the 2nd form, can be with the phase shift illustrated in the item of above-mentioned " 1. the 1st form " The content of the manufacturing method of mask is identical, so omit explanation herein.
[corrosion-resisting pattern forming method]
About the corrosion-resisting pattern forming method for the phase shifting mask for using the 2nd form, in addition to use the mask of the 2nd form with Outside, other can be identical as the content of corrosion-resisting pattern forming method illustrated in the item of above-mentioned " 1. the 1st form ", so omit this The explanation at place.
The implementation described above is recorded to make the understanding of the present invention become easy, and is not intended to limit this It invents and records.To which the purport of each element disclosed in the above embodiment is：Also include the technology for belonging to the present invention All design alterations in range or equipollent.
[embodiment]
Hereinafter, bys embodiment etc., the present invention will be described in detail, but the present invention is not by following implementations Example is equal and any way limited.
[test example 11
The phase shift portion for being 1 μm via the size being made of etching portion and size be 3 μm non-phase-shifted portion alternately side by side and At the pattern with line and gap-like phase shifting mask (embodiment 1), the case where exposing the photoresist being processed on material Under, the luminous intensity of the light (irradiation light) on the photoresist is exposed to by emulating to find out through phase shifting mask.
The emulation is carried out with simulation software using photoetching, as the conditions of exposure in emulation, uses liquid crystal display With large-scale exposure machine (resolution limit：3.5 μm, NA：0.083, coherence factor：0.75), light source be set as 365nm, 405nm and 3 kinds of wavelength mixing light sources of 436nm.In addition, the setting as phase shift, sets using the light of the exposure of wavelength 365nm as benchmark And phasing back 180 degree, the transmitance of the light of the exposure of phase shifting mask are set as 100%.In addition, as resist, eurymeric is used (AZ companies manufacture photoresist A, ProductName；AZ1500).
It the results are shown in Table 1.In addition, in table 1, Average indicates " the irradiation luminous intensity of directive photoresist Arithmetic mean of instantaneous value ", Max indicate " maximum value of the irradiation luminous intensity of directive photoresist ", Min indicate " directive it is photic resists Lose the minimum value of the irradiation luminous intensity of film ", Contrast indicates " difference of Max and Min ".
In addition, using having other than phase shift portion to be altered to the light shield layer comprising crome metal other and embodiment 1 The binary mask (comparative example 1) of identical composition is exposed the photoresist being processed on material via the binary mask In the case of, the luminous intensity of the irradiation light of the directive photoresist is found out by emulation similarly to Example 1.Result is closed And it is shown in table 1.
In turn, using in addition to phase shift portion is altered to the phase that the transmitance being set on transparent substrate 2A is 5% Move half-tone type (Halftone type) phase shifting mask (comparative example 2) of other compositions same as Example 1 other than film, warp By the half-tone type phase shift mask, in the case of being exposed to the photoresist being processed on material, similarly to Example 1 The luminous intensity of the irradiation light of the directive photoresist is found out by emulation.Result merging is shown in table 1.
[table 1]
Embodiment 1 Comparative example 1 Comparative example 2
Average 34.9 58.2 51.4
Max 60.0 76.9 72.6
Min 12.0 40.8 31.7
Contrast 48.0 36.1 40.9
As shown in table 1, it confirms：With existing binary mask (comparative example 1) or half-tone type phase shift mask (comparative example 2) It compares, the phase shifting mask of embodiment 1 can be such that the minimum value (Min) of the irradiation luminous intensity of directive photoresist significantly reduces.It should It is photic in the light path through light in phase shift portion that the minimum value (Min) of the irradiation luminous intensity of directive photoresist is that directive is located at The intensity of the irradiation light of etchant resist can make the shaded effect in phase shift portion excellent so according to the phase shifting mask of embodiment 1.
In addition, confirming：Compared with existing binary mask (comparative example 1) or half-tone type phase shift mask (comparative example 2), The phase shifting mask of embodiment 1 can make the difference of the maximum value (Max) and minimum value (Min) of the irradiation luminous intensity of directive photoresist (Contrast) is divided to significantly increase.The the difference (Contrast) the big more can improve resolution ratio, so think according to embodiment 1 Phase shifting mask can form corrosion-resisting pattern with high-resolution.
[test example 2]
The emulation being distributed by resist is to the binary mask and ratio by phase shifting mask, comparative example 1 via embodiment 1 Corrosion-resisting pattern (the line pattern size formed compared with the exposure of the half-tone type phase shift mask of example 2：2 μm, space pattern size：2μ M) it is compared.It the results are shown in Table 2.In addition, with emulate relevant condition (with simulation software, exposure device, phase shift, The relevant condition such as resist) etc. it is identical as test example 1.It the results are shown in Table 2.
[table 2]
Embodiment 1 Comparative example 1 Comparative example 2
Resist angle (deg) 71.88 < 50.0 58.7
Light exposure (mJ/cm2) 88.0 63.0 68.0
As shown in table 2, it confirms：With existing binary mask (comparative example 1) or half-tone type phase shift mask (comparative example 2) It compares, according to the phase shifting mask of embodiment 1, the Sidewall angles of corrosion-resisting pattern can be made to significantly increase.To pass through embodiment 1 Phase shifting mask and the Sidewall angles of corrosion-resisting pattern that are formed are larger, the thus big face in the manufacturing process of image display device etc. When long-pending exposure, position that can be in optic placode and to inhibit the phenomenon that corrosion-resisting pattern shape etc. upper generate it is uneven.
In addition, in phase shifting mask, the binary mask of comparative example 1 and the half-tone type phase shift of comparative example 2 using embodiment 1 Mask and in the corrosion-resisting pattern of line and gap-like that is formed, the size and space pattern size of line pattern are 2 μm.
[test example 3]
Using having other and implementation other than changing the size in phase shift portion and non-phase-shifted portion in a manner of shown in table 3 The phase shifting mask (embodiment 2~8) of 1 identical composition of example, by the exposure via the phase shifting mask, by changing exposure respectively Condition and form intended size (line pattern size：2 μm, space pattern size：2 μm) corrosion-resisting pattern in the case of, with experiment Example 2 is compared likewise by the emulation that resist is distributed.It the results are shown in Table 3.In addition, using the phase of embodiment 1 Move mask and the distribution of corrosion-resisting pattern that is formed also merges and is shown in table 3.
[table 3]
As shown in table 3, it confirms：By the way that the ratio between the size Y of the size X in phase shift portion and non-phase-shifted portion (X: Y) is set as 1 : 1.5~1: 5.6, the corrosion-resisting pattern with good Sidewall angles θ can be formed.Especially confirm：By the way that this is set than (X: Y) It is set to 1: 1.8~1: 4, the corrosion-resisting pattern (Examples 1 to 4, embodiment 6) with more good Sidewall angles θ can be formed, leads to It crosses and is set as 1: 1.8~1: 3, the corrosion-resisting pattern (Examples 1 to 3) with particularly good Sidewall angles θ can be formed.
In addition, for Examples 1 to 8, to obtain 4 μm of spacing dimension, 2 μm of line pattern size, 2 μm of space pattern size Line and the mode of corrosion-resisting pattern of space pattern set light exposure.
[test example 4]
The emulation being distributed likewise by resist with test example 2 has to using in addition to changing in a manner of shown in the table 4 The phase shifting mask (embodiment 9) of other compositions same as Example 1 other than the size in phase shift portion and non-phase-shifted portion, by via The exposure of the phase shifting mask and the corrosion-resisting pattern that is formed are compared.It the results are shown in Table 4.In addition, using embodiment 1 Phase shifting mask and the distribution of corrosion-resisting pattern that is formed, which also merge, to be shown in table 4.
[table 4]
As shown in table 4, it confirms：Even if total (X+Y) of the size X in the phase shift portion and size Y in non-phase-shifted portion is not up to The resolution of exposure equipment limit (being 3.5 μm in test example 4) can also form corrosion-resisting pattern (embodiment 9), pass through total (X+ Y it is) the resolution of exposure equipment limit or more, the corrosion-resisting pattern (embodiment 1) with good resist angle, θ can be formed.
[test example 5]
In addition to the positive light anti-etching agent A in test example 2 is altered to other positive light anti-etching agents B, (Tokyo should change public affairs Department's manufacture, ProductName：Ip3600) other than other similarly, by resist be distributed emulation to by via embodiment 1 The exposure of the half-tone type phase shift mask each of phase shifting mask, the binary mask of comparative example 1 and comparative example 2 and the resist pattern formed Case is compared.It the results are shown in Table 5.
[table 5]
As shown in table 5, it confirms：Be formed by corrosion-resisting pattern Sidewall angles θ can according to the type of photoresist and It changes, but by using the phase shifting mask of embodiment 1 in any photoresist, can be formed with two with comparative example 1 The half-tone type phase shift mask of first mask and comparative example 2 compares the corrosion-resisting pattern of more good Sidewall angles θ.
[test example 6]
Via by phase that there is size shown in following table 6, being made of the etching portion of square shape (referring to Fig.1 3) Shifting portion is as dark areas, the phase shifting mask that non-phase-shifted portion is used as area pellucida domain (embodiment 10~12, reference example 1~3), exposes Light be processed material on photoresist in the case of, by resist be distributed emulation find out formed by exposure it is against corrosion Pattern.In addition, with relevant condition (with the relevant condition such as simulation software, exposure device, phase shift, resist) etc. and examination is emulated It is identical to test example 1.In addition, about light exposure, become respectively in a manner of obtaining the size of corrosion-resisting pattern shown in following table 6 More.
In addition, Figure 13 is for the dark areas and the figure that illustrates of area pellucida domain to the phase shifting mask in test example 6.Separately Outside, indicate that dark areas is the example of 1 square shape (isolated square) in fig. 13.In addition, the size of dark areas is figure Distance shown in W1 in 13.
[table 6]
As shown in table 6, it confirms：In embodiment 10~12, Sidewall angles θ can be made good.
[test example 7]
Via the phase shift portion being made of the etching portion of wire shaped (referring to Fig.1 4) that will there is size shown in following table 7 The phase shifting mask (embodiment 13~14, reference example 4~5) used as area pellucida domain as dark areas, using non-phase-shifted portion exposes quilt In the case of processing the photoresist on material, the resist pattern formed by exposure is found out by the emulation that resist is distributed Case.In addition, with relevant condition (with the relevant condition such as simulation software, exposure device, phase shift, resist) etc. and experiment is emulated Example 1 is identical.In addition, about light exposure, changed respectively in a manner of obtaining the size of corrosion-resisting pattern shown in following table 7.
In addition, Figure 14 is for the dark areas and the figure that illustrates of area pellucida domain to the phase shifting mask in test example 7.Separately Outside, indicate that dark areas is the example of 1 wire shaped (isolated line) in fig. 14.In addition, the size of dark areas is W2 in Figure 14 Shown in distance.
[table 7]
As shown in table 7, it confirms：In embodiment 13~14, Sidewall angles θ can be made good.
[test example 8]
In addition to using the dimension modifying by the dark areas of the isolated square in test example 6 at size shown in following table 8 Embodiment 15~18 and reference example 6 phase shifting mask and about light exposure to obtain corrosion-resisting pattern shown in following table 8 Other than the mode of size changes respectively, other are found out by the emulation of resist distribution and are exposed identically as test example 6 Corrosion-resisting pattern.
In addition, film slip in table 8 is to indicate the maximum gauge of corrosion-resisting pattern and the difference pair of minimum thickness with ratio Than in the maximum gauge of corrosion-resisting pattern.
[table 8]
As shown in table 8, can confirm：Compared with 15~embodiment of embodiment 18, film slip becomes larger in reference example 6.
[test example 9]
In addition to using the reality by the dimension modifying of the dark areas of the isolated line in test example 7 at size shown in following table 9 Apply the phase shifting mask of example 19~21 and reference example 7 and about light exposure to obtain the size of corrosion-resisting pattern shown in following table 9 Mode change respectively other than, other identically as test example 7, by resist be distributed emulation find out exposed resist Corrosion figure case.
In addition, film slip in table 9 is to indicate the maximum gauge of corrosion-resisting pattern and the difference pair of minimum thickness with ratio Than in the maximum gauge of corrosion-resisting pattern.
[table 9]
As shown in table 9, can confirm：Compared with 19~embodiment of embodiment 21, film slip becomes larger in reference example 7.
From test example 6~9, confirm：In the formation of the linear corrosion-resisting pattern with 0.6 μm or more of multiple sizes In, by by by the present invention dark areas and the progress such as the light shielding part constituted such as area pellucida domain and photomask (for example, chromium film) Combination, 1 phase-shift photomask can be used to form above-mentioned corrosion-resisting pattern.
(industrial applicibility)
The phase shifting mask of the present invention is for having the image display devices such as not up to liquid crystal display or organic el display Manufacturing process used in the resolution of exposure equipment limit size corrosion-resisting pattern formation it is useful.
Symbol description
1A, 1B phase shifting mask
2A, 2B transparent substrate
3A, 3B phase shift portion
The non-phase-shifted portion 4A, 4B
5A, 5B light shielding part
6A, 6B area of the pattern
11A, 11B are processed material (substrate)
12A, 12B photoresist
13A, 13B corrosion-resisting pattern

Claims (7)

1. a kind of phase shifting mask, for by from used g rays, h rays, i rays mixed wavelengths light exposure device Exposure light to which the corrosion-resisting pattern for the design size for being not up to the resolution of exposure equipment limit is formed in processed material On, which is characterized in that
Have：
Transparent substrate；
Phase shift portion concavely or convexly, is set on above-mentioned transparent substrate, is assigned to the light of the exposure from above-mentioned exposure device Give given phase difference；And
Non-phase-shifted portion is adjacent to above-mentioned phase shift portion,
At least either in above-mentioned phase shift portion and above-mentioned non-phase-shifted portion is to be not up to the above-mentioned resolution of exposure equipment limit Size, and the size in above-mentioned phase shift portion is different from the above-mentioned size in non-phase-shifted portion,
Any one smaller performance of size in above-mentioned phase shift portion and above-mentioned non-phase-shifted portion does not make the light on above-mentioned processed material The function of etchant resist exposure, another one performance is caused to make the function that the photoresist on above-mentioned processed material exposes,
In above-mentioned phase shift portion and above-mentioned non-phase-shifted portion the size of the smaller dark areas of size be 0.7 μm~2.75 μ ms in, The ratio between the size of the size and above-mentioned dark areas in larger-size area pellucida domain in above-mentioned phase shift portion and above-mentioned non-phase-shifted portion, be In the case that the size of above-mentioned dark areas is set as 1, the size in above-mentioned area pellucida domain is 1.5 or more,
The size comprising the area of the pattern including above-mentioned phase shift portion and above-mentioned non-phase-shifted portion on above-mentioned transparent substrate is to be on one side 300mm or more,
At least in above-mentioned area of the pattern, the size of the not up to above-mentioned resolution of exposure equipment limit is not set and with photomask structure At light shielding part.
2. phase shifting mask as described in claim 1, wherein
The ratio between the size in above-mentioned phase shift portion and the size in above-mentioned non-phase-shifted portion are 1: 1.5~1: 5.6 or 1.5: 1~5.6: 1.
3. phase shifting mask as claimed in claim 1 or 2, wherein
The aggregate value of the size in above-mentioned phase shift portion and the size in the above-mentioned non-phase-shifted portion for being adjacent to the phase shift portion is that above-mentioned exposure fills Set resolution limit or more.
4. phase shifting mask as claimed in claim 1 or 2, wherein
In above-mentioned area of the pattern, there is the screening for being the size of the above-mentioned resolution of exposure equipment limit or more and being constituted with photomask Light portion.
5. phase shifting mask as claimed in claim 1 or 2, wherein
Above-mentioned concave phase shift portion is disposed on the etching portion of above-mentioned transparent substrate.
6. phase shifting mask as claimed in claim 1 or 2, wherein
The phase shift portion of above-mentioned convex is constituted with the light-transmissive film being set on above-mentioned transparent substrate.
7. a kind of corrosion-resisting pattern forming method, by the corrosion-resisting pattern with the not up to design size of the resolution of exposure equipment limit It is formed on processed material, which is characterized in that
Including：
Using above-mentioned exposure device, by the phase shifting mask of any one of claim 1~6, make to be set to above-mentioned processed material On photoresist exposure the step of；And
By making exposed above-mentioned photoresist develop, to form given corrosion-resisting pattern on above-mentioned processed material Step.
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KR20140104433A (en) 2014-08-28
TW201346430A (en) 2013-11-16
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CN104040428A (en) 2014-09-10
CN109298591A (en) 2019-02-01

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